Methanol To Olefin

Abstract
Process Economics Program Report 261

METHANOL TO OLEFINS
(November 2007)
Ethylene and propylene are by far the two largest volume chemicals produced by the
petrochemicals industry. In 2006 about 110 million metric tons of ethylene and 70 million metric
tons of propylene were produced worldwide. Global demand for light olefins (ethylene and
propylene) is expected to grow at an annual rate of 5% for propylene and 4% for ethylene. Today
the majority of light olefins are produced by the petrochemicals industry either from pyrolysis
(steam cracking) of naphtha or from fluid catalytic cracking (FCC) of naphtha. The recent
dramatic increase in oil prices is reviving a strong interest in the production of light olefins from
non-petroleum source among which low-cost methanol may play a significant role.
Because of the wide variety of feedstock sources and projected massive new capacity
additions in the near future, methanol has promise as an economical, non-petroleum source for
the production of light olefins. At present, the technologies for producing light olefins from
methanol appear ready for commercialization.
In this report, we evaluate one of the most promising new applications for low-cost methanol:
the catalytic conversion of methanol to light olefins. We develop and present conceptual designs
and preliminary economics of the two processes currently available for license—the UOP/Hydro
MTO (methanol-to-olefins) technology based on the MTO-100 silicoaluminophosphate synthetic
molecular sieve based catalyst, and Lurgi’s MTP (methanol-to-propylene) process based on
MTPROP, a proprietary ZSM-5 type of catalyst supplied from Süd-Chemie.
© SRI Consulting PEP Report 261

R eport No. 261
ME T HA NOL T O OL E F INS
by V IC T OR WA N
November 2007
A private report by the

P R OC E S S E C ONOMIC S P R OG R A M
SR I Menlo P ark, C alifornia 94025

SRIC agrees to assign professionally qualified personnel to the preparation of the
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the reports or other deliverables produced by SRIC pursuant to this agreement
For detailed marketing data and information, the reader is referred to one of the SRI
Consulting programs specializing in marketing research. THE CHEMICAL ECONOMICS
HANDBOOK Program covers most major chemicals and chemical products produced in the
United States and the WORLD PETROCHEMICALS PROGRAM covers major hydrocarbons and
their derivatives on a worldwide basis. In addition the SRIC DIRECTORY OF CHEMICAL
PRODUCERS services provide detailed lists of chemical producers by company, product, and
plant for the United States, Western Europe, Canada, and East Asia, South America and Mexico.
CONTENTS
GLOSSARY........................................................................................................................ x
1 INTRODUCTION ........................................................................................................ 1-1
2 SUMMARY ................................................................................................................. 2-1
GENERAL ASPECTS................................................................................................. 2-1
TECHNOLOGY ASPECTS......................................................................................... 2-2
Commercial Methanol to Olefins Technology ........................................................... 2-2
Analysis of Patents ..................................................................................................... 2-2
Process Design .......................................................................................................... 2-3
PROCESS ECONOMICS........................................................................................... 2-4
Methanol to Ethylene and Propylene ......................................................................... 2-4
Methanol to Propylene................................................................................................ 2-4
CONCLUSIONS ......................................................................................................... 2-6
3 INDUSTRY STATUS.................................................................................................. 3-1
ETHYLENE INDUSTRY ............................................................................................. 3-1
Ethylene Feedstock Considerations........................................................................... 3-4
Ethylene End Uses ..................................................................................................... 3-5
Ethylene Supply and Demand .................................................................................... 3-7
Ethylene Prices........................................................................................................... 3-8
PROPYLENE INDUSTRY .......................................................................................... 3-8
Propylene Transportation and Storage ...................................................................... 3-11
Propylene End Uses................................................................................................... 3-11
Supply and Demand of Propylene.............................................................................. 3-13
Propylene Prices ........................................................................................................ 3-14
Production of Primary Propylene................................................................................ 3-16
Propylene from Ethylene Plants ................................................................................. 3-18
Propylene from Refineries .......................................................................................... 3-19
© SRI Consulting iii PEP Report 261

CONTENTS (Continued)
Production of Secondary Propylene........................................................................... 3-20
Propane Dehydrogenation.......................................................................................... 3-21
Metathesis .................................................................................................................. 3-23
Methanol to Propylene................................................................................................ 3-26
METHANOL TO OLEFINS ......................................................................................... 3-28
Olefin Cracking ........................................................................................................... 3-29
R&D Activities by ExxonMobil .................................................................................... 3-30
DMTO Technology ..................................................................................................... 3-30
METHANOL AS FEEDSTOCK................................................................................... 3-31
Regional Capacity Trends .......................................................................................... 3-32
Methanol Prices .......................................................................................................... 3-35
Methanol Shipping...................................................................................................... 3-36
4 UOP/HYDRO MTO PROCESS .................................................................................. 4-1
INTRODUCTION ........................................................................................................ 4-1
COMMERCIAL DEVELOPMENTS ............................................................................ 4-1
Recent Advancements in UOP/Hydro MTO Technology ........................................... 4-3
TECHNOLOGY REVIEW ........................................................................................... 4-4
MTO Catalyst Development ....................................................................................... 4-4
MTO Reactor Design Consideration .......................................................................... 4-6

Fluidization Regimes ............................................................................................ 4-6
Fast-fluidized Bed MTO Reactor .......................................................................... 4-7
Effect of Reaction Temperature and Water as Diluent......................................... 4-9
Effect of Space Velocity........................................................................................ 4-10
Influence of Coke Deposition ............................................................................... 4-10
UOP/Hydro MTO Reaction Conditions................................................................. 4-10
MTO Reaction Mechanism................................................................................... 4-11
MTO Process Chemistry and Kinetics........................................................................ 4-12
© SRI Consulting iv PEP Report 261

CONTENTS (Continued)
Kinetic Models based on ZSM-5 .......................................................................... 4-12

Kinetic Models based on SAPO-34 ...................................................................... 4-12
Product Recovery ....................................................................................................... 4-15
METHANOL TO OLEFINS BY THE UOP/HYDRO PROCESS ................................. 4-15
Process Description.................................................................................................... 4-16

Section 100 - Methanol Conversion ..................................................................... 4-16
Section 200 - Product Separation ........................................................................ 4-17
Process Discussion .................................................................................................... 4-29
COST ESTIMATES .................................................................................................... 4-32
Comparison With Other Technologies ....................................................................... 4-43
MTO Applications ....................................................................................................... 4-43
5 METHANOL TO PROPYLENE BY THE LURGI MTP PROCESS ............................ 5-1
INTRODUCTION ........................................................................................................ 5-1
COMMERICAL DEVELOPMENTS ............................................................................ 5-2
TECHNOLOGY REVIEW ........................................................................................... 5-3
ZSM-5 Catalyst ........................................................................................................... 5-4
Reactor Design and Operation................................................................................... 5-5
Product Recovery ....................................................................................................... 5-6
PROCESS DESCRIPTION ........................................................................................ 5-7
Section 100 - Methanol Conversion ........................................................................... 5-7
Section 200 - Propylene Recovery............................................................................. 5-8
PROCESS DISCUSSION........................................................................................... 5-18
PROCESS ECONOMICS........................................................................................... 5-20
LURGI MTP PROCESS APPLICATIONS .................................................................. 5-28
APPENDIX A: PATENT SUMMARY TABLES.................................................................. A-1
APPENDIX B: DESIGN AND COST BASES .................................................................... B-1
© SRI Consulting v PEP Report 261

CONTENTS (Concluded)
APPENDIX C: CITED REFERENCES............................................................................... C-1
APPENDIX D: PROCESS FLOW DIAGRAM.................................................................... D-1
© SRI Consulting vi PEP Report 261

FIGURES
3.1 U.S Market Prices for Ethylene ............................................................................. 3-8
3.2 U.S. Market Prices for Propylene .......................................................................... 3-15
3.3 U.S. Polymer-Grade Propylene to Ethylene Production and Price Ratios............ 3-16
3.4 Block Diagram of Methanol-to-Propylene Process ............................................... 3-27
3.5 Block Diagram of Coal-to-Propylene Process....................................................... 3-28
3.6 Schematic the UOP/Hydro MTO Process ............................................................. 3-30
3.7 SChematic of the DMTO Process ......................................................................... 3-31
4.1 Reaction Network from MTO Over SAPO-34........................................................ 4-13
4.2 Methanol to Olefins by the UOP/Hydro Process

Flow Diagram ........................................................................................................ D-3
4.3 The UOP/Hydro MTO Process with a DME Recovery Block ................................ 4-30

Effect of Plant Capacity on Investment Cost ......................................................... 4-36

Effect of Methanol Price and Plant Capacity of Ethylene Product Value .............. 4-39

Historical Pre-tax Return on Investment (ROI)...................................................... 4-40

Production Economics at Historical Ethylene and Propylene Prices .................... 4-41
5.1 Lurgi MTP Process Carbon Product Yields, wt%.................................................. 5-5
5.2 Methanol to Propylene by the Lurgi MTP Process

Flow Diagram ........................................................................................................ D-7

Effect of Plant Capacity on Investment Cost ......................................................... 5-24

Effect on Methanol Price on Production Cost and Product Value......................... 5-27
© SRI Consulting vii PEP Report 261

TABLES
2.1 Comparative Economics for Production of Propylene

Economic Summary .............................................................................................. 2-5
3.1 Polymer Grade Ethylene Specifications ................................................................ 3-3
3.2 Global Ethylene Feedstock Consumption in 2006 ................................................ 3-5
3.3 World Capacity for Ethylene by Region................................................................. 3-7
3.4 Typical Propylene Quality Specifications .............................................................. 3-10
3.5 Typical Polymer Grade Propoylene Specifications ............................................... 3-10
3.6 Propylene Supply/Demand Summary for 2006..................................................... 3-14
3.7 Yields of Co-Product Propylene from Ethylene Production .................................. 3-18
3.8 Change in Expected Propylene Feedstock Utilization .......................................... 3-20
3.9 Producers of Propylene from Propane by Dehydrogenation ................................ 3-22
3.10 Producers of Propylene from Ethylene/Butylene Metathesis................................ 3-24
3.11 Historical and Projected World Methanol Capacity, Production and

Consumption by Region ........................................................................................ 3-34
3.12 U.S. Prices and Unit Sales Values for Methanol................................................... 3-35

Design Bases and Assumptions............................................................................ 4-19

Stream Flows......................................................................................................... 4-20

Major Equipment ................................................................................................... 4-25

Utilities Summary................................................................................................... 4-28
4.6 Yields from UOP/Hydro Process MTO Conversion Zone ..................................... 4-31

Total Capital Investment........................................................................................ 4-34

Capital Investment by Section ............................................................................... 4-35

Production Costs ................................................................................................... 4-37
© SRI Consulting viii PEP Report 261

TABLES (Concluded)


Design Bases and Assumptions............................................................................ 5-9

Stream Flow .......................................................................................................... 5-10

Major Equipment ................................................................................................... 5-15

Utilities Summary................................................................................................... 5-17

Total Capital Investment........................................................................................ 5-22

Capital Investment by Section ............................................................................... 5-23

A.1 Conversion of Methanol to Olefins Sapo Catalysts and Reaction Conditions

Patent Summary.................................................................................................... A-3
A.2 Conversion of Methanol to Olefins Zeolite Catalysts and Reaction Conditions

Patent Summary.................................................................................................... A-20
A.3 Conversion of Methanol to Olefins Reactor Design and Operation

Patent Summary.................................................................................................... A-25
A.4 Conversion of Methanol to Olefins Product Recovery

Patent Summary.................................................................................................... A-34
A.5 Conversion of Methanol to Olefins Other Catalysts/Process Integration

Patent Summary.................................................................................................... A-41
© SRI Consulting ix PEP Report 261

GLOSSARY
Symbol or Term Definition
304SS Grade 304 stainless steel

316L SS Grade 316L stainless steel
Å Ångström (1 E-10 m)
µm One millionth of a metre
ABB Asea Brown Boveri (Lummus)
ANSI American National Standards Institute
APC Air Products & Chemicals, Inc.
API American Petroleum Institute
APM 22% Cr, 6.0% Al alloy
ARA Amsterdam Rotterdam Antwerp
ASTM American Society for Testing Materials
ASTM American Standards & Testing Materials Institute
ATL Atlantic
ATR Autothermal reformer
AUD Australian dollar
Avails Availability of cargoes
Avgas Aviation gasoline for piston engines
Backwardation Market situation where prices are highest in the nearest date periods and
are lower in forward delivery dates
Barge A vessel carrying oil usually on rivers - containing between 8,000 to
50,000 bbl or weighing 1000 to 10000 mt.
Barrel A volumetric unit of measure for crude oil and petroleum products. 1 barrel
equals 42 US
bbl barrels of petroleum
BDO 1,4-butane diol
BFW Boiler feedwater
Bill of Lading Documentation associated with a specific cargo of oil and is signed by the
captain of the ship and the contract supplier
Blendstock A component combined with other materials to produce a finished refined
product.
BLI battery limits investment
bn billions
© SRI Consulting x PEP Report 261

GLOSSARY (Continued)
BP British Petroleum PLC

bpd barrels of petroleum per day
bpsd barrels per stream day
BS&W Bottom sediment and water, usually expressed as a percentage by weight.
BTU British Thermal Unit
BTX Benzene, toluene + xylene
BTX extraction The process for removing benzene, toluene and xylene from reformate or
pyrolysis asoline.
Bunker C A residual fuel used as ship’s fuel, usually has a high sulfur content and
high viscosity.
C+F Cost and Freight
CAAA US Clean Air Act Amendments
Cat gasoline (cat naphtha) A gasoline blending component made in a cat cracker.
Catfeed Feedstock to a catalytic cracker, usually vacuum gasoil.
CD Canadian dollar
Cetane A paraffinic hydrocarbon used hydrocarbon used as an additive in diesel
fuel.
Cetane Number Number equal to the percentage by volume of cetane added to basic
diesel fuel to achieve
CFD Contract For Differences. A type of crude oil swap.
Cfd standard cubic feed per day flow rate
CFPP Cold filter plugging point
CH4 Methane
CIF Cost, insurance + freight
CKR coker
Cloud Point The temperature at which a fuel, when cooled, begins to congeal and take
on a cloudy appearance due to the crystallization of paraffins
CNG compressed natural gas
CNR Charterer not revealed
CO Carbon monoxide
CO2 Carbon dioxide
CPOX Catalytic partial oxidation
© SRI Consulting xi PEP Report 261

Cracked fuel Residue remaining after a straight run fuel has been processed by
enhanced refining methods such as cat cracking
CST Centistokes - A way of measuring viscosity similar to seconds.
CTW Cooling tower water
CUM Cubic meters
°C Degree Celsius
°F Degree Fahrenheit
DIA Diameter
DICP Dalian Institute of Chemical Physics, affiliate of Chinese Academy of
Sciences
DME dimethyl ether
DMT dimethyl terephthalate
E-4 C.I.S. high sulfur straight-run feedstock. Formerly called F-10.
EFP Exchange of futures for physicals.
EIA United States Energy Information Administration
EOY End of year
EPA United States Environmental Protection Agency
EPC engineer, procure, construct
EPC Engineer, procure & construct
ETBE Ethyl tertiary-butyl ether
EU European Union
EU European Union
FBP Final boiling point
FCC First class charterer
FCC Fluid catalytic cracker or cat unit.
FCCU Fluid catalytic cracking unit.
FCE Fuel Cell Energy, Inc.
FEED Front end engineering design
FFR French franc
Flash Point The lowest temperature under very specific conditions at which a
combustible liquid will give off sufficient vapor to form a flammable mixture
with air in a standardized vessel
© SRI Consulting xii PEP Report 261

FOB Free on board

FOR Free on rail
FORTIES An oil sector in the British Portion of the North Sea
FOT Free on truck
FR France
FRN Full range naphtha
F-T Fischer-Tropsch
G&A general and administrative costs
G/L Grams per liter
gal gallon
Gasoil An intermediate distillate product used for diesel fuel & heating fuel
GBP Pound sterling
GC gas chromatograph instrument
GDP gross domestic product
GHR Gas-heated reformer
GHR Gas heated reformer
GM General Motors Corp
GOM Gulf of Mexico
GTL Natural gas to liquids
GTL Gas to liquids
H2 Hydrogen
H2O Water
HDA Hydrodealkylation, a process used for making benzene from toluene.
Heavy crude oil Has API gravity lower than 28 degrees. The lower the API gravity, the
heavier the oil.
HHV Higher heating value
HKD Hong Kong dollar
HLS Heavy Louisiana Sweet
HO Heating oil
HP-Mod 26% Cr, 35% Ni, 1.5% Si alloy
HPS High-pressure steam
© SRI Consulting xiii PEP Report 261

HS High sulfur content

HX Heat exchanger
IBP Initial boiling point
ICE Internal combustion engine
ICI Imperial Chemical Industries
IEEE Institute of Electrical & Electronic Engineers
IOC Indian Oil Corp
IPE International Petroleum Exchange
IRR internal rate of return
k thousands
KBR Kellogg, Brown & Root
Kero Kerosene
KO Knock out (drum)

KT Kilo tons
kty kilo tons per year
L.A. Los Angeles
Landed Cost (of The cost of oil off-loaded at a port.
oil)
LAO linear alpha olefins
LHV Lower heating value
Lifting Tankers and barges loading petroleum at a terminal or transfer point.
Light crude oil Has an API gravity higher than 33 degrees. The higher the API gravity, the
lighter the crude oil.
Light products, The group of petroleum products with lower boiling temperatures including
light ends gasolines and distillate fuels
LLS Light Louisiana Sweet
LNG Liquefied natural gas
LPG Liquefied petroleum gas
LPS Low-pressure steam
LS Low sulfur
LSTK Lump sum turn key
© SRI Consulting xiv PEP Report 261

Lurgi Lurgi AG, a company of Air Liquide Group

Micron Micrometre (µm)
MM millions
MON Motor Octane Number
MT metric ton
MTG Mobil Oil methanol to gasoline process
MPS Medium pressure steam
MTBE Methyl tertiary-butyl ether
MTP Methanol to propylene
MTO Methanol to olefins
MW megawatts
MWH megawatt hours
N/A Not applicable
N+A Naphthenes plus aromatics
Naphtha Straight-run gasoline fractions. Used as a feedstock for reforming and as a
petrochemical feedstock
Naphthenic A high naphthenes content
nd non detectable
NGL natural gas liquids
NOR Notice of readiness
NOX Nitrogen oxides
NPH Naphtha
NYMEX New York Mercantile Exchange
O&M operations and maintenance cost
Octane number A measure of the detonation quality of gasoline. The higher the octane
number, the higher the resistance to engine knock
OPEC Organization of Petroleum Exporting Countries
OSI offsites investment
OTO Oxygenates to olefins
Oxygenate Oxygen-containing blend stocks favored for their octane and their clean
burning quality.
Paraffinic A high paraffins content
© SRI Consulting xv PEP Report 261

PG Persian Gulf (Same as Arab Gulf--AG)

Pour Point Lowest temperature which oil will readily flow without disturbance when
chilled.
POX partial oxidation
PPB Parts per billion (weight)
ppm parts per million concentration
PPMV Parts per million by volume
PPMW Parts per million by weight
ROI Return on investment
RON Research octane number
RVP Reid vapor pressure, a measure of a gasoline's volatility.
SAPO Silico-alumino-phosphate
SASOL South African Synthetic Oil, Limited
scf standard cubic feed per day flow rate
scfm standard cubic feet per minute
SG Specific gravity
SHPS Super high pressure steam (120 bar superheated)
SMDS Shell Middle Distillate Synthesis GTL process
SMR Steam methane reformer/reforming
SR Stoichiometric ratio
TCF trillion cubic feet of natural gas
TFC total fixed capital cost
TOS Time on stream
T-T Tangent to tangent
US DOE US Dept of Energy
USAC US Atlantic Coast
USD US dollar
USGC United States Gulf Coast
UST Underground Storage Tank (regulations)
USWC United States West Coast
UOP UOP LLC, a Honeywell Company
© SRI Consulting xvi PEP Report 261

GLOSSARY (Concluded)
XOM Exxon Mobil

XTM 35% Cr, 48% Ni, 1.5% Si alloy
ZSM Zeolites Synthesized by Mobile
© SRI Consulting xvii PEP Report 261

1 INTRODUCTION
Light olefins (ethylene and propylene) have been traditionally produced from petroleum
feedstocks by either steam or catalytic cracking. Methanol, however, is becoming a desirable
feedstock for making light olefins as it is produced from a variety of sources including synthesis
gas derived from coal; natural gas; petroleum liquids; petroleum liquids coke; recycled plastics
and municipal wastes. Because of the wide variety of sources, methanol has promise as an
economical, non-petroleum source for light olefin production.
Recent advances in commercial methanol plant production technology coupled with mega-
methanol plant economies of scale may greatly reduce methanol production costs, especially in
regions with currently underutilized low cost hydrocarbon feedstocks, such as coal, “stranded”
natural gas and petroleum refinery residues. Once this low-cost methanol becomes available in
quantity and a marketing infrastructure becomes operative, a number of new markets for
methanol may emerge.
One of the most promising new applications is the conversion of methanol to light olefins.
Ethylene and propylene are important intermediates in the production of plastics, fibers and other
organic chemicals, which are ultimately consumed in the packaging, transportation and
construction industries and in a myriad of industrial and consumer markets. In 2006, global
ethylene production amounted to 110.3 million metric tons, while production of propylene totaled
69.6 million metric tons. Demand for these light olefins is driven primarily by the growth in
manufacture of polyolefins. Polyethylene resins (LDPE, LLDPE, and HDPE) accounted for 58%
of the global ethylene consumption in 2006. About 61% of the propylene went into the production
of polypropylene resins. Because the market for ethylene and propylene is much larger than that
for methanol itself, this potential new application as olefins feedstock could be an important new
source of demand for methanol. Between 2006 and 2011, world demand for propylene is
expected to grow at an average annual rate of 5.1%; ethylene growth is projected at 4.6%/yr. The
reason for the higher growth in propylene demand is the increasing popularity of polypropylene,
which is being substituted for many other materials and more expensive polymers, especially in
automotive parts.
The technology for producing light olefins from methanol has been investigated by several
companies worldwide. ExxonMobil has conducted significant research efforts in the area, and
since 1995, has developed a dominant patent position. In addition, two technologies are currently
available for licensing: UOP/Hydro MTO (methanol to olefins) and Lurgi’s MTP (methanol to
propylene). The MTO process achieves an overall yield of ethylene plus propylene of about 80%,
with an adjustable ethylene-to-propylene ratio between 0.75 and 1.5. In Lurgi’s MTP process,
propylene is obtained at about 71% yield; the remaining products are primarily higher
hydrocarbons.
This report analyzes recent developments in technologies for producing polymer grade light
olefins from methanol. We present technical and economic evaluations of two available for
license processes for producing propylene and ethylene from methanol. The comparable
production economics is based on the production of propylene.
© SRI Consulting 1-1 PEP Report 261

Recent implementation of numerous coal-to-methanol or dimethyl ether (DME) projects in
China has increased the availability of low cost methanol in China’s coal-rich regions. As a result,
the conversion of methanol to light olefins and higher value derivatives products has attracted
renewed interest.
In Section 4 of this report, we update the conceptual design and economics of the
UOP/Hydro MTO (methanol-to-olefins) technology, which is based on a modified SAPO-34
catalyst. We also evaluate Lurgi’s MTP (methanol-to-propylene) process using a modified ZSM-5
catalyst in Section 5. We previously examined the production of ethylene from methanol in PEP
Report 208, Ethylene from Methane (January 1994), and PEP Report 191, Utilization of Remote
Methane (July 1989).

2 SUMMARY
GENERAL ASPECTS
Methanol is a major chemical building block used to manufacture formaldehyde, MTBE,
acetic acid and a wide range of other chemical products. Because methanol can be produced
from a variety of sources including synthesis gas derived from natural gas; coal; petroleum liquids
coke; recycled plastics and municipal wastes, methanol-based chemicals will assume increasing
importance in replacing high cost petroleum resources.
As one of the most important feedstocks for the petrochemical industry, propylene is
experiencing fast growth driven by the increasing popularity of polypropylene (PP). Propylene is
currently produced almost exclusively as a by-product of either ethylene manufacture or
petroleum refining and expected capacity additions in the ethylene industry over the next few
years will result in less propylene production as a by-product from conventional ethylene plants
due to lighter cracker feedstocks. Because propylene demand is expected to grow faster than
that for ethylene and petroleum-based fuels in the next ten years, the net result is a shortfall of
propylene supply from steam and catalytic cracking relative to demand, a shortfall that will have
to be made-up by direct (or on-purpose) propylene production.
Recent advances in commercial methanol plant production technologies coupled with mega-
plant economies of scale may greatly reduce methanol production costs, especially in regions
with currently underutilized, low cost hydrocarbon feedstocks. For example: current
implementation of large scale coal-to-methanol or dimethyl ether (DME) projects in China has
increased the availability of low cost methanol in China’s coal-rich regions. As a result, the
conversion of methanol to light olefins and higher value derivatives products has attracted
interest in China.
In the meantime, recent discoveries of new natural gas fields in natural gas advantaged
countries combined with improved recovery of associated gas from crude oil production and
advances in LNG industry have somewhat increased the availability of natural gas.
Consequently, the conversion of methane to light olefins and other higher value products has
attracted renewed interest.
In the US, the slowdown in MTBE demand due to phasing out its use in the gasoline is
causing some of the producers in the world to explore alternate utilization of their existing
methanol plants. One such utilization is the conversion of methanol to olefins (MTO). Although a
commercially viable process for direct conversion of natural gas to olefins is not yet available, the
production of methanol by steam reforming of natural gas is a well-established technology. The
recent trend of mega-methanol plants, with capacities of 5,000 t/d or larger, is expected to
increase the availability of low cost methanol, providing a significant economic driving force for its
conversion to light olefins. Because the market for ethylene and propylene is much larger than
that for methanol itself, this potential new market as light olefins feedstock could be an important
new source of demand for methanol.

TECHNOLOGY ASPECTS
Commercial Methanol to Olefins Technology

Mobil (now ExxonMobil) conducted most of the original work on methanol conversion to
ethylene and other lower olefins, using the company’s ZSM-5 family of zeolite catalysts.
However, the conventional ZSM-5 type of zeolite is more suited for methanol conversion to an
aromatics-rich hydrocarbon mixture in the gasoline range. In the 1980s, Union Carbide
discovered that SAPO-34, an aluminophosphate molecular sieve, is an effective catalyst for the
conversion of methanol to lower olefins. The associated knowledge and manufacturing know-how
was later transferred to UOP. In 1992, UOP joined with Norsk Hydro to develop the porosity-
controlled MTO-100 catalyst, a proprietary improvement of the conventional SAPO-34 with better
stability and attrition resistance. The MTO-100 catalyst is the key to the UOP/Hydro MTO
process, which has been offered for license since 1995.
The UOP/Hydro MTO process uses a fluidized bed reactor system at 400-450°C to achieve
about 80% carbon selectivity to light olefins (ethylene and propylene) at almost complete
methanol conversion. The ethylene-to-propylene ratio can be modified within a range from about
0.75 to 1.5 by adjusting the operating severity, with higher temperatures leading to a higher
percentage of ethylene produced. Olefin yields and catalyst performance of the process have
been verified through a 1,100 lb/d (0.5 t/d) methanol demonstration unit operated at Hydro’s
facilities in Porsgrunn, Norway. Although no commercial scale plant using the UOP/Hydro MTO
technology has been constructed, several feasibility studies have been commissioned.
Lurgi has developed a process to convert methanol to propylene (MTP) based on a modified
ZSM-5 catalyst supplied from Süd-Chemie. The methanol feed is first contacted with a fixed bed
of an acidic catalyst to produce an equilibrium mixture of dimethyl ether (DME), methanol, and
steam. This mixture is then converted in a series of fixed catalyst beds at 400-450°C, with more
than 99% conversion of methanol and DME. Different olefin-containing streams are separated
and recycled to the reaction system, resulting in an overall carbon yield to propylene of about
71%. Lurgi built a demonstration plant of its MTP process at Statoil’s Tjeldbergodden, Norway
methanol complex in 2001.
In parallel, Lurgi has been optimizing the MTP process flowsheet including sequence of
component separation and heat integration studies for commercial process design packages. An
important design distinction of the Lurgi MTP process is the conversion of the methanol to
propylene in two sequential reaction steps using multiple catalyst beds in series to limit the
adiabatic temperature increase within each bed. This appears to facilitate the use of fixed-bed
reactors, performance of catalysts, and operational conditions that maximize propylene yields. A
fluidized-bed reactor would probably otherwise be required for temperature control purposes of
the exothermic methanol-to-propylene reaction if it were to be conducted in a single reaction
vessel configuration. Furthermore, a fluidized-bed reactor may limit the choice of catalysts to
those with high attrition resistance but which may not be optimal for propylene production.
Although no commercial-scale plants yet exist, Shenhua Group’s $1.5-billion, coal-to-
chemicals complex using Lurgi’s MTP technology is currently under construction in China’s
Ningxia coal area. Completion is scheduled for early 2009.
Analysis of Patents
SRIC has conducted an extensive survey of MTO patents filed or issued over the period of
1990-2007. To avoid duplication and facilitate the tabulation of results, we have used the U.S.

equivalent of each granted patent, when available. For pending applications in the U.S. or
abroad, the PCT application document (world patent) was used.
In our tabulation and analysis, patent divisions and continuations that describe substantially
the same invention (with slight changes in examples or claims) are treated as a single entry. A
comprehensive list of relevant patents is provided in the bibliography at the end of this report
(Appendices A and C).
ExxonMobil has the largest intellectual property position on methanol to olefins including the
patents transferred to the company after the acquisition of Mobil in 1999. Other companies with
MTO patent positions include UOP, Lurgi/Metallgesellschaft, Van Dijk Technologies, Phillips and
Dalian Institute of Chemical Physics.
UOP and Lurgi have been actively pursuing licensing opportunities for their respective
technologies. DMTO, a process of “Methanol or Dimethylether to Olefins” based on patents held
by Dalian Institute of Chemical Physics (DICP), reportedly has been successfully demonstrated in
a 50 mt(methanol)/d industrial scaling-up testing in 2006. DICP, an affiliate of Chinese Academy
of Sciences, collaborating with the Xinxing Coal Chemical Co., Ltd. of Shaanxi Province and the
SINOPEC Luoyang Petrochemical Engineering Co., reported the DMTO demonstration unit
achieved its product selectivity to lower olefins (ethylene, propylene and butylenes) greater than
90% when methanol conversion was close to 100%.
Process Design
The conceptual design using the UOP/Hydro MTO technology presented in this report is to
produce 611 million lb/yr (277,200 t/yr) of polymer grade propylene and 611 million lb/yr (277,200
t/yr) of polymer grade ethylene at a 0.90 stream factor. This design capacity refers to a feed rate
of 5,000 t/d of methanol. Using proprietary MTO-100 (modified SAPO-34) catalyst, the MTO
reaction section is based on a fast-fluidized system patented by UOP, while the product recovery
and fractionation section follows that of conventional naphtha steam cracking for light olefins
production flowsheet including a propylene-ethylene cascade refrigeration system. Because the
MTO reaction over SAPO-34 catalyst is highly exothermic (25-50 kJ/mol) and the catalyst life is
limited owing to coke formation, in commercial practice a fluidized-bed reactor system appears to
be the best choice. In addition to maintaining steady catalyst activity and constant olefin product
quality, the fluidized bed reactor-regenerator system has excellent heat exchange properties and
provides operational flexibility.
Our concept of the Lurgi MTP process presented in this section is based on the production
of 1,136 million lb/yr (515,000 t/yr) of polymer grade propylene (99.7 wt%) via a fixed-bed reactor
configuration using proprietary MTPROP (modified ZSM-5) catalyst supplied by Süd-Chemie.
Assuming an on stream factor of 0.90 and a propylene product yield of about 71 wt%, this also
corresponds to a methanol consumption of 5,000 t/d on a water free basis. Because the Lurgi
MTP process is for propylene production only with gasoline as a by-product, higher and lower
molecular-weight olefins and hydrocarbons need to be recycled to the reactor section in order to
maximize the overall propylene yield. However, the Lurgi MTP process does not include
requirement to extract and purify either ethylene or butanes. Compared to fluidized reactor
systems, the fixed-bed MTP reactor system is low in risk of scale-up while more complicated set-
up to control reaction temperature is required. Three MTP reactor trains are needed in order to
continuously process 5,000 t/d of methanol. Normally, two MTP reactor trains are in operation
while one reactor train is in either regeneration or in standby mode to ensure continuous
operation of the plant.

PROCESS ECONOMICS
Methanol to Ethylene and Propylene

We have developed a conceptual design using the UOP/Hydro MTO technology to produce
611 million lb/yr (277,200 t/yr) of ethylene and 611 million lb/yr (277,200 t/yr) of propylene at a
0.90 stream factor. With a PEP Cost Index of 718, the estimated total fixed capital (TFC)
requirement is $321.1 million. The FOB cost for battery limits equipment is about $59.6 million, of
which nearly 25% represents reactor costs. Direct installation costs (which include materials and
labor costs for piping, fittings, electrical equipment, instrumentation, insulation, structural
materials, and paint) are $45.2 million. When indirect costs, unscheduled equipment and
contingency are added, the battery limits investment amounts to $149.2 million, or about 63% of
the TFC. The total off-site investment of $134.6 million includes utilities and storage, general
service facilities and waste treatment.
The section-by-section capital investment breakdown for our conceptual UOP/Hydro MTO
plant of base case capacity indicates that the product recovery and fractionation section, which
includes the propylene-ethylene cascade refrigeration system, accounts for the major part (about
58%) of the battery limits investment.
Methanol to Propylene
Based on our interpretation of patents and literature available to us in the public domain, our
concept of the Lurgi MTP process is for the production of 1,136 million lb/yr (515,000 t/yr) of
polymer grade propylene (99.7 wt%) via a fixed bed reactor configuration using a proprietary
Süd-Chemie ZSM-5 catalyst. By-products of Lurgi’s MTP process are gasoline with a high octane
number, LPG and fuel gas.
Assuming an on stream factor of 0.90 and a PEP Cost Index of 718, our estimated total fixed
capital (TFC) requirement for the Lurgi’s MTP process base case design is $212.9 million, which
includes allowance for all off-sites such as waste treatment, utilities, and product storage. The
FOB cost for battery limits equipment is about $19.2 million, with reactor costs representing about
8% of this total. Direct installation costs (which include materials and labor costs for piping,
fittings, electrical equipment, instrumentation, insulation, structural materials, and paint) are $41.0
million. When indirect costs, unscheduled equipment and contingency are added, the battery
limits investment (BLI) amounts to $119.0 million, or about 56% of the TFC. The total off-site
investment of $75.1 million includes an allowance for general service facilities.
The section-by-section capital investment breakdown for our conceptual Lurgi MTP plant of
base case capacity indicates the methanol conversion section, which includes the reaction and
compression equipment, accounts for most of the battery limits investment because there is no
requirement to extract and purify either ethylene or butanes as in the UOP/Hydro MTO process.
Other factors lead to higher estimated cost of this section appears to be the multiple MTP reactor
trains setup and the extensive use of feed/effluent heat exchange equipment to maximize thermal
efficiency. The sizeable hydrocarbon recycle streams appear to be a major consideration in the
sizes and cost of most process equipment in this section.

Table 2.1
COMPARATIVE ECONOMICS FOR PRODUCTION OF PROPYLENE
ECONOMIC SUMMARY
PEP COST INDEX: 718
UOP/HYDRO MTO LURGI’S MTP

A
FEED CAPACITY (MT/DAY) 5,000 5,000
PROPYLENE PRODUCTION (MILLION LB/YR) 611 1,136
------------ ------------ ------------

INVESTMENT ($ MILLIONS)
BATTERY LIMITS (BLI) 186.5 119.0
OFFSITES 134.6 8939
--------- ---------
TOTAL FIXED CAPITAL (TFC) 321.1 212.9
B
PRODUCTION COSTS (¢/LB)
RAW MATERIALS 82.8 43.54

BY-PRODUCTS -62.08 -11.29
UTILITIES 6.70 4.54
--------- --------- ---------
VARIABLE COSTS 27.5 36.79
C
OPERATING LABOR, 5(3)/SHIFT , $41.5/HR 0.30 0.09
MAINTENANCE LABOR, 1.6%/YR OF BLI 0.49 0.17
CONTROL LAB LABOR, 20% OF OPER LABOR 0.06 0.02
--------- --------- ---------
LABOR COSTS 0.85 0.28
MAINTENANCE MATERIALS, 2.4%/YR OF BLI 0.73 0.25

OPERATING SUPPLIES, 10% OF OPER LABOR 0.03 0.01
--------- ---------
TOTAL DIRECT COSTS 27.03 37.33
PLANT OVERHEAD, 80% OF LABOR COSTS 0.68 0.22

TAXES AND INSURANCE, 2%/YR OF TFC 1.05 0.37
--------- ---------
PLANT CASH COSTS 30.79 37.93
DEPRECIATION, 10%/YR OF TFC 5.25 1.87

--------- ---------
PLANT GATE COSTS 36.05 39.80
G&A, SALES, RESEARCH 2.96 2.31

--------- ---------
NET PRODUCTION COST 39.01 42.11
ROI BEFORE TAXES, 25%/YR OF TFC 13.14 4.68

--------- ---------
PRODUCT VALUE 52.15 46.79
-----------------------------------
A
OF METHANOL FEED
B
of PROPYLENE
C
5 for MTO, 3 for MTP

Table 2.1 compares the economics for the production of propylene by the Lurgi MTP
technology and by the UOP/Hydro MTO technology with a common 5,000 mt/d methanol feed
rate. For both processes, the production costs are estimated with methanol priced at 13.6¢/lb,
which is produced in a world-scale plant from natural gas priced at $6.74/MMBtu during calendar
year 2006. All plants are assumed to be located on the U.S. Gulf Coast.
Between the two technologies, the Lurgi MTP process has a lower Total Fixed Capital
(TFC). The variable production costs of the UOP/Hydro MTO process are lower due higher due
to higher value of its by-products. However, the TFC for MTP is about 34% lower than that for the
UOP/Hydro MTO process, leading to a reduction in capital-related fixed costs. Furthermore, a
pre-tax ROI of 25%/yr places the product value of the Lurgi MTP process at 46.8¢/lb, which is
5.2¢ lower than that for the UOP/Hydro MTO process based on per lb of polymer grade
propylene produced using a 5,000 mt/d methanol feed rate.
Overall, the total fixed capital for the UOP/Hydro MTO process is high because of relatively
higher capital investment in its product recovery section. However, the process has an advantage
of shifting costs between ethylene and propylene as market demand for these products varies. In
spite of its relatively low capital investment, the MTP process requires very favorable olefin
pricing conditions to be economically attractive and the competitiveness of both processes
depends on the availability of low-cost methanol.
CONCLUSIONS
Based on our 2007 study for this report including methanol, light olefins supply/demand
trends, and our techno-economic analysis for the production of light olefins from methanol in the
U.S. Gulf Coast, we conclude:
• Conventional steam cracking technologies may be unable to close the gap between
future propylene demand and supply due to the upcoming build-up of ethane-based
crackers.
• As ethane cracking reduces world average ethylene production costs, propylene
production costs may increase.
• The increase in yield of light olefins from FCC units most likely comes at the expense of
gasoline and distillate products.
• In the next 10 years, substantially more propylene will come from direct (or on-purpose)
technological routes such as Lurgi’s methanol to propylene (MTP) process.
• In the light of the anticipated shortage in propylene and the possible oversupply in
methanol from large-scale units, there are excellent market opportunities for Lurgi’s MTP
process.
• Variable production costs including methanol feedstock cost and by-products credit
accounts for 70-85% of MTO/MTP net production cost.
• The UOP/Hydro MTO process offers product yield flexibility, it has an advantage of
shifting costs between ethylene and propylene as market demand for these products
varies.
• Featuring fixed bed reactors and cost-effective catalysts, Lurgi’s methanol to propylene
(MTP) process represents a relatively simple and cost-effective design and operation.

• Production of propylene from methanol via Lurgi’s MTP process would be economically
attractive for a U.S. Gulf Coast location during the calendar year 2006 if methanol
feedstock were available at a cost below 99¢/gal and at a propylene price of 50.5¢/lb –
our estimate of the average propylene price level in a U.S. Gulf Coast location for the last
12 months.
• The economics of the Lurgi MTP process are not particularly sensitive to byproduct
values or production capacity in the ranges investigated. The demand for propylene is
projected to increase at a higher rate than that for ethylene over the next ten years. An
integrated methanol/MTP/polypropylene production complex in the vicinity of a remote
natural gas field or coalmine will result in significant design, economic, and logistical
synergies.
• With one value-added gasoline stream by-product, it is more straightforward to integrate
a Lurgi’s methanol to propylene (MTP) process with a downstream polymer unit.
As the overall MTO/MTP process economics is dictated by the cost of methanol and the
average U.S. methanol market price over the last decade makes the MTO/MTP process highly
uneconomical, it is best suited for being part of an integrated complex in locations with available
low cost natural gas, coal or petroleum coke.

3 INDUSTRY STATUS
The main driving force of commercial methanol-to-olefins production is the use of low-cost
methanol to make value-added end products. This section examines the general characteristics
of the light olefins and methanol industries and presents their global and regional supply and
demand. We also discuss some of the potential new markets that may develop for low-cost
methanol from mega-methanol plants. Our analysis is based on data from SRIC’s World
Petrochemicals and Chemical Economics Handbook programs, as well as on information from
clients and from the trade literature.
ETHYLENE INDUSTRY
Ethylene is used as a raw material in the production of plastics, fibers and other organic
chemicals that are ultimately consumed in the packaging, transportation and construction
industries and in a multitude of industrial and consumer markets. As one of the largest volume
petrochemicals worldwide with such a diverse derivative portfolio, ethylene is often used as a
surrogate for the performance of the petrochemical industry at large. As such ethylene demand is
sensitive to both economic and energy cycles.
In 2006, global ethylene production amounted to 110.3 million metric tons, with an estimated
value of $122 billion. The 2006 production represents an average annual growth of 4.4% from the
2001 level. World consumption is driven mainly by growth in ethylene derivatives, polyethylenes
(low and linear low density and high density) and polyethylene terephthalate (PET), which
together represent 57% of consumption growing 2-6% per year, ethylene oxide/EG (15% of
consumption) growing 4.4% per year, ethylene dichloride/ polyvinylchloride (12%) growing 2-3%
per year, ethylbenzene/polystyrene (8%) growing 3% per year, and other derivatives such as
linear alpha olefins, vinyl acetate, acetaldehyde, EPDM rubber and synthetic ethanol. Linear low
density polyethylene and linear alpha olefins will remain the fastest growing markets with growth
over the next five years reaching 5.5-6% per year. Considering size and growth component, four
product groups in particular are crucial in development of composite ethylene growth and
consumption in the regional markets; these are ethylene oxide/EG, ethylbenzene/polystyrene,
ethylene dichloride/polyvinylchloride, and linear low density/high density polyethylene. Most of
these are ultimately tied to polymer materials, underscoring the importance they play in the world
markets.
A world-scale ethylene unit now produces over 1,000 thousand metric tons per year. The
largest single-unit ethylene plants in operation have capacities of 1,000-1,300 thousand metric
tons per year. The incentive to build these larger plants is the economic advantage of scale
resulting from the reduction in capital requirements and production, especially fixed utility,
maintenance and local tax costs per pound of ethylene.
Construction costs for ethylene plants vary with the choice of feedstock. Ethane-based
facilities require the least capital investment because the small quantities of by-product may not
warrant inclusion of recovery equipment for these products. Naphtha- and gas oil–based crackers
are about 1.5 and 1.7 times more capital intensive than ethane-based plants, respectively.
However, naphtha and gas oil many times are more attractive feedstocks versus ethane because

the value of the by-products obtained from their cracking lowers the overall feedstock cost to the
ethylene producer.
Ethylene can be economically transported by pipeline to achieve a high degree of
downstream integration to the production of value-added ethylene derivatives. Large, flexible
ethylene producers are often integrated upstream to the production of heavy ethylene feedstocks
such as gasoline and refined products; a few are integrated wholly or partially in NGL feedstocks
(ethane and propane) as well.
There is a high degree of product technology standardization in particular with regard to
product quality and purity of polymer grade ethylene product. Competitors therefore focus on
producing the ethylene product at the lowest unit cost. Because of the enormous capital involved
in world-scale ethylene plant construction as well as integration to downstream operations,
barriers to entry and exit are high. Many companies are creating joint projects and alliances in
either monomer or derivative production to spread the investment risk.
Demand for ethylene in the developed regions correlates very well with GDP although
changes in derivative inventories in the short run can have a pronounced influence. Economic
cyclicality therefore affects the timing (and profitability) of new investment in ethylene capacity, as
new capacity additions are typically very large and require lead times of four or more years. In the
United States, the recent major cycles in demand have been five, seven and ten years in
duration. Because of longer than anticipated construction timelines, plants approved around the
top of the demand cycle often start up near the bottom of the next cycle. Such unfortunate timing
for start-ups combined with increasing cracker design size tends to make the impact of
downturns particularly severe and has led to periods of extensive rationalization.
Steam cracking (also known as thermal pyrolysis) of hydrocarbons is the primary process
production of ethylene, accounting for most of the global capacity. After cracking a hydrocarbon
feedstock at 815-900°C and 2.0 atm, cracked gas stream is compressed to about 35
atmospheres pressure to remove condensates and acid gases (hydrogen sulfide and carbon
dioxide) by scrubbing the stream. The resulting stream is dried and cooled to 95-130°C. The gas
portion, consisting primarily of hydrogen, methane, and carbon monoxide, is purified to remove
hydrogen; the remainder is burned as plant fuel. Of the liquid byproducts, ethane and propane
are recycled; acetylene and propylene are hydrogenated to ethylene and propylene, respectively.
Ethylene is separated from propylene and other co-products by distillation. The yield of ethylene
depends on the feedstock and somewhat on the cracking conditions.
Ethylene yields for common feedstocks are as follows (wt%):
• Ethane, 75%
• Propane, 43%
• Butane, 38%
• Condensate, 29.5%
• Naphtha, 29.5%
• Gas oil, 22.0%
Ethylene is also recovered from refinery off-gas streams as well as from ethanol dehydration
(in India, Pakistan Peru), from coal and coal-based liquids (in South Africa) and from direct
cracking of crude United States). Various other schemes to produce ethylene employ a variety of
feedstocks such as acetylene, methane and methanol, but none of these processes is currently
commercialized.
Table 3.1 tabulates typical specifications of polymer grade ethylene.

Table 3.1
POLYMER GRADE ETHYLENE SPECIFICATIONS
ALL PPM BY VOLUME (LESS THAN MAXIMUM LISTED) EXCEPT AS NOTED
Component Typical Specification Specification Range Analysis Example
Ethylene, % min. 99.9 99.9-99.95 99.96-99.97
Methane 500 500 5
Ethane 500 500 360
Methane + Ethane 1,000 1,000 (balance) 365
Acetylene 5 1-5 <1
Propylene 10 10 --
C3+C4 10 10 --
C3+ 10 10-20 <10
C4 + 10 10 --
H2 5 5-10 <2
CO 2 1-5 <1
CO2 5 2.8-5 <1
O2 5 1-5 <1
Water 5 3-10 <3
Chlorides, ppmw 1 1 --
Sulfur as H2S 2 2-5 <1
Carbonyl sulfide -- 20 --
Total sulfur, ppmw 2 1-2 --
Solvents, total -- 10 --
Acetone 5 5 --
Methanol 5 1-5 --
Isopropanol -- -- --
Oil, ppmw 1 1 --
Nitrogen -- 10-100 --
Ammonia 1 1 --
Nitrogen Oxides, ppmw -- 5 --
Benzene 0.5 0.5 --
Total Combined Nitrogen -- 5 --

Sources: [261A028]

Ethylene Feedstock Considerations
Development of feedstock bases for ethylene in the industrial nations has followed varied
routes because of the different natural resource situations of the individual countries. In the
United States, relatively low-priced and abundant sources of natural gas liquids (NGLs—primarily
ethane and propane) were available from the large domestic reserves of natural gas. When
steam cracking processes were first commercialized in the late 1950s and 1960s, U.S. ethylene
producers built plants to utilize the domestic NGLs. U.S. producers, mainly petroleum companies
concerned about anticipated declines in the domestic production of ethane and propane in the
late 1960s and early 1970s, designed plants to crack more economical petroleum liquids—
naphtha and gas oil. However, this approach has two effects: (1) greater quantities of co-
products such as propylene, butadiene and pyrolysis gasoline are produced and must be
marketed to fully minimize net costs; and (2) ethane cracking becomes more attractive if oil
prices increase relatively faster than natural gas prices. U.S./Canadian producers are in a
quandary as to how and when to expand production capacity. Currently, world crude oil, naphtha
and U.S. natural gas prices are at or near record levels but the ratio of oil relative to natural gas
on an energy equivalent basis favor natural gas liquids cracking. On the other hand volatile world
oil prices as well as co-product values from time to time cause economics to favor naphtha
cracking especially in well integrated and developed countries and regions.
Western Europe and Japan lacked easily accessible NGL sources when their steam
cracking industries were developing. At the same time, refineries in Europe and Japan, which
were operating to optimize heating oil production, produced surplus naphtha, which was available
for chemical feedstock. Consequently, ethylene producers in these countries constructed their
steam crackers for petroleum liquid feeds, primarily naphtha, rather than the less accessible
NGLs.
The ethylene industries in Canada and Saudi Arabia have been heavily oriented toward
ethane cracking because of the availability of normally low-cost indigenous ethane supplies in
these countries. In contrast, ethylene producers in Asia (e.g., Singapore, the Republic of Korea
and Taiwan) do not have indigenous ethane and must develop their ethylene manufacture
around naphtha, which is readily available from petroleum refining and/or imports. Since gasoline
does not dominate the overall slate of production of petroleum products in these countries as it
does in the United States, naphtha is usually available for steam cracking. None the less, the
rapid build up in steam cracker capacity in Asia in particular, representing more than 40% of the
total is based on heavy liquid feedstocks. Many analysts are concerned that prices of
naphtha/condensate feedstocks will be in short supply as these new plants come on stream over
2009-2012.
Over the years, fluctuations in hydrocarbon prices and demand for ethylene co-products
(e.g., propylene) have encouraged producers worldwide to retrofit their plants to accept a wider
variety of feedstocks. Today, fortunately many producers have some kind of flexibility to crack
both heavy and light feedstocks in their ethylene plants.
Feedstock flexibility in an ethylene plant is much more complex than conventional fuel
switching in energy processes. The process equipment design in an ethylene plant is generally
optimized for a certain feedstock or mix of feedstocks. Mass flow rates and heat transfer are the
two critical factors that significantly influence process unit design. The ability to switch to
alternative feedstocks is constrained by capacity of critical equipment. For ethylene plants based
on naphtha cracking, light feedstocks such as ethane and propane can usually be interchanged
to minimize equipment constraints. Feedstock substitution is particularly attractive during periods
of low ethylene demand, because at a low operating rate, the process equipment constraints are

reduced or even eliminated. More and more new ethylene steam crackers—especially those with
lower cracking residence times—are being engineered with a mix of furnaces that are tuned to
run light feeds at high severities and at the same time heavier liquid feed at medium-to-lower
severities.
The approximate breakdown of global feedstock consumption in 2006 is shown in Table 3.2.
Table 3.2
GLOBAL ETHYLENE FEEDSTOCK CONSUMPTION IN 2006
Feedstock % Used
Ethane 22
Ethane/Propane 7
Propane 4
Butane 1
LPG (butane/propane) 3
Naphtha/Condensate 43
Gas oil 3
Mixed Feedstocks 14
Refinery off-gas 2
Coal-to-oil streams 1
Total 100
Ethylene End Uses

The largest consumption of ethylene in the world is in the production of low density
polyethylene (LLPDE and LPDE). In 2006, the percentage of global ethylene used for this
purpose was 32%. LDPE is widely used for manufacturing various containers, dispensing bottles,
wash bottles, tubing, plastic bags for computer components, and various molded laboratory
equipment. Its most common use is in plastic bags and rubber tubing. Other products made from
it include:
• Trays & general purpose containers
• Food storage and laboratory containers
• Corrosion-resistant work surfaces
• Parts that require flexibility
• Very soft and pliable parts
• Extrusion coating on paperboard and aluminum laminated for beverage cartons
• Computer components, such as hard drives, screen cards and disk-drives

High Density Polyethylene (HDPE) is the next highest consumer at 26%. It is a highly
resistant and durable thermoplastic often used in
• Food containers and chemical containers
• Chemical-resistant piping systems
• Heat-resistant fireworks display mortars
• Geothermal heat transfer piping systems
• Natural gas distribution pipe systems
• Water pipes, for domestic water supply
• Coax cable inner insulators (dielectric insulating spacer)
• Corrosion Protection for Steel Pipelines
• Snowboard rails/ boxes
• Bottles, suitable for use as refillable bottles
HDPE is also used for cell liners in subtitle D sanitary landfills, wherein large sheets of
HDPE are either extrusion or wedge welded to form a homogeneous chemical-resistant barrier,
preventing the pollution of soil and groundwater by the liquid constituents of solid waste.
Ethylene oxide uses 14%. Ethylene oxide (EO) is produced by the direct oxidation of
ethylene with either oxygen or air. The oxygen oxidation process consumes ~0.85 unit of
ethylene per unit of EO, for a yield of ~75% of theoretical. The air oxidation process consumes
about 0.9 unit of ethylene per unit of EO and represents about 71% of theoretical. Ethylene oxide
is generally converted to other chemicals, mostly glycols. Ethylene glycol is used as automotive
antifreeze and as an intermediate for terephthalate polyester resin for fibers, film and bottles. The
second-largest consumer of ethylene oxide is nonionic surface-active agents for detergents,
cosmetics, toiletries and cleaning compounds. Other outlets for ethylene oxide include di-, tri- and
polyethylene glycols, glycol ethers and ethanolamines.
Ethylene dichloride/vinyl chloride follows on the list with 13% of global consumption. All
ethylene dichloride (EDC) is produced by the direct chlorination or oxychlorination of ethylene.
Ninety-five percent of the EDC consumed worldwide is for the production of vinyl chloride (VCM).
The two main routes from ethylene to EDC involve different synthetic sequences, as follows:
• Direct Chlorination of Ethylene. The liquid- or vapor-phase reaction of ethylene with
chlorine in the presence of a metallic chloride catalyst at 60°C produces EDC
• Oxychlorination of Ethylene. A metal chloride catalyzes the reaction of ethylene with
hydrogen chloride and air or oxygen at 220°C to form EDC. The hydrogen chloride feed
is generally a co-product from the pyrolysis of EDC to vinyl chloride in an integrated vinyl
chloride plant.
Ethylbenzen uses 7%. Ethylbenzene is produced by the Friedel-Crafts alkylation of benzene
with ethylene. Approximately 0.28 unit of ethylene is consumed per unit of ethylbenzene.
Ethylbenzene is also isolated from a mixed xylenes stream by a commercial distillation process
known as superfractionation; however, less than 1% of the ethylbenzene produced worldwide is
manufactured by this process. Virtually all ethylbenzene is converted to styrene and polystyrene
is the largest use for styrene. Polystyrene resins are used in a wide range of products such as
packaging, disposables, toys and housewares. ABS resins are the second-largest outlet for
styrene and are used in the fabrication of pipe and fittings, components for appliances and

automobiles, and other durable items. Smaller uses for styrene include S/B copolymer latexes,
unsaturated polyester resins, SBR elastomers and SAN resins.
Other uses for ethylene include chemicals such as: alpha olefins, vinyl acetate, and
acetaldehyde.
Ethylene Supply and Demand

World capacity for ethylene as of early 2006 totaled 119.5 million metric tons. North
America, Western Europe and Asia accounted for ~80% of world capacity. Table 3.3 presents
world capacity for ethylene by region:
Table 3.3
WORLD CAPACITY FOR ETHYLENE BY REGIONa
(THOUSANDS OF METRIC TONS)
Average
Annual
Growth Rate,
2001-2006
2006 (percent)
North America 34,903 0.7

Western Europe 23,981 1.3
Africa and Middle East 13,497 6.0
Japan 7,593 0.6
China 8,779 13.1
Other Asia and Oceania 18,689 4.0
Central and Eastern 6,960 2.0
Europe
Central and South 4,993 2.9
America
Total 119,395 2.7%
a. Capacities are average for the year.
Approximately 39 million metric tons of global ethylene capacity will be added prior to 2011.
While world operating rates are forecast to remain at 90-92%—tight by historical standards (rates
were 92% during 1988/1987)—through 2007, rates could fall back only to ~85% in 2010 as the
new capacity impacts the market in the next few years. After that time, with higher growth
returning as the industry approaches the next cycle with lower rates of capacity addition,
operating rates will recover to end the next cycle peak in 2015-2016 in the low 1990s.
Of the 39 million metric ton ethylene capacity addition through 2011, 46% will be added by
the advantaged Middle East and another 45% by Asia. On the other hand, traditionally mature
producers such as the United States, Canada and Europe will be adding at best 3% or 1.5 million
metric tons of capacity over the next five years. The chart below presents the percentage of new
investment in a few ethylene derivatives that the Middle East will garner over the next five years.
By 2011, Africa and Middle Eastern, mono ethylene glycol (MEG), polyethylene (PE), styrene,
polystyrene (PS) and polyvinylchloride (PVC) will account for 20-55% of total world production
capacity added over the next five years through 2011 in each resin category.

As the fastest growing ethylene market, the Chinese ethylene industry has a mission to
reduce its reliance on imported derivatives to serve both its domestic needs and the downstream
export market for fabricated polymers/products. China is viewed as the premier manufacturer of
fabricated products for the future as the world takes advantage of its hard-working and low-cost
labor force. The Middle East has positioned itself as the largest geographically advantaged
energy region and the primary supplier to feed this growing “engine” via intermediates and
polymers. In spite the fast growing ethylene and derivative expansion programs in China, self
sufficiency will only be marginally improved as imports of ethylene will be maintained while major
ethylene derivative imports will actually grow.
Ethylene Prices
Figure 3.1 shows the prices of delivered ethylene, fob, U.S. Gulf Coast from 1982.
Figure 3.1
U.S. MARKET PRICES FOR ETHYLENE
1100
1000
900
800
dollars per metric ton
700
600
500
400
300
200
1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 2004 2006
PROPYLENE INDUSTRY
Propylene is second in importance to ethylene as a raw material for petrochemicals.
Propylene is used for the production of polypropylene or for chemical synthesis for acrylonitrile
propylene oxide, oxo chemicals, cumene, and others. It is produced mainly from steam crackers
as a co-product of ethylene production, and from refinery off-gases. It is also produced as on-
purpose product from metathesis of ethylene, dehydrogenation of propane, deep catalytic
cracking of vacuum gas oil, and conversion of methanol. The propylene from the former sources
is considered as primary propylene, while that from the latter sources considered as secondary
propylene.

Three grades of propylene are used to make derivatives:
• Refinery grade, which contains 50-70 wt% propylene, is suitable for making cumene,
isopropyl alcohol, and propylene oligomers, often called polygas chemicals
• Chemical grade (92-96 wt% purity) is used to make acrylonitrile, oxo alcohols, propylene
oxide, cumene, isopropyl alcohol, and acrylic acid
• Polymer grade (>99.5 wt% purity) is used for polypropylene, allyl chloride, and ethylene-
propylene elastomers.
Table 3.4 tabulates typical propylene quality specifications. Table 3.5 shows typical
specifications of polymer grade propylene.
Low-cost natural gas makes the Middle East and countries such as Venezuela and Mexico
particularly attractive sites for propylene capacity export where mixed NGL feeds (including
propane and butane) are increasingly utilized for ethylene production. These countries have been
building propylene supply chain infrastructure to generate volume derivative surplus for export in
the rapidly growing derivatives such as polypropylene, where turnkey increasingly efficient
technology exists. This enables the energy advantaged regions to ship not only propylene but
also the more easily exported "solid" propylene polymers. Where there is strong consumption
demand for derivatives (e.g., China, India), and where these countries may face large imports in
the short term, they are in the process of building their own homeland propylene sources as
much as possible to serve growing demand for polypropylene and other propylene derivatives.
About 6-7% of propylene, nearly twice the percentage of ethylene is traded between regions
on the world market. The cost of shipping the product can become prohibitive if world values are
low. Shipping propylene requires shipping infrastructure and care that are somewhat comparable
to propane. If regions build or increase infrastructure to supply or receive shipments of other
monomers such as ethylene they may also consider the prospects of propylene trade. Yet in
most cases it is usually much more economical to ship propylene derivatives such as
polypropylene, acrylonitrile, propylene oxide, etc. With ample availability of propylene, the U.S. is
currently a large net exporter of propylene derivatives.
Currently the Middle East, North America and Central Europe have surpluses of propylene
to meet the deficits in Western Europe, Asia and South America. By 2011 total propylene trade
flux will actually fall but growing deficits--mostly in Europe (up to 1,000,000 metric tons per year)
and Central Eastern Europe--will be balanced by increased export potential from Africa and the
Middle East. In the meantime, Asia will run only a small deficit and North America will lose its
propylene exporting edge to be become a much smaller world supplier.

Table 3.4
TYPICAL PROPYLENE QUALITY SPECIFICATIONS
Refinery Chemical Polymer

Grade Grade Grade
Propylene (min.), wt% 65.0 92.0 99.5
H2, CO, CO2, N2 (max.), ppmw 100 100 5

C2 & Lighter (max.), ppmw 10,000 4,000 150
Ethylene (max.), ppmw 10,000 100 100
C4 & Heavier (max.), ppmw 10,000 800 150
Butadiene (max.), ppmw 200 20 10
MAPD (max.), ppmw 150 100 10
Sulfur (max.), ppmw 20 1 1
Water (max.), ppmw 100 30 10
Source: [261A030]
Table 3.5
TYPICAL POLYMER GRADE PROPYLENE SPECIFICATIONS
Purity wt% min 99.5

Methane ppmw max 400
Ethane ppmw max 500
Acetylene ppmw max 5
MAPD ppmw max 10
Non-sat C4 ppmw max 10
Sulphur ppmw max 1
Water ppmw max 5
Alcohol + Ketone ppmw max 5
Hydogen ppmw max 5
CO ppmw max 3
CO2 ppmw max 3
O2 ppmw max 5
Propane ppmw max 400
COS ppmv 0.5
C4+ ppmv 10
ethylene ppmv 100
H2O ppmv 5
Butadiene ppmv 5
total di-olefin ppmv 10
green oil ppmv 20
hydrogen ppmv 5
arsenic arsenic 30
phosphide phosphide 30
ammonia ppmv 5
chlorine (as HCI) ppmv 1
Source: [261A029]
© SRI Consulting 3 - 10 PEP Report 261

Propylene Transportation and Storage
Long-distance transport of propylene is generally not necessary, since the olefin is normally
consumed at or near the production site. This is especially true for refinery-grade propylene
producers, which recover propylene from refinery streams for nearby manufacture of such
derivatives as cumene, oligomers and isopropyl alcohol. Most other derivatives plants are
situated near olefin crackers, particularly on the U.S. Gulf Coast, where supplies of chemical- and
polymer-grade propylene are available. Whenever convenient, propylene is distributed by
pipeline, but some supplies are also shipped by tank trucks, tankers and barges. Overall the
equivalent of about 7-8% of world consumption of propylene is traded.
Underground salt caverns or domes are storage sites for most propylene in North America,
particularly in the United States. About half of underground olefins storage capacity is reserved
for propylene.
Salt dome olefin storage in Western Europe is located in Germany, France and the United
Kingdom, but inventory volume data on propylene are not known. Likewise, data on Japanese
inventories of propylene are not available. The bulk of international propylene movement occurs
within continental Europe and North America, using pipelines, tankers and barges for
transportation. However, some propylene traded internationally has also been shipped by sea.
The major drawbacks for seaborne propylene shipments are the high cost of shipping relative to
propylene price and the lack of sufficient receiving terminals and storage facilities. Producers
consider world trade in value-added derivatives more cost-effective and desirable than propylene
shipments. Thus, substantial ocean transport of propylene will probably occur only when
shortages or surpluses of the olefin occur in certain regions.
Propylene End Uses

Propylene is used for the production of polypropylene or for chemical synthesis for acryloni-
trile propylene oxide, oxo chemicals, cumene, and others. The 2006 global consumption can be
breakdown on propylene end use as follows:
Polypropylene (PP) is the major use, accounting for 61% of global propylene consumption.
Polypropylene resins are the fastest-growing commodity thermoplastics worldwide. PP has a low
3
specific gravity (0.90-0.91 g/cm ) and other desirable properties such as relatively high stiffness,
high tensile strength, good clarity, good stress crack resistance and relatively high heat deflection
temperatures. Combining these properties with a relatively inexpensive base price makes PP a
favorable choice in applications where its properties suffice for the intended use. Consequently,
PP has been successful in replacing traditional materials such as paper, glass or metal and has
been able to compete effectively with other polymers such as polyethylene and styrenic polymers
in many applications. Polypropylene resins can be injection molded, blow-molded and extruded
into fibers, films and sheets. Catalyst technology has advanced to provide higher-yield, higher-
selectivity (HY/HS) catalysts that increase PP yields in general and in particular decrease the
need for by-product and catalyst removal steps. The recent commercialization of metallocene
catalysis is expected to produce PP resins with dramatically improved physical and mechanical
properties. At the same time, work continues on advancing traditional Ziegler-Natta catalysts,
some with properties approaching metallocene’s single-site behavior. Catalyst work on PP has
also led to the development of other propylene-based engineering materials (e.g., products from
Montell Polyolefin’s Catalloy and Hivalloy processes). Polymers produced from these
technologies provide access to a broader range of applications for polyolefin-based materials.
Copolymerization improves PP’s impact resistance (particularly at low temperatures) and
changes thermal properties and flexibility. As a result, compounding gives producers more
opportunities to gain competitive advantage through differentiated PP products. For example,

polypropylene compounds with high stiffness have begun to replace ABS in some applications,
particularly in the automotive segment, and glass filled PP can compete with nylons.
Compounding also allows the PP supplier to extend and/or tailor the properties of the resin to fit
the price/performance requirements of a wider range of applications. As the developing countries
in this region shift from a largely agrarian to an industrial economy, there will be growth
opportunities for PP to substitute for paper, metal, wood, glass and natural fibers. In China and
Southeast Asia, consumption of PP is already significant because of the importance of PP film in
the packaging of textiles and general consumer goods and the high usage of polyolefin fibers in
production of agricultural bags and twine. Countries such as South Korea and Taiwan have
expanding automotive industries that consume PP. Unlike many other commodity thermoplastics,
PP consumption in North America and Western Europe continue to exhibit vigorous growth even
though current per-capita consumption suggests a trend toward maturation. Substitution for other
polymers has been one of the most significant driving forces to this growth.
Acrylonitrile, the second-largest chemical derivative of propylene accounting for 8% of global
consumption, is used strictly as an intermediate. Its major outlets include acrylic fibers,
acrylonitrile-butadiene-styrene (ABS) and styrene-acrylonitrile (SAN) resins, adiponitrile (an
intermediate for nylon 66), acrylamide, and nitrile elastomers.
Propylene oxide, accounting for 7% of global propylene, is consumed almost exclusively as
a chemical intermediate for the production of urethane polyether polyols, propylene glycols,
glycol ethers and others.
Oxo alcohols accounts for 6% of global propylene consumption. 2-Ethylhexanol (2-EH), n-
butanol, and isobutanol account for almost all oxo-alcohol production when propylene monomer
feed is used. 2-EH is commonly used as a plasticizer alcohol and is converted primarily to
phthalate esters (DOP) for plasticization of flexible PVC. n-Butanol is a solvent for lacquers and
coatings, especially water-based products, and an intermediate for several chemicals: glycol
ethers and n-butyl acetate solvents, n-butyl acrylate and methacrylate for surface coatings, n-
butylamines, plasticizers and amino resins. Isobutanol and its acetate are also primarily solvents
for surface coatings.
Cumene accounts for 6% of global propylene consumption. Essentially all cumene produced
worldwide is used as a feedstock in phenol plants, which convert it to phenol and acetone by
cumene peroxidation.
Acrylic acid accounts for 4% of global propylene consumption. Most of the acrylic acid
produced worldwide is converted into acrylate esters, such as n-butyl, ethyl, 2-ethylhexyl and
methyl acrylate. The remaining acrylic acid is polymerized to make either polyacrylic acid or
copolymeric materials.
Isopropyl alcohol (IPA) accounts for 2% of global propylene consumption. A variety of
solvent applications comprise the bulk of IPA consumption: surface coatings, printing inks,
rubbing alcohol and household products such as glass cleaners and pine oil disinfectants,
pharmaceutical production, cosmetics, pesticides and chemical processing. IPA provides
appropriate properties, including solvency and evaporation rate, to most of these applications.
IPA is also consumed for the manufacture of chemical derivatives, including isopropylamines,
methyl isobutyl ketone (MIBK), methyl isobutyl carbinol (MIBC), diisobutyl ketone (DIBK) and
isopropyl acetate. Monoisopropylamine (MIPA) demand is split equally between the herbicides
atrazine and glyphosate. MIBK, DIBK and isopropyl acetate are used primarily as solvents in
paints, coatings and inks. MIBC is used in lube oil additives and in froth flotation for ore
beneficiation
Polygas chemicals, which include nonene, dodecene, and heptenes, account for 2% of
global propylene consumption. Nonene, or propylene trimer, has two major end uses:

nonylphenol and isodecyl alcohol. Nonylphenol is an intermediate for surfactants, lubricating oil
additives and phosphite antioxidants. Isodecyl alcohol is a raw material for production of
diisodecyl phthalate, a major polyvinyl chloride plasticizer. Dodecene, or propylene tetramer, is
consumed primarily in the production of dodecylphenol and tridecyl alcohol. Salts of
dodecylphenol are used in lubricating oil additives, mostly for transportation and industrial
equipment. Tridecyl alcohol is consumed for the manufacture of the PVC plasticizer, ditridecyl
phthalate. This phthalate finds use in PVC-jacketed wire and cable applications that require high
temperature ratings. Other dodecene derivatives include dodecylbenzene (DDB) and t-dodecyl
mercaptan.
Other propylene uses include allyl chloride, ethylene-propylene elastomers, and acrolein.
Allyl chloride is an intermediate to crude epichlorohydrin, which is used to produce synthetic
glycerin or refined to a purer material for synthesis of other products, such as epoxy resins.
ethylene-propylene elastomers are consumed primarily in automotive parts.
Supply and Demand of Propylene

Global demand for propylene as crucial petrochemical raw material is forecast to grow at
nearly 5.0% per year over the 2006-2011 time frame, 1.5 times the world economic growth.
Growth will fall back to 4.1% per year over the latter portion of the forecast period with increasing
maturity of the propylene product value chain.
Despite the extra raw material costs generated by propylene shortages, polypropylene, the
main propylene derivative, is still maintaining above average growth at 5.2% over the next five
years as it continues to replace other polymers, especially in packaging. It has remained
competitive against aromatic derivatives, such as polystyrene and PET, although sometimes by
sacrificing margins. At a time when retailers and consumer product companies are trying to cut
packaging costs, polypropylene is still able to prove itself to be more cost effective than
polystyrene in packaging foams. Because polypropylene is stronger than polystyrene,
polypropylene foams require as much as 70% less material.
In film applications, polypropylene is replacing PET because not only does it have greater
price stability but also higher temperature resistance at a time of growing popularity of
microwaveable ready meals. Polypropylene and polyethylene are also benefiting from the way
flexible packaging is expanding its share of the total packaging market because of the need for
retailers and brand owners to save costs by using less and lighter packaging
World propylene consumption is driven by growth in derivatives, particularly polypropylenes
(homopolymer, copolymer and impact grades), which represent 61% of consumption of total
propylene and 97% of polymer grade propylene. Consumption of polymer, chemical and refinery
grade propylene currently represent 64%, 26% and 10%, respectively, of the total world industry
propylene stream. Other than polypropylene the remaining 3% of polymer grade is mainly
demand from EPDM rubber and allyl alcohol. For chemical grade, acrylonitrile (plastics),
propylene oxide (urethanes and PG), 2-ethyl hexanol (PVC plasticizers and functional esters)
and acrylic acid (functional plastic films) are the critical uses representing 32%, 27%, 14%, and
13% each of chemical grade consumption growing 4-6% per year. In the refinery grades, cumene
(60% of refinery grade) and isopropyl alcohol (22%) are the largest uses, growing 5.0% and 3.3%
respectively over the next ten years. As is the case with ethylene, the propylene supply chain is
heavily weighted (representing 75-80% of the total consumption) toward the polymers and their
growth in both mature and developing marketplaces.
In the longer term the availability of new technologies seems likely to avert critical shortages
of propylene.

Table 3.6 summarizes the supply and demand of propylene in major regions of the world in
2006.
Table 3.6
PROPYLENE SUPPLY/DEMAND SUMMARY FOR 2006
(THOUSAND METRIC TONS)
Anticipated Actual
Region Capacity Production Imports Exports Consumption
Africa 876 702 213 56 859
Asia 28,667 27,004 1,140 944 27,200
Central & Eastern Europe 4,415 3,090 267 262 3,095
Middle East 2,987 2,674 2 322 2,353
North America 22,043 17,265 199 612 16,829
Oceania 524 305 305
South & Central America 3,283 2,627 325 194 2,759
Western Europe 17,651 15,910 2,757 2,514 16,179
World Total 80,446 69,577 4,903 4,903 69,577

_______
Source: SRI Consulting
Propylene Prices
Figure 3.2 shows the prices of delivered propylene, fob, U.S. Gulf Coast from 1982. Contract
prices for polymer-grade and chemical-grade propylene are discounted lower than the market
price. These discounts can be a percentage or cents per kilogram discount. Percentage
discounts are usually around 5% below the market price and some can be as high as 9% below
the market price.

Figure 3.2
U.S. MARKET PRICES FOR PROPYLENE
1100
1000
900
800
dollars per metric ton
700
Polymer Grade
Chemical Grade
600
500
400
300
200
1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 2004 2006
_______
Refinery plant economics highly influence the U.S. prices for propylene for chemical use
because chemical propylene produced from refineries must compete economically with potential
energy alternatives for propylene, including gasoline alkylate, LPG and refinery fuel. The
economics of operations at each refinery vary and thus internal values of propylene are
determined on an individual plant basis.
In the long term, the range of propylene values from refiners must also be balanced against
the price that can be obtained for propylene as co-product from ethylene manufacture. Propylene
from olefin plants must be priced to clear supply and allow competing derivatives of ethylene and
propylene (e.g., HDPE and polypropylene or linear alcohols and 2-ethylhexanol) to maintain
satisfactory supply/demand balances. Heavy-feedstock olefin plant economics must consider the
sale of both ethylene and co-product propylene to chemical markets. Otherwise, derivative
market demands will force realignment of olefins prices or substitution of the derivatives. The
price differential, expressed as a ratio of propylene to ethylene prices, was close to parity in
1982, 1984-1985 and 1987. In 1988-1989, the ratio returned to 0.7-0.77, when ethylene
shortages drove prices up significantly in comparison with propylene prices. With the start-up of
additional ethylene capacity, the ratio has been gradually increasing since 1990. It had not
reached parity because of the past predominance of light-feed cracking, which lowers the amount
of co-product propylene produced.
With the increase of U.S. natural gas and NGL prices since the early 2000s ratios had
tended to weaken but strong growth differentials for the main polypropylene vs. polyethylene

derivatives compensated somewhat. As oil prices strengthened in 2004/2005 even the high
natural gas prices in the U.S. put NGL olefins manufacturers at an advantage relative to the rest
of the world. As a rule of thumb whenever the ratio of world oil ($/Bbl) to U.S. natural gas prices
($/MM Btu) is below 7-8, U.S. manufacturers of light feed olefins are at a disadvantage to world
naphtha-fed manufacturers. As oil has pushed even higher recently toward a ratio of 10+ to
natural gas in the U.S., manufacturers have swung toward light feeds with lower resulting
propylene coproduct yields.
Complicating the analysis is the changing octane pool in U.S. gasoline. Rapid removal of
MTBE from the gasoline pool since 2003 has stressed gasoline marketers to substitute ethanol
and/or alkylates of first butylenes and then propylenes as octane backfill. Today alkylates may be
providing high enough value potential for lower-purity refinery propylene relative to higher-purity-
requirement chemical uses to siphon off propylene from the supply base. It is possible that the
extremely high ratios of propylene/ethylene prices in early 2007 are a result of these dynamics
and a harbinger of the future markets.
Figure 3.3 shows historical trends in the relationship.
Figure 3.3
U.S. POLYMER-GRADE PROPYLENE-TO-ETHYLENE PRODUCTION AND PRICE RATIOS
_______
Production of Primary Propylene

Worldwide production of propylene in 2006 was around 70 million tons. Propylene is mostly
obtained from three sources:
• Co-product from steam crackers (accounts for just under 60% of global propylene
capacity) using LPG, naphtha, and gas oil feedstocks, limited quantities of propylene are
also produced at ethane-based plants.
• By-product of petroleum refining represents about 35% of the total propylene production.
Off-gases from catalytic cracking are the primary refinery source of propylene. Other

sources include coking and visbreaking operations. Some refiners will upgrade the
stream through "propylene splitters" (i.e., fractionators of propylene from propane and
other compounds with comparable boiling points) to make chemical or polymer grade.
• On Purpose routes currently represent only 5% of total propylene production.
Dehydrogenation of propane (3% of total) is a relatively expensive alternative, but can be
attractive where propylene from refineries and/or ethylene crackers cannot meet demand
and/or low-cost propane is available.
Small quantities of propylene are made using other specialized routes, including cracking of
vacuum gas oil (VGO). For example, deep catalytic cracking of VGO is a growing source of
propylene in China.
The percentage of propylene obtained from these sources varies throughout the world. In
the United States, where 60% of ethylene is made from ethylene co-product streams by cracking
natural gas liquids, a greater proportion of propylene must be obtained from refineries.
In Western Europe and Japan, cracking of naphtha predominates as the source for
ethylene, so relatively more propylene is available as a co-product. Yet availability is constrained
by lack of investment (as in the United States) in underlying new ethylene units and expansions.
In Western Europe and Japan, about 68-70% of the propylene capacity is based on ethylene co-
product streams.
In Asia, the fastest growing demand region for polypropylene in the world, propylene has
been in tight supply. To alleviate the situation, some major oil companies may build facilities to
recover more refinery propylene. More on purpose units will be built.
The Middle East is the fastest growing production region, based on abundant and low cost
raw materials. Propylene will be manufactured in the Middle East predominantly as an ethylene
co-product and incrementally by propane dehydrogenation.
The leading global propylene producers as of 2006 are listed below. The figures include
participation levels in joint venture operations.
Total Propylene
Company (kmt/y) Global Capacity
Exxon Mobil Corporation 5,850

Shell 4,731
China Petrochemical Corporation 4,490
Total 3,456
Dow Chemical Company 2,940
China National Petroleum 2,932
Lyondell Chemical 2,700
Formosa Plastics Group 2,340
Ineos 2,233
BASF 1,882
ConocoPhillips 1,782
SABIC 1,723
Reliance Industries 1,690
EniChem 1,591
Enterprise Products 1,487
All others 38,621
TOTAL 80,446
_______

Propylene from Ethylene Plants
It is widely recognized that naphtha steam crackers are the largest source of propylene with
approximately 60% of the production of propylene in the world is supplied from thermal steam
cracking. Ethylene units provide both chemical and polymer grade of propylene.
In ethylene manufacture by steam cracking, propylene is a coproduct with ethylene. The
degree to which propylene is made depends on the feedstock and the severity of the reaction
conditions. Heavier, petroleum-based (or liquid) feedstocks produce more propylene than lighter,
natural gas-based feedstocks for a given ethylene yield. Milder reaction conditions (i.e., lower
temperatures and longer residence times) also result in a higher proportion of propylene
production than do more severe conditions. Because the price of propylene has historically been
lower than that of ethylene, olefin producers are concerned primarily with the production of
ethylene, propylene production being of secondary importance. The amount of propylene that an
existing ethylene producer is willing to produce depends on the technical configuration of the
plant and the economic incentive for increasing production.
Table 3.7 presents the minimum and maximum amounts of propylene typically obtained from
cracking various feedstocks. The approximate amount of feedstock required to produce ethylene
and its co-products is also presented. Ethane and propane are assumed to be recycled to
extinction for all feedstock categories.
Table 3.7
YIELDS OF CO-PRODUCT PROPYLENE FROM ETHYLENE PRODUCTION
Pounds of Pounds of
Cracking Feedstock per Propylene per
Feedstock Severity Pound of Ethylene Pound of Ethylene
Ethane High 1.24 0.024
Propane Medium to high 2.18-2.67 0.37-0.45
n-Butane High 2.65 0.41
Naphtha Medium to high 2.60-3.77 0.40-0.57
Atmospheric Gas Oil Medium to high 3.60-4.09 0.54-0.62
Vacuum Gas Oil Medium 4.24-4.44 0.58
_______
For gaseous feeds, ethane requires the highest coil outlet temperature and longest
residence time to achieve a commercially acceptable conversion. As the molecular weight of the
feedstock increases, it becomes easier to crack, and reaction severity decreases. Propane is
easier to crack than ethane at a given operating condition. Normal butane should be cracked at
the highest possible conversion per pass because unconverted n-butane dilutes the C4s product,
making butadiene recovery more difficult. For liquid feeds, straight-run gasoline, naphtha, and
gas oil compositions vary with source and with refinery operating conditions. Some feedstocks
are highly saturated; some are naphthenic; and some are aromatic.
In the United States, main feedstock for the steam crackers is C2-C4 paraffins, which
produce less amounts of propylene with respect to ethylene. The yield of propylene from a
naphtha cracker is about 15 wt% of the naphtha feedstock while the yield of ethylene is about
twice the propylene yield. Thus, the propylene/ethylene product ratio for a naphtha cracker is

approximately 0.5. Because ethylene has historically averaged a higher market price than
propylene, ethylene producers have primarily built naphtha crackers to meet their ethylene
demands and recovered propylene as a co-product. Depending on the type of feedstock and
cracking severity, cracking of naphtha or gas oil produces propylene at a weight ratio of
propylene to ethylene (C3=/C2=), ranging from 0.35 to 0.65. As shown in Table 3.6, ethane yields
only small amounts of propylene with a C3=/C2= ranging from 00.2 to 0.04. In the latter case,
propylene is recovered from the splitters only when economic incentive exists so that propylene
from FCC is not used to produce high octane alkylates for gasoline.
In the Middle East, the availability of ethane at stranded gas prices has attracted a large
build-up of ethane-based steam cracking capacity over the next few years. As a result of the
build-up of ethane-based crackers, the propylene production rate from steam crackers is
anticipated to fall to 0.36 tons of propylene per ton of ethylene by 2014. Over the same time
period, the demand for propylene is expected to increase relative to the demand for ethylene
(from 0.59 tons of propylene per ton of ethylene today to 0.62 tons of propylene per ton of
ethylene in 2014.
Propylene from Refineries

The second largest source of propylene produced as a building block of petrochemicals is
from fluid catalytic cracking (FCC) units. The primary function of the FCC unit is to produce
gasoline and propylene is produced as a co-product. Conventional FCC technology yields
approximately 3-5 wt% propylene and about 1-2 wt% ethylene. It is often uneconomical to
recover the ethylene from conventional FCC units, while propylene is utilized for motor fuel
production through the use of alkylation or catalytic condensation processes. However, higher
growth of propylene demand in recent years has attracted the refiners to shift the production from
alkylates for gasoline to propylene and some refineries have installed a propylene recovery unit
(PRU) to produce polymer-grade or chemical-grade propylene. This is especially prevalent in
locations such as the U.S. gulf coast where refineries are in close proximity to petrochemical
plants. However this situation could be reversed again as the economic incentive disappears,
particularly when alkylates are used as alternative to MTBE, which is phasing out its use in
gasoline in the U.S.
Assuming the refinery can satisfy its gasoline demand, it has an option to recover surplus
propylene for the chemical markets. Refinery grade propylene typically contains 50-70%
propylene and 30-50% propane. For most chemical purposes, this propylene must first be
purified to either chemical or polymer grade, with typical specifications shown in Table 3.5.
In a typical recovery system, refinery grade propylene is first washed with a caustic solution
to remove hydrogen sulfide and mercaptans. The C3 stream is sent to a deethanizer, where the
small amounts of ethane and ethylene present in the feed are distilled overhead. Propylene is
then separated from propane in a C3 splitter. Because of the small volatility differences between
propylene and propane, this separation typically requires high reflux ratios and a large number of
distillation trays. Frequently the distillation column is divided into two towers to reduce the column
height-to-diameter ratio. Many propylene fractionator designs incorporate vapor recompression
schemes based on the principle of the heat pump, i.e. the overhead vapors are compressed and
used as heat medium in the column’s reboiler. Through vapor recompression, it is possible to
operate at lower tower pressures (85-135 psig, versus 250 psig for conventional distillation). As a
result, lower reflux ratios and fewer distillation stages are required.
The production of polymer grade propylene usually requires additional purification steps
after propane separation. Contaminants such as water, carbonyl sulfide (COS), arsine, and
phosphine can be removed via solid bed adsorption with a combination of molecular sieves and

activated alumina. Hydrogenation reactors may also be required to meet the tight specifications
on dienes and acetylenes.
Refinery FCC units are expected to fill some of the propylene supply/demand gap but there
are logistic and strategic issues that inhibit some refineries from recovering the full propylene
potential from their FCC units. For example, some refiners may choose to increase the propylene
yield and selectivity from FCC unit by using specially formulated catalysts and/or shape-selective
catalyst additives but the increased yield of propylene and other light olefins is at the expense of
gasoline and distillate products.
Other propylene-producing processes that can be integrated into refineries include the Total
Petrochemicals/UOP Olefin Cracking process and the KBR Superflex process, which is a
fluidized catalytic cracking technology that converts low-value streams such as mixed butenes,
pentenes in ethylene plants and FCC light gasoline and coker gasoline streams in refineries with
a high degree of selectivity to light olefins. It is licensed by KBR and is based on Lyondell
Chemical Company's developments and patents. According to KBR, Superflex technology can be
used for stand-alone production units or integrated into existing olefins plants. The first
commercial Superflex unit is currently under start-up for SASOL in South Africa.
Production of Secondary Propylene

Table 3.8 summarizes main propylene sources in 2006 and forecast for the next decade.
Table 3.8
CHANGE IN EXPECTED PROPYLENE FEEDSTOCK UTILIZATION
Propylene Feedstocks 2006 2011 2016
Ethylene coproduct - chemical grade 19.40% 14.94% 13.63%
Ethylene coproduct - polymer grade 39.72% 36.29% 37.47%
Refinery byproduct - refinery grade 8.73% 7.29% 6.36%
Refinery byproduct - chemical grade 9.98% 8.90% 7.65%
Refinery byproduct - polymer grade 16.37% 18.15% 18.06%
Deep catalytic cracking of VGO 0.61% 0.76% 0.62%
Others/On purpose routes 5.20% 13.67% 16.20%

_______
At present, only about 5% of total propylene production worldwide is produced by on-

purpose processes including propane dehydrogenation (PDH) and metathesis of ethylene and
butylenes. The product thus prepared from these processes is considered as secondary
propylene. So far, the propane dehydrogenation process has been the major source. Technically,
dehydrogenation of n-butane or n-butene to butadiene also yields some propylene. However, the
amount of propylene per unit of butadiene is very small. It is often not economical to recover
propylene from such a plant.

Other on-purpose processes gaining interests include Lurgi’s Methanol-to-Propylene (MTP)
process and UOP/Hydro Methanol-to-Olefins (MTO) process using a fluidized bed reactor-
catalyst-regenerator system to co-produce propylene and ethylene from crude methanol. Both
technologies are discussed in details in Section 4 and 5.
Propane Dehydrogenation
Propane can be catalytically dehydrogenated at 500-675°C to propylene and produce
hydrogen as a byproduct according to the following general reaction:
C3H8 C3H6 + H2 Endothermic (+30.4 kcal/g-mole)
This highly endothermic reaction is typically carried out in the gas phase over a solid
catalyst. The reaction is an equilibrium reaction, with the forward reaction favored at high
temperature and low pressure. In commercial applications, however, the use of very high
temperatures is limited by side reactions, such as further dehydrogenation of the olefin product,
and cracking, which can result in unwanted by-products and excessive coke formation.
Commercially, several processes are available for the production of secondary propylene by
catalytic dehydrogenation of propane. Among the technologies are UOP’s Oleflex® propane-
butane dehydrogenation process and Sud-Chemie’s (United Catalysts Inc./ABB Lummus Houdry)
CATOFIN® process. Krupp Uhde entered the propane dehydrogenation licensing business by
acquiring Phillip’s Star process in 1999. Linde of Germany also licenses a propane-butane
dehydrogenation process. Phillips Petroleum and Shell hold patents on similar processes.
The first commercial plant based on propane dehydrogenation (PDH) was started up by
Thailand’s National Petrochemical Company in early 1990, followed by plants in the Republic of
Korea, Belgium, Malaysia and Mexico in 1995. These plants have not operated consistently since
start-up because of operating problems and/or prevailing propylene market conditions. The
economics of propane dehydrogenation have been improved by technological advancements.
For example, the Olexflex process uses a platinum DeH-14 catalyst, which was introduced in
2001 as the fifth generation of catalyst. As a result, propylene selectivity has increased. The
ability to build large-scale propane dehydrogenation plants should also improve the economics of
propane dehydrogenation production of propylene.
The economic incentive for propane dehydrogenation (PDH) depends largely on the price
differential between propylene and propane. For propane dehydrogenation to be cost
competitive, there must be a price differential between propylene and propane of at least $200
per metric ton. Consequently, the most likely candidates to invest in the PDH route are
companies with a strategic interest in propylene derivatives, located in areas with abundant
supply of propane and little supply of traditional propylene sources. In the United States, because
the overall supply of propylene from existing refinery and co-product sources will be more than
adequate to meet demand and since propane is valued as a premium LPG fuel; these methods
are not likely to be commercialized. However, propane dehydrogenation could prove economical
in areas that have limited availability of heavy feedstocks such as naphtha and/or gas oil.
Propane dehydrogenation could also be commercially viable in areas that lack sufficient refinery
propylene for recovery for chemical purposes
The following table lists current producers of propylene from propane as well as companies
that have announced capacity projects in the future:

Table 3.9
PRODUCERS OF PROPYLENE FROM PROPANE BY DEHYDROGENATION
Annual Capacitya
(thousands of
metric tons)
Company and Date on
Plant Location 2006 Future Stream
Belgium
Borealis Kallo (formerly NSP Olefins N.V.) Kallo 480 480
Egypt
Egyptian Propylene & Polypropylene Port Said -- 350 2009
Oriental Petrochemicals Ataqua -- 320 2007
Korea, Republic of
Hyosung Corporation (formerly Tong Yang Nylon Co., Ltd.) Ulsan 165 165
Tae Kwang Industrial Co., Ltd. Ulsan 250 250
Malaysia
MTBE Malaysia Sdn. Bhd. Gebeng Gebeng 300 80 300 80
Mexico
Pemosa Morelos, Veracruza
On standby since 1995. (175) (175)
Russia
Irtyshpolymer (formerly known as Tobolsk Neftekhimkombinat) Tobolsk 180 180
Saudi Arabia
Ibn Zahr Al Jubail 75 75
National Propylene Yanbu -- 420 2010
Saudi Polyolefins Yanbu 460 460 2004
Spain
BASF SONATRACH PropanChem
Tarragona 350 350
Thailand
PTT Chemical
(formerly National Petrochemical)
Map Ta Phu -- 310 2008
Map Ta Phu 126 126
Venezuela
Petropropanos
Jose -- 250 2007
Total 2,466 4,116
_______

As shown in Table 3.8, global propane dehydrogenation on-purpose propylene capacity will
increase rapidly. By 2011 about 4,100 thousand metric tons will be in operation. Of interest is the
fact that companies adding metathesis capacity will not be adding propane dehydrogenation
capacity and vice versa. The only exception is Saudi Arabia, which will be adding large amounts
of both types of on-purpose capacity.
Also, in many cases, the above companies produce or have plans to produce polypropylene
resins. The growing propylene requirement for polypropylene in these areas, coupled with the
lack of sufficient domestic sources of ethylene co-product or refinery-generated propylene,
makes propane dehydrogenation an attractive route to propylene.
Metathesis
Olefin metathesis (or disproportionation) processes are based on the conversion of one or
more olefinic compounds into other olefins of different molecular weights. These processes are
commercially attractive because they allow rebalancing the light olefins from steam or catalytic
cracking (ethylene, propylene and butylenes) according to different process needs and market
conditions. Other metathesis applications include the oligomerization of ethylene to long-chain α-
olefins and the synthesis of polyalkenamers from cyclic alkenes.
Propylene is formed by the metathesis reaction of ethylene and butylene-2 according to the
following general reaction:
C2H4 + CH3-CH=CH-CH3 2C3H6 Exothermic (-0.4 kcal/g-mole)
The reaction is essentially equilibrated and can be made to proceed in either direction. For
propylene production, an excess of ethylene can be used to favor the forward reaction. Typical
operating temperatures are 300–500°C (572–932°F) using W- or Mo-based catalysts, or 20–
50°C (68–122°F) using Re-based catalysts. The main reaction by-products are C5+ compounds,
such as pentene-2 and hexene-3.
If a C4 feedstock is not readily available, ethylene can be converted to propylene by first
dimerizing ethylene to butylene-2 and then reacting additional ethylene with butylene-2 to form
propylene by metathesis. This alternative was examined in PEP Review 85-2-1, Propylene from
Ethylene by Disproportionation (May 1986).
Phillips Petroleum developed its metathesis technology, known as the Triolefin Process, in
the 1960s. The process uses a vapor-phase fixed-bed reactor with a tungsten oxide catalyst that
is periodically regenerated. In 1985, ARCO installed the first plant using this technology to
produce propylene from ethylene. The plant was integrated into ARCO’s Channelview, Texas
facility (currently owned by Lyondell) and has a capacity of 1 billion lb/yr (454,000 t/yr) of polymer
grade propylene.
Phillips’ metathesis technology was acquired by ABB Lummus in 1997 and is now offered for
license as Olefins Conversion Technology (OCT). In addition to Lyondell’s 270 thousand metric
ton-per-year plant, BASF Total Petrochemicals built a 310 thousand metric ton-per-year
propylene unit using OCT, which came on stream in 2003. The BASF Fina olefins unit at Port
Arthur, Texas which converts local ethylene and butylenes to propylene started up in 2004 and
augments production from the ethylene plant, which has an annual capacity for 880 thousand
metric tons of propylene.
Institut Français du Pétrole (IFP) has also developed an ethylene-to-propylene metathesis
process, called Meta-4. The process uses a moving-bed, liquid-phase reactor with a
rheniumbased catalyst that is continuously regenerated. A demonstration plant of the Meta-4
process was operated at the Chinese Petroleum’s Kaoshiung facility in Taiwan during 1988-1990.

Although the capital investment for a metathesis plant is relatively low, the process requires
very favorable olefin pricing conditions to be economically attractive because metathesis of
ethylene is a process in which Ethylene (40%) and Butylenes (60%) are combined in a
disproportionation reaction to produce propylene. This process is especially valuable where
incremental propylene is desirable from undervalued butylenes streams. As a result, the benefits
of the metathesis technology are more evident when it is integrated with a steam cracker or FCC
unit. In a typical naphtha cracker, propylene production can only be increased by reducing the
cracking severity, which reduces the ethylene yield and increases the C4s fraction. With an
integrated metathesis unit, the naphtha cracker can operate at propylene-to-ethylene ratios
above 1.0 without significant reduction in ethylene production. This increased flexibility allows
operation to be optimized according to the relative prices of ethylene, propylene and butylenes.
Table 3.10 presents current and future producers of propylene from ethylene and butylene
metathesis:
Table 3.10
PRODUCERS OF PROPYLENE FROM ETHYLENE/BUTYLENE METATHESIS
a
Annual Capacity
(thousands of
metric tons)
Company and Date on
China
Shanghai Secco Petrochemical
Caojing, Shanghai 140 140
Germany
OMV Deutschland
Burghausen -- 350 2010
Indonesia
Pertamina
Balongan -- 100 2008
Israel
Carmel Olefins
Haifa 20 40
(40)
Japan
Nippon Petrochemicals
Kawasaki, Kanagawa 113 150
(150)
Osaka Petrochemicals
Sakai, Osaka 148 148

Table 3.10 (Concluded)
PRODUCERS OF PROPYLENE FROM ETHYLENE/BUTYLENE METATHESIS
a
Annual Capacity
(thousands of
metric tons)
Company and Date on
Korea, Republic of
Korea Petrochemical
Onsan 110 110
LG Petrochemical
Yeochon 30 30
Malaysia
Titan Petrochemical
Tasir Gudang -- 150 2008
Qatar
Qatar Honam JV
Messaieed -- 350 2010
Saudi Arabia
Al Kayan
Al Jubail -- 300 2010
Ibn Zahr
Al Jubail -- 150 2008
Singapore
Petrochemical Corp. of
Singapore
Pulau Ayer Merba 80 160
(160)
Taiwan
Formosa Petrochemical
Mailio -- 250 2007
United Arab Emirates
Borouge
Ru Wais -- 700 2009
United States
BASF Total
Port Arthur, Texas 315 315
Lyondell (Equistar)
Channelview, Texas Total 300 300
Total 1,256 3,743
a. Data in parentheses represent full nameplate capacity.

As shown in Table 3.10, nearly two times as much as the current 1,256 thousand metric ton-
per-year metathesis capacity will be added over the next five years. By 2011, ~3,700 thousand
metric tons will be in operation. The Middle East, by virtue of its access to undervalued butylenes,
will add nearly 1,500 thousand metric tons.
Methanol to Propylene
The conversion of methanol into light olefins has been studied as a source to boost
propylene output for the industry. Lurgi has developed a MTP (methanol-to-propylene) process
using a propriety catalyst exclusively supplied by Süd-Chemie. This zeolite based MTP catalyst
was a result of several years of intensive co-development between Süd-Chemie and Lurgi.
Lurgi’s MTP process begins with a vapor phase dehydration of methanol to dimethyl-ether
(DME) process, in which vaporized methanol is catalytically converted over γ-alumina at
temperatures between 250°C and 300°C to produce an equilibrium mixture of DME, methanol
and steam. This mixture is then converted in a fixed-bed MTP reactor at 450-500°C (842-932°F)
in the presence of steam, with more than 99% conversion of methanol and DME. The low coking
tendency of the catalyst makes it sufficient to provide for a simple, discontinuous catalyst
regeneration process in the reactor itself. The raw propylene is obtained which can be purified to
polymer grade propylene. Different olefin-containing streams are separated and recycled to the
reaction system, resulting in an overall carbon yield to propylene of about 71%. By-products of
Lurgi’s MTP process are gasoline with a high octane number (RON ~98.7 / MON ~85.5), LPG
and fuel gas.
The viability of the Lurgi MTP process has been proved at a demonstration unit operated
jointly with Statoil at Statoil's methanol plant in Norway [261A018]. In 2001 Lurgi built a skid-
mounted MTP demonstration unit and installed it at Statoil’s Tjeldbergodden, Norway methanol
complex to gain valuable insights of MTP process design and operation while demonstrating
MTP technology’s capability of producing true polymer-grade propylene. In 2003, to confirm the
quality of the propylene obtained in the MTP demonstration unit, samples were sent to Borealis'
Innovation center in Rønningen, Norway, where it was polymerized with Borealis' Borstar process
to polypropylene that met all specifications, and converted into thermoformed cups.
The results helped Lurgi to determine the service life of the catalysts under realistic
conditions by continuously taking in the methanol feed from the final purification column of the
Statoil plant and testing influence of “real“ hydrocarbon recycles on product yield and catalyst
activity. The results from the demonstration unit tests proved that the MTP catalyst life exceeds
one year of operation. The results also showed that the zeolite-based catalyst could be easily
regenerated more than a dozen times.
propylene in two sequential reaction steps. DME is produced as the primary intermediate in the
first step, which is then converted to propylene in a separate reactor system in the second step.
This appears to facilitate the use of fixed-bed reactors, performance of catalysts, and operational
conditions that maximize propylene yields.
Methanol can be produced from a variety of sources including synthesis gas derived from
natural gas; coal; petroleum liquids coke; recycled plastics and municipal wastes. Soaring oil
prices have caused coal producers to investigate the possibility of using coal gasification as a
route to make petrochemicals at a competitive cost.

chemicals complex (block diagram shown in Figure 3.5) using Lurgi’s MTP technology is
currently under construction in China’s Ningxia coal area. The facility will produce 540,000
mt/year of polypropylene from coal via the methanol-to-propylene (MTP) route. Completion is
scheduled for early 2009 [261A017]. Reportedly, Datang International Power Generation’s MTP
project in China and Fanavaran Petrochemicals’ MTP project in Iran have been experiencing
delays [261A017].
As stated earlier, it is usually much more economical to ship value-added olefin derivatives
because the cost of shipping coal can be prohibitive. In addition, there are now scenarios
developing in which it could be viable the low cost methanol being shipped to some countries
where there is not much refining or ethylene capacity as a source of propylene then be turned
into propylene through the MTP process.
Figure 3.4 presents a block diagram of the Lurgi’s MTP process, which is discussed in detail
in Section 5.
Figure 3.4
BLOCK DIAGRAM OF METHANOL-TO-PROPYLENE PROCESS
[Source: 261A125]

Figure 3.5
BLOCK DIAGRAM OF COAL-TO-PROPYLENE PROCESS
[Source: 261A125]
METHANOL TO OLEFINS
One of the attractive methods for ethylene and propylene production is based on catalytic
conversion of methanol because methanol can be manufactured in large quantities from a wide
range of resources including natural gas, coal and renewable biomass.
The availability of low-cost methanol provides a significant driving force for its conversion to
olefins. As one of the two technologies currently available for licensing, the UOP/Hydro methanol-
to-olefins (MTO) process achieves an overall yield of ethylene plus propylene of about 80%, with
an adjustable ethylene-to-propylene ratio between 0.75 and 1.5.
Because the market for ethylene and propylene is much larger than that for methanol itself,
this potential new application as olefins feedstock could be an important new source of demand
for methanol. According to SRIC’s estimates, for every 10 million metric tons of additional
ethylene and propylene capacity and If all this incremental demand were supplied by the
conversion of methanol to olefins, about 30 million tons of methanol would be required, which is
equivalent to the total world production of methanol in 2001.
UOP/Hydro has developed a MTO (methanol-to-olefins) process using a fluidized bed
reactor-catalyst regenerator system to co-produce ethylene and propylene from crude methanol.
In 1992, UOP joined with Norsk Hydro to develop the porosity-controlled MTO-100 catalyst, a
proprietary improvement of the SAPO-34 with better stability and attrition resistance for use in a
fluidized bed MTO reactor. The MTO-100 is the key to the UOP/Hydro MTO process, which has
been offered for license since 1995.
The UOP/Hydro MTO process uses a fluidized bed reactor at 420-480°C to achieve about
80% carbon selectivity to light olefins (ethylene and propylene) at almost complete methanol
conversion. The ethylene-to-propylene ratio can be modified within a range from about 0.75 to
1.5 by adjusting the operating severity, with higher temperatures leading to a higher percentage
of ethylene produced. Olefin yields and catalyst performance of the process have been verified at
a 1,100 lb/d (0.5 t/d) methanol demonstration unit operated at Hydro’s facilities in Porsgrunn,
Norway. Although no full-scale plant using the process has been licensed, several feasibility
studies have been commissioned [261A126]. Egypt Arab Trading (EATCO) was the first

company to announce firm plans for an MTO project. The initial plan was for a 400,000 t/yr olefins
unit (with an ethylene: propylene ratio of 1:1) located in Suez and expected onstream in 2004.
According to recent news, however, the project has been delayed [261A127]. Other potential
sites for MTO units include Nigeria, China, Trinidad, Australia, and the Netherlands.
Figure 3.6 presents a schematic of the UOP/Hydro MTO process, which is discussed in
detail in Section 4.
Olefin Cracking
Integration of MTO and Olefin Cracking processes (OCP) could be advantageous because
the UOP/Hydro MTO process converts methanol to ethylene and propylene along with some
heavier olefins and Olefin Cracking processes such as the Total Petrochemicals/UOP Olefin
Cracking process are able to convert these heavier olefins predominantly to propylene with some
associated ethylene.
According to UOP, the Olefin Cracking process offers the option to upgrade low value C4 to
C8 olefins to propylene and ethylene at high propylene to ethylene ratios. In mid-2003, the Olefin
Cracking process was introduced after TOTAL Petrochemicals and UOP completed extensive
development and demonstration activities. Following initial work by TOTAL Petrochemicals in the
mid 1990s, UOP and TOTAL Petrochemicals formed a joint-development alliance in late 2000.
The development activities included successful operation of a demonstration unit, catalyst
performance testing in pilot plants, yield determination, catalyst manufacturing scale-up and
process design development. The demo unit, started in 1998 at an industrial facility associated
with TOTAL Petrochemicals in Antwerp, Belgium, processes commercial feedstocks from
operating plants. The demo unit includes feed pretreatment, the reactor section, catalyst
regenerationfacilities, and internal recycle capabilities.
The Olefin Cracking process features fixed-bed reactors with operating temperatures
o
between 500 to 600 C and pressures between one to five bars gauge. The process utilizes a
proprietary zeolitic catalyst from UOP and provides high yields of propylene at
propylene/ethylene product ratios of about 4 to 1. A swing reactor system is used for catalyst
regeneration. The ability of the Olefin Cracking process to upgrade C4 to C8 olefins means it has
the flexibility to take its feedstock from a naphtha cracker, a methanol-to-olefins (MTO) unit
and/or an FCC unit.

Figure 3.6
SCHEMATIC THE UOP/HYDRO MTO PROCESS
[Source: 261A043]
R&D Activities by ExxonMobil

The technology for producing olefins from methanol has also been investigated by
ExxonMobil. Mobil conducted most of the original work on methanol conversion to ethylene and
lower olefins, using the company’s ZSM-5 family of zeolite catalysts. However, the conventional
ZSM-5 type of zeolite is more suited for methanol conversion to an aromatics-rich hydrocarbon
mixture in the gasoline range. Mobil’s Methanol-to-Gasoline (MTG) process was commercialized
in 1985. Development work on methanol conversion to lower olefins was later adapted for making
C3+ olefins, which are easily oligomerized into a gasoline-distillate product. Mobil’s Methanol-to-
Olefins (MTO) and Olefins-to-Gasoline-and-Distillates (MOGD) processes have been
demonstrated. In 1999, the technology was transferred to ExxonMobil as a result of the merger of
the two companies.
ExxonMobil has been conducting significant research efforts in the area. As shown in
Appendices A and E, ExxonMobil has the largest intellectual property position on oxygenates
(including methanol) to olefins and holds a particularly large number of patents on SAPO-based
catalysts and reaction conditions. Most of the company’s patents using zeolite catalyst were
acquired from Mobil or are continuations of Mobil’s original patents. UOP and Lurgi have
concentrated their efforts on the SAPO-based and zeolite based processes, respectively.
In spite of its dominant patent position, ExxonMobil has not yet announced plans to use the
technology on a commercial scale.
DMTO Technology
In late 2006, China publicized its Di-methyl ether/methanol-to-olefins (DMTO) technology,
producing light olefins including ethylene and propylene from DME and/or methanol, is jointly
developed by China Dalian Institute of Chemical and Physics (DICP), Chinese Academy of
Sciences, Shaanxi Xinxing Coal Chemical Company and Sinopec Luoyang Engineering Corp.

After pilot plant test, it is reported that the DMTO process consumes about 3 tons of methanol to
produce 1 ton of light olefins, with more than 99% oxygenates conversion and 78% selectivity
towards ethylene and propylene.
The State Development & Reform Commission of China and the Chinese Academy of
Sciences are rendering supports to accelerate an early realization of commercializing this
process. In 2006, China National Development and Reform Commission (NDRC) released
regulation on Coal Chemical Industry, encouraging China chemical producers to use domestically
owned technologies.
China’s DMTO technology has been chosen by two projects. One is the MTO project of
Shaanxi Xinxing Coal Chemical Co. in Yulin, Shaanxi Province; the under-construction project
includes a 600,000 tonnes/year coal based methanol, a 600,000 tonne/year Methanol-to-Olefins,
100,000 tonnes/year PE and 100,000 tonnes/year PP units. The other one approved by NDRC is
the Baotou Shenhua Coal Chemical Company coal-to-olefins project near Baotou, Inner
Mongolia. The project, jointly developed by Shenhua Group (76%) and Shanghai Huayi Group
(24%), will produce 600,000 tonnes olefins from coal. It is expected to come onstream in 2010. In
the meantime, Shenhua Group and Dow Chemical are studying a proposed MTO joint venture
project, and Dow chemical is evaluating the DMTO technology.
Figure 3.7 shows a preliminary schematic DMTO process.
Figure 3.7
SCHEMATIC OF THE DMTO PROCESS
[Source: 261A128]
METHANOL AS FEEDSTOCK
Having a variety of uses, methanol is one of the most important commodity chemicals. It is
primarily used as an intermediate feedstock for the production of other chemical derivatives, such
as formaldehyde, methyl tertiary-butyl ether (MTBE), and acetic acid. The largest end use of
methanol is formaldehyde with 34 percent of total 2006 methanol consumption. MTBE is the
second largest use of methanol with 16 percent. The next important use is acetic acid. Other
smaller applications are chlorinated methanes, methylamines, and methyl methacrylate.

The total worldwide methanol market is about 36 million metric tons in 2006. This is
expected to grow to almost 53 million metric tons in 2016 assuming a phase out of MTBE usage
in the United States by 2010 that negatively affects methanol demand. Under a European Union
(EU) directive of May 2003, the proportion of biofuels as a percentage of fuel sales (motor
gasoline and diesel fuels) must be increased to 5.75% by 2010 (2% in 2005). Methanol
consumption into MTBE will decrease to represent 9 percent of total methanol consumption in
2016. On the positive side, there will be substantial methanol consumption in direct fuel use
(motor gasoline) in China, Iran, and South Africa. From 2006 to 2011, global methanol
consumption will increase at an average rate of 5.6 percent, led by direct fuels use (27.6
percent), and acetic acid (6.5 percent). The SRIC forecast assumes that one new methanol-to-
olefins plant in China will start up in 2010.
Table 3.11 presents total worldwide methanol production capacity, production and
consumption levels, and growth rates on a regional basis. Global demand for methanol, which
grew at an annualized rate of 5.6% in 2006-2011, is expected to slow to an annual growth rate of
2.9% through 2016. Methanol capacity is expected to grow at an annual rate of 8.9%/yr,
corresponding to about 4.5 million metric t/yr of additional capacity between 2006 and 2011.
Regional Capacity Trends

At the end of 2004, world effective capacity was 41.7 million metric tons per year. By 2006,
this had increased to over 46 million metric tons. Methanex is the largest producer and marketer
in the world, accounting for approximately 16% of worldwide 2006 methanol capacity. Methanex
is a true worldwide supplier, with plants currently operating in Trinidad and Tobago, Chile and
New Zealand. Methanex has little or no captive use and accounts for a substantial portion of the
worldwide merchant market. The next largest world producer is SABIC, with approximately 6.5%
of world capacity.
Much of the new capacity added during the last two decades has been in regions with
abundant supplies of low-cost natural gas. Countries with large reserves of natural gas and often
limited domestic consumption have built world-scale methanol facilities, exporting much of their
product to developed regions such as the United States, Western Europe, and Japan.
Consequently, producers in the more economically developed regions have shut down inefficient
methanol capacity as cheaper imports have become available. For example, Japan, once a major
methanol producer, now has no operating capacity. North American capacity, which accounted
for 50% of global methanol capacity in 1984, had decreased to about 6% by 2006 and is
expected to reduce even further as older units are shut down.
As shown in Table 3.11, the largest producing region in 2006 was Central and South
America, whereas in 2011, China (Northeast Asia) and the Middle East will be the largest
producing regions in terms of both capacity and expected production.
Another significant factor is that the size of the new mega-methanol plants (1.5-2.0 million
metric tons per year) is much larger than existing plants. Thus, they will have reduced fixed costs,
as well as greatly reduced natural gas costs due to strategically located feedstock giving a
significant cost advantage. This trend will drive down the production cost of methanol, and cause
major shifts in trade patterns. Locations for these large new methanol plants will be Iran, Saudi
Arabia, Qatar and Trinidad and Tobago. These natural gas–advantaged countries export much of
their product to developed regions such as North America, Western Europe and Japan.
Consequently, producers in the more economically developed regions have shut down inefficient
methanol capacity as cheaper imports have become more readily available.
The Caribbean and South America are strategically positioned for the production of
methanol. Their competitive advantage lies in the availability of cheap natural gas, combined with

the relative ease of reaching the North American methanol market. Trinidad and Tobago, in
particular, is well positioned to serve the United States and Mexican markets. South American
and Caribbean methanol capacity, approximately 7.8 million t/yr in 2001, had increased to almost
12.5 million t/yr by the end of 2006, and additional capacity expansions are projected in the
region for the near future.
In the Middle East, total methanol capacity has increased considerably from 6.6 million
metric tons in 2004 to about 8.7 million metric tons by the beginning of 2007. The latest capacity
additions have been International Methanol Company’s 970 thousand metric ton plant, which
started in 2005, and Fanavaran Petrochemical, which started in 2004; in 2005, Saudi Methanol
expanded all four of its production lines. Two additional plants (not included in the table) are set
to commence in 2007: Sohar Methanol Project in Oman, with almost one million metric tons of
capacity, and Zagros Petrochemical in Iran with 1.65 million metric tons of capacity. All new
plants will be based on natural gas feedstock. Because of the significant growth in Middle
Eastern methanol capacity, the region’s methanol exports will roughly double from 2006 to 2011.
More than half of China’s methanol capacity uses an integrated methanol/ammonia process.
The main feedstocks used are coal (57%), natural gas (24%), LPG (11%) and acetylene off-gas
(4%). From 2006 to 2011, estimated nameplate capacity of methanol in China is expected to
grow at an average rate of 20% per year, yet consumption is not expected to grow as fast,
operating rates are not expected to be above 70% from 2008 to 2011. For this reason, interests
of converting methanol to olefins are growing in China. In next decade, DME, olefins, acetic acid,
fuel, and MMA are the fastest-growing markets in China.
Many Chinese producers plan to build methanol, methanol/DME, or methanol to olefins
(MTO) projects, mostly based on coal material. In light of China’s rapid economic growth and its
large coal reserves, there are environmental concerns related to the growth of China’s emission
of greenhouse gases. China can make greater use of its coal reserves if carbon sequestration
can be improved upon, and thus curtail its imports of crude oil. Additionally, technology
companies and investors will likely to make claims that with modern coal gasification
technologies, greenhouse gas emissions can be minimized. The challenging question is the cost
associated. Nevertheless, the tremendous economic growth in China and its environmental
implications may possibly make coal-based ventures much more difficult to get approval on in the
future. However, the government will likely not pass legislation if it means the possibility of
curtailed economic growth or inhibiting its goal of more energy independence. In July 2006, the
Chinese government issued a circular on regulating the coal-chemical industry, urging local
governments to tighten control of new projects. According to this circular released by the National
Development and Reform Commission (NDRC), the government will not approve coal-to-
methanol or dimethyl ether (DME) projects of less than one million metric tons, and coal-to-
alkene projects of less than 600 thousand metric tons. Most of these coal-to-methanol or DME
and MTO projects, with more than 1.5 million metric tons of potential methanol capacity, are still
waiting for approval.

Table 3.11
HISTORICAL AND PROJECTED WORLD METHANOL CAPACITY,
PRODUCTION AND CONSUMPTION BY REGION
(THOUSANDS OF TONS)
Average Annual
Actual Forecast Growth Rate (%/yr)
2001- 2006- 2011-
2001 2006 2011 2016 2006 2011 2016
Africa
Anticipated Capacity 1,358 1,839 1,858 1,858 6.3 0.2 0.0
Operating Rate (%) 74 71 65 71
Total Production 1,004 1,311 1,215 1,315 5.5 -1.5 1.6
Asia
Total Production 3,913 8,328 17,332 21,939 16.3 15.8 4.8
Central and Eastern Europe
Anticipated Capacity 4,546 5,101 2,816 2,427 2.3 -11.2 -2.9
Total Production 2,418 3,265 1,605 1,405 6.2 -13.2 -2.6
Middle East
North America
Anticipated Capacity 5,638 2,611 195 195 -14.3 -40.5 0.0
Total Production 4,194 1,949 165 150 -14.2 -39.0 -1.9
Oceania
Anticipated Capacity 2,495 398 530 530 -30.7 5.9 0.0
Total Production 2,196 284 0 0 -33.6 0.0 0.0
South and Central America
Total Production 7,211 10,645 9,931 10,731 8.1 -1.4 1.6
Western Europe
Anticipated Capacity 3,716 2,790 1,775 1,735 -5.6 -8.6 -0.5
Total Production 2,884 2,145 1,250 1,300 -5.7 -10.2 0.8
World
_______
Source: SRI Consulting.

Methanol Prices
U.S. prices and unit sales values for methanol are summarized in Table 3.12.
The price for methanol in the United States depends on the supply/demand balance,
inventory levels, the availability of imports, and the price of natural gas. The blending value of
MTBE (which is tied to the price of gasoline) used to affect methanol prices but now that it is no
longer blended for the domestic gasoline pool and will soon be entirely banned, it very minimally
affects methanol, only to the extent that when export demand for MTBE is high, some of the
MTBE still being produced may provide just enough incremental demand to cause prices to
increase.
Prices in 2006 increased considerably worldwide as a result of both robust demand and, in
particular, several plant outages in the second half of the year.
Table 3.12
U.S. PRICES AND UNIT SALES VALUES FOR METHANOL
Contract Price List Price Synthetic

Dollars per Cents per Dollars per Cents per Dollars per Cents per
Year Metric Ton Gallon Metric Ton Gallon Metric Ton Gallon
1955 -- -- 99.8 30.0 82.9 24.9
1960 -- -- 99.8 30.0 79.4 23.9
1965 -- -- 89.8 27.0 69.4 20.8
1970 -- -- 89.8 27.0 57.3 17.2
1975 -- -- 119.7 36.0 124.3 37.4
1980 -- -- 236.1 71.0 207.8 62.5

1981 -- -- 264.4 79.5 207.8 62.5
1982 163-196 49-59 237.8 71.5 166.3 50.0
1983 143-190 43-57 159.6 48.0 147.1 44.2
1984 126-150 38-45 149.6-237.7 45.0-71.5 132.5 39.8
1985 126-163 38-49 172.9-237.7 52.0-71.5 159.6 48.0

1986 80-133 24-40 172.9-237.7 52.0-71.5 164.0 49.3
1987 80-146 24-44 99.8-106.4 30.0-32.0 103.9 31.3
1988 80-146 24-44 182.9-199.5 55.0-60.0 160.0 48.1
1989 143-193 43-58 162.9 49.0 145.9 43.9
1990 123-140 37-42 133.0-139.7 40.0-42.0 122.9 37.0

1991 153-167 46-50 166.25 50 152.2 45.6
1992 116-176 35-53 132.9-146.2 40-44 124.2 37.4
1993 133-176 40-53 146.2-166.1 44-50 123.7 37.2
1994 169-531 51-160 172.8-448.5 52-135 241.1 72.5
1995 140-515 42-155 100-465 30-140 -- --

1996 117-167 35-50 106-176 32-53 -- --
1997 170-216 51-65 196-206 59-62 -- --
1998 83-196 25-59 73-196 22-59 -- --

U.S. PRICES AND UNIT SALES VALUES FOR METHANOL
Contract Price List Price Synthetic

Dollars per Cents per Dollars per Cents per Dollars per Cents per
Year Metric Ton Gallon Metric Ton Gallon Metric Ton Gallon
1999 70-133 21-40 73-137 22-41 -- --
2000 90-256 27-77 97-243 29-73 -- --

2001 133-306 40-92 93-353 28-106 -- --
2002 113-206 34-62 93-216 28-65 -- --
2003 206-272 62-82 189-352 57-106 -- --
2004 222-279 67-84 229-329 69-99 -- --
2005 281-321 84-96 257-317 77-95 -- --

2006 321-461 96-138 271-802 81-240 -- --
Methanol Shipping
Methanol shipping is an exception to the conventional chemical parcel ocean transportation
environment. The methanol industry’s remote locations close to large gas fields and far from
established shipping lanes result in a different shipping approach. Methanol shippers can:
1. Charter tanker services
2. Operate a fleet of dedicated tankers
3. Secure long-term contracts of affreightment
From the shipper’s perspective, tanker service is probably incompatible with methanol
shipping because the average tanker has a large number of tanks used to carry a wide variety of
products. From the carrier’s perspective, loading backhaul cargoes for delivery to the methanol
homeport is unlikely, and thus a methanol cargo would impose an economic penalty. Also the
average methanol cargo parcel is about 25,000 tons. A methanol shipper is likely to seek volume
discounts, whereas shippers of specialty chemicals are likely to par higher rates.
The second option, contracting for a dedicated fleet of methanol tankers, offers benefits
such as economy of scale, known costs, ability to deliver product of consistent quality in the most
time-efficient manner, and control of the ship. On the negative side, to operate a fleet profitably
would require rates that are lower then the long-term freight rates in the marketplace. Additionally
a long-term charter at a fixed rate would be required. Clearly, fleet ownership for dedicated
shipping has substantial rate risks.
The third option, contracts of affreightment, seems to be the most attractive. With these
contracts, the shipper realizes several of the advantages of ownership, control over the period o
commitment, positioning, annual volumes, and parcel size. The carrier maintains responsibility for
tanker operations. However, dedicated shippers have been gaining market share in the methanol
market.
More details can be found in PEP Report No 224, Ocean Transportation Freight Rates, June
2001.

4 UOP/HYDRO MTO PROCESS
INTRODUCTION
Methanol is a major chemical building block used to manufacture formaldehyde, MTBE,
acetic acid and a wide range of other chemical products. The slowdown in MTBE demand in the
US, due to phasing out its use in the gasoline, is causing some of the producers in the world to
explore alternate utilization of their existing methanol plants. One such utilization is the
conversion of methanol to olefins (MTO). In the meantime, recent discoveries of new natural gas
fields and improved recovery of associated gas from crude oil production have increased the
world reserves of natural gas. As a result, the conversion of methane to light olefins and other
higher value products has attracted renewed interest. Although a commercially viable process for
direct conversion of natural gas to olefins is not yet available, the production of methanol by
steam reforming of natural gas is a well-established technology. The recent trend of mega-
methanol plants, with capacities of 5,000 metric t/d or larger based on low cost natural gas or
coal feedstocks, is expected to increase the availability of low cost methanol, providing a
significant economic driving force for its conversion to light olefins. Because the market for
ethylene and propylene is much larger than that for methanol itself, this potential new market as
light olefins feedstock could be an important new source of demand for methanol.
On the other hand, light olefins such ethylene and propylene are important raw materials for
polymers production. Currently, most ethylene and propylene are commercially produced by
steam cracking of C2 - C4 paraffins and petroleum fractions in so called hydrocarbons pyrolisis
process. The continuous rising of demand in light olefins combined with the oil reserve shortage
in the future drive the search for new light olefins manufacture technologies from non-petroleum
raw materials.
One of the attractive methods for ethylene and propylene production is based on catalytic
conversion of methanol because methanol can be manufacture in large quantities from a wide
range of resources including natural gas, coal and renewable biomass.
This section reviews the technology for production of light olefins from methanol and
presents a conceptual design and its economics for the UOP/Hydro MTO (methanol-to-olefins)
technology based on a modified SAPO-34 catalyst.
COMMERCIAL DEVELOPMENTS
The production of light olefins from methanol was first realized around 1977, during the
development of Mobil’s methanol to gasoline (MTG) process. In the MTG process, where ZSM-5
(MFI) is used as a catalyst, methanol is first dehydrated to dimethylether (DME). The equilibrium
mixture of methanol, DME and water is then converted to light olefins. A final reaction step leads
to a mixture of higher olefins, n/iso-parrafins, aromatics and naphthenes [261A092, 261A090,
261A060]:

n/iso-paraffins
- H2O - H2O higher olefins
2 CH3OH CH3OCH 3 light olefins
aromatics
+ H2O
naphthenes
Because they are intermediate in the process of producing gasoline, an interruption of the
reaction leads to a production of light olefins instead. Since then several attempts were made to
selectively produce light olefins from methanol on zeolite catalysts, not only on medium-pore
zeolites but also on small-pore zeolites and to a lesser extent, on large-pore zeolites. Mobil
conducted most of the original work on methanol conversion to ethylene and lower olefins, using
the company’s ZSM-5 family of zeolite catalysts. However, the conventional ZSM-5 type of zeolite
is more suited for methanol conversion to an aromatics-rich hydrocarbon mixture in the gasoline
range. Mobil’s Methanol-to-Gasoline (MTG) process was commercialized in 1985. Development
+
work on methanol conversion to lower olefins was later adapted for making C3 olefins, which are
easily oligomerized into a gasoline-distillate product. Mobil’s Methanol-to-Olefins (MTO) and
Olefins-to-Gasoline-and-Distillates (MOGD) processes have been demonstrated.
The typical ethylene yield in Mobil’s MTO process is only about 6 wt%. Mobil has shown that
the ZSM-5 system can be adapted for lower olefins (mainly ethylene) production by modifying the
catalyst composition and/or structure and the reaction conditions. The adapted process was
designated MTE. However, the objective of ethylene production is only partially achieved with
MTE because the process still makes a significant amount of by-product gasoline. At a limited
methanol conversion of 45% per pass, the selectivities to ethylene and propylene are 45 and 25
mol%, respectively.
Research of conversion of methanol into olefins has gone on worldwide since the discovery
of the mixed silico-alumina-phosphorous type catalysts by Union Carbide around 1980. Initial
work was carried out at Union Carbide by Jeffrey M. O. Lewis and Giacomo Corvini. This work
was at first carried out in a micro-reactor with a fixed bed of unbound SAPO catalyst, the particles
of which were most likely of a size of about 1 micron. Tests with low conversion of methanol
showed a high ratio for production of the C2 olefin over the C3 olefin, but this ratio decreased
especially at higher conversion of methanol. Finally at very high conversion of methanol the C3
yield was even higher than that of ethylene. When they later switched to a larger catalyst
aggregate, the time on stream (TOS) became smaller. This led to a switch to fluid bed operation.
The associated knowledge and manufacturing know-how was later transferred to UOP. The
research work was then taken over by UOP and described in many patents and also in the
literature [261A092].
In 1992, UOP joined with Norsk Hydro to develop the porosity-controlled MTO-100 catalyst,
a proprietary improvement of the SAPO-34 with better stability and attrition resistance for use in a
fluidized bed MTO reactor. The MTO-100 is the key to the UOP/Hydro MTO process, which has
been offered for license since 1995.
The UOP/Hydro MTO process uses a fluidized bed reactor at 420-480°C to achieve about
80% carbon selectivity to light olefins (ethylene and propylene) at almost complete methanol
conversion. The ethylene-to-propylene ratio can be modified within a range from about 0.75 to
1.5 by adjusting the operating severity, with higher temperatures leading to a higher percentage
of ethylene produced. Olefin yields and catalyst performance of the process have been verified at
a 1,100 lb/d (0.5 t/d) methanol demonstration unit operated at Hydro’s facilities in Porsgrunn,
Norway. Although no full-scale plant using the process has been licensed, several feasibility
studies have been commissioned [261A126]. Egypt Arab Trading (EATCO) was the first
company to announce firm plans for an MTO project. The initial plan was for a 400,000 t/yr olefins

unit (with an ethylene: propylene ratio of 1:1) located in Suez and expected onstream in 2004.
According to recent news, however, the project has been delayed [261A127]. Other potential
sites for MTO units include Nigeria, China, Trinidad, Australia, and the Netherlands.
Recent Advancements in UOP/Hydro MTO Technology

While improvement in catalyst performance/cost is still evolving, recent publications suggest
that UOP/Hydro MTO technology improvements in product selectivity (carbon efficiency) and
energy efficiency have been gained through better process design with slightly increased process
complexity and capital intensity.
US Pat. No. 6,872,867 to UOP discloses a start-up method for the UOP/Hydro fluidized
MTO reactor section without a dedicated start-up compressor.
US Pat. No. 7,132,580 and 7,138,557 to UOP disclose improved methanol-to-olefin (MTO)
product recovery schemes which lead to substantial reduction in the amount of light olefins
captured in a dimethylether (DME) recycle stream and improved recovery of methanol when a
portion of the methanolic feed to the MTO reactor is used as the scrubbing solvent in a DME
absorber (and an optional methanol absorber) in order to recycle oxygenates to the MTO reactor.
US Pat. No. 7,138,558 to UOP discloses an improved design for sending the recovered
unreacted oxygenate stream directly to the reaction zone through nozzle inlets or injection tubes.
In the past, the unreacted oxygenates such as methanol, DME and diolefins recovered from the
reactor effluent stream were returned to the feed stream. However, due to impurities such as
diolefins within the recycle stream, it has been found that the feed distribution grid to the reaction
zone through which the feed streams pass may collect coke deposits that eventually interfere
with the flow of the feed stream through this distribution grid. These diolefins and other reactive
recycle materials, even in trace amounts; have been found to be the cause of significant degrees
of undesired polymerization and fouling and even undesirable coke deposits formation. The
distribution grid is located at the bottom of the MTO reactor and serves to disperse the feed
stream into the MTO reactor.
On the process side, significant advancements have been made over the past few years
that further enhance the performance of the UOP/Hydro MTO process [261A039]. The MTO
process can now be integrated with the olefin cracking process (OCP) based on technology
developed and demonstrated by Total Petrochemicals and UOP [261A051]. This can be used to
increase the carbon selectivity from methanol to ethylene-plus-propylene to about 85–90%. With
the integrated process, C4 - C6+ olefins generated as by-products from the MTO unit can now be
fed to the olefin cracking unit in which the heavier olefins are cracked to ethylene-plus-propylene,
but with a preponderance of propylene. The combined process has great flexibility to produce a
product with a range of propylene/ethylene ratios up to 1.75, or even higher as will be discussed
later. Furthermore, nearly an 80% reduction in C4+ by-product formation and a 20% increase in
light olefin yield can be achieved.
The recovery section of the MTO unit remains unchanged, except that it has to be sized to
accommodate the added circulation to and from the olefin cracking unit. On the catalyst side,
continued development has led to MTO catalyst with superior performance compared to earlier
formulations. The optimized catalyst offers greater flexibility to achieve higher propylene
production as propylene-to-ethylene ratios can be almost 20% higher than were available using
earlier catalysts. With the optimized catalyst and in combination with well-integrated MTO and
olefin cracking units, the enhanced MTO and OC processes can produce propylene to ethylene
product ratios over 2.0 to meet the growing demand for propylene.

TECHNOLOGY REVIEW
Table A.1 through A.5 (in Appendix A) summarizes the patents related to the conversion of
methanol to lower olefins filed during the last decade. Companies with patent positions during
this period include ExxonMobil, Exxon, Metallgesellschaft (Lurgi), Mobil, Phillips, S. C. Zecasin,
Showa Shell, and UOP. Summaries of older patents can be found in PEP Report 208, Ethylene
from Methane (January 1994), and PEP Report 191, Utilization of Remote Methane (July 1989).
MTO Catalyst Development

The MTO process is an acid catalyzed reaction of which SAPO-34 and ZSM-5 are the most
common catalysts [261A035, 261A092]. Mobil’s pentasil-type zeolite ZSM-5 was the first catalyst
shown to be effective for the conversion of methanol to hydrocarbons. Since the hydrocarbon
product distribution of the ZSM-5-based reaction can be controlled by changes in zeolite structure
and/or reaction conditions, Mobil developed three principal modes of operation: the production of
an ethylene-rich olefins mixture (as in the MTE or methanol to ethylene process), the production
+
of a mainly C3 lower olefins-rich product (as in the MTO or methanol to olefins process), and the
production of an aromatics-rich gasoline mixture (as in the MTG or methanol to gasoline
process).
The main control parameters of the ZSM-5 based reaction are space times and methanol
partial pressures (concentrations). The yield to light olefins initially increases with space time but
reaches a maximum, indicating the intermediate character of the light olefins formed [261A092].
A decrease of the partial pressure also tends to enhance the olefin formation by suppressing the
aromatization reaction. Thus, olefin yields are maximized by operating at partial methanol
conversions and by using steam as an inert diluent. Even at reduced methanol conversions,
however, the production of aromatics is still significant. Typical yields of a ZSM-5 based MTO
reaction are 6 wt% ethylene, 42 wt% propylene, 12 wt% butylenes, and 27 wt% C5+ [261A031].
In the last two decades the main focus of this research has been on the methanol-to-olefin
(MTO) part of the reaction due to the increasing demand for light olefins [261A039]. This has
become even more pronounced with the high price of crude oil. Several modified ZSM-5 catalysts
have been proposed to improve the selectivity to light olefins. Earlier Mobil work, for example,
had indicated that olefins synthesis is favored by small pore zeolites, by phosphorus modified
ZSM-5, and by using large crystal forms of ZSM-5, particularly when the structure is modified by
specified components, such as MgO, Pd, and Zn. However, small pore zeolites are more
susceptible to coke deposition, necessitating frequent regeneration. Mobil patents have proposed
other catalyst variants for olefins production, such as treated forms of high silica ZSM-5 [US
4929780], and catalysts with diffusional barriers, particularly when a co-aromatic feed is used
[WO 0121561, US 6046372, US 6048816].
The SAPO-n family of silicoaluminophosphates, discovered by researchers at Union Carbide
in the 1980s, comprises a wide range of molecular sieves with shape selectivity and carefully
controlled acid strength. SAPO-34, in particular, has an isomorphous structure to chabazite,
consisting of channels (spaces between 8 atoms of oxygen) with a maximum diameter of 4.4 Å
and a minimum diameter of 3.1 Å, and intersections between channels that give way to cavities of
10 Å maximum diameter and 6.7 Å minimum diameter [261A078] The moderate acid strength
and relatively small pore opening of the SAPO-34 catalyst lead to high selectivities (more than
90%) to lower (C2-C4) olefins at near complete methanol conversion.
Compared to the medium pore ZSM-5 catalyst, SAPO-34 with its cage like framework
structure shows superior selectivity towards lower olefins. When SAPO-34 is used, the ethylene-
to-propylene ratio of the product can be varied over a wide range (0.75 to 1.5), depending on the
severity of the reaction conditions. As temperature increases, higher selectivity to ethylene is

obtained, although the overall carbon efficiency to light olefins suffers slightly [261A018].
According to a patent by ExxonMobil [WO 0160770], the combined ethylene and propylene
selectivity is maximized by keeping reaction conditions at specified parameters of weight hourly
space velocity (WHSV) and partial pressure of oxygenate. The oxygenate proportion index (OPI)
at the reaction inlet, defined as the molar flow of oxygenate divided by the molar flow of
oxygenate plus diluent is maintained above 0.5. The partial pressure-velocity compensation
factor, defined as WHSV divided by the partial pressure of the oxygenate at the reactor inlet, is
kept above 0.1 psia-1hr-1, preferably between 0.2 and 25 psia-1hr-1. As in the ZSM-5-based
reaction, the addition of water to the methanol feed reduces light paraffin production, chain
growth, and aromatics formation [261A087].
In its catalyst patents, UOP uses a SAPO-34 with small particle size (less than 1 μm) and
reduced silicon content (less than 0.05 mol%) [US 5912393, US 5126308]. This combination of
properties is claimed to reduce propane by-product formation and increase catalyst life.
Hydrothermal treatment of SAPO-34 to reduce acidity can also have a beneficial effect on
performance [US 5095163].
ExxonMobil and Exxon Chemical have filed many patents on the use of framework-
substituted and metal-exchanged forms of SAPO-34 catalysts. Examples of modifying agents
include single ring aromatics [WO 0162382], surface silica [WO 0160746], oxygenated chelating
agents [US 6005155], fluor [US 5932512], polynuclear aromatic heterocyclic compounds [US
6051746], ytterbium or titanium [WO 9829370], phosphorus [US 5925586], alkaline earth metal
[US 6040264], nickel or cobalt [US 5962762]. Phillips patents describe the use of silylated [US
6046371] and nitried [US 6051745] SAPO-34 catalysts. Finally, Showa Shell [EP 418142] uses a
nickel-modified SAPO-34 that achieves very high selectivity to ethylene (88% at 450°C and 100%
methanol conversion).
Many efforts have also been made to improve selectivity towards ethylene by various
physic-chemical modifications of these small pore materials. The SAPO-34 molecular sieve after
incorporating transition metals such as nickel in the framework has been found to yield high
ethylene selectivity in the MTO process [261A074, 261A0121, 261A123]. The higher selectivity is
attributed to framework distortion and acidity modification after the incorporation of nickel.
Since MTO conversion on microporous silico-aluminophosphates is particularly well-suited
for the application of molecular-level concepts to the development of well-defined supported
catalysts and the active site of a typical MTO catalyst is a nm-size inorganic cage with an
essential organic component, opportunities for altering the selectivity of such catalysts include
tailoring the organic component and modification of the cage with additional inorganic material
through ship-in-a-bottle synthesis. US Pat. No. 7,078,364 to Haw and Song claims that the latter
possibility has already been realized experimentally by the development of a useful and practical
phosphate-modified catalyst.
Although the SAPO-34 catalyst is highly selective to light olefins, it has the disadvantage of
rapid deactivation by coke formation during methanol conversion reaction. The coke, which
consists mainly of C9-C13 paraffins, completely blocks the internal channels of the SAPO-34
crystals and subsequently blocks the mesopores (intercrystalline and those of the bentonite used
as binder) [261A080]. Aromatics and heavy branched compounds can be formed inside the large
cages at temperatures above 300°C. These molecules cannot diffuse through the porous
structure because their kinetic diameter is larger than the pore-opening size of the small-pore
molecular sieves. Thus, they remain inside the big cages where they can form carbonaceous
deposits blocking the pore openings and preventing the access of reagent molecules to the
active sites. The rate of deactivation depends on the acidity: the higher the catalyst acidity, the
faster the deactivation by coke formation. The presence of water in the feed reduces coke
formation, either by converting Lewis to Brønsted sites or by competing for surface sites with

coke precursors. Thus, coke formation is attenuated by dilution of methanol with water in the
feed, or by operating conditions that favor the formation of water as a by-product [261A091]. Still,
accumulated coke must be removed by combustion with oxygen to maintain catalyst activity.
Usually, the activity of small-pore molecular sieves can be restored by burning the coke with
air at high temperature. Liang et. al [261A119] carried out a study on SAPO-34, erionite and
erionite-offretite zeolites comprising 55 regenerative cycles. The catalysts were regenerated at
530°C in air after reaction at 450°C and 5 h-1 WHSV. With SAPO-34 the initial conversion of
methanol after 55 regenerations was still 100%, while the total hydrocarbon yield and content of
light olefins in the hydrocarbon fraction were also constant.
MTO Reactor Design Consideration

Fluidization is the operation by which an ensemble of solid particles and a fluid is behaving
like a fluid. In general, fluidized bed reactors have many advantages over the fixed bed reactors.
The most important are as follows:
• Ensembles of fluidized solids behave like liquids, thus can be easily transported
• The high turbulence created in the fluid-solid mixture leads to much higher heat transfer
coefficients than those which can be obtained in fixed beds. Therefore, a fluidized bed
reactor is much more suitable for exothermic processes requiring close temperature
control.
• The circulation of solids between two fluidized beds makes it possible to remove or add
huge quantities of heat produced or needed in large reactors.
• Fluidized bed operation requires particle sizes that are much smaller than in fixed beds.
This reduces the resistance to diffusion through the particles.
• The pressure drop in a fluidized bed is much smaller than in a fixed bed.
The exothermic character (~50 kJ/mol) and the necessity of frequent catalyst regeneration in
the conversion of methanol to light olefins over SAPO-34 catalyst make a fluidized-bed reactor
system much more attractive than a fixed-bed reactor system in view of the more efficient heat
removal and the possibility of removing deactivated catalyst from the reactor during operation
and replacing it with a fresh or regenerated one [261A108].
Because the MTO reaction over SAPO-34 catalyst is highly exothermic (25-50 kJ/mol) and
the catalyst life is limited owing to coke formation, in commercial practice a fluidized-bed reactor
system is the best choice for the conversion of methanol to olefins over SAPO-34 catalyst. In
addition to maintaining steady catalyst activity and constant olefin product quality, the fluidized
bed reactor-regenerator system has excellent heat exchange properties and provides operational
flexibility [261A108].
Fluidization Regimes
Typically, undesirable by-products are formed in MTO reaction systems in addition to the
desired light olefins. One method for reducing the production of undesirable by-products in a
fluidized bed reactor involves operating in a hydrodynamic flow regime such that the superficial
gas velocity obtains a velocity high enough to cause a net flow of catalyst in the reactor in the
same direction as the flow of the feedstock and other vapors. That is, the feedstock and other
vapors essentially carry the catalyst particles along with them. These flow regimes are known to
those skilled in the art as fast-fluidized bed and riser regimes.

In fluidization, there are a number of regimes where the fluid-bed behaves differently as
velocities, gas properties and solid properties are varied. The nature of these fluidization regimes
and the velocities at which they occur depend on the properties of the catalyst particles and, to a
lesser extent the properties of the gas [261A102].
When the flow of fluid passes upwards through a particle bed and the drag force acting on
the constituent particles is attained to balance the gravitational force exercised on the particles,
the bed starts to be fluidized. With an increase in the flow rate, each particle is put in motion from
its quiescent state to a continuously agitated state in the upward stream of fluid. As the superficial
gas velocity (μ0) increases further, the pressure loss will increase slowly and eventually a point
will be reached where the upward drag exerted on the particles by the fluid just equals the weight
of the particles. This point is known as the minimum fluidization and the corresponding gas
velocity is the minimum fluidization velocity (μmf). The magnitude of the minimum fluidization
velocity depends on the solid particle properties, such as density and size distribution, as well as
the gas properties, particularly the density and viscosity.
A further increase in superficial gas velocity μ0 will result in bubble formation. For fine
particles, bubbles do not appear as soon as minimum fluidization is reached. There is a range of
velocities in which uniform expansion is observed with no observed bubbling. However, at a gas
velocity of about 3μmf, bubbles begin to form and bed height begins to increase. This is known as
the minimum bubbling point and the corresponding gas velocity as the minimum bubbling velocity
μmb. At higher flow rates, agitation becomes more violent and the movement of solids becomes
more vigorous. In addition, the bed does not expand much beyond its volume at minimum
fluidization. Such a bed is called bubbling fluidized bed.
Under certain circumstances, the increase in bubble size as the gas velocity is increased
can lead to slug flow. This type of flow is characterized by adjacent bubbles from the gas
distributor coalescing to form larger bubbles or slugs that grow to the same order as the vessel
diameter, resulting in poor contacting of the gas and solids. In general, slugging can be avoided
by reducing the height to diameter ratio. As the gas velocity is increased beyond the terminal or
free-fall velocity, the turbulent regime is encountered. With further increase in gas velocity, i.e. in
the fast fluidization and dilute phase transport or riser regimes, solids are carried out of the bed
with the gas. In the riser regime there is no wall or down flow of the particles and the solid volume
fraction is very small.
Fast-fluidized Bed MTO Reactor

It has been found that in catalytic conversion of hydrocarbon oxygenates to olefins, use of a
fast-fluidized zone significantly reduces catalyst inventory compared to dense fluidized catalytic
reactions.
U.S. Pat. No. 6,166,282 disclosed a fast-fluidized flow regime for oxygenate to olefins
conversion. Fast-fluidization defines a condition of fluidized solid particles lying between the
turbulent bed of particles and complete particle transport mode. A fast-fluidized condition is
characterized by a fluidizing gas velocity higher than that of a dense phase turbulent bed,
resulting in a lower catalyst density and vigorous solid/gas contacting. In a fast- fluidized zone,
there is a net transport of catalyst caused by the upward flow of fluidizing gas. The superficial gas
velocity for a fast-fluidized flow regime is conventionally believed to be between about 1.1 and
3
about 2.1 m/s (3.5 and 7 ft/s) and the density is typically between about 48 and about 320 kg/m
3
(3 and 20 lb/ft ). Catalyst exits the reaction zone a small amount slower than the vapor exiting the
reaction zone. Hence, for a fast-fluidized flow regime the slip velocity is typically greater than or
equal to 0.3 m/s (1.0 ft/s) and the slip ratio is greater than or equal to 2.5 for most FCC catalysts.

UOP patents advocate the use of fast-fluidized regimes in the MTO reactor with a gas superficial
velocities above 3 ft/s, claiming the fast-fluidized bed reaction zone offers significant size and
cost savings over the traditional bubbling bed reactor system [WO 0185871, WO 0185872, US
6166282]. This mode of operation minimizes backmixing in the reactor, which increases the
selectivity to light olefins, and reduces catalyst inventory requirements. When compared to a
conventional bubbling bed reactor system for the production of 120,000 metric tones per annum
of polymer grade ethylene, a close to 250 percent decrease in total rector catalyst inventory is
reported [US 6166282]. The temperature rise in the fluidized bed can be controlled by
recirculating/cooling a portion of the catalyst, using a partially vaporized feed, and/or injecting
liquid feed along the fluidized bed [WO 0185871, WO 0162689].
A number of studies have shown that coke deposits on the SAPO-34 based catalyst induce
steric hindrance and enhance the product selectivity to lower olefins [261A031, 261A032]. An
excessive amount of coke, however, reduces the amount of active sites accessible to methanol
molecules, leading to lower methanol conversion. U.S. Pat. No. 6,023,005 discloses a method for
selectively converting hydrocarbon oxygenates to light olefins in which desirable carbonaceous
deposits are maintained on the total reaction volume of catalyst by regenerating only a portion of
the total reaction volume of catalyst and mixing the regenerated portion with the unregenerated
total reaction volume of catalyst. The method incorporates a fluidized catalytic bed reactor with
continuous regeneration. In a preferred arrangement, the oxygenate feed is mixed with
regenerated catalyst and coked catalyst at the bottom of a riser and the mixture is lifted to a
disengaging zone. In the disengaging zone, coked catalyst is separated from the gaseous
materials by means of gravity or cyclone separators. A portion of the coked catalyst to be
regenerated is sent to a stripping zone to recover adsorbed hydrocarbons. Stripped spent
catalyst is passed to a regenerator.
U.S. Pat. No. 4,547,616 discloses an improvement in a process for the conversion of
hydrocarbon oxygenates to olefins by the operation of a turbulent bed at elevated temperatures
and controlled catalyst activity. The turbulent bed is maintained in a vertical reactor column to
achieve good mixing at a velocity greater than the dense bed transition velocity to a turbulent
regime and less than transport velocity for the average catalyst particle. The superficial fluid
velocity is disclosed in a range between about 0.3 to 2 meters per second. Provision is made for
passing partially regenerated catalyst to the reactor’s fluidized bed of catalyst beneath the upper
interface and sufficiently below to achieve good mixing in the fluid bed.
U.S. Pat. No. 6,023,005 discloses a method for selectively converting hydrocarbon
oxygenates to light olefins in which desirable carbonaceous deposits are maintained on the total
reaction volume of catalyst by regenerating only a portion of the total reaction volume of catalyst
and mixing the regenerated portion with the unregenerated total reaction volume of catalyst. The
method incorporates a fluidized catalytic bed reactor with continuous regeneration. In a preferred
arrangement, the oxygenate feed is mixed with regenerated catalyst and coked catalyst at the
bottom of a riser and the mixture is lifted to a disengaging zone. In the disengaging zone, coked
catalyst is separated from the gaseous materials by means of gravity or cyclone separators. A
portion of the coked catalyst to be regenerated is sent to a stripping zone to recover adsorbed
hydrocarbons. Stripped spent catalyst is passed to a regenerator.
U.S. Pat. No. 7,169,293 addressed the difficulty of maintaining a fast-fluidized reaction zone
in a MTO reactor. This is because the feed to in a MTO reactor is the primary fluidization medium
and the reactant that is undergoing catalytic conversion to recoverable product. The selectivity
and conversion of the gas phase reaction must be optimized. Selectivity and conversion are
functions of temperature, residence time and space velocity. The space velocity is related to both
catalyst and reactant feed flow rates and reactor volume. The residence time is related to reactor
volume. Hence, in a MTO reactor, greater consideration should be given to the flow

characteristics, space velocity and residence time. Controlling these flow characteristics provides
for achieving and maintaining a desired fluidization regime, particularly a fast-fluidized flow
regime.
Effect of Reaction Temperature and Water as Diluent

A diluent is required to maintain the selectivity of the SAPO-34 catalyst to produce light
olefins, particularly ethylene and propylene. Water (steam) has been proven to be a good choice
for reducing methanol partial pressure to increase olefin selectivity and decrease the rate of
catalyst deactivation.
The use of steam as the diluent provides certain equipment cost and thermal efficiency
advantages. The phase change between steam and liquid water can be employed to advantage
in transferring heat between the feedstock and the reactor effluent, and the separation of the
diluent from the product requires simple condensation of the water to separate the water from the
hydrocarbons. When the methanol to hydrocarbon reaction is carried out over SAPO-34 catalyst,
the temperature and water content in the feed play a very important role in the selectivity toward
light olefins. Special attention has been paid to the role of water on activity and selectivity as
water is present because it is a reaction product and because it is fed together with methanol to
reduce deactivation by coke.
Low methanol partial pressure favors more olefin formation. Water (steam) is the best
choice since it can be cheaply and easily obtained. Liang et al. [261A119] and Marchi and
Froment [261A114] have proven that as the reaction temperature and water concentration in the
feed were raised, the paraffin yield decreased and light olefin yield increased, which,
nevertheless, was not observed when nitrogen is used as the diluent. The increase of the
reaction rate of olefin conversion into paraffin with temperature may be less important than that of
the dehydration of oxygenated compounds to light olefins. On the other hand, Marchi and
Froment attribute the presence of water in the feed gives way to a considerable increase in the
selectivity to light olefins to the competition of water against olefins for adsorption on the strong
acid sites. It has also been shown by Van Niekerk et al. [261A103] and Wu et al. [261A067] that
water is the most adequate diluent for a MTO reactor in terms of methanol conversion, olefin
selectivity, and catalyst deactivation rate. Therefore, most of the work described hereafter was
conducted on a methanol/water feed.
The UOP/Hydro MTO process can be operated on “crude” or unpurified methanol as well as
the chemical grade methanol. The choice of feedstock quality generally depends on project-
specific situations because there can be advantages in either case.
When the feed was composed of 20 mol% methanol and 80 mol% water, Wu et al.
[261A049] experimentally studied the impact of reaction temperature for methanol conversion to
light olefins over SAPO-34 catalyst in a bench-scale fixed-bed reactor. Temperature was found to
be the strongest factor that affects product ethylene-to-propylene ratio. Adjusting reaction
temperature or controlling the deactivation state of the SAPO-34 catalyst can lead to different
ethylene-to-propylene ratios. Higher temperature or partially deactivated catalyst produced higher
ethylene-to-propylene ratios. Over SAPO-34, when the feed was composed of 20 mol% methanol
and 80 mol% water the optimum MTO reaction temperature in terms of methanol conversion,
selectivity to ethylene-to-propylene and catalyst deactivation rate appeared to be approximately
400°C. Higher temperatures led to faster catalyst deactivation due to coke formation and lower
selectivities to propylene and butenes; while lower temperatures led to higher selectivities to
undesirable CO + CO2 and CH4, lower methanol conversion, and faster catalyst deactivation due
to oligomer blockage of SAPO-34 pores. Gayubo, et al. [261A091] also disclosed that in

methanol conversion to olefins, higher average reaction temperatures at a given coke level on
the catalyst increases selectivity to ethylene.
Effect of Space Velocity

The feedstock flow rate affects olefin production. Increasing the feedstock flow rate
(expressed as weight hourly space velocity, or WHSV) enhances the formation of olefin
production relative to paraffin production. However, the enhanced olefin production relative to
paraffin production is offset by a diminished conversion of oxygenate to hydrocarbons.
U.S. Pat. No. 5,952,538 discloses an optimal range of space velocities which are suitable for
methanol to light olefins conversion.
Chen et al. [261A073] investigated the effect of space velocity over a SAPO-34 catalyst. It
was found that the coking rate was lower with high methanol feed rates under partial methanol
conversion conditions and the coke content was proportional to the amount of hydrocarbon
formed (per mass of catalyst) and independent of space velocity. Similar results were observed
when by Benito et al. utilizing a ZSM-5 type catalyst [261A107]. The increased coking rate was
largely attributed to the increased conversion of oxygenates and, to a small extent, to the space
velocity.
Feeding a mixture composed of 20 mol% methanol and 80 mol% water over SAPO-34
catalyst in a bench-scale fixed-bed reactor, Wu et al. [261A049] have shown that the optimum
methanol weight hourly space velocity in terms of methanol conversion, selectivity to light olefins
−1
and catalyst deactivation rate, was in the range of 2.6–3.6 h . Lower methanol space velocities
led to lower selectivity to light olefins and faster catalyst deactivation; while higher methanol
space velocities led to lower methanol conversion. By optimizing reaction conditions, selectivity to
light olefins can be around 90% with 100% methanol conversion at a catalyst capacity of
cumulative methanol 20 g/g-catalyst in a fixed-bed reactor in a single pass mode.
U.S. Pat. No. 6,455,747 to Lattner et al. describes the effect of gas superficial velocity in the
MTO reactor, which is defined as the volumetric flow rate of vaporized feedstock, products and
any diluent, divided by the reactor cross-sectional area. Because the oxygenate is converted to a
product including a light olefin while flowing through the reactor, the gas superficial velocity may
vary at different locations within the reactor depending on the total number of moles of gas
present and the cross section of a particular location in the reactor, temperature, pressure, and
other relevant reaction parameters. The optimum gas superficial velocity, including any diluents
present in the feedstock, should be maintained at a rate greater than 2.5 m/s.
Influence of Coke Deposition

U.S. Pat. No. 6,023,005 discloses the importance of maintaining optimal average coke levels
on oxygenates to olefins conversion catalyst to effect improved lower olefin selectivity.
Methanol to olefins (MTO) and coke deposition over SAPO-34 have been studied in an
isothermal fixed-bed integral reactor with emphasis on effects of the coke content [261A052] and
it has shown that the deposition of coke on SAPO-34 during methanol conversion to olefins at
temperatures of 350–550°C was observed to be rapid. Micropores are blocked badly at coke
contents of ~ 4 wt%. The coke deposition influences olefins selectivity significantly and selectivity
of ethylene plus propylene reach maximum at a coke content of about 5.7 wt%. The nature of
coke deposition seems to be mainly paraffinic at relatively low reaction temperatures and more
aromatic at higher temperatures.

UOP/Hydro MTO Reaction Conditions
Reaction parameters such as temperature, space velocity, pressure, and feed composition
also have significant effects on product distribution. In general, reductions in contact time, weak
acidity, water dilution, and modification with suitable promoters can enhance the selectivity of
light olefins.
Reaction conditions over SAPO-34 in the MTO process, plays an important role for methanol
conversion, selectivity to olefins, and catalyst deactivation. In order to optimize operation of
methanol conversion to light olefins, it is desirable to set various parameters associated with the
fast-fluidized bed MTO reactor system. Such optimal operating conditions can enhance methanol
conversion and/or selectivity for prime olefins, especially for ethylene and propylene. U.S. Pat.
No. 6,166,282 observes that oxygenate conversion processes can be sensitive to reaction
variables such as temperature, catalytic activity, and space velocity.
The UOP/Hydro MTO reactor operating conditions can be adjusted to the desired product
requirements. The pressure is normally dictated by mechanical considerations since its effect on
overall MTO reaction is not significant. The fluidized bed MTO reactor operates in the vapor
phase at temperature 350-550°C and pressure between 1–3 bar gauge [261A043]. On a percent
carbon basis, a typical UOP/Hydro MTO operation converts up to 80% of the methanol feed to
ethylene and propylene, with approximately 10% going to butanes. The overall carbon yield can
be increased to almost 90% by converting the C4+ hydrocarbon by-product, mostly to propylene.
MTO Reaction Mechanism

Mechanism of ethanol-to-olefin (MTO) conversion is essentially about how an initial ethylene
C-C bond is formed from a C1 species. Since insights into the methanol to olefins mechanism to
control product distribution are highly desirable, for more than 30 years the actual mechanism of
the conversion of methanol to olefins in acidic zeolites has been the source of considerable
debate, fueled by countless different and often conflicting propositions. Though there is little
doubt that ethylene is dissociated from some much larger organic species when the reaction
proceeds beyond induction time, with possible routes include paring and side-chain-growth
mechanisms [261A024], the exact mechanism of how ethylene is formed is still not clear largely
as a result of complications from secondary reactions, which make it hard to differentiate primary
products from secondary products.
The trickiest step to elucidate has always been the formation of the first carbon bond, for
which more than 20 distinct mechanisms have been proposed [261A092]. Speculation mainly
centered on mechanisms based on the “direct” formation of small olefins from only methanol,
dimethyl ether, and other single-carbon derivates [261A098, 261A101]. Current studies are
steadily shifting toward alternative “hydrocarbon pool” proposals from the direct mechanisms to
produce ethylene from methanol only [261A013]. The organic intermediates, which are referred
to as the hydrocarbon pool, serve as platforms to which C1 species can bind and from which
primary olefin products can dissociate. Polymethyl benzenes are the most active hydrocarbon
pool species on HSAPO-34. On ZSM-5, cyclopentenyl cations play an important role [261A024].
There is an ongoing debate about what happens during the induction time largely as a result
of complications from secondary reactions, which make it hard to differentiate primary products
from secondary products. Besides the hydrocarbon pool mechanism, several direct mechanisms
have been proposed to explain at least the initial olefin formation during the induction time. A
direct mechanism involves only C1 species to form the C-C bond. While Haw and co-workers
argued that organic impurities in the methanol feed were responsible for forming the initial small
amount of hydrocarbon pool species, [261A056] Hunger and co-workers contended that C-C
bonds could formed directly from surface methoxy groups. [261A053, 261A023]

More detailed studies are underway for a better understanding of MTO mechanisms, A
recent study [261A024] suggests that C-H bonds on methanol groups were activated—which is
an essential step in the MTO process—in the presence of toluene through a paring mechanism.
As parts of the paring mechanism were observed in the MTO process for the first time in the
absence of complications from secondary reactions, the paring mechanism is thus supported as
a possible mechanism for MTO conversions. Kolboe and Haw have also speculated on the role
of the paring mechanism for the MTO process [261A040, 261A041].
MTO Process Chemistry and Kinetics

During the last decades, increasing efforts were made to clarify the mechanism of the
methanol-to-olefin reaction and a hydrocarbon pool mechanism proposed by Dahl and Kolboe
[261A105] has gained wide supports for post induction-time MTO chemistry.
Previous studies revealed that, in the MTO process, the conversion of an equilibrium mixture
of methanol and DME is dominated by a hydrocarbon pool route in which methanol is added to
reactive organic compounds formed in the pores of acidic zeolite catalysts. These compounds
can be branched olefins, polyalkylbenzenzes, cyclic carbenium ions, and polyalkylbenzenium
cations. Light olefins are formed via an elimination of alkyl groups from these hydrocarbon pool
compounds [261A092].
Kinetic Models based on ZSM-5

A number of simplified MTO kinetic models have been developed based upon kinetic studies
over HZSM-5 catalysts, and the complexity of the model varies according to the degree of
lumping proposed [261A107]. More than 30 reactions were used has been used in a very
detailed analysis performed by Mihail et al. [261A124]. Park and Froment [261A059, 261A060]
have performed single-event kinetic modeling of MTO process over H-ZSM-5 on the basis of a
detailed mechanistic description of the MTO reaction.
Kinetic Models based on SAPO-34

Bos and Tromp developed a kinetic model for MTO process over SAPO-34 based on results
obtained from a plug flow fixed-bed reactor at 450°C [261A108]. The conversion and the product
selectivity were studied as a function of the coke content on the catalyst. An exponential
dependency was found to give the best representation of the effect of coke on the reaction rate.
In 1999, Keil, F.J. gave a review on process technologies on Methanol-to Hydrocarbons
[261A093].
The MTO reaction results were examined by Gayubo et al. as a function of time on-stream,
and the initial reaction rates at different conditions were obtained by extrapolating ration rates to
zero time. The authors have proposed a reaction network of MTO taking into account four
individual steps for the production of ethylene, propylene, butanes, and other hydrocarbons
(pentenes + paraffins) [261A078].
S. Soundararajan et al. simulated the MTO process carried out in circulating fluidized bed
(CFB) reactor with SAPO-34 as the catalyst at 450°C and atmospheric pressure [261A068].
Alwahabi and Froment [261A048 have developed a single-event kinetic model of the MTO
reaction over SAPO-34 catalyst in a fixed-bed reactor. The catalyst deactivation caused by coke
formation was modeled by fitting the conversion changes with time on-stream in the fixed-bed
reactor.

Recently, the kinetics of the reactions involved in the conversion of methanol to light olefins
(defined as ethylene, propylene, and butylenes) over SAPO-34, including deactivation caused by
coke deposition, has been studied in an oscillating microbalance reactor (TEOM) between 400
and 550°C, space velocities from 50 to 2000 g/g,h and methanol partial pressures from 7 to 83
kPa by Chen et al. [261A015]. The authors claim an oscillating microbalance reactor provides an
opportunity to achieve a better quantitative understanding of the activity and the selectivity
changes with the coke formation. The proposed reaction network is shown in Figure 4.1. All the
hydrocarbons are formed mainly as parallel products from DME. The methanol molecule might
also contribute to the olefin formation as a methylating agent inserted into the surface
intermediates, yielding a chain growth.
However, it is difficult to determine the degree of olefin formation from DME and directly from
methanol, so Figure 4.1 illustrates only the possible pathways for olefin formation from DME. In
the meantime, the proposed MTO reaction network can be explained by the “hydrocarbon pool”
mechanism [261A040, 261A041], regardless of the nature of the “hydrocarbon pool”, which is still
in debate.
Figure 4.1
REACTION NETWORK FOR MTO OVER SAPO-34
Methane
Ethylene
Proylene Coke
MeOH DME C4 Paraffins
C5
C6
Coke
Source: [261A015]

A kinetic model for this reaction network is developed, including the deactivation due to coke
deposition.
Where:
FMeOH = molar flow rate of methanol (mol/h)
W = catalyst loading, g of cat
i = 1, 2, 3, 4, 5, 6, 7 represents ethene, propene, butenes (C4), C5,C6, oxygenates, and ethane +
propane, respectively.
→
x =[x1, x2, x3, x4, x5, x6, x7]; matrix of conversion
xi = conversion to i
yi = mole fraction of component i on a CH2 basis
k0i = initial rate constant for the formation of component i, kmol (g of cat, kPa,h) -1
P0: initial methanol partial pressure, kPa
r→ = [r1, r2, r3, r4, r5, r6, r7]; matrix of reaction rate, kmol (g of cat, h) -1
ri = rate of formation of i, kmol (g of cat,h) -1
αi = empirical deactivation constant for the reaction corresponding the formation of i defined by
eq 7
øi = deactivation function for the formation of component i

C = weight percent of coke on the catalyst (g of coke/100 g of cat)
Source: [261A015]

Product Recovery
The crude product from methanol conversion to olefins is much more tractable than that
from steam cracking of hydrocarbons. However, since the effluent stream withdrawn from an
MTO conversion zone will contain substantial amounts a water by-product as well as unreacted
methanol, substantial quantities of DME intermediate, ethylene, propylene, C4+ olefins and minor
amounts of other hydrocarbons and oxygenates. Typically, with the preferred SAPO-34 catalyst
system when it is run at 97%+ conversion levels, approximately 70 - 78% of the methanol
equivalent carbon entering the conversion step will be converted to the desired C2 and C3 olefins
with 2 - 5% of the carbon converted to coke and approximately 0.5 - 1% converted to DME. The
level of saturated hydrocarbons produced in the MTO conversion step such as methane, ethane
and propane are characteristically held at very low levels with a SAPO-34 catalyst and will
approximately be 2 - 5% of the carbon balance [US 7138557].
The effluent stream exiting the MTO reactor is substantially cooled prior to entering a
downstream phase separation section. This cooling is typically done by first heat exchange
against the feed methanol stream and then by the use of an aqueous quench stream in a
quenching tower. The quench tower operates at 50-95% of reactor operating pressure. The
pressure drop of reactor effluent flow path should be kept small in order to reduce the down
stream compression. The overhead recovered from the quench tower runs it through a series of
suction drums and compressors to elevate its pressure to 365 psia, while more water is
condensed and taken out. The hydrocarbon gas stream is then processed using standard olefins
technology, which includes acid gas removal, drying, and front-end deethanization. The
cryogenic needs of the UOP/Hydro MTO process are met by a propylene-ethylene refrigeration
system in order to produce polymer-grade ethylene and propylene.
Conventional separation vessels are provided including an oxygenate stripper for removal of
unreacted oxygenates, a demethanizer section for removal of methane, a depropanizer section
for removal of propane, and a deethanizer for removal of ethane. The unreacted oxygenate
stream is returned to the MTO reaction zone to increase the efficiency of the MTO conversion.
Polymer-grade ethylene is produced in a C2 splitter, whereas a C3 splitter separates polymer-
grade propylene.
Several patents have proposed methods to reduce the cryogenic needs of the product
recovery section, particularly in the demethanizer. By allowing some ethylene and ethane to be
present in the overhead along with hydrogen and methane, the demethanizer condenser can be
maintained above -45°C. This potentially eliminates the need for a dedicated low temperature
refrigeration system [US 6303841, US 5811621, WO 9829366]. The ethylene rich overhead
stream can be separated in adsorption beds [US 6303841] or used in the production of ethylene
derivatives.
METHANOL TO OLEFINS BY THE UOP/HYDRO PROCESS

We have developed a conceptual design for a UOP/Hydro MTO plant via a fluidized reactor
regenerator configuration using the proprietary MTO-100 (modified SAPO-34) catalyst to produce
611 million lb/yr (277,200 t/yr) of polymer-grade ethylene and 611 million lb/yr (277,200 t/yr) of
polymer-grade propylene at a 0.90 stream factor. This design capacity refers to a feed rate of
5,000 t/d of methanol. Since there is no commercial-scale plants yet exist, our conceptual design
is intended to resemble the UOP/Hydro MTO technology and is based on information derived
from patents, articles and industry contacts.

Process Description
Table 4.2 provides the design bases and assumptions for the process. Figure 4.2 (foldout in
Appendix D) shows the process flow diagram, and Table 4.3 sets forth the stream flows. Tables
4.4 and 4.5 summarize the major equipment and utility requirements, respectively. The process
consists of two sections:
• Section 100—Methanol Conversion
• Section 200—Product Separation
Section 100—Methanol Conversion

Recovering sensible heat from the water stripper bottom stream, crude methanol from tanks
T-150 A-D is preheated in E-101, then vaporized by LP steam in E-102 and mixed with a vapor
stream containing recycled methanol. The combined stream is superheated to 116°C (241°F) in
the reactor feed-effluent exchanger, E-103, and then fed to fluidized reactor R-101 through a feed
distributor, which consists of a uniformly flat sieve plate permitting the vapor phase feed mixture
to pass through while retaining all catalyst above the sieve plate. The fast-fluidized MTO reactor,
that is described in details in the US Pat. No. 6,166,282 and 6,872,867, comprises a dense
phase catalyst section that contains an inventory of MTO-100 catalyst particles, a riser section
and a catalyst disengagement section. The need to remove the high exothermic heat of the MTO
reaction as well as the need for frequent regeneration led to a fluidized reactor and regenerator
design. At outlet conditions of 410°C (770°F) and 45 psia, the reaction proceeds to almost
complete conversion of methanol (99.8%). The net reaction product effluent stream withdrawn
from R-101 comprises less than 70 ppm-wt of catalyst in order to minimize catalyst loss/makeup.
The MTO-100 catalyst (based on SAPO-34) supplied by UOP and Norsk Hydro is expected to
have attrition resistance and stability suitable to withstand multiple regeneration steps and
fluidized reactor operating conditions described.
As the reaction proceeds, the activity of the catalyst in the reaction zone gradually is
reduced by the buildup of coke on the catalyst. To maintain the conversion and selectivity of the
reaction at acceptable levels, a portion of the catalyst mixture is withdrawn as a spent catalyst
stream from the upper disengaging section and passed through a spent catalyst standpipe,
where the spent catalyst stream is stripped with steam. The spent catalyst standpipe typically
includes a stripping section that contains grids or baffles to improve contact between the catalyst
and steam. The stripped catalyst is conveyed the spent catalyst slide valve (not shown) to
catalyst regenerator R-102. In the regenerator, coke deposited on the spent catalyst particles is
burned off by an air stream that flows upward. An adiabatic, electrically driven centrifugal
compressor, K-101, feeds air to the regenerator at 226°C (439°F). The regenerator operates at
outlet conditions of 600°C (1,112°F) and 50 psia; it reduces the catalyst carbon level from 5 wt%
to 0.05 wt%. Regenerated catalyst stream is returned to the lower reaction zone via a standpipe
with a regenerated catalyst slide valve to a point above the dense phase zone in R-101.
As catalyst particles are recovered by the cyclones located in the catalyst disengagement
section, the gaseous product stream exiting R-101 is cooled to 125°C (257°F) by exchanging
heat with the reaction feed in E-103, and is quenched to 38°C (100°F) so that a large mount of
water is condensed in quench tower C-101. The quench medium consists of an aqueous stream
recycled from the bottom of C-101 through air and water coolers E-104 and E-105. Unconverted
methanol is then removed from the liquid phase in stripper C-102 and recycled to the reactor as a
vapor stream. The bottom product from C-102, which contains most of the water introduced with
crude methanol and generated in the reaction, is sent to waste treatment after exchanging heat
with the reactor feed in E-101.

The vapor stream from quench tower C-101 is compressed in three stages to 365 psia by a
multicasing, steam turbine driven centrifugal compressor K-102. Intercoolers E-108, E-109, and
E-110, located at the discharge points of each of these stages, cool the gas to 38°C (100°F). The
condensate formed during cooling is separated from the gaseous stream in V-102. Two liquid
phases are formed: an aqueous layer, which is recycled to stripper C-102, and an organic layer,
which is stripped by steam in C-103. The stripped organic condensate exiting from C-103 is sent
forward to depropanizer C-206.
Section 200—Product Separation

The compressed vapor stream from V-102 is scrubbed with a 50 wt% aqueous caustic
solution to remove acid gases (mainly CO2). The caustic scrubber, C-201, operates in two loops:
a lower loop, where MTO product stream is scrubbed with makeup and recirculated caustic
solution, and an upper loop, where a stream of fresh makeup water is injected. The acid-free
vapor exiting C-201 is cooled to 22°C (50°F) by heat exchange with the downstream
demethanizer reboiler E-208 and then dried against a suitable desiccant (such as a Type 3A
molecular sieve) in packed dryer system C-202 A&B. While one dryer is on stream, the other is
being regenerated or is on stand-by.
Dried gas from C-202 A&B is cooled to 10°C (50°F) in the deethanizer feed cooler, E-201,
before it is fed to the front-end deethanizer, C-203, where most ethylene (99.99%) is recovered
overhead, with a minimal (0.5%) carryover of propylene. The deethanizer operates at an
overhead condenser temperature of -23°C (-9°F) and a base temperature of to 67°C (153°F).
The overhead vapor stream from the deethanizer is compressed to 475 psia in the fourth
stage of compressor K-102, and is heated to 80°C (176°F) in E-204 and E-205. The heated gas
downflows through acetylene converter R-201 to hydrogenate acetylene to ethane over a Pd-
based catalyst. Because C3 and heavier components have been preseparated from the stream,
gum and green oil formation in the reactor is minimized. The R-201 reactor does not require
frequent regeneration, and a spare reactor is not required. The catalyst is replaced every 3 to 4
years during plant turnarounds.
After heat exchange in E-204 and cooling to -20°C (-4°F) in E-206, the effluent from the
acetylene converter is fed to demethanizer C-204. The demethanizer separates a methane rich
stream overhead (including H2 and CO in the feed) and an essentially C2 mixture as the bottom
product. An overhead temperature of -61°C (-78°F) is necessary to achieve the separation;
ethylene refrigeration is used in condenser E-207. As described above, the demethanizer
reboiler, E-208, which operates at a column bottom temperature of -11°C (12°F), obtains its
energy by heat exchange with the dryer feed.
Polymer grade ethylene is recovered from the demethanizer C2 stream by distillation in the
C2 splitter column, C-205. The column is operated with a partial condenser at -12°C (-10°F), so
that the ethylene product is removed as a vapor. An ethane rich by product, which contains about
70 vol% C2H6, is separated at the bottom of the column. Reboiler E-210 is heated by liquefaction
of compressed propylene from the refrigeration system.
The bottom product from the deethanizer, C-203, which mainly contains C3s and higher
hydrocarbons, is fractionated in the depropanizer, C-206, to recover a C3 rich mixture overhead
and remove C4s and higher hydrocarbons at the bottom. The operating pressure of the
depropanizer top is set at 350 psia, which permits overhead condensation against cooling water,
while keeping the bottom temperature sufficiently low to minimize polymerization reactions.
Polymer grade propylene (99.5 wt% purity) is obtained from the fractionation of the C3s rich
mixture in the C3 splitter, C-207. Because of the large number of trays required for the separation,
the C3 splitter is divided in two separate columns that are linked to each other in series.

The cryogenic needs of the UOP/Hydro MTO process are met by a propylene-ethylene
refrigeration system. The propylene refrigeration system is a four-stage closed loop system that
exchanges heat with process streams, cooling water, and with the ethylene refrigeration system.
Flashing liquid propylene provides refrigerant temperature levels of –7°C (20°F), –27°C (–26°F)
and –36°C (–33°F), -46°C (-51°F).
The propylene refrigerant is compressed in the fourth stage to 232 psia. The 73°C (163°F)
gas is condensed with cooling water to 38°C (100°F) and charged to flash drum V-301. The liquid
is next flashed to the hottest refrigerant temperature, -7°C (20°F) at 70 psia. Portions are
vaporized in the load exchanger E-201; the remainder is flashed at V-302. Similarly, the liquid in
successive stages is flashed, a portion at each load exchanger, and the remainder at the next
stage separator drum. The vapor from the drums is compressed at the respective compressor
stage. At the lowest temperature refrigerant level, the propylene is superheated and collected in
drum V-305 completing the recycle loop.
Ethylene refrigeration is used solely for the demethanizer condenser (E-207) and is provided
at a single temperature of -102°C (-152°F). The power requirements of the refrigeration
compressors and of product compressor K-102 are met by turbine drives operating with 1,500
psig steam. After pressure reduction, the recovered steam is used to provide heat to methanol
vaporizer E-102 and to the several distillation column reboilers.

Table 4.2
DESIGN BASES AND ASSUMPTIONS
C selectivity
Product selectivity (H2O-free basis) Mol% Wt% (%)
Hydrogen 0.15 2.48 —
CO 0.03 0.04 0.02

CO2 0.12 0.09 0.04
Methane 2.43 5.03 2.13
Ethylene 38.75 45.85 38.87
Ethane 0.83 0.92 0.78
Propylene 38.75 30.57 38.87
Propane 0.52 0.39 0.50
Butenes 11.95 7.07 11.99
Butanes 0.09 0.05 0.09
Pentenes 4.38 2.07 4.39
+
C5 alkanes 0.04 0.02 0.04
Coke 1.96 5.41 2.29
Reactor system Fluidized Reactor Regenerator

Catalyst MTO-100
Reactor temperature (°C) 410 600
Reactor pressure (psia) 50 55
WHSV (based on total feed) 2.5
Superficial velocity (ft/s) 10 3

(upper reaction zone)
Product specifications
Ethylene Polymer grade, 99.9 wt% min
Propylene Polymer grade, 99.5 wt% min
Product recovery losses
Ethylene 1.0%
Propylene 1.5%
Methanol conversion 99.8%
Source: US 7138558, US 6121504, 261A125

Table 4.3
STREAM FLOWS
CAPACITY: 611 MILLION LB/YR (277,200 T/YR) OF
ETHYLENE
AT A 0.90 STREAM FACTOR
STREAM FLOWS, LB/HR

(1) (2) (3) (4) (5) (6)
Methanol Reactor Reactor Air Vent Vapor
Mol. WT. Feed Feed Effluent Feed Gas Stream
Hydrogen 2 — — 303 — — 303
CO 28 — — 60 — 92 60
CO2 44 — — 243 — 14,396 243
Methane 16 — — 4,905 — — 4,905
Ethylene 28 — 3 78,218 — — 78,215
Ethane 30 — — 1,675 — — 1,675
Propylene 42 — 2 78,217 — — 78,215
Propane 44 — — 1,050 — — 1,050
Butenes 56 — — 24,121 — — 24,121
Butanes 58 — — 182 — — 182
+
C5 — — 8,922 — — 8,922
Methanol 32 460,183 461,014 937 — — 71
Dimethyl ether 46 282 282 1 — — 1
+
C2 alcohols 564 564 1 — — 1
Water 18 103,059 103,895 362,934 — — 1,185
Oxygen 32 — — — 12,249 1,751 —
Nitrogen 28 — — — 40,319 40,319 —
NaOH 40 — — — — — —
Other — — — — — —
Total, lb/hr 564,088 565,761 561,767 52,568 56,525 199,147

kg/hr 255,866 256,625 254,813 23,845 25,640 90,332

Table 4.3 (Continued)
STREAM FLOWS
ETHYLENE
STREAM FLOWS, LB/HR

(7) (8) (9) (10) (11) (12)
+
Liquid Vapor Organic Stripped C4 Aqueous
Mol. WT. Stream Stream Phase Vapor Stream Phase
Hydrogen 2 — 303 2 2 — —
CO 28 — 60 1 1 — —
CO2 44 — 243 16 16 — —
Methane 16 — 4,905 106 106 — —
Ethylene 28 3 78,215 4,769 4,769 — —
Ethane 30 — 1,675 138 138 — —
Propylene 42 2 77,483 14,639 13,907 732 —
Propane 44 — 1,021 218 190 29 —
Butenes 56 — 18,061 8,693 2,633 6,060 —
Butanes 58 — 128 71 18 53 —
+
C5 — 4,302 5,079 460 4,620 —
Methanol 32 866 30 43 2 41 —
Dimethyl ether 46 — 1 — — — —
+
C2 alcohols — 1 — 1 —
Water 18 361,749 307 224 34 191 688
Oxygen 32 — — — — — —
Nitrogen 28 — — — — — —
NaOH 40 — — — — — —
Other — — — — — —
Total, lb/hr 362,621 186,733 34,001 22,275 11,726 688

kg/hr 164,482 84,701 15,423 10,104 5,319 312

STREAM FLOWS
ETHYLENE
STREAM FLOWS, LB/HR

(13) (14) (15) (16) (17) (18)
Stripper Vapor Waste Aqueous Process Spent
Mol. WT. Feed Recycle Water NaOH Water NaOH
Hydrogen 2 — — — — — —
CO 28 — — — — — —
CO2 44 — — — — — —
Methane 16 — — — — — —
Ethylene 28 3 3 — — — —
Ethane 30 — — — — — —
Propylene 42 2 2 — — — —
Propane 44 — — — — — —
Butenes 56 — — — — — —
Butanes 58 — — — — — —
+
C5 — — — — — —
Methanol 32 867 831 36 — — —
Dimethyl ether 46 — — — — — —
+
C2 alcohols — — — — — —
Water 18 362,437 836 361,600 485 2,079 2,663
Oxygen 32 — — — — — —
Nitrogen 28 — — — — — —
NaOH 40 — — — 485 — 44
Other — — — — — 608
Total, lb/hr 363,309 1,673 361,636 970 2,079 3,316

kg/hr 164,794 759 164,036 440 943 1,504

STREAM FLOWS
ETHYLENE
STREAM FLOWS, LB/HR

(19) (20) (21) (22) (23) (24)
+
Dried C1/C2 C3 Tail C2 Ethylene
Mol. WT. Feed Stream Stream Gas Stream Product
Hydrogen 2 303 303 — 303 — —
CO 28 36 36 — 36 — —
CO2 44 — — — 0 — —
Methane 16 4,905 4,905 — 4,881 25 25
Ethylene 28 78,215 78,207 8 391 77,816 77,427
Ethane 30 1,675 1,645 30 1 1,644 8
Propylene 42 77,483 387 77,095 — 387 —
Propane 44 1,021 1 1,020 — 1 —
Butenes 56 18,061 — 18,061 — — —
Butanes 58 128 — 128 — — —
+
C5 4,302 — 4,302 — — —
Methanol 32 30 — 30 — — —
Dimethyl ether 46 1 — 1 — — —
+
C2 alcohols — — — — — —
Water 18 — — — — — —
Oxygen 32 — — — — — —
Nitrogen 28 — — — — — —
NaOH 40 — — — — — —
Other — — — — — —
Total, lb/hr 186,160 85,484 100,675 5,611 79,873 77,460

kg/hr 84,441 38,775 45,666 2,545 36,230 35,135

STREAM FLOWS
ETHYLENE
STREAM FLOWS, LB/HR

(25) (26) (27) (28) (29) (30)
+ +
Ethane C3 C3 C4 Propylene Propane
Mol. WT. Stream Stream Stream Stream Product Stream
Hydrogen 2 — — — — — —
CO 28 — — — — — —
CO2 44 — — — — — —
Methane 16 — — — — — —
Ethylene 28 389 8 8 — 8 —
Ethane 30 1,636 30 30 — 30 —
Propylene 42 387 77,827 77,438 389 77,051 387
Propane 44 1 1,049 1,023 25 205 819
Butenes 56 — 24,121 121 24,000 — 121
Butanes 58 — 182 — 181 — —
+
C5 — 8,922 — 8,922 — —
Methanol 32 — 71 — 71 — —
Dimethyl ether 46 — 1 — — — —
+
C2 alcohols — 1 — 1 — —
Water 18 — 191 — 191 — —
Oxygen 32 — — — — — —
Nitrogen 28 — — — — — —
NaOH 40 — — — — — —
Other — — — — — —
Total, lb/hr 2,413 112,401 78,621 33,780 77,294 1,327

kg/hr 1,095 50,984 35,662 15,322 35,060 602

Table 4.4
MAJOR EQUIPMENT
ETHYLENE

EQUIPMENT
NUMBER NAME SIZE MATERIAL OF CONSTRUCTION REMARKS
------------------- ---------------------------------------------- ---------------------------------------- ---------------------------------------------------------- ----------------------------------------------------------------------------------
REACTORS
R-101 FLUIDIZED REACTOR 22 FT DIA SHELL: CR-MO STEEL WITH 40 FT OF FLUIDIZED BED
70 FT H (SAPO-34 CATALYST)
R-102 REGENERATOR 8 FT DIA SHELL: CR-MO STEEL WITH 45 FT OF FLUIDIZED BED

72 FT H (SAPO-34 CATALYST)
R-201 ACETYLENE CONVERTER 4 FT DIA SHELL: C.S. WITH 10 FT OF PD-ALUMINA CATALYST

16 FT H
COLUMNS
C-101 QUENCH TOWER 10 FT DIA SHELL: 316 SS 10 VALVE TRAYS, 24 INCH SPACING
25 FT TRAYS: 316 SS
C-102 WATER STRIPPER 7 FT DIA SHELL: 316 SS 48 VALVE TRAYS, 24 INCH SPACING
120 FT TRAYS: 316 SS
C-103 CONDENSATE STRIPPER 3 FT DIA SHELL: 316 SS 12 VALVE TRAYS, 24 INCH SPACING
35 FT TRAYS: 316 SS
C-201 CAUSTIC SCRUBBER 4 FT DIA SHELL: 316 SS 30 VALVE TRAYS, 24 INCH SPACING
65 FT TRAYS: 316 SS
C-202A,B GAS DRYERS 6 FT DIA EACH SHELL: C.S. WITH 13 FT OFALUMINA PACKING
20 FT EACH
C-203 DEETHANIZER 7 FT DIA SHELL: C.S. 36 VALVE TRAYS, 24 INCH SPACING
90 FT TRAYS: 316 SS
C-204 DEMETHANIZER 6 FT DIA SHELL: 5% NI 20 VALVE TRAYS, 24 INCH SPACING
60 FT TRAYS: 316 SS
C-205 C2 SPLITTER 10.5 FT DIA SHELL: C.S. 97 VALVE TRAYS, 18 INCH SPACING
155 FT TRAYS: 316 SS
C-206 DEPROPANIZER 9 FT DIA SHELL: C.S. 44 VALVE TRAYS, 24 INCH SPACING
95 FT TRAYS: 316 SS
C-207A,B C3 SPLITTER 14 FT DIA EACH SHELL: C.S. 190 VALVE TRAYS 18 INCH SPACING
150 FT EACH TRAYS: 316 SS DIVIDED IN TWO SECTIONS
COMPRESSORS
K-101 AIR COMPRESSOR 1,740 BHP CAST STEEL
K-102 PRODUCT COMPRESSOR 9,270 BHP CAST STEEL 4 STAGES, STEAM TURBINE DRIVEN
HEAT EXCHANGERS
E-101A,B FEED HEATER 6,310 SQ FT EACH SHELL: 316 SS

86.4 MMBTU/HR TUBES: 316 SS
E-102A-C FEED VAPORIZER-1 4,520 SQ FT EACH SHELL: C.S.
143 MMBTU/HR TUBES: 316 SS
E-103 FEED VAPORIZER-2 6,480 SQ FT SHELL: 316 SS
E-104 RECYCLE COOLER-1 47,650 SQ FT C.S. AIR COOLED
E-105A-E RECYCLE COOLER-2 6,270 SQ FT EACH SHELL: C.S.
E-106A,B WATER STRIPPER CONDENSER 3,170 SQ FT EACH SHELL: C.S.
E-107A-C WATER STRIPPER REBOILER 2,850 SQ FT EACH SHELL: C.S.

MAJOR EQUIPMENT
ETHYLENE

EQUIPMENT
------------------- ---------------------------------------------- ---------------------------------------- ---------------------------------------------------------- ----------------------------------------------------------------------------------
HEAT EXCHANGERS (Concluded)
E-108 INTERCOOLER-1 32020 SQ FT SHELL: C.S.

E-109 INTERCOOLER-2 2,820 SQ FT SHELL: C.S.
E-110 INTERCOOLER-3 4,500 SQ FT SHELL: C.S.
E-111 CONDENSATE STRIPPER REBOILER 280 SQ FT SHELL: C.S.
E-201 DEETHANIZER FEED COOLER 2,580 SQ FT SHELL: C.S.
7.2 MMBTU/HR TUBES: C.S.
E-202A,B DEETHANIZER CONDENSER 6,230 SQ FT EACH SHELL: C.S.
E-203 DEETHANIZER REBOILER 2,210 SQ FT SHELL: C.S.
E-204A-D HEAT EXCHANGER 5,830 SQ FT EACH SHELL: C.S.
E-205 C2H2 REACTOR FEED HEATER 190 SQ FT SHELL: C.S.
E-206 DEMETHANIZER FEED COOLER 2,150 SQ FT SHELL: C.S.
E-207A,B DEMETHANIZER CONDENSER 5,980 SQ FT EACH SHELL: 316 SS
E-208 DEMETHANIZER REBOILER 2,010 SQ FT SHELL: 316 SS
E-209A-D C2 SPLITTER CONDENSER 4,620 SQ FT EACH SHELL: C.S.
E-210A-C C2 SPLITTER REBOILER 4,090 SQ FT EACH SHELL: C.S.
E-211 DEPROPANIZER CONDENSER 5,610 SQ FT SHELL: C.S.
E-212 DEPROPANIZER REBOILER 2,650 SQ FT SHELL: C.S.
E-213 C4+ COOLER 680 SQ FT SHELL: C.S.
E-214A-G C3 SPLITTER CONDENSER 4,020 SQ FT EACH SHELL: C.S.
E-215A,B C3 SPLITTER REBOILER 3,140 SQ FT EACH SHELL: C.S.
TANKS
T-151A-F CRUDE METHANOL TANK 3,500,000 GAL EACH C.S.

T-251A-C AQUEOUS CAUSTIC SODA 30,000 GAL EACH 304 SS
T-252A,B C4+ FRACTION TANK 90,000 GAL EACH C.S. NOT SHOWN ON FLOW DIAGRAM
PRESSURE VESSELS
V-101 WATER REFLUX DRUM 1,780 GAL 316 SS

V-102 PHASE SEPARATOR 6,000 GAL 316 SS
V-151 LP STEAM DRUM 1,500 GAL C.S. NOT SHOWN ON FLOW DIAGRAM
V-201 DEETHANIZER REFLUX DRUM 4,000 GAL 316 SS
V-202 DEMETHANIZER REFLUX DRUM 1,900 GAL 316 SS
V-203 C2 SPLITTER REFLUX DRUM 43,100 GAL 316 SS
V-204 DEPROPANIZER REFLUX DRUM 19,400 GAL C.S.
V-205 C3 SPLITTER REFLUX DRUM 80,800 GAL C.S.

MAJOR EQUIPMENT
ETHYLENE

EQUIPMENT
------------------- ---------------------------------------------- ---------------------------------------- ---------------------------------------------------------- ----------------------------------------------------------------------------------
SPECIAL EQUIPMENT
S-201 PROPYLENE REFRIGERANT SYSTEM INCLUDES 21,000 BHP COMPRESSOR,

CONDENSER, VESSELS, ETC.
S-202 ETHYLENE REFRIGERANT SYSTEM INCLUDES 6,000 BHP COMPRESSOR,

CONDENSER, VESSELS, ETC.
PUMPS
SECTION OPERATING SPARES OPERATING BHP

--------------- ------------------- -------------- -------------------------
100 6 5 400
200 13 10 800

Table 4.5
UTILITIES SUMMARY
ETHYLENE
AT 0.90 STREAM FACTOR
BATTERY LIMITS SECTION SECTION

UNITS TOTAL 100 200
--------------- ---------------------- --------------- ---------------
AVERAGE CONSUMPTIONS
COOLING WATER GPM 40,780 15,770 25,010
ELECTRICITY KW 3,780 3,170 610
STEAM, 1500 PSIG M LB/HR 420 -- 420
PEAK DEMANDS
ELECTRICITY KW 4,030 3,350 680

Process Discussion
Our design assumes that the feedstock is a crude methanol mixture obtained from a
conventional natural gas based methanol production process without purification section.
Typically, such a crude methanol product contains about 82 wt% methanol, with the balance
comprising mainly water; small amounts of dimethyl ether and C2 and higher alcohols are also
present. The presence of water in the MTO reactor feed is desirable for reasons mentioned
earlier. However, if the process is based on purchased methanol of high purity, then heat transfer
considerations may warrant that water be recycled to the reactor feed.
The MTO reactor design is based on the fast–fluidized system patented by UOP [US
6166282]. Catalyst inventory requirements are minimized by combining in the same reactor with
a dense phase zone and a transition zone with faster fluidization. The transition zone extends
from the lower dense phase zone through a riser and into the upper disengaging zone, and is
designed to increase the superficial gas velocity from less than 1 m/s (3 ft/s) to about 3 m/s (10
ft/s). The methanol mixed with diluent is introduced in the dense phase zone to effect a partial
conversion to olefins and then passed to the transition zone to achieve essentially complete
conversion. In the disengaging zone, two cyclone separation stages are used to separate the
catalyst from the reaction product. A portion of the catalyst is withdrawn from above the transition
zone in the disengaging zone, sent to the regenerator, and returned to a point above the dense
phase zone, while catalyst is continuously circulated from the disengaging zone to the reaction
zone.
The single quench tower flow scheme in the downstream of the reaction section is based on
description of patents [WO 99/55650, US 7138557]. An alternative two-stage quench tower
process can also be employed in the MTO flowsheet to concentrate the impurities into a relatively
small stream and results in significant energy and capital savings [US 6,459,009].
The heat integration scheme in the reaction section of our conceptual UOP/Hydro MTO
process is based on the method proposed in US 6121504. Water stripper C-102 operates at a
pressure of 80 psia, so that the temperatures of the overhead and bottom streams are sufficiently
high to generate LP steam in the condenser, and preheat the liquid methanol feedstock,
respectively. Although alternative integration methods can be used, we have not attempted to
optimize heat recovery in our design.
The back integration of MTO process with methanol production process provides savings in
both capital and operating costs, particularly when methanol purification (fractionation) step is
excluded from the upstream methanol plant [US 5714662]. ExxonMobil proposes a more
comprehensive integration approach, involving syngas, methanol, synfuel, and MTO processes
[US 6444712, US 6486219]. In a patent filed by JGC, a methanol-DME mixture is produced from
syngas at milder reaction conditions (such as lower pressure) than those in the reaction to form
only methanol [WO 0198237]. After product recovery, the vaporized methanol-DME stream is fed
to a reactor containing a SAPO-34 or ZSM-5 catalyst to produce light olefins. The presence of
DME in the reactor feed reduces the total amount of exothermic heat released in the conversion
reaction. As a result, the integrated method can lead to cost reductions in both methanol and
MTO processes.
UOP has proposed in its patents the combination of MTO with a catalytic cracker [US
5914433] or a metathesis unit [US 5990369] to change the equilibrium distribution of olefins
produced. In the first case, a secondary fluidized reaction zone is used to convert butylenes and
heavier olefins from the MTO process into additional ethylene and propylene. In the metathesis
process, butylenes react with ethylene in the presence of a molybdenum oxide or tungsten oxide
catalyst, producing additional propylene.

Comparing to Lurgi’s MTP process, the UOP/Hydro MTO process offers some flexibility for
altering the relative amounts of ethylene and propylene products by adjusting the MTO reactor
operating severity. The flexibility of ethylene-to-propylene product ratio between 0.75 and 1.5 can
be gained through process design and operation to reflect the relative market pricing for ethylene
and propylene.
Recently, US Pat. No 7,138,557 discloses that using the preferred SAPO-34 catalyst system
when MTO reactor is run at a typical 97+ % conversion levels, approximately 70 to 78% of the
methanol equivalent carbon entering the conversion step will be converted to the desired C2 and
C3 olefins with 2 to 5% of the carbon converted to coke and approximately 0.5 to 1% converted to
DME. The level of saturated hydrocarbons produced in the MTO conversion step such as
methane, ethane and propane are approximately 2 to 5% of the carbon balance. In order to
operate the unit at the desired MTO reactor operating severity, extra DME and/or methanol
absorber columns not included in our PEP conceptual design maybe required to recover and
recycle of DME and other oxygenates found in the MTO reactor effluent stream. Figure 4.3 is a
schematic of the UOP/Hydro MTO process with a DME recover block.
Figure 4.3
THE UOP/HYDRO MTO PROCESS WITH A DME RECOVERY BLOCK
[Source: 261A043]

Table 4.6
YIELDS FROM UOP/HYDRO PROCESS MTO CONVERSION ZONE
Selectivity (Mass- % of
Component Methanol Equivalent)
Methane 0.85
Ethylene 33.50
Ethane 0.65
Propylene 44.50
Propane 0.30
Butylene 9.5
Butane 0.01
C5+ 5.00
Coke 2.85
Unreacted Methanol 0.50
DME 1.05
Others (H2,COx,Dienes) 1.29
TOTAL 100.0
Source: [US 7138557]
For the product recovery section, our design approach follows conventional ethylene
technology. We have opted for a front-end deethanization system because of the relatively low
methane content of the reaction effluent. Although the SAPO-34-based reaction produces low
levels of acetylene and diolefinic compounds [261A058], we have included a fixed-bed reactor to
convert acetylene by hydrogenation. As previously mentioned, the hydrogenation reactor does
not require frequent regeneration, and a spare unit is not required.
The main waste effluent streams of the process can be summarized as follows:
Streama Description Disposal Method

5 Gaseous, regeneration vent gas Discharged to gas treatment
15 Aqueous, containing trace methanol and Discharged to drainage via bio-pond

hydrocarbons
18 Aqueous, mainly containing Na2CO3 plus Discharged to drainage after neutralization (can be
some NaOH used to neutralize acid effluents on site)
22 Gaseous, methane rich tail gas Consumed internally as fuel for steam generation
_______
a
Refer to Table 4.3 and Figure 4.2

COST ESTIMATES
Our cost estimates are based on the conceptual design described above and on the
following assumptions:
• A PEP Cost Index of 718
• A stream factor of 0.90
• Overnight construction and on the U.S. Gulf Coast during calendar year 2006
• Methanol priced at 13.6¢/lb, is produced in a world-scale plant from natural gas priced at
$6.74/MMBtu
• No royalty or license fee
Table 4.7 shows that the total fixed capital (TFC) investment breakdown of a stand-alone
UOP/Hydro MTO plant for the production of 611 million lb/yr (277,200 t/yr) of ethylene. As
indicated, our estimated total fixed capital (TFC) requirement is $321.1 million. The FOB cost for
battery limits equipment is about $59.6 million, of which nearly 25% represents reactor costs.
Direct installation costs (which include materials and labor costs for piping, fittings, electrical
equipment, instrumentation, insulation, structural materials, and paint) are $45.2 million. When
indirect costs, unscheduled equipment and contingency are added, the battery limits investment
(BLI) amounts to $149.2 million, or about 63% of the TFC. The total off-site investment of $134.6
million includes utilities and storage, general service facilities and waste treatment.
Table 4.9 details the section-by-section capital investment breakdown for our conceptual
UOP/Hydro MTO plant of base case capacity. The product recovery section, which includes the
propylene-ethylene cascade refrigeration system, accounts for the major part (about 58%) of the
BLI.
Figure 4.4 illustrates the effect of plant capacity on capital investment. The estimated TFC at
plant capacities of 0.5 and 2.0 times the base capacity are $194.7 million and $576.2 million,
respectively.
Table 4.8 shows the estimated production costs for ethylene production using the
UOP/Hydro MTO process. We have taken methanol at 90¢/gal (13.6¢/lb), delivered from a mega-
methanol plant in a U.S. Gulf Coast location using natural gas priced at $6.74/MMBtu as
feedstock and fuel. This methanol feedstock cost to UOP/Hydro MTO process is derived from the
“Methanol From Natural Gas” cost scenario outlined in the Section 5 of PEP Report 43E,
Methanol From Coal (December 2006), for a “fuel grade” methanol produced at a capacity of
5,000 t/d in a U.S. Gulf Coast location.
By-products, which account for a total credit of 62.8¢/lb, were taken at average U.S. Gulf
Coast prices during the course of year 2006. After accounting for fixed costs and allowing a
25%/yr pretax return on TFC, the ethylene product value for the base case amounts to 51.27¢/lb,
which is about 2.8¢/lb more than the market price of ethylene at 48.5¢/lb in the U.S. as of
September 2007.
Figure 4.5 illustrates the dependence of ethylene product value on both capacity and
methanol feedstock price. It is apparent that the ethylene product value is somewhat sensitive to
plant capacity for the indicated ethylene capacity range. Based on historical U.S. Gulf Coast price
levels for methanol, the UOP/Hydro MTO process would not be economical assuming our
estimated historical average ethylene level of 29.7¢/lb and propylene price level of 26.5¢/lb while
the methanol price level has generally ranged between 43-90¢/gal (6.5-13.6¢/lb) over the past
decade.

Figure 4.6 illustrates the historical pre-tax return on investment (ROI) for the period of 1992-
2006, using the two different assumptions for methanol prices. Clearly, the U.S. methanol market
over the last decade has supported price levels that make the MTO process highly
uneconomical. With methanol taken at a mega-plant delivered cost of 25¢/gal, however, the MTO
process would maintain a positive ROI during the entire period.
The economics of MTO process is also sensitive the credit assigned to by-products,
particularly propylene. This is evidenced in Figure 4.7, which shows the economics of a
UOP/Hydro MTO plant for the production of 400,000 t/yr ethylene using less extreme historical
U.S. market prices for ethylene and propylene during the time period of 1992-2001. Assume that
the MTO plant is located in the United States but consumes methanol delivered at 25¢/gal from a
remote mega-methanol plant. With a propylene-to-ethylene ratio set at 1:1, the product value for
ethylene (including 25%/yr pre-tax return on TFC) is inversely related to propylene prices during
the time period.

Table 4.7
TOTAL CAPITAL INVESTMENT

ETHYLENE
PEP COST INDEX: 718
CAPACITY
EXPONENT
COST --------------------------
($1,000) UP DOWN
------------ ---------- ----------
BATTERY LIMITS EQUIPMENT, F.O.B.
REACTORS 14,828 0.96 0.94
COLUMNS 7,644 0.93 0.88
VESSELS & TANKS 2,021 0.90 0.86
HEAT EXCHANGERS 14,166 0.91 0.79
COMPRESSORS 5,863 0.76 0.76
PROPYLENE REFRIG. SYSTEM 9,825 0.80 0.77
ETHYLENE REFRIG. SYSTEM 4,360 0.82 0.78
PUMPS 909 0.69 0.66
---------
TOTAL 59,616 0.88 0.83
DIRECT INSTALLATION COSTS 45,204 0.77 0.58

INDIRECT COSTS 30,806 0.76 0.62
UNSCHEDULED EQUIPMENT, 10% 13,562 0.81 0.70
---------
BATTERY LIMITS, INSTALLED 149,187 0.81 0.70
CONTINGENCY, 25% 37,296 0.81 0.70

---------
BATTERY LIMITS INVESTMENT 186,485 0.81 0.70
OFF-SITES, INSTALLED
CLARIFIED WATER 1,384 0.74 0.74
COOLING WATER 7,704 0.95 0.92
PROCESS WATER 800 0.62 0.62
BOILER FEED WATER 2,418 0.61 0.61
STEAM 26,774 0.95 0.89
TANKAGE 11,799 0.93 0.63
---------
UTILITIES & STORAGE 50,879 0.91 0.81
GENERAL SERVICE FACILITIES 47,473 0.82 0.70

WASTE TREATMENT 9,324 0.82 0.70
---------
TOTAL 107,675 0.86 0.74
CONTINGENCY, 25% 26,918 0.86 0.74

---------
OFF-SITES INVESTMENT 134,595 0.86 0.74
TOTAL FIXED CAPITAL 321,079 0.82 0.70

Table 4.8
CAPITAL INVESTMENT BY SECTION

ETHYLENE
PEP COST INDEX: 718
METHANOL CONVERSION PRODUCT SEPARATION

------------------------------------------------- -------------------------------------------------
CAPACITY CAPACITY
EXPONENT EXPONENT
COST ------------------------- COST -------------------------
($1,000) UP DOWN ($1,000) UP DOWN
------------ ----------- ---------- ------------ ----------- ----------
REACTORS 14,789 0.96 0.94 39 0.60 0.56
COLUMNS 591 0.79 0.47 7,054 0.94 0.92
VESSELS & TANKS 193 0.72 0.65 1,827 0.92 0.88
HEAT EXCHANGERS 7,040 0.92 0.81 7,125 0.91 0.77
COMPRESSORS 5,863 0.76 0.76 -- -- --
PROPYLENE REFRIG. SYSTEM -- -- -- 9,825 0.80 0.77
ETHYLENE REFRIG. SYSTEM -- -- -- 4,360 0.82 0.78
PUMPS 290 0.71 0.66 619 0.69 0.66
--------- ---------
TOTAL 28,766 0.90 0.85 30,850 0.87 0.81
DIRECT INSTALLATION COSTS 15,330 0.74 0.55 29,874 0.79 0.60

INDIRECT COSTS 16,960 0.77 0.64 17,847 0.75 0.61
UNSCHEDULED EQUIPMENT, 10% 5,705 0.82 0.72 7,857 0.81 0.68
--------- ---------
BATTERY LIMITS INSTALLED 62,760 0.82 0.72 86,428 0.81 0.68
CONTINGENCY, 25% 15,690 0.82 0.72 21,607 0.81 0.68

--------- ---------
BATTERY LIMITS INVESTMENT 78,450 0.82 0.72 108,034 0.81 0.68
OFFSITES, INSTALLED
CLARIFIED WATER 479 0.74 0.74 905 0.74 0.74
COOLING WATER 2,979 0.95 0.92 4,726 0.95 0.92
PROCESS WATER 309 0.62 0.62 491 0.62 0.62
BOILER FEED WATER -- -- -- 2,418 0.61 0.61
STEAM -- -- -- 26,774 0.94 0.89
TANKAGE 10,817 0.94 0.65 981 0.62 0.45
--------- ---------
UTILITIES & STORAGE 14,585 0.93 0.70 36,294 0.90 0.85

Figure 4.4
EFFECT OF PLANT CAPACITY ON INVESTMENT COSTS
800.000
Basis:
700.000
PEP Cost Index = 718
Stream Factor = 0.9
600.000
Total Fixed Capital

INVESTMENT- $millions
500.000
400.000
300.000
Battery Limits Investment

200.000
100.000
Base Case
0.000
0.000 100.000 200.000 300.000 400.000 500.000 600.000 700.000
PLANT CAPACITY- 1000 t/yr of ethylene

Table 4.9
PRODUCTION COSTS
PEP COST INDEX: 718
VARIABLE COSTS
CONSUMPTION
a a
UNIT COST PER LB ¢/LB
------------------------- -------------------------- ----------
RAW MATERIALS
METHANOL (IN 82% AQ.) 13.6 ¢/LB 5.94096 LB 80.80
CAUSTIC SODA (IN 50% AQ.) 17 ¢/LB 0.00626 LB 0.11
CATALYST AND MISC. 1.75
---------
GROSS RAW MATERIALS 82.66
BY-PRODUCTS
METHANE RICH GAS 2.2 $/MMBTU -0.0016 MMBTU -0.33
ETHANE RICH GAS 20.05 ¢/LB -0.03134 LB -0.62
PROPANE RICH GAS 23.8 ¢/LB -0.01656 LB -0.39
PROPYLENE 47.5 ¢/LB -0.99837 LB -47.42
C4/C5 MIXTURE 32.1 ¢/LB -0.4367 LB -14.01
---------
TOTAL BY-PRODUCTS -62.77
CONSUMPTION CONSUMPTION
a a
UNIT COST PER LB PER KG
------------------------- -------------------------- --------------------------
UTILITIES
COOLING WATER 10.15 ¢/MGAL 31.2 GAL 261 LITERS 0.32
STEAM, 1500 PSIG 11.3 $/MLB 5.4 LB 5.4 KG 6.10
ELECTRICITY 5.4 ¢/KWH 0.0483 KWH 0.106 KWH 0.26
---------
TOTAL UTILITIES 6.69
-----------------------------------
a
OF ETHYLENE

PRODUCTION COSTS
PEP COST INDEX: 718
a b
CAPACITY (MILLION LB/YR) 306 611 1,222
------------ ------------ ------------
BATTERY LIMITS (BLI) 115.1 186.5 329.0
OFFSITES 79.6 134.6 247.1
--------- --------- ---------
TOTAL FIXED CAPITAL (TFC) 194.7 321.1 576.2
SCALING EXPONENTS 0.70 0.82
a
PRODUCTION COSTS (¢/LB )
RAW MATERIALS 82.7 82.7 82.7

BY-PRODUCTS -62.77 -62.77 -62.77
UTILITIES 6.69 6.69 6.69
--------- --------- ---------
VARIABLE COSTS 26.6 26.6 26.6
OPERATING LABOR, 5/SHIFT, $41.5/HR 0.60 0.30 0.16

MAINTENANCE LABOR, 1.6%/YR OF BLI 0.60 0.49 0.43
CONTROL LAB LABOR, 20% OF OPER LABOR 0.12 0.06 0.03
--------- --------- ---------
LABOR COSTS 1.32 0.85 0.62
MAINTENANCE MATERIALS, 2.4%/YR OF BLI 0.91 0.73 0.65

OPERATING SUPPLIES, 10% OF OPER LABOR 0.06 0.03 0.02
--------- --------- ---------
TOTAL DIRECT COSTS 28.87 28.19 27.86
PLANT OVERHEAD, 80% OF LABOR COSTS 1.06 0.68 0.49

TAXES AND INSURANCE, 2%/YR OF TFC 1.27 1.05 0.94
--------- --------- ---------
PLANT CASH COSTS 31.19 29.92 29.29
DEPRECIATION, 10%/YR OF TFC 6.36 5.25 4.71

--------- --------- ---------
PLANT GATE COSTS 37.55 35.17 34.00
G&A, SALES, RESEARCH 2.96 2.96 2.96

--------- --------- ---------
NET PRODUCTION COST 40.51 38.13 36.96
ROI BEFORE TAXES, 25%/YR OF TFC 15.94 13.14 11.79

--------- --------- ---------
PRODUCT VALUE 56.45 51.27 48.75
-----------------------------------
a
OF ETHYLENE
b
BASE CASE

Figure 4.5
EFFECT OF METHANOL PRICE AND PLANT CAPACITY

ON ETHYLENE PRODUCT VALUE
65
60 Ethylene Capacity
139 kt/yr
ETHYLENE PRODUCT VALUE - ¢/lb
55 277 kt/yr
554 kt/yr
50
45
40
35
30
25
6 7 8 9 10 11 12 13 14 15
METHANOL PRICE - ¢/lb

Figure 4.6
HISTORICAL PRE-TAX RETURN ON INVESTMENT (ROI)
100
90
80
70
60
Case 1
ROI BEFORE TAXES - % OF TFC
50
40
30
20
10
0
-10
-20
-30 Case 2
-40
-50
-60
Case 1: Methanol from mega-plant at 25¢/gal
-70
-80 Case 2: Methanol at prevailing U.S. prices
-90
-100
1992 1994 1996 1998 2000 2002 2004 2006

Figure 4.7
PRODUCTION ECONOMICS AT HISTORICAL ETHYLENE AND PROPYLENE PRICES

WITH LOW-COST METHANOL FEEDSTOCK FROM MEGA-PLANT AT 25 ¢/GAL
50
MTO Design Basis:
45
400,000 t/yr of ethylene
400,000 t/yr of propylene
40 0.90 stream factor
PRICE OR PRODUCT VALUE - ¢/lb
35
30
MTO Ethylene Value
25
20
Ethylene Price
15
Propylene Price
10
5
Methanol Price
0
1992 1993 1994 1995 1996 1997 1998 1999 2000 2001

Table 4.10
PRODUCTION COSTS
PEP COST INDEX: 718
a b
CAPACITY (MILLION LB/YR) 305 610 1,219
------------ ------------ ------------
OFFSITES 79.6 134.6 247.1
--------- --------- ---------
a
PRODUCTION COSTS (¢/LB )
RAW MATERIALS 82.8 82.8 82.8

BY-PRODUCTS -62.08 -62.08 -62.08
UTILITIES 6.70 6.70 6.70
--------- --------- ---------

--------- --------- ---------
LABOR COSTS 1.32 0.85 0.62

OPERATING SUPPLIES, 10% OF OPER LABOR 0.06 0.03 0.02
--------- --------- ---------

--------- --------- ---------

--------- --------- ---------

--------- --------- ---------

--------- --------- ---------
PRODUCT VALUE 57.33 52.15 49.63
-----------------------------------
a
OF PROPYLENE
b
BASE CASE

Comparison With Other Technologies
In order to compare the economics of the UOP/Hydro MTO process with that of Lurgi’s
methanol to propylene process for propylene production, detailed in Section 5, we have tabulated
the estimated production costs for propylene production using the UOP/Hydro MTO process in
table 4.10. Unlike that of Lurigi’s MTP process, the propylene product value of the UOP/Hydro
MTO process appears to be more sensitive to production capacity in the indicated range. For the
production of 1,136 million lb/yr (515,000 t/yr) of polymer grade propylene, the propylene product
value by Lurgi’s MTP process amounts to 46.8¢/lb, which is about 3.2¢/lb less than the 50.0¢/lb
of propylene product value by UOP/Hydro MTO process.
The economics of the UOP/Hydro MTO process for ethylene production appeared to
compare unfavorably with that of an ethane cracker or a wide-range naphtha cracker as
evaluated by PEP at the assumed methanol cost of 40¢/gal delivered from a remote mega-
methanol plant. Details of this comparison may be found in PEP Report 111A, Methanol-based
Chemicals (July 2002).
MTO Applications
Our analysis shows that the UOP/Hydro MTO process has competitive economics only
when low-cost methanol is available from a mega-methanol plant. In this context, the following
applications of the MTO technology can be considered:
• The design and construction of an entire mega-methanol/MTO/polyethylene/
polypropylene production complex in the vicinity of a major coalmine. The use of crude
methanol directly from the methanol converter may eliminate the need for the usual
fractionation requirements for producing chemical grade or fuel grade methanol. Typical
commercial methanol specifications limiting DME byproduct production may become less
of a factor in methanol converter design and operating conditions, which may lead to
further improvement in economics of feedstock methanol production and overall coal-to-
plastics complex. This may be particularly advantageous for extremely remote locations
where transportation logistics makes converting low cost, bulky coal feedstock to value
added polymer products.
• Production of methanol in large quantity at a stranded natural gas field site and
transportation of the methanol to an MTO plant located close to the market for olefin
derivatives. One advantage of this alternative, which is consistent with our base case
design, is that the total capital investment is split between the olefin and methanol
producers.
• Integrated Gas-to-Olefins (GTO) production. In this alternative, the methanol and MTO
plants are located in a single site, typically close to the ethylene derivatives market. The
back integration of MTO with methanol reduces capital costs, particularly when the
purification (fractionation) step is excluded from the methanol production system.
However, the integrated complex is still very capital-intensive, requiring a TFC of over $1
billion for a world-scale plant. The choice of integrated versus segregated production of
methanol and olefins depends on several project-specific factors, such as location of
remote gas field, transportation costs, location of markets for olefin derivatives, etc.
• Integration of MTO into an existing naphtha or LPG cracker. The UOP/Hydro MTO
process can switch between high-ethylene and high-propylene modes, by simply
changing the operating severity, to achieve a propylene-to-ethylene ratio between 0.67
and 1.3. Because of the low amount of paraffins produced by the MTO reaction, the

existing cracker separation section can be easily debottlenecked to handle the additional
olefins produced. Synergies between the processes also include using excess low-
pressure steam from the cracker to vaporize the methanol in the MTO unit, and recycling
the small amounts of MTO ethane and propane to the pyrolysis furnaces to enhance
yields.
• An integrated MTO and Olefin Cracking Process. Total Petrochemicals and UOP are
building an integrated MTO and OCP process demonstration plant at Total
Petrochemical’s site in Feluy, Belgium. Integration of MTO and olefin cracking processes
(OCP) could be advantageous because as earlier described, the UOP/HYDRO MTO
process converts methanol to ethylene and propylene along with some heavier olefins
and Olefin Cracking processes such as the Total Petrochemicals/UOP Olefin Cracking
process are able to convert these heavier olefins predominantly to propylene with some
associated ethylene. By integrating the two processes, Total Petrochemicals and UOP
hope to demonstrate a significant increase in the production of light olefins, particularly
propylene.

5 METHANOL TO PROPYLENE BY THE LURGI MTP PROCESS
INTRODUCTION
Propylene is one of the most important feedstocks for the petrochemical industry. The main
derivatives of propylene are polypropylene (PP), acrylonitrile, propylene oxide, oxo alcohols,
cumene and acrylic acid.
Propylene is currently produced almost exclusively as a by-product of either ethylene
manufacture or petroleum refining and expected capacity additions in the ethylene industry over
the next few years will result in less propylene production as a by-product from conventional
ethylene plants due to lighter cracker feedstocks. Propylene demand is expected to grow faster
than that for ethylene in the next ten years. Because propylene demand is also expected to grow
faster than demand for petroleum-based fuels, the net result is a shortfall of propylene supply
from steam and catalytic cracking relative to demand, a shortfall that will have to be made-up by
direct (or on-purpose) propylene production.
Most co-product propylene originates from steam cracking of feedstocks other than ethane,
although propylene is recovered in certain large ethane-based ethylene plants. Catalytic cracking
provides the bulk of the refinery-produced propylene; thermal refinery operations also produce
small volumes. Direct (or on-purpose) propylene production by propane dehydrogenation or by
metathesis of ethylene and butylenes accounts for only about 6% of the world propylene supply.
Because of the wide variety of feedstock sources and projected massive new capacity
additions in the near future, methanol has promise as an economical, non-petroleum source for
light olefin production. Methanol can be produced from a variety of sources including synthesis
gas derived from natural gas; coal; petroleum liquids coke; recycled plastics and municipal
wastes. In the meantime, recent advances in commercial methanol plant production technologies
coupled with mega-plant economies of scale may greatly reduce methanol production costs,
especially in regions with currently underutilized, low cost hydrocarbon feedstocks. Once this low-
cost methanol becomes available in quantity and a marketing infrastructure becomes operative, a
number of new markets for methanol may emerge.
Driven by growth in derivatives, particularly polypropylenes (homopolymer, copolymer and
impact grades), global demand for the crucial petrochemical raw material propylene is forecast to
grow a nearly 5.0% per year over the 2006-2011 time frame, 1.5 times world economic growth.
Growth will fall back to 4.1% per year over the latter portion of the forecast period with increasing
maturity of the propylene product value chain. Overall, propylene will continue to grow .5% faster
than ethylene at 4.5% for the next decade. This trend of imbalance in olefin demand combined
with growing demand of transportation fuels have generated more interest in technologies for
direct production of propylene. These on-purpose propylene production technologies could be
used to fill anticipated gap between propylene demand and available supply from steam crackers
and refineries.
One of the most promising new on-purpose propylene production technologies is the
conversion of methanol to propylene. This section reviews the technology for production of

polymer grade propylene from methanol and presents a conceptual design and its economics for
the Lurgi MTP (methanol-to-propylene) process technology based on a proprietary ZSM-5 type of
catalyst MTPROP® supplied from Süd-Chemie.
Our concept of the Lurgi MTP process presented in this section is based on the production
of 1,136 million lb/yr (515,000 t/yr) of polymer grade propylene (99.7 wt%) via a fixed-bed reactor
configuration using proprietary Süd-Chemie catalysts. Assuming an on stream factor of 0.90 and
an overall carbon yield to propylene product yield of about 71%, this corresponds to a methanol
consumption of 3,621 million lb/yr (1,642,500 t/yr) or 5,000 t/d on a water free basis. Our
conceptual design for the Lurgi MTP process is primarily based on our interpretation of patents
and literature available to us in the public domain.
COMMERCIAL DEVELOPMENTS
Mobil (now ExxonMobil) conducted most of the original work on methanol conversion to both
olefins and hydrocarbons in the gasoline range, using the company’s ZSM-5 family of zeolite
catalysts. However, the conventional ZSM-5 type of zeolite is more suited for methanol
conversion to an aromatics-rich hydrocarbon mixture boiling in the gasoline range. Mobil’s
Methanol-to-Gasoline (MTG) process was commercialized in 1985. Development work on
methanol conversion to lower olefins was later adapted for making C3+ olefins, which are easily
oligomerized into a gasoline-distillate product. Mobil’s Methanol-to-Olefins (MTO) and Olefins-to-
Gasoline-and-Distillates (MOGD) processes have been demonstrated.
The typical ethylene yield in Mobil’s MTO process is only about 6 wt%. Mobil has shown that
the ZSM-5 type catalyst can be adapted for production of lower olefins (mainly ethylene) by
modifying the catalyst composition and/or structure and the reaction conditions. The adapted
process was designated MTE (methanol to ethylene). However, the objective of ethylene
production is only partially achieved with MTE because the process still makes a significant
amount of by-product gasoline. At a limited methanol conversion of 45% per pass, the
selectivities to ethylene and propylene are 45 and 25 mol%, respectively.
In 1996, as part of its gas-based petrochemistry initiatives, Lurgi started developing a
process to convert methanol to propylene (MTP) based on a propriety catalyst exclusively
supplied by Süd-Chemie. This zeolite based MTP catalyst was a result of several years of
intensive co-development between Süd-Chemie and Lurgi.
Lurgi’s MTP process begins with a vapor phase dehydration of methanol to dimethyl-ether
(DME) process, in which vaporized methanol is catalytically converted over γ-alumina at
temperatures between 250°C and 300°C to produce an equilibrium mixture of DME, methanol
and steam. This mixture is then converted in a fixed-bed MTP reactor at 450-500°C (842-932°F)
in the presence of steam, with more than 99% conversion of methanol and DME. The low coking
tendency of the MTP catalyst makes it sufficient to provide for a simple, discontinuous catalyst
regeneration process in the reactor itself. The raw propylene is obtained which can be purified to
polymer grade propylene. Different olefin-containing streams are separated and recycled to the
reaction system, resulting in an overall carbon yield to propylene of about 71%. By-products of
Lurgi’s MTP process are gasoline with a high octane number (RON ~98.7 / MON ~85.5), LPG
and fuel gas.
In 1999 and 2000, Lurgi set up an initial single fixed-bed adiabatic reactor (PDU 308, 0.3
kg/h methanol feed) pilot unit and subsequently a three-reactor (1.2 kg/h methanol feed per
reactor) pilot unit at the Frankfurt research and development center, where the catalyst
performances were investigated and the process conditions were optimized for maximum
propylene yield [261A018]. Lurgi claims its MTP unit design basis is derived from more than
9,000 hours of pilot plant operating data at its research and development center in Germany.

It’s been reported that the viability of the Lurgi MTP process has been proved at a
demonstration unit operated jointly with Statoil at Statoil's methanol plant in Norway [261A018]. In
2001 Lurgi built a skid-mounted MTP demonstration unit (3 reactors, 360 kg/day methanol feed
per reactor), and installed it at Statoil’s Tjeldbergodden, Norway methanol complex to gain
valuable insights of MTP process design and operation while demonstrating MTP technology’s
capability of producing true polymer-grade propylene. In 2003, to confirm the quality of the
propylene obtained in the MTP demonstration unit, samples were sent to Borealis' Innovation
center in Rønningen, Norway, where it was polymerized with Borealis' Borstar process to
polypropylene that met all specifications, and converted into thermoformed cups.
After the demonstration unit was operated between November 2001 and April 2004. The
results helped Lurgi to determine the service life of the catalysts under realistic conditions by
continuously taking in the methanol feed from the final purification column of the Statoil plant and
testing influence of “real“ hydrocarbon recycles on product yield and catalyst activity. The results
from the demonstration unit tests proved that the MTP catalyst life exceeds one year of operation.
The results also showed that the zeolite-based catalyst could be easily regenerated more than a
dozen times.
propylene in two sequential reaction steps. DME is produced as the primary intermediate in the
first step, which is then converted to propylene in a separate reactor system in the second step.
This appears to facilitate the use of fixed-bed reactors, performance of catalysts, and operational
conditions that maximize propylene yields. A fluidized-bed reactor would probably otherwise be
required for temperature control purposes of the exothermic methanol-to-propylene reaction if it
were to be conducted in a single reaction vessel configuration. Furthermore, a fluidized-bed
reactor may limit the choice of catalysts to those with high attrition resistance but which may not
be optimal for propylene production.
chemicals complex using Lurgi’s MTP technology is currently under construction in China’s
Ningxia coal area. The facility will produce 540,000 mt/year of polypropylene from coal via the
methanol-to-propylene (MTP) route. Completion is scheduled for early 2009 [Chemical Week,
Nov. 1, 2006, p. 20]. Reportedly, Datang International Power Generation’s MTP project in China
and Fanavaran Petrochemicals’ MTP project in Iran have been experiencing delays [261A017].
TECHNOLOGY REVIEW
The conversion of methanol to hydrocarbons over solid acid catalysts is believed to proceed
through the following reaction path [261A092, 261A090, 261A060]:
n/iso-paraffins
- H2O - H2O higher olefins
2 CH3OH CH3OCH 3 light olefins
aromatics
+ H2O
naphthenes
Methanol is first dehydrated to an equilibrium mixture of dimethyl ether (DME), methanol,

and water, which is then converted to light olefins. In the last step, light olefins partially react to

form paraffins, aromatics, naphthenes, and higher olefins by hydrogen transfer, alkylation, and
polycondensation.
ZSM-5 Catalyst
MTPROP®, a ZSM-5-type zeolite catalyst supplied by Süd-Chemie, is the basis for Lurgi’s
Methanol-to-Propylene (MTP) process. Zeolites are defined crystalline agglomerations of
tetrahedral by oxygen coordinated building cations resulting in a defined structure (framework)
consisting of defined pores and cages of molecular dimensions (3Å to 8Å). In contrast to the
corresponding amorphous materials (i.e. alumosilicates) these defined pores and cages are
allowing the so-called shape selective catalysis.
Mobil’s pentasil-type zeolite ZSM-5 was the first catalyst shown to be effective for the
conversion of methanol to hydrocarbons. ZSM-5 is one of the medium-pore zeolites that can be
generally described as crystalline molecular sieves consisting of linked silica- and alumina-
tetrahedra forming 10-membered oxygen ring channels. The dimensions of these medium-size
pores are 5Å to 6Å. The empirical formula of ZSM-5 can be represented by:
NanAlnSi96-n0192.H2O with n<27 and typically about 3.
One of the most important features of zeolite catalysts is their ability to act as a molecular
sieve because the channels have molecular dimensions. ZSM-5’s shape selectivity is utilized to
achieve high propylene selectivity in Lurgi’s MTP process.
Since the product distribution of the ZSM-5-based methanol-to-hydrocarbon reaction can be
controlled by changes in zeolite structure and/or reaction conditions, Mobil developed three
principal modes of operation: the production of an ethylene-rich olefins mixture (as in the MTE or
methanol to ethylene process), the production of a mainly C3+ lower olefins-rich product (as in the
MTO or methanol to olefins process), and the production of an aromatics-rich gasoline mixture
(as in the MTG or methanol to gasoline process).
The main control parameters of the ZSM-5 catalyst based methanol-to-hydrocarbon reaction
are space times and methanol partial pressures (concentrations). The yield to light olefins initially
increases with space time but reaches a maximum, indicating the intermediate character of the
light olefins formed [261A092]. A decrease of the partial pressure also tends to enhance the
olefin formation by suppressing the aromatization reaction. Thus, olefin yields are maximized by
operating at partial methanol conversions and by using steam as an inert diluent. Even at
reduced methanol conversions, however, the production of aromatics is still significant. Typical
yields of a ZSM-5 based MTO reaction are 6 wt% ethylene, 42 wt% propylene, 12 wt% butylenes,
and 27 wt% C5+ [261A031].
ZSM-5 catalyst is shape selective as hydrocarbon product distribution of the ZSM-5 based
reaction can be controlled by changes in zeolite structure. ZSM-5’s shape selectivity combined
with occurrence of coke formed on the active catalyst surfaces is a crucial feature and inherent in
catalytic conversion of methanol to olefins due to inevitable side reactions. Cause and amount of
coke formation have a decisive impact on the combination of the MTP reactor system and the
catalyst selection. In Lurgi’s MTP process, high propylene selectivity is achieved through
changes in zeolite catalyst structure, coke formation, and/or reaction conditions.
Modification of zeolite composition, synthesis procedure, post-synthesis thermal treatment
and other methods allow tailoring Lewis- and Brønsted-acidity. Introduction of metals can also
generate reductive or oxidative properties to the zeolite. Several modified ZSM-5 type of catalysts
have been proposed to improve the product selectivity to light olefins. Earlier Mobil work, for
example, had indicated that olefins synthesis is favored by small pore zeolites, by phosphorus
modified ZSM-5, and by using large crystal forms of ZSM-5, particularly when the structure is

modified by specified components, such as MgO, Pd, and Zn. However, small pore zeolites are
more susceptible to coke deposition, necessitating frequent regeneration. More recent Mobil
patents propose other catalyst variants for olefins production, such as treated forms of high silica
ZSM-5 [US 4929780], and catalysts with diffusional barriers, particularly when a co-aromatic feed
is used [WO 0121561, US 6046372, US 6048816].
The ZSM-5-type zeolite catalyst developed by Süd-Chemie is customized for Lurgi’s
Methanol-to-Propylene (MTP) process. In patents filed by Metallgesellschaft and Süd-Chemie
[EP 448000, US 5981819], the MTP catalyst is described as having a Si/Al atomic ratio of at least
10, an alkali content of less than 380 ppm, a BET surface area of 300 to 600 m2/g, and a pore
volume of 0.3 to 0.8 cm3/g. At 100% methanol conversion, the selectivity to ethylene is at least 5
wt% and the selectivity to propylene is at least 35 wt%. However, because C2 and C4+ olefin
fractions are partially recycled to the reaction system, the MTP process can achieve a propylene
yield of more than 70% on a carbon basis as shown in Figure 5.1 [261A032].
Figure 5.1
LURGI MTP PROCESS CARBON PRODUCT YIELDS, WT%
80.0%
71.0%
70.0%
60.0%
50.0%
40.0%
30.0%
20.0% 16.1%
8.5%
10.0%
1.1% 1.6% 1.6%
< 0.01%
0.0%
C2- C2= C3= C3 C4/C5 C6+ Coke
Reactor Design and Operation

The methanol-to-olefin reactions over ZSM-5 type catalyst can be carried out in both fixed-
bed and fluidized-bed reactors. When coke formation is not very fast, adiabatic fixed-bed reactors
are usually preferred because of lower cost and simplicity of scale-up. However, the highly
exothermic MTO reaction (about 10 kcal/mol for ethylene production) normally requires the use of
an intermediate step of dimethyl ether (DME) production. In Lurgi’s MTP process, the vaporized
methanol feed is first contacted with a fixed-bed of an aluminum oxide (γ-Al2O3) catalyst to
produce an equilibrium mixture of DME, methanol, and steam, according to the following
equation:
2CH3OH → CH3OCH3 + H2O (5.1)

The reaction is exothermic, and its equilibrium is nearly independent of the operating
pressure. At about 300°C, the vapor phase reaction in the DME reactor achieves almost
thermodynamic equilibrium with a high methanol conversion.
In the MTP reactor, the mixture exiting the DME reactor is converted to olefins over a zeolite
based catalyst according to the following summary reaction:
nCH3OCH3 → 2CHnH2n + nH2O n = 2, …,8 (5.2)
For a better approach to isothermal conditions, the MTP reactor is designed with five
catalyst beds in series. Steam is added to the feed of first MTP reaction stage to reduce
carbonization. A fraction of cold mixture exiting the DME reactor is divided into four streams, each
feeding one of the last four fixed catalyst beds in the MTP reactor. Aiming at optimal catalyst
performances the temperature is kept at 400-450°C in the MTP reactor by adjusting the inter-
stage cooling to maintain similar catalyst/reaction conditions in each catalyst bed [WO 0001643].
At this temperature, propylene is favored over ethylene.
In order to maximum overall propylene yield, several olefin-containing streams are recycled
to the first MTP reaction stage [WO 9915482, US 7015369]. All olefins other than propylene are
recycled to extinction, purged as fuel gas, or ended up as gasoline-range hydrocarbon product.
The recycled hydrocarbons also serve as a heat sink.
The MTP reactor catalyst needs to be regenerated when the overall DME-Methanol-feed
conversion falls below the economical limit (typically after a cycle of approx. 500 – 600 hours of
operation or the overall methanol-DME conversion drops below 95%). The MTP catalyst
regeneration is done in situ via controlled coke burn-off with an air-nitrogen mixture. The in situ
catalyst regeneration procedure is designed to prevent unusual temperature-swing caused stress
and attrition of catalyst particles. Regeneration of the catalysts is completed when the oxygen
content of the air-nitrogen stream at the input and output of the catalyst bed is the same. The
MTP reactor catalyst regeneration time is estimated to be around one week. The catalyst
regeneration gas consisting of nitrogen-diluted air with somewhat elevated CO2 content is routed
to plant emission system.
The MTP reactions are favored by low pressure. When proper flow distribution is
maintained, large reactor diameters reduce pressure drop, which is also desirable for a fixed-bed
reactor system with recycles. Limited by the largest practical reactor vessel diameters and the
need of catalyst regeneration, it appears Lurgi’s standard-sized MTP design consists of three
MTP reactor trains. Normally, two MTP reactor trains are in operation while one train is in either
regeneration or in standby mode to ensure continuous operation of the plant [261A125].
The aluminum oxide catalyst in the DME reactor has an expected life of 10 years, whereas
the zeolite based MTP catalyst life is more than one year. Both spent catalysts can be easily
disposed as landfill.
Product Recovery
The crude product from methanol conversion to olefins is much more tractable than that
from steam cracking of hydrocarbons. However, since each mole of methanol generates a mole
of water, the hydrocarbon yield is only approximately 44 wt%. The by-product water is typically
separated in a quench tower, which also removes most of the unconverted methanol [US
6121504]. Small amounts of organic acids can be neutralized through caustic solution injection
into the quench tower sump. After recovering methanol in a methanol stripper, the stripped water

containing approximately 3500 ppmwt of methanol is routed to battery limits as process water,
which can be treated to supplement raw water.
Because the MTP reactions are favored by low pressure, the use of a quench tower
minimizes the pressure drop. The hydrocarbon gas stream is then processed using standard
olefins technology, which includes compression, drying, CO2 removal and front-end
deethanization. Polymer-grade propylene is produced in a C3 splitter separate propane and
polymer-grade propylene. In Lurgi’s methanol-to-propylene process, the C2- stream is partially
recycled to the reaction system. A dehexanizer is used to separate the gasoline by-product from
C4-C6 hydrocarbons for recycle.
PROCESS DESCRIPTION
The process flow diagram for our concept of the Lurgi MTP process is illustrated by Figure
5.2. Tables 5.1, 5.2, and 5.3 respectively present the design bases and assumptions, the stream
flows, and the major equipment. Table 5.4 summarizes the utility requirements of the process. As
illustrated by process flow diagram, the Lurgi MTP process consists of two sections:
• Section 100—Methanol Conversion
• Section 200—Propylene Recovery
Section 100—Methanol Conversion

Methanol feed from offsite storage is preheated in E-101 to 88°C (190°F) by heat exchange
with hot wastewater effluent from methanol stripper C-101. The methanol feed is then vaporized
in E-102 and superheated in E-103 to 260°C (500°F) prior to feeding the fixed-bed DME reactor
R-101. The hot effluent vapor leaves the DME reactor at a temperature of 300°C (572°F) and a
pressure of 18.7 psig.
After preheating the DME reactor feed in E-103, the DME reactor effluent vapor is then
combined with light C1 – C2 and C4 – C6 hydrocarbons recycled from the propylene recovery
section. About 10% of the mixture bypasses E-104, H-101 and is injected directly into the
exothermic MTP reactor for temperature control via interbed quench cooling. The reactant vapor
mixture undergoes further heating via feed/effluent exchanger E-104. The DME/methanol/water
mix is then combined with steam and recovered methanol from the methanol stripper C-101 and
then fired heater H-101 brings the stream to a MTP reaction temperature of 470°C (878°F). The
feed stream is spit into two (for two reactor trains) prior to feeding R-102A, the first stage of the
five-bed MTP reactor. The stripper steam appears to play an important role in suppressing coke
formation, although it is not favorable from the standpoint of DME conversion equilibrium. While
coke formation is extremely low, less than 0.01 wt% of the carbon product yield distribution, a
decoking cycle is required for the MTP reactors every 500-600 hours of operation. Decoking is
accomplished by combustion of the coke particles with nitrogen/air mixture, following with a
nitrogen purge to eliminate residual oxygen from the system. Since the coke combustion
temperature is similar to that required for normal reactor operation, it is not anticipated that this
regeneration cycle will thermally stress the mechanical components of the reaction system.
The crude propylene vapor effluent leaves the final MTP reactor stage at a temperature of
452°C (846°F) and at a pressure of around 5.6 psig. It undergoes cooling to 115°C (239°F) via
feed/effluent exchangers E-104 and then E-102 prior to feeding quench column C-102. This
column, which uses externally cooled recycle quench water, cools the crude propylene vapor to
about 42°C (107°F) while removing most of the water and methanol content. The condensed
quench water leaves the quench column bottoms at a temperature of 95°C (203°F). While most
of the quench column bottoms is cooled and recycled, the net bottoms are routed to the methanol

stripper C-101 for recovery of the residual methanol content prior to disposal. The quench column
recycle is cooled to a temperature of about 41°C (105°F) by a series of three heat exchangers, E-
106, E-107, and E-108 respectively. The recycle hydrocarbon from the propylene recovery
section is used as the cooling medium for E-106, while E-107 serves as a cooler/reboiler for the
propylene product column C-206 in that section.
The crude propylene vapor leaving the quench column overhead undergoes compression to
333 psig via compressor K-101, in order to condense the propylene and other hydrocarbons as
required for propylene recovery. Three intercooled stages and decanter KO drums are assumed
to be required. The residual water content in the condensate is separated as a heavy phase in
the boots of the respective KO drums V-103, V-104, and V-105 and recycled to the quench
column. The condensed hydrocarbons are recovered as light phases from these KO drums and
are fed forward to the propylene recovery section. A propylene refrigerant assumed for E-114
reduces the outlet temperature of the compressed vapor leaving the final compression stage to
15°C (59°F), in order to achieve essentially complete condensation of the condensable vapor.
The compressor is assumed to be driven by a HP steam turbine drive. LP steam extracted from
the turbine exhaust is used to help satisfy the LP steam requirements of the MTP process.
Section 200—Propylene Recovery

All three of the hydrocarbon condensate streams recovered as light phases from
compressor KO drums contain propylene and are fed to the deethanizer C-203 at their respective
optimal feed tray locations. Any non-condensables from V-105 are also routed to the deethanizer,
as indicated by the dotted line. The deethanizer bottoms product consists of propylene and
heavier hydrocarbons. Virtually all of the lighter hydrocarbons and any residual water vapor are
assumed to be stripped overhead for recycle to the MTP reactor. A purge of this C1 – C2 recycle
prevents the excessive buildup of methane, and is assumed to be suitable for use as fuel. The
column operates at a pressure of 333 psig, with propylene refrigerant used to reduce the reflux
temperature to -25°C (-13°F) in E-216. The recycled distillate vapor is heated to a temperature of
about 10°C (50°F) by feed/effluent heat exchange with E-218 and E-219. Intermittent methanol
injection to reflux drum V-207 is used for deicing purposes, if necessary. Most of any residual
water and methanol is assumed to end up in the column bottoms.
The deethanizer bottoms product feeds the depropanizer column C-204, which operates at
a pressure of 290 psig. The distillate from the depropanizer consists primarily of propylene with
some residual propane. The bottoms product consists primarily of C4 and heavier hydrocarbons,
along with any trace methanol and water components entering the column with the feed.
The depropanizer distillate is fed to the propylene column C-206, where the propylene
product is recovered as a distillate and stored offsite. The purity of the recovered propylene
product is assumed to be polymer graded with a purity of 99.7 wt%. The bottoms product from
this column consists primarily of propane, and is assumed to be equivalent to a LPG type fuel.
The process heat for the propylene column reboiler is provided by circulating quench water in
cooler/reboiler E-107.
The depropanizer bottoms product is fed to the dehexanizer column C-205 for recovery of
the gasoline byproduct fraction. The gasoline fraction is recovered as a bottoms product for
offsite storage, and is assumed to be equivalent to pyrolysis gasoline. The distillate vapor
consists primarily of C4 – C6 hydrocarbons and is recycled to the MTP reactor in combination with
the C1 – C2 hydrocarbon recycle stream from the deethanizer. A small purge of the C4 – C6
hydrocarbon stream prevents excessive buildup of hydrocarbons such as isobutane and
isopentane in the MTP reaction system. This purge is recovered as a liquid distillate stream from
the dehexanizer, and contains residual unconverted DME. It is also assumed to be suitable for
use as fuel.

Table 5.1
METHANOL TO PROPYLENE BY THE LURGI MTP PROCESS
DESIGN BASES AND ASSUMPTIONS
Methanol Dehydration
Reactor Adiabatic reactor with one fixed bed

of catalyst
Catalyst Aluminum oxide (γ-Al2O3)
Reaction temperature (°C) 250-300
Reaction pressure (psig) 10-20
Methanol conversion 75%
MTP Reaction
Reactor Fixed-bed (5) reactor with inter-stage cooling
Catalyst MTPROP® (Modified ZSM-5 zeolite)

Reaction temperature (°C) 450-500
Reaction pressure (psig) 5-15
Methanol conversion 96.2%
Product selectivity (H2O-free basis, wt%)
Hydrogen <0.01
CO 0.01
Methane 0.90
Ethylene 0.85
Ethane 0.06
Propylene 71.20
Propane 0.98
Butenes 1.31
Butanes 3.69
Pentenes 0.61
Pentanes 3.68
Hexenes 0.21
Hexanes 0.59
Gasoline 15.90
Propylene specification Polymer grade, 99.5 wt% min
Propylene recovery losses 2.8%

Source: EP 448000, WO 0192190, 261A125

Table 5.2
STREAM FLOWS
CAPACITY: 1,136 MILLION LB/YR (515,000 T/YR) OF
PROPYLENE
STREAM FLOWS, LB/HR

Mol. WT. (1) (2) (3) (4) (5) (6) (7)
Hydrogen 2 — — — — 44 44 —
CO 28 — — — — 106 106 —
Methane 16 — — — — 7,339 7,339 —
Ethylene 28 — Trace Trace Trace 6,896 6,896 —
Ethane 30 — — — — 507 507 —
Propylene 42 — Trace Trace Trace 3,384 3,384 —
Propane 44 — — — — 26 26 —
Butenes 56 — Trace Trace Trace 85,031 85,031 —
Butanes 58 — — — — 241,311 241,311 —
Pentenes 70 — Trace Trace Trace 35,497 35,497 —
Pentanes 72 — — — — 231,190 231,190 —
Hexenes 84 — Trace Trace Trace 1,116 1,116 Trace
Hexanes 86 — — — — 9,021 9,021 Trace
Gasoline — — — — 5,798 5,798 Trace
Methanol 32 459,291 114,822 11,482 103,340 — 103,340 9,259
Dimethyl ether 46 Trace 247,601 24,760 222,841 3,831 226,672 —
Water 18 Trace 96,868 9,687 87,181 — 87,181 259,716
Total, lb/hr 459,291 459,291 45,929 413,362 631,097 1,044,459 268,975

kg/hr 208,333 208,333 20,833 187,500 286,264 473,764 122,006

STREAM FLOWS
PROPYLENE
STREAM FLOWS, LB/HR

Mol. WT. (8) (9) (10) (11) (12) (13) (14)
Hydrogen 2 27 28 55 — — — —
CO 28 61 65 132 — — — —
Methane 16 4,341 4,529 9,173 — — — —
Ethylene 28 4,082 4,258 8,627 — — — —
Ethane 30 301 314 637 — — — —
Propylene 42 53,280 69,278 147,765 — — — —
Propane 44 855 1,005 2,015 — — — —
Butenes 56 43,527 43,769 87,688 — — — —
Butanes 58 123,494 124,183 248,789 — — — —
Pentenes 70 18,221 18,323 36,729 — — — —
Pentanes 72 118,432 119,093 238,659 — — — —
Hexenes 84 760 764 1,532 — — — —
Hexanes 86 5,074 5,094 10,218 — — — —
Gasoline 15,583 17,955 38,036 Trace Trace Trace Trace
Methanol 32 25,353 11,353 10,141 118,387 10,141 108,246 882
Dimethyl ether 46 31,746 7,937 3,968 Trace Trace Trace Trace
Water 18 234,545 251,734 515,200 6,009,740 515,200 5,494,540 255,484
Total, lb/hr 679,682 679,682 1,359,364 6,128,127 525,341 5,602,786 256,366

kg/hr 308,302 308,302 616,603 2,779,700 238,293 2,541,407 116,287

STREAM FLOWS
PROPYLENE
STREAM FLOWS, LB/HR

Mol. WT. (15) (16) (17) (18) (19) (20) (21)
Hydrogen 2 — 55 — — — — 55
CO 28 — 132 — — 2 — 130
Methane 16 — 9,173 20 — 362 — 8,792
Ethylene 28 — 8,627 86 — 1,369 — 7,172
Ethane 30 — 637 11 — 154 — 472
Propylene 42 — 147,765 7,676 — 71,731 — 68,358
Propane 44 — 2,015 130 — 1,055 — 830
Butenes 56 — 87,688 14,030 — 57,932 — 15,725
Butanes 58 — 248,789 35,578 — 162,834 — 50,377
Pentenes 70 — 36,729 15,307 — 20,311 — 1,111
Pentanes 72 — 238,659 71,925 — 155,153 — 11,581
Hexenes 84 — 1,532 957 — 507 — 68
Hexanes 86 — 10,218 6,034 Trace 4,072 — 112
Gasoline Trace 38,036 31,973 Trace 6,030 Trace 33
Methanol 32 110 110 Trace 110 Trace Trace —
Dimethyl ether 46 Trace 3,968 353 Trace 2,579 Trace 1,036
Water 18 21,667 21,667 Trace 16,574 Trace 4,345 Trace
Total, lb/hr 21,777 855,800 184,080 16,684 484,091 4,345 165,852

kg/hr 9,878 388,188 83,498 7,568 219,582 1,971 75,230

STREAM FLOWS
PROPYLENE
STREAM FLOWS, LB/HR

Mol. WT. (22) (23) (24) (25) (26) (27)
Hydrogen 2 — 55 44 11 — —
CO 28 — 132 106 26 — —
Methane 16 — 9,173 7,339 1,834 — —
Ethylene 28 — 8,620 6,896 1,724 7 —
Ethane 30 — 635 507 128 2 —
Propylene 42 — 3,858 3,086 772 143,907 306
Propane 44 — 7 5 1 2,008 22
Butenes 56 — 110 88 22 87,578 87,412
Butanes 58 — 132 106 26 248,657 248,216
Pentenes 70 — 22 18 4 36,707 36,685
Pentanes 72 — 66 53 13 238,593 238,427
Hexenes 84 — Trace Trace Trace 1,532 1,532
Hexanes 86 — Trace Trace Trace 10,218 10,218
Gasoline — Trace Trace Trace 38,036 38,036
Methanol 32 — Trace Trace Trace Trace Trace
Dimethyl ether 46 — 44 35 9 3,924 3,902
Water 18 747 — — — Trace Trace
Total, lb/hr 747 22,855 18,284 4,571 811,168 664,756

kg/hr 339 10,367 8,294 2,074 367,943 301,532

STREAM FLOWS
PROPYLENE
STREAM FLOWS, LB/HR

Mol. WT. (28) (29) (30) (31) (32) (33)
Hydrogen 2 — — — — — —
CO 28 — — — — — —
Methane 16 — — — — — —
Ethylene 28 7 — — — 7 —
Ethane 30 2 — — — 2 —
Propylene 42 143,601 — 298 9 143,583 18
Propane 44 1,986 — 21 1 441 1,545
Butenes 56 165 110 84,943 2,359 2 163
Butanes 58 441 309 241,205 6,702 4 437
Pentenes 70 22 220 35,479 985 — 22
Pentanes 72 165 882 231,137 6,409 — 165
Hexenes 84 — 386 1,116 31 — —
Hexanes 86 — 948 9,021 249 — —
Gasoline — 32,077 5,798 161 — —
Methanol 32 — — — — — —
Dimethyl ether 46 22 — 3,796 106 — 22
Water 18 Trace — Trace Trace — —
Total, lb/hr 146,412 34,932 612,814 17,011 144,040 2,372

kg/hr 66,412 15,845 277,971 7,716 65,336 1,076

Table 5.3
MAJOR EQUIPMENT
PROPYLENE
EQUIPMENT
------------------- ---------------------------------------------- ---------------------------------------- ---------------------------------------------------------- ----------------------------------------------------------------------------------
REACTORS (ONE MTP REACTOR TRAIN SHOWN)
R-101 DME REACTOR 16 FT DIA SHELL: C.S. 33 FT OF ALUMINUM OXIDE CATALYST

40 FT T-T PACKING: ALUMINUM OXIDE
R-102A MTP REACTOR STAGE 1 16 FT DIA SHELL: 304 SS 9 FT OF MTPROP® CATALYST

15 FT PACKING: MTPROP®
R-102B MTP REACTOR STAGE 2 16 FT DIA SHELL: 304 SS 9 FT OF MTPROP® CATALYST
R-102C MTP REACTOR STAGE 3 16 FT DIA SHELL: 304 SS 9 FT OF MTPROP® CATALYST
R-102D MTP REACTOR STAGE 4 16 FT DIA SHELL: 304 SS 9 FT OF MTPROP® CATALYST
R-102E MTP REACTOR STAGE 5 16 FT DIA SHELL: 304 SS 9 FT OF MTPROP® CATALYST
COLUMNS
C-101 METHANOL STRIPPER 13 FT DIA SHELL: C.S. 10 VALVE TRAYS, 18 INCH SPACING
26 FT TRAYS: C.S.
C-102 QUENCH TOWER 19 FT DIA SHELL: C.S. 30 VALVE TRAYS, 18 INCH SPACING
56 FT TRAYS: C.S.
C-203 DE-ETHANIZER 5 FT DIA X 36 FT SHELL: C.S. 20 VALVE TRAYS, 18 INCH SPACING
15 FT DIA X 85 FT TRAYS: C.S. 43 VALVE TRAYS, 18 INCH SPACING
C-204 DEPROPANIZER COLUMN 15 FT DIA SHELL: C.S. 70 VALVE TRAYS, 18 INCH SPACING
128 FT TRAYS: C.S.
C-205 DEHEXANIZER COLUMN 16 FT DIA SHELL: C.S. 35 VALVE TRAYS, 24 INCH SPACING
92 FT TRAYS: C.S.
C-206 PROPYLENE COLUMN 19 FT DIA SHELL: C.S. 160 VALVE TRAYS, 15 INCH SPACING
225 FT TRAYS: C.S.
COMPRESSORS
K-101 MTP EFFLUENT COMPRESSOR 19,200 BHP C.S.
HEAT EXCHANGERS
E-101 METHANOL PREHEATER 4,500 SQ FT SHELL: C.S.

22 MMBTU/HR TUBES: C.S.
E-102A-C METHANOL EVAPORATOR 9,800 SQ FT EACH SHELL: C.S.
E-103A-D METHANOL SUPERHEATER 9,000 SQ FT EACH SHELL: C.S.
E-104A-T DME-MTP EXCHANGER 9,700 SQ FT EACH SHELL: C.S.
318 MMBTU/HR TUBES: 304 SS
E-105A,B METHANOL STRIPPER REBOILER 9,100 SQ FT EACH SHELL: C.S.
E-106A-C RECYCLE PREHEATER 8,900 SQ FT EACH SHELL: C.S.
E-107A-D PROPYLENE COLUMN REBOILER 9,750 SQ FT EACH SHELL: C.S.
E-108A-D QUENCH TOWER COOLER 8,500 SQ FT EACH SHELL: C.S.
E-109A,B STAGE 1 INTERCOOLER 6,400 SQ FT EACH SHELL: C.S.

MAJOR EQUIPMENT
PROPYLENE
EQUIPMENT
------------------- ---------------------------------------------- ---------------------------------------- ---------------------------------------------------------- ----------------------------------------------------------------------------------
HEAT EXCHANGERS (Concluded)
E-110A,B STAGE 2 INTERCOOLER 8,700 SQ FT EACH SHELL: C.S.

E-111 STAGE 3 AFTERCOOLER 1 7,400 SQ FT SHELL: C.S.
E-112 STAGE 3 AFTERCOOLER 2 5,400 SQ FT SHELL: C.S.
E-216 DEETHANIZER REFLUX 2 2,200 SQ FT SHELL: C.S.
E-217 DEETHANIZER REBOILER 5,400 SQ FT SHELL: C.S.
E-218 DEETHANIZER REFLUX 1 1,100 SQ FT SHELL: C.S.
E-219 DEETHANIZER FEED 1,100 SQ FT SHELL: C.S.
E-220A,B DEPROPANIZER REBOILER 7,500 SQ FT EACH SHELL: C.S.
E-221A,B DEPROPANIZER REFLUX 10,000 SQ FT EACH SHELL: C.S.
E-222 DEHEXANIZER REFLUX 8,040 SQ FT SHELL: C.S.
E-223 DEHEXANIZER REBOILER 8,600 SQ FT SHELL: C.S.
E-224 GASOLINE COOLER 320 SQ FT SHELL: C.S.
E-225A-F PROPYLENE REFLUX 9,700 SQ FT EACH SHELL: C.S.
DIRECT-FIRED HEATERS
H-101 MTP RECYCLE HEATER 80 MMBTU/HR C.S.
TANKS
T-101A-C METHANOL STORAGE TANK 5,000,000 GAL EACH C.S. NOT SHOWN ON PFD
T-201 GASOLINE STORAGE TANK 1,500,000 GAL C.S. NOT SHOWN ON PFD
T-202A,B PROPYLENE STORAGE TANK 400,000 GAL EACH C.S. NOT SHOWN ON PFD
PRESSURE VESSELS
V-103 STAGE 1 COMPRESSOR DRUM 26,000 GAL C.S.

V-207 DEETHANIZER REFLUX DRUM 700 GAL C.S.
V-209 DEPROPANIZER REFLUX DRUM 20,000 GAL C.S.
V-211 DEHEXANIZER REFLUX DRUM 30,000 GAL C.S.
V-213 PROPYLENE REFLUX DRUM 15,000 GAL C.S.
PUMPS
SECTION OPERATING SPARES OPERATING BHP

--------------- ------------------- -------------- -------------------------
100 8 6 1,070
200 5 4 468

Table 5.4
UTILITIES SUMMARY
PROPYLENE
BATTERY LIMITS SECTION SECTION

UNITS TOTAL 100 200
--------------- ---------------------- --------------- ---------------
AVERAGE CONSUMPTIONS
ELECTRICITY KW 1,274 887 388
STEAM, 600 PSIG M LB/HR 461 461 --
REFRIGERATION, -31°F TONS 367 -- 367
REFRIGERATION, 53°F TONS 1,000 1,000 --
PEAK DEMANDS
STEAM, 600 PSIG M LB/HR 553 553 --
REFRIGERATION, -31°F TONS 440 -- 440
REFRIGERATION, 53°F TONS 1,200 1,200 --

PROCESS DISCUSSION
Our plant design was developed on the basis of a stand-alone MTP facility operating on an
assumed low cost “fuel” grade methanol imported from a remote location. While the water
content of such a methanol grade is assumed to be above 1.5 wt%, this is not anticipated to be a
critical feedstock specification. Even crude methanol with water content as high as 20-25 wt%, as
typical for un-fractionated methanol converter effluent, could represent an acceptable feed if
available in the vicinity of the MTP unit.
The indicated design should be considered preliminary and has not been optimized.
Because of the general lack of design information available to us in the public domain, we have
made a number of key assumptions in our preliminary design of the reactor systems and the
effluent processing scheme that may not be considered optimal. In sizing the DME reactor, we
have assumed a space velocity of about 570 hr-1 and a methanol conversion of 75%. For
temperature control, previous PEP reports have used multiple fixed beds of catalyst with interbed
injection of methanol-DME mixture and assumed the proprietary catalyst inside the DME reactor
made by Süd-Chemie was based on an acidic alumina type catalyst [EP 448000]. According to
Lurgi, the dehydration catalyst has high activity and selectivity for DME production, and achieves
near thermodynamic equilibrium conditions [Rothaemel_01]. There was also a question about if a
ZSM-5 type catalyst was actually used in the DME reactor in the previous PEP studies. In this
report, however, the design of DME reactor is based on a recent Lurgi publication indicating that
the DME reactor in the Lurgi MTP process is a single-stage adiabatic reactor that contains a
fixed-bed of aluminum oxide (γ-Al2O3) catalyst [261A125].
Our sizing of the MTP reactor is based on the assumption of 2 lb hydrocarbon feed per lb of
catalyst. The MTPROP® catalyst is a ZSM-5 type zeolite, which is also proprietary to Süd-
Chemie. Overall propylene yield is maximized by recycling higher and lower molecular-weight
olefins and hydrocarbons to the reactor. A five-stage fixed-bed reactor configuration is described
by the available literature. Overall conversion of the DME/methanol mix is claimed to be
potentially well in excess of 99% under optimal propylene production conditions. Details of the
actual reactor design are proprietary to Lurgi.
Compared with other methanol to olefins technologies, the Lurgi MTP process is for
propylene production only, which does not include requirement to extract and purify either
ethylene or butanes. Compared to fluidized reactor system, the fixed-bed MTP reactor system is
low in risk of scale-up while more complicated set-up to control reaction temperature is required.
Built on to its Mega-methanol process technology expertise, Lurgi appears to be in a good
position to meet the challenges related to its MTP reactor scale-up. Recent literature indicates
that three MTP reactor trains are needed in order to continuously process 5,000 t/d of methanol.
Normally, two MTP reactor trains are in operation while one reactor train is in either regeneration
or in standby mode to ensure continuous operation of the plant [261A125].
On a single pass non-recycle basis, Lurgi MTP reactor product selectivity expressed in
terms of carbon molar yields have been reported as follows [261A034]:
Mole-C %
Ethylene 4.6
Propylene 46.6
Butylenes 21.1
C5= 8.9
C6= 4.9
C7= 0.6
C8= 0.3

In the MTP process, because all olefins other than propylene are recycled any incremental
improvement in single-pass propylene selectivity over other olefins would therefore result in a
substantial reduction in hydrocarbon recycle requirements and equipment sizes.
Producing only propylene with high selectivity from methanol/DME conversion, in one-pass
without recycle, is highly desirable and still work in progress. A recent publication [261A036]
suggested that using zirconia and orthophosphoric acid modified H-ZSM-5 catalysts in the direct
conversion of DME under atmospheric pressure; a desired production distribution with high
single-pass selectivity to propylene was achieved. The ratio of propylene to ethylene was 16 and
the prominent olefin product distribution was shown associated with the adjusted acid properties
and microspores of H-ZSM-5 after modification. On a single pass non-recycle basis, reactor
product selectivity expressed in terms of carbon molar yields have been reported as follows:
Mole-C %
Ethylene 2.7
Propylene 44.5
Butylenes 15.9
C1= 0.3
n-C4= 11.2
C5s= 15.5
C6s= 6.0
C7s= 2.0
C8s 1.9
If the production of a relatively small percentage of ethylene was desirable on a co-product

basis, perhaps as a comonomer for captive polypropylene production, substantial further process
simplification may be possible.
As shown in Table 5.2, gasoline is the main by-product of the Lurgi MTP process. Due to the
pore architecture, ZSM-5 increases the octane number of the gasoline by selectively upgrading
low octane gasoline components into lower molecular weight compounds with a higher octane
number [261A033]. An analysis of gasoline produced from the MTP demo unit at Tjeldbergodden,
Norway has shown its composition as follows:
wt %
Olefins ~20
Paraffins ~50
Aromatics ~30
No benzene
No sulfur
Lurgi’s MTP process appears to be well suited for the coal-to-chemicals complexes in
China’s coal-rich regions as the main product propylene can be readily converted into value-
added polyproylene product while by-product gasoline with a high octane number (RON ~95 /
MON ~85) is in demand.
In our purification design scheme, we have assumed that essentially complete water
removal from the propylene product can be achieved via fractionation without the use of
molecular sieve dryers. Intermittent methanol injection is assumed if necessary to prevent
potential icing problems in the deethanizer column.

About 0.56 pounds of process wastewater is produced per pound of methanol consumed,
and is assumed to contain residual methanol as the primary contaminant. With appropriate
treatment, the wastewater may be rendered suitable as make-up water for process steam
generation and cooling tower water systems, or for agricultural purposes.
The main waste and fuel purge streams of the process can be summarized as follows:
Streama Description Assumed Disposal Method

25 Gaseous, methane rich purge gas Consumable internally as fuel gas
14 Aqueous, containing trace methanol and Discharged to drainage via bio-pond

hydrocarbons
31 Butane, pentane rich liquid fuel purge Consumable locally in plant complex for
miscellaneous fuel uses.
_______
a
Refer to Table 5.2 and Figure 5.2
PROCESS ECONOMICS
We have developed preliminary capital cost estimates and production economics for our
conceptual design of the Lurgi MTP process based on the following key assumptions:
• A PEP Cost Index of 718
• A stream factor of 0.90
• Overnight construction on the U.S. Gulf Coast during calendar year 2006
• Methanol, priced at 13.6¢/lb, is produced in a world-scale plant from natural gas priced at
$6.74/MMBtu.
• No royalty or license fee
Table 5.5 summarizes the total capital investment breakdown for the production of 1,136
million lb/yr (515,000 t/yr) of polymer grade propylene. As indicated, our estimated total fixed
capital (TFC) requirement is $212.9 million, which includes allowance for all off-sites such as
waste treatment, utilities, and product storage. The FOB cost for battery limits equipment is about
$19.2 million, with reactor costs representing about 8% of this total. Direct installation costs
(which include materials and labor costs for piping, fittings, electrical equipment, instrumentation,
insulation, structural materials, and paint) are $41.0 million. When indirect costs, unscheduled
equipment and contingency are added, the battery limits investment (BLI) amounts to $119.0
million, or about 56% of the TFC. The total off-site investment of $75.1 million includes an
allowance for general service facilities.
Table 5.6 indicates the breakdown of the investment on a section-by-section basis. The
methanol conversion section, which includes the reaction and compression equipment, accounts
for most of the BLI because there is no requirement to extract and purify either ethylene or
butanes as in the UOP/Hydro MTO process. Other factors lead to higher estimated cost of this
section appears to be the multiple MTP reactor trains setup and the extensive use of feed/effluent
heat exchange equipment to maximize thermal efficiency. The sizeable hydrocarbon recycle
streams appear to be a major consideration in the sizes and cost of most process equipment in
this section.

Figure 5.3 illustrates the effect of plant capacity on capital investment. The estimated TFC at
plant capacities of 0.5 and 2.0 times the base capacity are $117.9 million and $402.6 million,
respectively.
Table 5.7 summarizes our estimated propylene production economics for the Lurgi
methanol-to-propylene process. We have assumed a methanol feedstock cost of 90¢/gal
(13.6¢/lb), which is based on delivery from a mega-methanol plant using a natural gas priced at
$6.74/MMBtu as feedstock and fuel. This methanol feedstock cost to Lurgi MTP process is
derived from the “Methanol From Natural Gas” cost scenario outlined in the Section 5 of PEP
Report 43E, Methanol From Coal (December 2006), for a “fuel grade” methanol produced at a
capacity of 5,000 t/d in a U.S. Gulf Coast location.
By-products, which account for a total credit of 11.3¢/lb, were taken at average U.S. Gulf
Coast prices during the year of 2006. We assumed the costs for G&A, sale and research at
2.3¢/lb. After accounting for fixed costs and allowing a 25%/yr pretax return on TFC, the
propylene product value for the base case amounts to 46.8¢/lb, which is about 5.7¢/lb less than
the market price of polymer-grade propylene at 52.5¢/lb as of September 2007.
The estimated net production cost component of this product value is 42.1¢/lb. It is apparent
that the propylene product value is not particularly sensitive to plant capacity for the indicated
propylene capacity range, nor would it be particularly sensitive to byproduct values. Since the
variable costs account for about 80% of the product value, any reduction or increase in costs of
the raw material and utilities would certainly affect the outcome of propylene product value by the
Lurgi MTP process.
Figure 5.4 illustrates the dependence of propylene product value and the production cost
component on methanol feedstock price. The average U.S. Gulf Coast market price level for
polymer-grade propylene for the period of September 2006 to September 2007 is estimated to be
50.5¢/lb. At this propylene price level and base case production capacity, it is apparent that
propylene production via the Lurgi MTP process would be potentially cost competitive at a U.S.
Gulf Coast location and assuming remotely produced methanol delivered at a cost of 90¢/gal
(13.6¢/lb). From inspection of Figure 5.4, methanol delivered at a cost below 99¢/gal would result
in an economically viable proposition with a pretax investment return of 25%/yr. However, based
on historical U.S. Gulf Coast price levels for chemical grade methanol, the Lurgi MTP process
would not be economical assuming our estimated historical average propylene price level of
26.5¢/lb. Over the past decade, this methanol price level has generally ranged between 43-
90¢/gal (6.5-13.6¢/lb).
Demand for propylene derivatives has been growing extremely rapidly in some locations. In
China for example, during 1995-2005, the production of propylene in China increased at an
average annual rate of 14.6%, and almost all production was consumed domestically.
Historically, the domestic market for propylene has been capacity-limited, and China has
imported significant quantities of propylene derivatives [Propylene China Report, 2007]. Because
of such demand, some sources are suggesting that future average price levels of propylene may
increase in certain locations.
The economics of the Lurgi MTP process appear to compare favorably with that of other
single product (on-purpose) propylene production processes evaluated by PEP at the assumed
methanol cost of 25¢/gal delivered from a remote mega-methanol plant. Details of this
comparison may be found in PEP Report 43D, Mega Methanol Plants (December 2003), and
PEP Report 128D, Technologies for the Production of Secondary Propylene (November 2004).

Table 5.5
TOTAL CAPITAL INVESTMENT

PROPYLENE
PEP COST INDEX: 718
CAPACITY
EXPONENT
COST --------------------------
($1,000) UP DOWN
------------ ---------- ----------
REACTORS 1,531 0.95 0.80
COLUMNS 3,148 0.95 1.06
VESSELS & TANKS 273 0.69 0.62
HEAT EXCHANGERS 7,654 0.93 0.91
FURNACES 563 0.95 0.95
COMPRESSORS 5,593 0.95 0.95
PUMPS 453 0.68 0.61
---------
TOTAL 19,216 0.93 0.92
DIRECT INSTALLATION COSTS 40,986 0.96 0.85

INDIRECT COSTS 26,343 0.89 0.81
UNSCHEDULED EQUIPMENT, 10% 8,654 0.93 0.86
---------
BATTERY LIMITS, INSTALLED 95,199 0.93 0.86
CONTINGENCY, 25% 23,799 0.93 0.86

---------
BATTERY LIMITS INVESTMENT 118,998 0.93 0.86
OFF-SITES, INSTALLED
CLARIFIED WATER 1,419 0.74 0.74
COOLING WATER 9,233 0.94 0.95
PROCESS WATER 804 0.62 0.62
BOILER FEED WATER 1,601 0.58 0.43
STEAM 14,530 0.89 0.87
REFRIGERATION 2,545 0.83 0.70
TANKAGE 7,661 0.93 0.86
---------
UTILITIES & STORAGE 37,792 0.89 0.84
GENERAL SERVICE FACILITIES 31,359 0.92 0.85

WASTE TREATMENT 5,950 0.93 0.86
---------
TOTAL 75,099 0.90 0.85
CONTINGENCY, 25% 18,775 0.90 0.85

---------
OFF-SITES INVESTMENT 93,875 0.90 0.85
TOTAL FIXED CAPITAL 212,873 0.92 0.85

Table 5.6
CAPITAL INVESTMENT BY SECTION

PROPYLENE
PEP COST INDEX: 718
METHANOL CONVERSION PROPYLENE RECOVERY

------------------------------------------------- -------------------------------------------------
CAPACITY CAPACITY
EXPONENT EXPONENT
COST ------------------------- COST -------------------------
($1,000) UP DOWN ($1,000) UP DOWN
------------ ----------- ---------- ------------ ----------- ----------
REACTORS 1,531 0.95 0.80 -- -- --
COLUMNS 242 0.95 0.79 2,907 0.95 1.09
VESSELS & TANKS 103 0.65 0.58 171 0.72 0.65
HEAT EXCHANGERS 6,433 0.93 0.92 1,222 0.91 0.85
FURNACES 563 0.95 0.95 -- -- --
COMPRESSORS 5,593 0.95 0.95 -- -- --
PUMPS 279 0.66 0.63 175 0.71 0.58
--------- ---------
TOTAL 14,742 0.94 0.91 4,473 0.92 0.98
DIRECT INSTALLATION COSTS 36,016 0.96 0.91 4,971 0.90 0.50

INDIRECT COSTS 22,211 0.90 0.84 4,132 0.86 0.64
UNSCHEDULED EQUIPMENT, 10% 7,297 0.94 0.89 1,358 0.89 0.69
--------- ---------
BATTERY LIMITS INSTALLED 80,265 0.94 0.89 14,934 0.89 0.69
CONTINGENCY, 25% 20,067 0.94 0.89 3,734 0.89 0.69

--------- ---------
BATTERY LIMITS INVESTMENT 100,332 0.94 0.89 18,666 0.89 0.69
OFFSITES, INSTALLED
CLARIFIED WATER 849 0.74 0.74 570 0.74 0.74
COOLING WATER 5,392 0.94 0.95 3,841 0.94 0.95
PROCESS WATER 469 0.62 0.62 334 0.62 0.62
BOILER FEED WATER 1,201 0.58 0.58 401 0.58 0.06
STEAM 12,973 0.91 0.89 1,556 0.74 0.74
REFRIGERATION 1,196 0.95 0.70 1,348 0.70 0.71
TANKAGE 4,041 0.95 0.83 3,620 0.90 0.89
--------- ---------
UTILITIES & STORAGE 26,123 0.90 0.86 11,669 0.85 0.81

Figure 5.3
EFFECT OF PLANT CAPACITY ON INVESTMENT COSTS
450.0
400.0 Basis:
Stream Factor = 0.9
350.0
Total Fixed Capital
300.0
INVESTMENT- $millions
250.0
200.0
150.0
Battery Limits Investment
100.0
50.0 Base Case
0.0
0 200 400 600 800 1,000 1,200
PLANT CAPACITY- 1000 t/yr of propylene

Table 5.7
PRODUCTION COSTS
PEP COST INDEX: 718
VARIABLE COSTS
CONSUMPTION
UNIT COST PER LB ¢/LB
------------------------- -------------------------- ----------
RAW MATERIALS
METHANOL 13.6 ¢/LB 3.189 LB 43.24
CATALYSTS & MISC 0.30
---------
GROSS RAW MATERIALS 43.54
BY-PRODUCTS
C1/C2 PURGE 2.2 $/MMBTU -0.0007 MMBTU -0.15
PROPANE RICH PURGE 23.8 ¢/LB -0.0165 LB -0.39
C4/C6 PURGE 32.1 ¢/LB -0.1181 LB -3.79
GASOLINE 28.7 ¢/LB -0.2425 LB -6.96
---------
TOTAL BY-PRODUCTS -11.29
CONSUMPTION CONSUMPTION
UNIT COST PER LB PER KG
------------------------- -------------------------- --------------------------
UTILITIES
COOLING WATER 10.15 ¢/MGAL 40.4 GAL 337 LITERS 0.41
ELECTRICITY 5.4 ¢/KWH 0.00884 KWH 0.0195 KWH 0.04
REFRIGERATION, -31°F 15.3 ¢/TON-HR 0.00255 TON-HR 0.0198 KWH 0.04
REFRIGERATION, 53°F 6.75 ¢/TON-HR 0.00694 TON-HR 0.0538 KWH 0.05
---------
TOTAL UTILITIES 4.54

PRODUCTION COSTS
PEP COST INDEX: 718
a b
CAPACITY (MILLION LB/YR) 568 1,136 2,272
------------ ------------ ------------
OFFSITES 52.2 8939 175.7
--------- --------- ---------
PRODUCTION COSTS (¢/LB)
RAW MATERIALS 43.54 43.54 43.54

BY-PRODUCTS -11.29 -11.29 -11.29
UTILITIES 4.54 4.54 4.54
--------- --------- ---------

--------- --------- ---------
LABOR COSTS 0.41 0.28 0.23

OPERATING SUPPLIES, 10% OF OPER LABOR 0.02 0.01 NEGL
--------- --------- ---------

--------- --------- ---------

--------- --------- ---------

--------- --------- ---------

--------- --------- ---------
PRODUCT VALUE 47.82 46.79 46.34
-----------------------------------
a
OF PROPYLENE
b
BASE CASE

Figure 5.4
EFFECT OF METHANOL PRICE ON

PRODUCTION COST AND PRODUCT VALUE
55.0
50.0
Propylene Capacity = 515,000 t/yr
Stream Factor = 0.9
PRODUCT VALUE/PRODUCTION COST - ¢/lb
45.0
40.0
Product Value
35.0 Base Case
30.0
Production Cost
25.0
20.0
15.0
5 6 7 8 9 10 11 12 13 14 15
METHANOL PRICE - ¢/lb

LURGI MTP PROCESS APPLICATIONS
It is apparent that the economics of Lurgi MTP process is highly dependent on methanol
feedstock price and it will certainly benefit from economics of integration with a new generation
mega-methanol production process. The use of crude methanol directly from the methanol
converter may eliminate the need for the usual fractionation requirements for producing chemical
grade or fuel grade methanol. Typical commercial methanol specifications limiting DME
byproduct production may become less of a factor in methanol converter design and operating
conditions, which may lead to further improvement in economics of feedstock methanol
production and overall MTP process.
Since propylene is rather an intermediate than an end product and the most important
derivatives of propylene is polypropylene with 60% of global propylene consumption be covered
by polypropylene, improved economics may also result from the integration of the Lurgi MTP
process with polypropylene production. For polypropylene processes requiring ethylene
comonomer, this may reduce the light hydrocarbon recycle requirements of the MTP process in
order to suppress net ethylene production. While reducing the cost of the methanol conversion
section of the MTP process, this may also permit the elimination of some fractionation equipment
required in the propylene fractionation section.
The “ultimate” integration scenario would most likely be the design and construction of an
entire mega-methanol/MTP/polypropylene production complex in the vicinity of a stranded natural
gas field or an entire coal-to-chemicals production complex in the vicinity of a major coal mine.
This may be particularly advantageous for extremely remote locations where transportation
logistics may limit the desirability of any products other than the solid polypropylene product. The
application of a pre-reformer to convert higher hydrocarbons, which may be present in the
wellhead natural gas, may represent another desirable element of production flexibility to
maximize intermediate methanol and polypropylene product production from the existing gas
source. Another possible approach to maximizing polypropylene production would be to feed
such wellhead higher hydrocarbons directly to the MTP reactor.
China is currently the most active country in the world in investing in new coal gasification
technologies for commercial production of chemicals. Rapid growth in the country’s coal to
chemicals projects is largely driven by the country’s seemly insatiable demand for chemicals and
liquid fuels. A Chinese coal-to-plastics scenario in the vicinity of a major coal mine utilizing Lurgi’s
MTP technology would benefit from low cost coal feedstock and high value product
polypropylene and by-product liquid fuels.

Appendix A
PATENT SUMMARY TABLES
Table A.1
CONVERSION OF METHANOL TO OLEFINS
SAPO CATALYSTS AND REACTION CONDITIONS
PATENT SUMMARY
Reference Earliest
Number Assignee Date Shown
EP 0646613 Idemitsu Petrochemical Company 10/5/93
This patent discloses a process to produce a branched polycarbonate with good heat
stability, resistance to corrosion of molds, and good color tone. Typically branched
polycarbonates produced by the interfacial process have inferior heat stability and will cause
corrosion of molds. Branched polycarbonates produced by the melt process have inferior
heat stability and inferior color tone. The patent discloses that using branching agent with
less than 200 ppm of sulfur will improve the properties of the resulting branched
polycarbonate. Sulfur is present as an impurity in the branching agent.
US 7071136 ExxonMobil Chemical May 21, 2003

Attrition resistant molecular sieve catalysts
Hardened SAPO molecular sieve catalyst can be made highly attrition resistant. The catalyst
composition is made by mixing together molecular sieve, liquid, and an effective hardening
amount of a dried molecular sieve catalyst to form a slurry. The slurry is dried, and then
calcined to form the hardened molecular sieve catalyst composition.
US 7119241 ExxonMobil Chemical September 27, 2002

Catalyst handling
The catalyst fines in the effluent stream of an oxygenate-to-olefin process are separated from
the effluent stream. Then the carbonaceous deposits are removed from the catalyst fines by
incineration.
US 7160831 ExxonMobil Chemical June 24, 2002

Molecular sieve catalyst composition
Making a formulated molecular sieve catalyst composition from a slurry of formulation
composition of a synthesized molecular sieve that has not been fully dried, a binder and an
optional matrix material. The weight ratio of the binder to the molecular sieve and/or the solid
content of the slurry is controlled to provide an improved attrition resistant catalyst
composition.
© SRI Consulting A-3 PEP Report 261

Table A.1 (Continued)
PATENT SUMMARY
Reference Earliest
Use of modified SAPO-34 catalyst
In making olefin product from an oxygenate-containing feedstock, a silicoaluminophosphate
molecular sieve catalyst is contacted with the oxygenate-containing feedstock in a reactor at
an average catalyst feedstock exposure index of at least 1.0. The method produces lower
coke yield and provides an olefin product that is low in C1-C4 paraffin content.
WO 03084660 ExxonMobil Chemical March 29, 2002

Methanol is converted to olefins in the presence of a SAPO-34 treated with an organometallic
compound, which reacts at the acid sites of the molecular sieve and leads to interior surface
modification. Treatment with dimethyl zinc, a preferred reagent, results in a catalyst with
improved selectivity to ethylene. In an example, methanol is converted at 450°C, 15 psig,
and a WHSV of 30 hr-1, in the presence of a SAPO-34 catalyst treated with dimethyl zinc. At
92% methanol conversion, ethylene and propylene yields are 44.5 wt% and 37.2 wt%,
respectively, as compared to 38.5 wt% and 38.3 wt% when an untreated catalyst is used.
WO 03074177 ExxonMobil Chemical February 28, 2002

Longer catalyst lifetime, increased selectivity to propylene and lower yield of by-products are
obtained with a SAPO-34 catalyst containing a metal oxide of a Group 3 element (lanthanum,
scandium, and yttrium) and/or an oxide of element of the Lanthanide or Actinide series, such
as cerium. In an example, methanol is converted at 475°C, 25 psig, and a WHSV of 100 hr-1,
in the presence of a SAPO-34 catalyst containing La2O3 and Ce2O3. Ethylene and propylene
yields are 29.85 wt% and 40.80 wt%, respectively, as compared to 34.50 wt% and 38.49 wt%
when the modifier is not used.

Longer catalyst lifetime, increased selectivity to propylene and lower yield of by-products are
obtained with a SAPO-34 catalyst containing ZrO2 and a metal oxide of a Group 2 or Group 3
element, such as calcium, barium, lanthanum, yttrium, or scandium. In an example, methanol
is converted at 475°C, 25 psig, and a WHSV of 100 hr-1, in the presence of a SAPO-34
catalyst containing ZrO2 and La2O3. Ethylene and propylene yields are 34.59 wt% and 41.25
wt%, respectively, as compared to 35.82 wt% and 38.83 wt% when the modifier is not used.

PATENT SUMMARY
Reference Earliest
Longer catalyst lifetime and increased selectivity to propylene in the conversion of methanol
to olefins are obtained with a SAPO-34 catalyst containing MgO and a metal oxide of a
Group 3 element, such as lanthanum, yttrium, or scandium. In an example, methanol is
converted at 475°C, 25 psig, and a WHSV of 100 hr-1, in the presence of a SAPO-34
catalyst containing MgO and La2O3. Ethylene and propylene yields are 34.54 wt% and 42.02
wt%, respectively, as compared to 37.65 wt% and 39.80 wt% when the modifier is not used.
WO 03068395 ExxonMobil Chemical January 17, 2002

Catalyst with improved attrition resistance
SAPO molecular sieve is produced by mixing previously dried catalyst particles with water to
produce a slurry, which is then dried and calcined. The resulting catalyst is attrition resistant
and has a particle size distribution that is suited for use in fluidized bed reactors.

Modified catalyst consists of a SAPO molecular sieve containing a CO oxidation metal, such
as platinum or vanadium. The metal favors the complete conversion of coke to CO2 within the
dense phase of the regenerator reactor. As a result, excessive temperatures in the upper
dilute phase of the regenerator (due to afterburning of CO to CO2) are avoided. According to
patent examples, the catalyst modification does not significantly affect the selectivity to light
olefins.

Catalyst stabilization
SAPO molecular sieve is treated with ammonia to reduce catalyst degradation by exposure
to moisture during storage. The chemisorbed ammonia may be easily desorbed from the
catalyst before use in the MTO reaction.

PATENT SUMMARY
Reference Earliest
WO 03048084 ExxonMobil Chemical November 29, 2001
Use of improved SAPO-34 catalyst
Higher catalytic activity is obtained by reducing the crystal dimension of the SAPO-34
molecular sieve, while simultaneously increasing its silicon content. A preferred catalyst has
at least one crystal dimension less than 0.20 µm and a Si/Al molar ratio greater than 0.15. In
an example, a 290% increase in catalyst activity is obtained by reducing the crystal
dimensions from to 0.3-0.6 µm to 0.1-0.4 µm, while simultaneously increasing the Si/Al ratio
from 0.07 to 0.179. The combined selectivity to ethylene and propylene is not significantly
affected.
WO 03084661 ExxonMobil Chemical July 2, 2001

SAPO molecular sieve is treated with an amine or other nitrogen containing compound to
reduce catalyst degradation by exposure to moisture during storage. The chemisorbed and/or
physisorbed compound may be easily desorbed from the catalyst before use in the MTO
reaction.
WO 03000413 ExxonMobil Chemical June 25, 2001

WO 03000412
SAPO catalyst with improved attrition resistance is obtained by controlling the weight ratio of
the binder to the molecular sieve during catalyst preparation.

SAPO catalyst with improved attrition resistance is prepared by a calcination method that
removes most of the halogen in the molecular sieve. The method includes heating the
catalyst in a low moisture environment, followed by steam treatment at 400-1000°C in the
presence of oxygen.

PATENT SUMMARY
Reference Earliest
Use of SAPO-34/SAPO-18 catalyst
Methanol conversion catalyst contains at least one intergrown phase of molecular sieves
having AEI and CHA framework types, preferably SAPO-34 and SAPO-18, respectively.
The intergrown phase has an AEI/CHA ratio of 5/95 to 40/60 as determined by X-ray
diffraction analysis. In an example, methanol is converted at 450°C, 25 psig and WHSV of
0.8 h-1, in the presence of a SAPO catalyst with AEI/CHA ratio of 0.25. The selectivities to
ethylene and propylene are 35.9 wt% and 40.0 wt%, respectively.
US 6518475 ExxonMobil Chemical February 16, 2001

Reaction conditions
Improved selectivity to ethylene during conversion of methanol to olefins is obtained by
adding 2-5 wt% of acetone to the methanol feed. Alternatively, a portion of the regenerated
catalyst is contacted with a pre-feed containing 30-70 wt% of acetone, before directing the
catalyst to the methanol conversion reactor. Unconverted acetone in the reactor effluent is
recovered as a dilute stream in methanol and DME, and recycled to the reactor.
In an example, methanol is converted at 450°C and WHSV of 130 h-1, in the presence of a
SAPO-34 catalyst activated in an acetone pre-feed. At 91.1% methanol conversion, the
selectivities to ethylene and propylene are 36.9 wt% and 44.5 wt%, respectively. Ethylene
and propylene selectivities at similar reaction conditions, but without acetone co-feed, are
32.4 wt% and 44.8 wt%, respectively.
US 6639117 ExxonMobil Chemical January 4, 2001

US 6537941
Catalyst rejuvenation
Loss of catalyst activity due to contact with moisture is reversed by cooling or freezing the
SAPO molecular sieve under vacuum (freeze drying).

PATENT SUMMARY
Reference Earliest
US 6441261 ExxonMobil Chemical July 28, 2000
Reaction conditions
Methanol is converted to olefins in the presence of a SAPO-34 catalyst and a co-feed diluent
such as water, hexanes, or C4+ olefins. The reaction is carried out at relatively high total
pressure (150-550 psia) but low partial pressure of methanol (15-90 psia), so that the
compression requirement for product recovery is reduced. In an example, a SAPO-34
catalyst is used to convert a mixture of methanol and water at 450°C, 150 psig of total
pressure, and 26 psig of partial pressure of methanol. The combined yield of ethylene and
propylene is only about 5% lower than that using undiluted methanol at 25 psig.

US 6541415
US 6509290 Exxon Chemical
Catalyst composition containing recycled particles
Catalyst fines and attrition particles from the reaction system and/or catalyst manufacture are
recovered and used in the preparation of a molecular sieve composition. The attrition
particles are recovered by conventional separation equipment, such as cyclones, filters, or
electrostatic precipitators. Virgin molecular sieve, which may contain dried catalyst fines in
clumps, is mixed with attrition particles and binder and then spray dried to form the catalyst
composition.

Methanol is converted to olefins in the presence of a SAPO catalyst containing one or
more metals, preferably copper and/or zinc. The catalyst surface is heat impregnated with
the metal at 160-220°C. In an example, SAPO-34 catalysts impregnated with zinc and copper
are used to convert a nitrogen-diluted methanol feed at 450°C and WHSV of 2 h-1. At 100%
methanol conversion, the selectivities to ethylene and propylene are 66.0 wt% and 20.7 wt%,
respectively, for the Cu-SAPO-34 catalyst. Ethylene and propylene selectivities for the Zn-
SAPO-34 catalyst at the same reaction conditions are 52.5 wt% and 35.3 wt%, respectively.

PATENT SUMMARY
Reference Earliest
US 6498120 ExxonMobil Chemical April 26, 2000
Catalyst rejuvenation
Loss of catalyst activity due to contact with moisture is reversed by treating the SAPO
molecular sieve with an anhydrous liquid or vapor methanol stream.

Methanol is converted to olefins in the presence of a SAPO-34 catalyst containing thorium.
The presence of thorium increases the selectivity to ethylene, reduces the amount of
undesirable by-products such as C1-C4 paraffins, and reduces coke formation on the catalyst
surface.

Methanol is converted to olefins in the presence of a SAPO-34 catalyst containing 0.1-23
wt% of a single ring aromatic, which acts as a co-catalyst in the porous framework of the
catalyst. In an example, a pure methanol feed is converted at 450°C, 175.8 kPa, and
WHSV of 25 h-1, in the presence of a SAPO-34 catalyst containing xylenes and tri-
methylbenzenes. Ethylene yields are 10 wt% higher than those obtained with an unmodified
catalyst.

Reaction conditions
A combined ethylene and propylene selectivity of at least 62 wt% is achieved by keeping
reaction conditions at specified parameters of weight hourly space velocity (WHSV) and
partial pressure of oxygenate. The oxygenate proportion index (OPI) at the reaction inlet,
defined as the molar flow of oxygenate divided by the molar flow of oxygenate plus diluent is
maintained above 0.5. The partial pressure-velocity compensation factor, defined as WHSV
divided by the partial pressure of the oxygenate at the reactor inlet, is kept above 0.1 psia-
1hr-1, preferably between 0.2 and 25 psia-1hr-1. The reaction is carried out in the presence
of a SAPO-34 catalyst.

PATENT SUMMARY
Reference Earliest
Methanol is converted to olefins in the presence of a SAPO-34 catalyst with a high
concentration of surface silica. The catalyst is first treated with a silicon containing
compound, followed by heating to form a residual layer of silica on the catalyst surface. The
molecular kinetic size of the silicon compound should be large enough to prevent diffusion
into the catalyst pores. In an example, a SAPO-34 catalyst treated with polydimethylsiloxane
is used to convert methanol at 450°C. The relative selectivity of ethylene to propylene is 2.50
and the relative selectivity of C4+ to ethylene is 0.17, as compared to 0.90 and 0.45,
respectively, using an unmodified catalyst.

Reaction conditions
Methanol is converted to olefins with low yield of propane in the presence of a SAPO-34
catalyst. To minimize C1-C4 paraffin content, the average catalyst feedstock exposure
(ACFE) in the reactor is kept above 1, and preferably between 2 and 12. The ACFE index is
defined as the total weight of methanol plus hydrocarbon fed to the reactor divided by the
total weight of fresh and regenerated SAPO catalyst. The index measures the extent to which
the entire catalyst in the reactor has been exposed to the feedstock. Low feedstock exposure
(i.e. an ACFE index above 1) leads to substantially higher propane and coke yields.

US 6316683
SAPO catalytic sites are covered with a shield to prevent loss of activity during storage. The
shield may consist of a template or carbonaceous material within the porous structure of the
catalyst, or simply a gas or liquid anhydrous environment.

The step of template removal during synthesis of SAPO catalyst is carried out by heating in
an oxygen depleted environment, so that the number of acid catalyst sites is preserved. The
method reduces the risk of catalyst degradation by exposure to moisture during storage.
© SRI Consulting A - 10 PEP Report 261

PATENT SUMMARY
Reference Earliest
WO 0006493 Exxon Chemical July 29, 1998
WO 0006494
Colloidal seed crystals are used in the synthesis of the SAPO-34 catalyst to control particle
size and accelerate the formation of the molecular sieve. The seeds preferably have a
maximum size of 100 nm and are present in the synthesis mixture at concentrations of 100 to
250 ppm. In an example, a seeded SAPO-34 catalyst is used to convert a mixture of
methanol and nitrogen at 450°C, WHSV of 1.0 h-1, and partial pressure of methanol of 0.12
atm. The ethylene yield using the seeded SAPO-34 is 50.1 wt%, as compared to 47.9 wt%
using an unseeded catalyst.
US 6187983 Exxon Chemical April 29, 1998

US 6046373
Reaction conditions
Electromagnetic energy is used in the conversion of methanol to olefins in the presence of a
SAPO-34 catalyst. Preferred frequencies are in the microwave region of 100 MHz to about
30,000 MHz. In an example, a pure methanol feed is converted at 230°C and WHSV of 0.5 h-
1, in the presence of continuous electromagnetic energy with frequency of 2450 MHz and
power of 100 watts. At 95% methanol conversion, the combined selectivity of ethylene,
propylene and butene exceeds 90 wt%.
US 6137022 Exxon Chemical December 3, 1997

Reaction conditions
Methanol is converted to olefins in a reaction zone containing less than 15 vol% of a
SAPO-34 catalyst. A low level of by-products is obtained when methanol conversion is
maintained between 80 and 99 wt%, at the conditions effective to convert 100% of the feed
when the reaction zone contains 33 vol% of the catalyst material.
In patent examples using a pure methanol feed, the combined ethylene and propylene yield
at 450°C and WHSV of 10 h-1 increases from 77.6 wt% to 85 wt%, as methanol conversion
decreases from 100% to 88%.

PATENT SUMMARY
Reference Earliest
Methanol is converted to olefins with low yield of methane in the presence of a SAPO-34
catalyst modified by an oxygenated chelating agent. Preferred modifiers include EDTA, oxalic
acid, maleic acid, maleic anhydride and others. In an example, a 1:4 (molar ratio) mixture of
methanol and water is converted at 450°C and WHSV of 0.8 h-1, in the presence of a SAPO-
34-EDTA catalyst. Ethylene and methane yields are 50.4 wt% and 1.8 wt%, respectively, as
compared to 49.2 wt% and 4.0 wt% when the modifier is not used.
US 6153552 Exxon Chemical October 29, 1997

SAPO catalyst with improved attrition resistance is prepared by mixing a molecular sieve with
pore diameter less than 10 Ǻ, an inorganic sol, and an external phosphorus source. The
slurry is then dried by conventional methods.
US 6455749 ExxonMobil Chemical October 3, 1997

Reaction conditions
Higher ethylene and propylene yields during conversion of methanol to olefins are obtained
by recycling heavy hydrocarbons produced in the reaction. The heavy hydrocarbons can be
recycled to the primary reactor after removing the light olefins, or can be converted to light
olefins in a separate auxiliary reactor. In an example, a SAPO catalyst is used to convert a
1:1 (volume ratio) mixture of methanol and 1-butene. At 84.3% conversion, the selectivity’s
to ethylene and propylene are 45.7 wt% and 41.5 wt%, respectively.
US 5932512 Exxon Chemical August 19, 1997

Fluorination of the SAPO-34 catalyst modifies the electronegativity of the molecular sieve and
increases ethylene selectivity in the conversion of methanol to olefins. In an example, a
SAPO-34-SiF catalyst is used to convert a 1:4 (molar ratio) mixture of methanol and water at
450°C and WHSV of 0.8 h-1. The ethylene yield using the fluorinated SAPO-34 is 55.9 wt%,
as compared to 48.6 wt% using an unmodified catalyst.

PATENT SUMMARY
Reference Earliest
US 6051746 Exxon Chemical June 18, 1997
Higher ethylene selectivity (and lower methane yield) in the conversion of methanol to olefins
is obtained by using a SAPO-34 catalyst modified with a polynuclear aromatic heterocyclic
compound. The modifier, preferably phenazine or 1,10-phenanthroline, may be adsorbed
onto the catalyst or introduced with the methanol feed. In an example, a 1:4 (molar ratio)
mixture of methanol and water is converted at 450°C and WHSV of 0.7 h-1, in the
presence of a SAPO-34 catalyst and 100 ppm of 1,10-phenanthroline. Ethylene and methane
yields are 52.2 wt% and 2.2 wt%, respectively, as compared to 49.2 wt% and 4.0 wt% when
the modifier is not used.

Reaction conditions
Methanol is converted to olefins with low yield of methane and other light saturate by-
products, in the presence of a SAPO-34 catalyst. To minimize methane formation at
temperatures above 400°C, the reaction is carried out at a WHSV (on a methanol basis)
above 20 h-1. In patent examples using a 1:4 (molar ratio) mixture of methanol and water,
the normalized methane selectivity (methane yield/ethylene yield) at 450°C reduces from
0.057 to 0.040, as the WHSV increases from 0.7 to 21 h-1.
WO 9829370 Exxon Chemical December 31, 1996

Incorporation of lanthanide metal, actinide metal, scandium, yttrium, or Group IVB/VB
metals to SAPO catalyst increases the selectivity to ethylene during methanol conversion.
When SAPO-34 is used, preferred metals include ytterbium and titanium. In an example, a
Yb-SAPO-34 catalyst is used to convert a 1:4 (molar ratio) mixture of methanol and water at
450°C and WHSV of 0.7 h-1. At 99.8% methanol conversion, the ethylene yield using the Yb-
SAPO-34 is 50.4 wt%, as compared to 45.8 wt% using an unmodified catalyst.

PATENT SUMMARY
Reference Earliest
Catalyst support
Methanol is converted to olefins using a SAPO catalyst carried on a monolithic support
comprising inorganic materials with low surface area or with very little surface porosity. The
catalyst comprises at least 5 wt% of the monolithic support. Appropriate support materials
include glass, metals, and enamel. The use of a monolithic support results in lower pressure
drop and more uniform temperature distribution in the catalyst bed.

Ethylene selectivity in the conversion of methanol to olefins is increased by using a SAPO-
34 catalyst modified with phosphorus. The modification consists of incorporating a
phosphonitrilic oligomer (preferably a trimer) with the catalyst, and then calcining the
catalyst at temperature sufficient to decompose the phosphonitrilic oligomer and deposit
from about 0.05 to 40 wt% of phosphorus on the catalyst. In an example, a phosphorus-
modified SAPO-34 catalyst is used to convert a 1:4 (molar ratio) mixture of methanol and
water at 450°C and WHSV of 0.7 h-1. The ethylene yield using the modified SAPO-34 is 49.9
wt%, as compared to 46.4 wt% using an unmodified catalyst.

Methanol is converted to olefins using a catalyst containing SAPO crystals, nickel, cobalt
and/or iron, and an aluminophosphate (ALPO)-based binder. The presence of the metal
increases the selectivity to ethylene and propylene in comparison with SAPO, and reduces
the by-products formed during olefin conversion.

Methanol is converted to olefins using a SAPO catalyst bound with an ALPO-based
molecular sieve. The acidity and structure type of the ALPO binder are carefully selected, so
that the performance of the catalyst is enhanced.
In an example, a SAPO-34 catalyst bound with ALPO-17 is used to convert a 1:4 (molar
ratio) mixture of methanol and water at 450°C and WHSV of 0.7 h-1. The selectivities to
ethylene and propylene are 47 wt% and 37 wt%, respectively.

PATENT SUMMARY
Reference Earliest
US 6004898
Incorporation of alkaline earth metal ion (strontium, calcium, or barium) to SAPO-34 catalyst
increases the selectivity to C2-C3 olefins during methanol conversion. In an example, a Sr-
SAPO-34 catalyst is used to convert a 1:4 (molar ratio) mixture of methanol and water at
450°C and WHSV of 0.7 h-1. The combined ethylene and propylene yield using the Sr-
SAPO-34 is 89.5 wt%, as compared to 83.2 wt% using an untreated catalyst.

Methanol is converted to olefins in the presence of a silicoaluminophosphate (SAPO)
containing a transition metal ion, preferably nickel or cobalt. The metal is incorporated after
the synthesis of the catalyst, allowing more flexibility in catalyst preparation, choice of metal
additive, metal concentration, and physical characteristics of the molecular sieve. In an
example, a Co-SAPO-34 catalyst with a silicon to cobalt atomic ratio of 1:10 is used to
convert a 1:4 (molar ratio) mixture of methanol and water at 450°C and WHSV of 0.7 h-1.
The combined ethylene and propylene yield using the Co-SAPO-34 is 86.2 wt%, as
compared to 83.2 wt% using an untreated catalyst.
US 6121503 Exxon Chemical May 27, 1992

Reaction conditions
Methanol is converted to olefins with low paraffin content in the presence of ZSM-5, ZSM-48,
FeZSM-5, or SAPO-34 catalysts. In an example, a methanol:water mixture (1:4 molar ratio)
is converted to olefins in a fixed bed of SAPO-34 catalyst at 450°C and WHSV of 1.0 h-1.
The olefin product has a propane/propylene ratio of 0.001.

Catalyst treatment
Extraction of SAPO-34 catalyst with a mineral acid alters the crystallinity of the molecular
sieve and enhances ethylene yield. Preferred acids include hydrochloric, hydrofluoric,
sulfuric, phosphoric, and acetic acids, at concentrations from 0.001N to 0.1N. In an example,
SAPO-34 is extracted with 0.001N HCl for 24 hours. When used for converting a
methanol/water mixture (1:4 molar ratio) at 450°C and WHSV of 1.0 h-1, the treated catalyst
increases ethylene yield from 32 wt% (without treatment) to 43 wt%.

PATENT SUMMARY
Reference Earliest
US 6334994 Norsk Hydro October 9, 1996
Use of SAPO-34/SAPO-18 catalyst
Methanol conversion catalyst contains an intergrown phase of molecular sieves having AEI
and CHA framework types, preferably SAPO-34 and SAPO-18, respectively. The catalyst is
claimed to be more stable towards deactivation by coking.
US 6046371 Phillips Petroleum May 5, 1999

Methanol is converted to olefins in the presence of a silylated SAPO-34 catalyst. Preferred
silylating agents include tetraethyl orthosilicate and poly (methylphenyl) siloxane. In an
example, a SAPO-34 catalyst impregnated with tetraethyl orthosilicate is used to convert a
1:4 (molar ratio) mixture of methanol and water at 449°C and WHSV of 3.6 h-1. The
selectivity to C2-C4 olefins using the modified SAPO-34 is 98.6%, and the rate of coke
formation is 1.0 wt%/hr.
US 6472569 Phillips Petroleum April 16, 1999

Methanol is converted to olefins and/or DME in the presence of a SAPO-34 catalyst
impregnated with phosphoric acid, boric acid, and/or tributyltin acetate. In an example, a
SAPO-34 catalyst impregnated with a 5 wt% phosphoric acid solution is used to convert a 1:4
(molar ratio) mixture of methanol and water at 452°C and WHSV of 3.5 h-1. At 86.7 %
methanol conversion, the selectivity to C2-C4 olefins using the modified SAPO-34 is 90.2%.
When the catalyst is impregnated with a 10 wt% phosphoric solution, the selectivity to DME is
100%.
US 6051745 Phillips Petroleum March 4, 1999

Methanol is converted to olefins in the presence of a nitrided SAPO-34 catalyst. Examples of
suitable compounds for nitriding the catalyst include amines, pyridine, ammonia, and
mixtures of hydrogen and a nitrogen oxide. In an example, a SAPO-34 catalyst nitrided by
ammonia is used to convert a 1:4 (molar ratio) mixture of methanol and water at 449°C and
WHSV of 3.7 h-1. At 100% methanol conversion, the selectivity to C2-C4 olefins using the
modified SAPO-34 is 98.0%, as compared to 96.9 wt% using an unmodified catalyst. Coke
formation is also reduced from 1.5 wt%/hr to 0.72 wt%/hr.

PATENT SUMMARY
Reference Earliest
EP 418142 Showa Shell September 14, 1989
Incorporation of nickel to SAPO-34 catalyst increases the selectivity to ethylene during
methanol conversion. In an example, a Ni-SAPO-34 catalyst (Si/Ni atomic ratio of 40) is used
to convert a 1:4 (molar ratio) mixture of methanol and nitrogen at 450°C and GHSV of 2000
h-1. At 100% methanol conversion, the selectivities to ethylene and propylene are 88.0% and
5.3%, respectively.
WO 0205952 UOP July 13, 2000

SAPO catalyst with improved attrition resistance contains inorganic oxide binder and a filler,
preferably a clay. The content of the matrix material (binder + filler) is maintained above 60
wt%.
US 6534692 UOP December 9, 1997

US 6207872
US 5912393
Methanol is converted to olefins in the presence of a SAPO-34 catalyst with a plate crystal
morphology such that the average smallest crystal dimension is at least 0.1 μm, and the
aspect ratio (largest/smallest crystalline dimension) is no greater than 5. In an example, a
SAPO-34 catalyst with average smallest particle size of 0.17 μm is used to convert a 1/0.44
(molar ratio) mixture of methanol and water at 435°C, 5 psig and WHSV of 2.5 h-1. At 99%
methanol conversion, the combined ethylene and propylene yield is 81.2% and the
ethylene/propylene ratio is 1.41. Under the same reaction conditions, the use of a SAPO-
34 catalyst with average smallest particle size of 0.08 μm results in a combined ethylene
and propylene yield of 79.2% and a ethylene/propylene ratio of 1.18.

PATENT SUMMARY
Reference Earliest
US 5817906 UOP August 10, 1995
Use of intermediate step of DME production
The amount of water generated during conversion of methanol to olefins is reduced by using
an intermediate step of converting crude methanol to DME by catalytic distillation. The
etherification reaction is carried out at temperatures in the range of 80 to 250°C in the
presence of a catalyst selected from the group of ion-exchange resins, amorphous silica-
alumina, zeolite Y and zeolite B. The DME produced is then mixed with a diluent and
converted to olefins using a SAPO-34 catalyst. Because less water is produced by
conversion of DME than by conversion of methanol, the SAPO-34 catalyst is exposed to a
lower concentration of water, resulting in extended catalyst life and greater catalyst stability.
The amount of water in the reaction system can be further reduced by using recycled
propylene or butylene as diluents (instead of steam).
US 5744680 UOP August 10, 1995

Use of methane as reaction diluent
Higher catalyst stability in the conversion of methanol to olefins is obtained by using methane
instead of steam as reaction diluent. The preferred ratio of moles of reaction feed to moles of
methane diluent is 1:1 to about 1:5. After reaction in the presence of a SAPO-34 catalyst, the
gas effluent exchanges heat with the reaction feed and passes through a water scrubber to
remove catalyst fines. The gas stream is then compressed and sent to the conventional
steps of flashing (for removing water generated in the reaction), drying, CO2 removal, and
demethanization. Part of the methane recovered in the demethanizer overhead (with less
than 1 mol% ethylene) is recycled to the reaction as the diluent.
US 5191141 UOP November 13, 1991

US 5126308
Methanol is converted to olefins in the presence of a SAPO-34 catalyst with reduced particle
size and low silicon content. At least 50% of the catalyst particles have a particle size less
than 1 μm and no more than 10% of the particles have a particle size greater than 2 μm. In
an example, a SAPO-34 catalyst with average particle size of 0.9 μm and silicon molar
fraction of 0.03 is used to convert a 1:4.6 (molar ratio) mixture of methanol and water at
400°C, 5 psig and WHSV of 1 h-1. At 100% methanol conversion, the combined ethylene and
propylene yield is 73.9% and the catalyst life is 36 hours. Under the same reaction
conditions, the use of a SAPO-34 catalyst with average particle size of 1.2 μm and silicon
molar fraction of 0.14 results in a combined ethylene and propylene yield of 70.6% and a
catalyst life of 15 hours.

Table A.1 (Concluded)
PATENT SUMMARY
Reference Earliest
US 5248647 UOP February 28, 1991
US 5233117
US 5095163
Catalyst treatment
Methanol is converted to olefins in the presence of a SAPO-34 catalyst which has been
subjected to hydrothermal treatment to reduce acidity. The catalyst is treated with at least 5
psia steam at a temperature above 700°C, for a period of time sufficient to reduce the acidic
sites to less than 0.003 per cc of micropore volume, while maintaining a degree of crystallinity
of at least 80%. In an example, a treated SAPO-34 catalyst is used to convert pure methanol
at 400°C, 5 psig and WHSV of 0.5 h-1. The combined ethylene and propylene yield using the
treated SAPO-34 is 70-80 wt%, as compared to 60-70 wt% using an untreated catalyst.
US 6710218 Casale Chemicals SA October 22, 2001

Methanol is converted in light olefins C2-C4 with 93-100% degree of transformation and more
than 90% selectivity in which more than 80% are ethylene and propylene upon a
microspherical catalyst based on SAPO-34 zeolite in a fluidized bed reactor-regenerator
system. Ethylene/propylene ratio is changed in relatively large limits 0.69-1.36, by the
modification of reaction temperature and space velocity of the feed.
WO 0032543 Van Dijk, C. P. December 2, 1998

Use of intermediate step of DME production
Methanol is converted to olefins using an intermediate step of DME production. The methanol
feed is first contacted with an acid catalyst at 260-315°C to produce an equilibrium mixture of
DME, methanol and steam. This mixture is then converted to olefins at 370-480°C using
multiple fixed-bed reactors containing ZSM-5 or SAPO-34 catalyst. Different ratios of
ethylene to propylene in the olefin product can be obtained by varying the conditions in the
second reaction stage (catalyst contact time, reactants partial pressure and adiabatic
temperature rise), and by adjusting the quantity of the total methanol feed that by-passes the
DME reactor.

Table A.2
ZEOLITE CATALYSTS AND REACTION CONDITIONS
PATENT SUMMARY
Reference Earliest
US 5573990 Dalian Institute of Chemical Physics May 3, 1992
US 5367100
Use of modified ZSM-5 catalyst
feed is first contacted with a fixed bed of an acidic catalyst at 300-400°C, 1-4 atm, and WHSV
of 1-1.5 h-1 to produce an equilibrium mixture of DME, methanol and steam. This mixture is
then converted to olefins in the presence of a modified ZSM-5 catalyst at 500-550°C, 1-4
atm, and WHSV of 1-5.4 h-1, using a series of fixed-bed reactors with interstage cooling. The
modified ZSM-5 catalyst contains 1.3-1.7 wt% of phosphorus and 2.5-3.5 wt% of lanthanum,
which enhance the selectivity and hydrothermal stability of the catalyst at high temperature.
At 100% methanol conversion, the selectivity to C2-C4 olefins is above 85%.
WO 03020667 ExxonMobil Chemical August 30, 2001

Process using two zeolite catalysts
Process combines the use of ZSM-5 catalyst for methanol conversion and ZSM-35 catalyst
for the conversion of recycled butylenes. The ZSM-5 can be unmodified, phosphorous
modified, or steam treated to modify the micropore volume. The ZSM-5 and ZSM-35
catalysts can be mixed together in one reactor, arranged in separate beds, or used in
separate reactors in series.

Methanol is converted to olefins in the presence of a gallium-modified ZSM-5 catalyst and a
co-aromatic feed, such as xylenes. The zeolite has a Si/Ga molar ratio of 5-500 and pore
sizes of 5-7 Ǻ. In an example, a 50/50 wt% methanol:p-xylene feed is converted in the
presence of a Ga-ZSM-5 catalyst at 400°C and 40 psia. The selectivities to ethylene and
propylene are 44.0 wt% and 33.5 wt%, respectively. The ethylene to propylene ratio can be
varied by adjusting the fraction of aromatics in the feed.

PATENT SUMMARY
Reference Earliest
US 6680418 ExxonMobil Chemical November 21, 2000
Reaction conditions
Methanol is converted to olefins in the presence of a ZSM-5 catalyst and a co-aromatic feed,
such as benzene, toluene, or xylene. The reaction mixture also contains at least 10 wt% of a
polymethylbenzene component, preferably tri- or tetramethylbenzene, which is formed during
methanol conversion and is subsequently separated and recycled to the reactor. The ZSM-5
catalyst has a pore size greater than the critical diameter of the aromatic compound and a
diffusion parameter for 2,2 dimethylbutane of at least 500 s-1. In an example, a 3:1 molar
methanol:xylene feed is converted in the presence of a ZSM-5 catalyst at 275°C and 1 atm.
At methanol conversions of about 24%, the selectivities to ethylene and propylene are 36
wt% and 35 wt%, respectively.
US 6613951 Mobil Oil September 23, 1999

Reaction conditions
Methanol is converted to olefins in the presence of a ZSM-5 catalyst. The selectivity to
ethylene and propylene is increased by a combination of high reaction temperature and
pressure and a low diffusion parameter ZSM-5 catalyst (such as that described in US
6048816). In an example, a phosphorus-modified ZSM-5 catalyst is used to convert methanol
at 430°C and 120 psia. At 70%, methanol conversion, the selectivity to ethylene is 19 wt%,
as compared to 10 wt% when the reaction is run at 15 psia.
US 6506954 Exxon Chemical October 2, 1996

Reaction conditions
Methanol is converted to olefins and other hydrocarbons in the presence of a ZSM-5 catalyst.
The selectivity to ethylene is increased by using a co-aromatic feed, which consists of C9+
aromatics recycled from the product separation zone. The molar ratio of methanol to C9
aromatics is maintained at above 10:1, and methanol conversion is preferably below 80%. To
increase the concentration of aromatics in the catalyst pores, it may be desirable to use a
catalyst having increased diffusional barriers (diffusion parameter for 2,2 dimethylbutane of
0.2-5 s-1). In an example, a 12:1 molar methanol:toluene feed is converted in the presence of
a ZSM-5 catalyst at 440°C, 1 atm, and WHSV of 0.5-5 h-1. At methanol conversions of
about 74%, the selectivities to ethylene and propylene are 24.4 wt% and 20.4 wt%,
respectively.

PATENT SUMMARY
Reference Earliest
US 6538167 ExxonMobil Chemical October 2, 1996
US 6046372 Mobil Oil
Reaction conditions
Methanol is converted to olefins in the presence of a ZSM-5 catalyst. The selectivity to
ethylene is increased by using a co-aromatic feed, such as toluene or xylenes, and by limiting
the methanol conversion to less than 80%. To increase the concentration of aromatics in the
catalyst pores, it may be desirable to use a catalyst having increased diffusional barriers,
such as that described in US 6048816. In an example, a 26:1 molar methanol:toluene feed is
converted in the presence of a phosphorus-modified ZSM-5 catalyst at 430°C, 1 atm, and
WHSV of 0.5-10 h-1. At methanol conversions of 74%, the selectivity to ethylene is about 30
wt%.
US 6048816 Mobil Oil October 2, 1996

Methanol is converted to olefins in the presence of a ZSM-5 catalyst containing 0.05 to 20
wt% of an oxide of phosphorus on an elemental basis. The diffusivity of the zeolite is reduced
to about 0.2-5 s-1 (measured at 120°C and a 2,2-dimethylbutane pressure of 60 Torr) by
steaming the catalyst at 1000-1050°C from 30 min to 5 hours.
In an example, a ZSM-5 catalyst containing 4.5 wt% phosphorous is steamed at 1 atm
and 1025°C for 45 min and then tested for methanol conversion activity. At 430°C and 1.0
WHSV, the modified catalyst converts 97% of the feedstock methanol to hydrocarbon
products.
US 5491273 Mobil Oil November 17, 1994

Use of ZSM-35 catalyst for the production of C4+ olefins
Methanol is converted to butenes and pentenes in the presence of a large crystal ferrierite
aluminosilicate catalyst, such as ZSM-35. Preferably, the average crystal size of the catalyst
is above 1.0μ. In an example, a ZSM-35 catalyst with average crystal size of 1-3 μ is used to
convert methanol at 400°C, WHSV of 2.0 h-1, and methanol partial pressure of 0.13 atm. At
95% methanol conversion, the yield to n-butene and isobutene is 20.1 wt% and the yield to n-
pentene and isopentene is 47.8 wt%.

PATENT SUMMARY
Reference Earliest
Use of ECR-1, mazmorite, or ECR-18 zeolite catalysts
Methanol is converted to olefins in the presence of synthetic mazmorite-type and/or
paulingite-type zeolite catalysts. In an example, an ECR-18 catalyst with silica-to-alumina
molar ratio of 6.4 is used to convert a mixture of methanol and water (1:4 methanol:water
molar ratio). The reaction is carried out in a fixed bed reactor at 450°C, with a WHSV of 1.0
h-1. Ethylene and propylene account for 38 wt% and 30 wt%, respectively, of the
hydrocarbon product.
US 7015369 MG Technologies AG May 22, 2001

Process for producing propylene from methanol
A process for producing propylene from methanol, wherein methanol vapor is reacted on a
first catalyst to obtain a first vapor mixture containing dimethyl ether (DME), which is reacted
on a form-selective zeolite catalyst disposed as bed in at least two series-connected shaft
reactors to produce a product mixture containing propylene.
WO 0192190 Metallgesellschaft May 31, 2000

Process for producing propylene from methanol
Methanol is converted to propylene and gasoline using an intermediate step of DME
production. The methanol feed is first contacted with a fixed bed of an acidic catalyst at 250-
350°C to produce an equilibrium mixture of DME, methanol and steam. This mixture is then
converted to olefins at 400-550°C in the presence of the modified pentasil catalyst described
in EP 448000. Three fixed bed reactors with intermediate cooling are used in series, and the
feed mixture of methanol, DME and water is split between the first two reactors. In the
product recovery section, the reaction effluent is compressed, cooled, and separated by
fractional distillation into a water stream, a gasoline fraction, and the propylene product.
Intermediate streams containing light products (including ethylene) or olefins heavier than
propylene but lighter than naphtha are all recycled to the reaction system. Small purge
streams are used to avoid the accumulation of inert products.

PATENT SUMMARY
Reference Earliest
EP 882692 Metallgesellschaft April 6, 1997
Process for producing C2-C4 olefins from methanol
feed is first contacted with a fixed bed of an acidic Al2O3 catalyst at 250-350°C to produce an
equilibrium mixture of DME, methanol and steam. This mixture is then converted to olefins in
the presence of a modified pentasil catalyst at 400-550°C and using a salt bath tubular
reactor. After compression and cooling, the reaction effluent is separated by fractional
distillation into a water stream, a C2-C4 stream, and a C5+ heavy fraction. The C5+ stream is
vaporized, mixed with steam and fed to a separate zeolite-based reactor at 400-600°C. The
lighter hydrocarbons produced are recycled to the separation section.
EP 448000 Metallgesellschaft / Sud-Chemie March 23, 1990

Use of modified ZSM-5 catalyst for propylene production
feed is first contacted with a fixed bed of an acidic Al2O3 catalyst at 250-350°C to produce an
equilibrium mixture of DME, methanol and steam. This mixture is then converted to olefins in
the presence of a modified pentasil catalyst at 400-550°C and using a salt bath tubular
reactor. The modified pentasil zeolite (ZSM-5) has a Si/Al atomic ratio of at least 10, an alkali
2
content of less than 380 ppm, a BET surface area of 300 to 600 m /g, and a pore volume of
3
0.3 to 0.8 cm /g. At 100% methanol conversion, the selectivity to ethylene is at least 5 wt%
and the selectivity to propylene is at least 35 wt%.

Table A.3
REACTOR DESIGN AND OPERATION
PATENT SUMMARY
Reference Earliest
Fines co-feed for maintaining efficient reactor hydrodynamics
To maintain a desired particle size distribution in an oxygenate to olefin reaction system, lost
catalyst fines is replaced with less active co-catalyst particles. By adding less active co-
catalyst particles to the reaction system, desirable fluidization characteristics and
hydrodynamics can be maintained without affecting the overall (or primary catalyst)
performance and product selectivities.

Adding heat to a reactor system
The reactor system comprising an OTO reactor and a regenerator requires the addition of
heat to the reactor system. The OTO reaction is exothermic, requiring an initial heating to
initiate the reaction, after which it is self-sustaining. There are also periods where the
oxygenate feed must be interrupted, at which time it would be desirable to keep the reactor
and regenerator hot. In addition, the initial start-up of the regenerator and heating of the
catalyst also requires heat.
US 7084319 ExxonMobil Chemical December 5, 2003

Reactor operation
The reactor system comprising an OTO reactor and a regenerator often requires the addition
of heat to the reactor system. The OTO reaction is exothermic, requiring an initial heating to
initiate the reaction, after which it is self-sustaining. There are also periods where the
oxygenate feed must be interrupted, at which time it would be desirable to keep the reactor
and regenerator hot. In addition, the initial start-up of the regenerator and heating of the
catalyst also requires heat.
By fluidizing a molecular sieve catalyst composition with a reactive fluidizing medium under
conditions effective to convert at least a portion of the fluidizing medium, which comprises
byproducts of the oxygenate to olefin conversion reaction, to additional light olefin product in
an oxygenate-to-olefin reaction system.

PATENT SUMMARY
Reference Earliest
Reactor feed vaporization
A feed vaporization process for oxygenate to olefin conversion, comprises a vapor-liquid
disengaging drum separating non-volatiles and/or low-volatiles from volatiles in the
oxygenate feed while at the same time maintaining the effluent at optimal temperature and
pressure as a feed for oxygenate to olefin conversion is particularly well suited for selectively
removing non-volatile contaminants such as soot and rust from an oxygenate-containing
feed, which may have become contaminated during shipping.
US 7115791 ExxonMobil Chemical December 19, 2002

Reactor operation
Controlling an oxygenates to olefin reactor is carried out by contacting oxygenate-containing
feedstock, e.g., methanol, in a reaction zone in the presence of a molecular sieve oxygenate
to olefins conversion catalyst under conditions sufficient to provide an olefins-containing
effluent containing methanol and dimethyl ether; analyzing a single gas phase of the effluent
determine alkyl alcohol concentration and dialkyl ether concentration; and adjusting reactor
conditions, e.g., WHSV, as a function of alkyl alcohol concentration and dialkyl ether
concentration, as necessary to provide a substantially consistent effluent composition.

Reactor operation
Metal-catalyzed side reactions in the reactor feed system are suppressed by reducing the
temperature at the inner surface of the feed introduction system. At least part of the feed
nozzle is thermally insulated or cooled by a cooling system.
WO 03099747 ExxonMobil Chemical December 31, 2001

Reactor operation
Heating fuel is added directly to the fluidized bed of the regenerator reactor to provide
supplemental heat during startup and short-term outages of the methanol feed. The heating
fuel consists of a torch oil having low autoignition temperature (below 480°C) and low sulfur
and nitrogen content.

PATENT SUMMARY
Reference Earliest
Reactor operation
Coke formation during the conversion of methanol to olefins is reduced by cooling part of the
spent catalyst after product separation, and by recycling the cooled catalyst to the reactor
without regeneration. The temperature of the cooled portion of the catalyst is 10-30°C below
the average reactor temperature. Accordingly, the average coke content of the total spent
catalyst is between 2 and 30 wt%, and the average coke content of the regenerated portion
of catalyst is less than 2 wt%.

Reactor operation
Methanol is converted to olefins in the presence of a SAPO-34 catalyst, using a fluidized bed
reactor at specified operating conditions. Important variables include the gas superficial
velocity (GSV), the mass of catalyst in the reaction zone relative to that in both the reaction
and regeneration zones, and the ACFE index, defined as the total weight of methanol plus
hydrocarbon fed to the reactor divided by the total weight of fresh and regenerated SAPO
catalyst. The most preferred ranges for these variables are a GSV above 4 m/s, a catalyst
mass ratio between 0.3 and 0.99, and an ACFE index between 2 and 12.

Reactor operation
An auxiliary fluidized bed reactor is placed between the methanol conversion reactor and the
catalyst regenerator. The auxiliary reactor converts one or more alcohols selected from
ethanol, 1-propanol, or 1-butanol, to olefins in the presence of fresh and regenerated SAPO-
34 catalyst. Preferably, the temperature of the auxiliary reactor is 50-80°C less than that in
the methanol conversion reactor. This method allows the production ratio of ethylene to
propylene to butylenes to be varied by using different types of alcohol feeds in the auxiliary
reactor.

Catalyst stripping
Coke deposition on the SAPO-34 catalyst during methanol conversion is controlled by
stripping a portion of the catalyst with a gas (typically steam) and returning at least a portion
of the stripped catalyst directly to the reaction zone without regeneration. A stripping rate of
1-4 lb steam per 1000 lb of catalyst per hour is typically used, leaving less than 1 wt% of
hydrocarbons (exclusive of coke) on the stripped catalyst.

PATENT SUMMARY
Reference Earliest
WO 0185872 ExxonMobil Chemical May 4, 2000
Reactor geometry
A hydrocarbon reactor useful in the conversion of methanol to olefins consists of a plurality of
riser reactors extending to a common separation zone. Several catalyst return lines transfer
the catalyst from the separation zone to the feed ends of the riser reactors. By using multiple
risers, each riser reactor can have a relatively small diameter (cross sectional area less than
3.5 m2) and operate at high superficial velocity. As a result, plug flow regime can be achieved
at lower reactor heights than those in conventional reactors.

Reactor operation
Ethylene selectivity in the conversion of methanol to olefins is improved by using staged
injection of methanol along the axial direction of the fluid bed reactor. In an example, pure
methanol is reacted in the presence of SAPO-34 in a small fluid bed reactor at 375-470°C
and WHSV of 0.15-0.7 h-1. The selectivity to ethylene using 3 methanol injection zones is
24.1 wt%, as compared to 19.9 wt% without staged injection.

Reactor operation
Methanol is converted to olefins in the presence of a SAPO-34 catalyst using a circulating
fluid bed reactor with continuous regeneration of a portion of the coked catalyst. The
regenerated catalyst is returned to a location in the reactor that contains at least a portion of
the methanol conversion by-products. This contact promotes catalyst ìselectivationî, i.e.
selective deposition of coke on the catalyst surface by conversion of C4+ olefins. When
contacted with the fresh methanol feed, the selectivated catalyst increases the yields to
ethylene and propylene.

PATENT SUMMARY
Reference Earliest
US 6444868 Exxon Chemical February 17, 1999
Reactor operation
Improvement of US 6482999. Methanol is converted to olefins in the riser region of a fluidized
bed reactor, with continuous removal of a portion of the coked SAPO-34 catalyst for
regeneration. The riser region is immediately followed by a dense bed region, where
regenerated catalyst is introduced to convert C4+ olefins and promote catalyst ìselectivationî,
i.e. selective deposition of coke on the catalyst surface. This selectivated catalyst is then
recycled to the riser region of the reactor. The dense bed zone has a greater diameter than
that of the riser region, and is maintained at a temperature at least 25°C higher.

US 6455747
Reactor operation
In the conversion of methanol to olefins using a fluidized bed reactor, plug flow behavior is
approached by maintaining a total gas superficial velocity above 2 m/s, preferably above 8
m/s, which minimizes backmixing and increases selectivity to C2-C3 olefins. In order to
reduce the temperature rise in the reaction zone to less than 30°C, spent catalyst is
recirculated to the reaction feed at a rate of 10 to 50 times the methanol feed rate.

Catalyst regeneration
Liquid water is injected into the catalyst regeneration vessel to moderate temperature rise
during combustion of coke with air. A sufficient amount of water is introduced to eliminate the
need for a separate catalyst cooler. The regeneration process results in hydrothermal
treatment of the molecular sieve catalyst and improves selectivity to light olefins. The steam
generated during regeneration is removed with the combustion gases.

PATENT SUMMARY
Reference Earliest
US 6023005 Exxon Chemical July 3, 1997
Catalyst regeneration
fluid bed reactor with continuous catalyst regeneration. The selectivity to ethylene and
propylene is increased by removing only a portion of the total reaction volume of coked
catalyst and totally regenerating only that portion of catalyst in a separate vessel. The flow of
coked catalyst sent to regeneration is adjusted so as to maintain the coke level in the
reactor at about 2ñ30 wt% of the total volume of catalyst. These ìdesirableî carbonaceous
deposits block less selective portions of the catalyst and increase the yield to C2-C3 olefins.
Catalyst regeneration occurs at 550 - 700°C, 0.1 - 5 vol% of oxygen, and a residence time of
1ñ100 min, so that the coke content of the regenerated catalyst is reduced to less than 0.5
wt%.
WO 03051510 Lurgi December 14, 2001

Regeneration of ZSM-5 catalyst
Improved method for removing coke of a fixed-bed reactor containing ZSM-5 catalyst.
Hydrocarbons are first removed from the reactor bed by a nitrogen stream at 460-500°C. The
reactor is then cooled by a nitrogen stream at 420-460°C and completely decoked by a
nitrogen/air mixture at 460-500°C. Finally, a nitrogen stream at 460-500°C is passed through
the reactor bed to remove residual hydrocarbons.
WO 0041986 S. C. Zecasin January 11, 1999

Reactor operation
Methanol is converted to olefins in the presence of a SAPO-34 catalyst. The feed is injected
in the dense bed of a fluidized bed reactor and the coked catalyst is continuously circulated
to a separate regeneration vessel. By changing the reaction temperature within the range of
400-490°C and the liquid space velocity between 0.6 and 2.7 h-1, the ethylene/propylene
ratio of the product is adjusted within the range of 0.69-1.36. The use of steam or nitrogen
purging in the risers of the reactor and regenerator reduces the amount of adsorbed
methanol in the catalyst sent to the regenerator and the amount of adsorbed oxygen in the
catalyst sent to the reactor.

PATENT SUMMARY
Reference Earliest
US 7138558 UOP September 27, 2005
Direct return of oxygenate recycle stream
In converting oxygenate to olefins in the presence of a SAPO-34 catalyst, the unreacted
oxygenate and diolefins from light olefins and by-products is separated and returned to the
reactor. The unreacted oxygenate and diolefins are sent through at least one feed nozzle into
said reactor at a point separate from the oxygenate feed stream.
US 6872867 UOP July 17, 2003

Reactor start-up operation
A catalytic conversion process using a fluidized reactor, which requires a minimum superficial
gas velocity to function properly, and a motor-driven, capacity-limited product compressor is
started up using a thermal compressor by establishing two start-up gas recirculation circuits,
one using the product compressor running at high pressure to recirculate about 40 to 60 vol-
% of the effluent gas stream from the reactor and the other running at low pressure and
carrying the remaining portion of the effluent gas stream from the fluidized reactor where the
high pressure circuit supplies motive gas to the thermal compressor and the low pressure
circuit supplies suction gas to the thermal compressor and the resulting compressed
discharge gas enables the catalytic process to start up without the use of a dedicated motor-
driven start-up compressor.

Controllable space velocity reactor geometry
To space velocity in a fluidized catalytic conversion reactor. The catalyst flux rate can be
adjusted during the process of the reaction to adjust the space velocity and maintain a fast
fluidized flow regime therein. The set parameter in the reactor may be pressure drop which is
proportional to catalyst density.

PATENT SUMMARY
Reference Earliest
US 6166282 UOP August 20, 1999
Reactor geometry
A fast-fluidized bed reactor is used to convert methanol to olefins in the presence of a SAPO-
34 catalyst. The reactor comprises a lower reaction zone and an upper disengaging zone.
The reaction zone is divided into a dense phase zone and a transition phase zone, which
extends from the lower reaction zone through a riser and into the upper disengaging zone. A
reducing zone is included in the transition zone to reduce the flow path diameter and
increase the superficial velocity from less than 1 m/s to about 3 m/s. The methanol and
diluent feedstream is introduced in the dense phase zone to effect a partial conversion to
olefins and then passed to the transition zone to achieve essentially complete conversion. In
the disengaging zone, at least one cyclone separation stage is used to separate the catalyst
from the reaction product. A portion of the catalyst is withdrawn from above the transition
zone in the disengaging zone, at least partially regenerated, and returned to a point above
the dense phase zone, while catalyst is continuously circulated from the disengaging zone to
the reaction zone.

Reactor operation
moving bed reactor with continuous catalyst regeneration. The catalyst particles are fed into
the upper portion of the reactor, moving by gravity in countercurrent direction to the flow of
gas. The selectivity to desirable products is increased by carefully selecting the rate of
catalyst addition, so that at a sufficient quantity of active catalyst sites is provided within the
reaction zone. When a radial flow reaction zone is employed, the thickness of the annulus
through which the catalyst flows is kept higher in the lower section of the reactor. The higher
residence time of the catalyst in the lower section compensates for the loss of activity by
coking, so that a relatively constant amount of active catalyst sites are maintained through
the reactor.

PATENT SUMMARY
Reference Earliest
US 6433239 Van Dijk Technologies July 2, 1998
Reactor operation
Methanol is converted to olefins in the presence of a fixed bed of ZSM-5 or SAPO-34
catalyst. Ethylene yields above 60% are claimed to be obtained by using small catalyst
particles (below 0.1 mm) and by operating at a WHSV that limits the methanol conversion to
80-95%. At least four parallel reactor aggregates operate in a stepwise sequence, so that
after the last reactor aggregate is taken off-line, the first one is regenerated and ready to start
a new cycle. Each reactor aggregate consists of a series of fixed bed reactors with methanol
injection between the catalyst beds. The adiabatic temperature rise in each fixed bed reactor
is limited to about 5-25°C.
US 6399844 Van Dijk Technologies September 24, 1997

Reactor operation
Methanol is converted to olefins in a series of four fixed bed reactors with methanol injection
between the catalyst beds. This arrangement allows the control of methanol conversion in
each bed to about 6-10%, so as to reduce the adiabatic temperature rise and increase the
selectivity to ethylene. In addition, by reducing the methanol partial pressure throughout the
reaction to less than 0.2 atm, less coke is formed. Further reduction of the adiabatic
temperature rise is achieved by recycling part of the reaction effluent at each stage.
Removing catalyst fines from an oxygenate-to-olefin reactor effluent stream that has catalyst
fines therein. Withdrawing the reactor effluent stream from the reactor, the reactor effluent
stream is transported in a first conduit to a quench device and is quenched to form a
quenched effluent stream and a liquid fraction containing a majority of the catalyst fines. The
liquid fraction is transported in a second conduit to a solids separation device. The process
conditions are adjusted to prevent catalyst fines accumulation.

Table A.4
PRODUCT RECOVERY
PATENT SUMMARY
Reference Earliest
US 7141711 ExxonMobil Chemical March 24, 2003
Removal of catalyst fines
Removing catalyst fines from an oxygenate-to-olefin reactor effluent stream that has catalyst
fines therein. Withdrawing the reactor effluent stream from the reactor, the reactor effluent
stream is transported in a first conduit to a quench device and is quenched to form a
quenched effluent stream and a liquid fraction containing a majority of the catalyst fines. The
liquid fraction is transported in a second conduit to a solids separation device. The process
conditions are adjusted to prevent catalyst fines accumulation.

Removal of oxygenate contaminants
A method of removing dimethyl ether from an olefin stream. Dimethyl ether is removed from
the olefin stream by first separating the olefin stream into a first stream comprising dimethyl
ether and lighter boiling point compounds, and a second stream comprising C4+ olefin and
higher boiling point hydrocarbons. The dimethyl ether is then separated from the first stream
using extractive distillation.
WO 03020670 ExxonMobil Chemical April 19, 2002

Removal of acetaldehyde
Following quenching and compression, the crude olefin product is sent to an extractive
distillation column for acetaldehyde removal. Methanol is added as an extraction agent, so
that acetaldehyde is removed in the bottom product with methanol and C4+ hydrocarbons.
The overhead olefin stream is then washed with caustic solution to remove CO2, dried in an
adsorbent column, and sent for further fractionation in a conventional distillation system.

Similar to WO 03020672. DME separation is carried out by distillation at a pressure higher
than 200 psig (as opposed to low pressure as in WO 03020672). The method reduces the
refrigeration duty of the overhead condenser and allows better control of free water and
clathrate formation in the distillation equipment.

PRODUCT RECOVERY
PATENT SUMMARY
Reference Earliest
Following cooling in a quench tower, the crude olefin product is compressed and sent to a
distillation column, where C2/C3 olefins are separated from DME, propadiene, methyl
acetylene and C4+ hydrocarbons. The column operates at pressures below 200 psig,
resulting in lower bottom temperatures and less fouling problems. To reduce the DME
content in the column overhead, most of the propane is removed in the bottom product. A
methanol stream is also added to the column to avoid separation of a water liquid phase and
to reduce gas hydration and consequent clathrate formation. Alternatively, excess water can
be removed by methanol washing prior to the distillation column.
WO 03033441 ExxonMobil Chemical December 31, 2001

The crude olefin product is quenched, compressed, dried, and sent to a sequence of
distillation columns for separation of the olefin components. The distillation scheme is
designed so as to separate propane, DME and C4+ olefins from the other lighter
components. DME and propane are then distilled as an overhead stream.

Removal and recovery of oxygenate contaminants
Following cooling in a quench tower, the crude olefin product is compressed and washed
with methanol and/or water. The aqueous liquid streams from the quench and washing steps
are combined and sent to a distillation column, where a stream of oxygenates is recovered
overhead. The oxygenates can be recycled to the reactor or disposed of as fuel.

After quenching, the reaction effluent stream is compressed, washed with caustic soda, and
sent to an absorption column for removal of oxygenate contaminant. The absorbent is
selected from the group consisting of a polyol, amine, amide, nitrile, and heterocyclic nitrogen
containing compound. Following the absorption system, the olefin stream may be directed to
one or more adsorbent beds for additional removal of water and oxygenated components.

PRODUCT RECOVERY
PATENT SUMMARY
Reference Earliest
WO 03037834 ExxonMobil Chemical October 30, 2001
Reduction of catalyst fouling
The amount of heat removed from the reaction effluent is controlled such that the stream
temperature is maintained above its dew point prior to entering the quench column. This
method avoids the formation of liquid droplets and consequent accumulation of solid particles
in the product recovery train.

Improved heat recovery
The heat duty of the reaction effluent is used to generate HP and LP steam and to vaporize
part of the fresh methanol feed, while the remaining methanol is vaporized by steam heating.
The two streams of vaporized methanol are combined and sent to the olefin synthesis
reactor.

Following quenching and condensation of heavy hydrocarbons, the crude olefin product is
sent to a wash column for removal of contaminants such as dimethyl ether. The feed gas is
washed with fresh methanol in the lower section of the column, and by water in the upper
section. The water washed olefin product stream is then sent to drying and fractionation.
US 6559248 ExxonMobil Chemical August 31, 2001

Oxygenate contaminants in the crude olefin product, particularly dimethyl ether and
acetaldehyde, are removed by an extractive distillation process. After quenching, the
reaction effluent stream is compressed and contacted countercurrently with a liquid
extractant. Preferably, the extractant consists of water or a water-alcohol mixture containing
at least 75 wt% water. Separation of the extractant from the absorbed products in carried out
in a conventional distillation column.

PRODUCT RECOVERY
PATENT SUMMARY
Reference Earliest
WO 03020678 ExxonMobil Chemical July 2, 2001
Dimethyl ether is removed from the crude olefin product by the extractive distillation process
described in US 6559248. Preferably, the extractant consists of water or a water-alcohol
mixture containing at least 75 wt% water. Prior to extractive distillation, the C4+ hydrocarbons
are separated from the olefin stream by conventional distillation.
US 6580010 ExxonMobil Chemical January 3, 2001

Use of hydration reactor
Methane and hydrogen are separated from olefins by a less energy intensive process,
such as absorption in a solvent, instead of the conventional demethanizer column. The
olefins present in the by-product streams are then converted to alcohols in a hydration
reactor and recycled to the methanol conversion reactor. The hydration reaction is carried out
at 180-300°C and 350-1000 psig, in the presence of a phosphoric acid catalyst.
US 6482998 ExxonMobil Chemical April 29

Quench system with improved heat recovery
Direct product quenching is used to improve heat recovery in the conversion of methanol to
olefins. After exchanging heat with the methanol feedstock, the reaction effluent is fed to the
bottom of a quench tower, where it contacts a countercurrent aqueous stream. The light
components, including light olefins and alkanes, are removed as overhead vapor, while
water, unreacted methanol and heavy hydrocarbons are separated as a liquid bottom stream.
Part of this liquid stream is cooled and used as quench medium in the quench tower. The
remainder is sent to a fractionator that separates water from dissolved organic components.

PRODUCT RECOVERY
PATENT SUMMARY
Reference Earliest
WO 9829367 Exxon Chemical December 31, 1996
Use of transport membrane
Olefins are separated from the reaction effluent by using a facilitated transport membrane,
which eliminates the need for demethanizer and deethanizer towers. After water removal, the
reaction product is sent to an olefins selective membrane module, which consists of two
chambers separated by a polyvinyl alcohol membrane containing a complex-forming metal.
The olefins-rich permeate stream, containing less than 0.1 wt% of saturates, passes through
an adsorber to remove residual carbon monoxide and water, and is sent to cryogenic
separation of the olefins. The saturate rich retentate is used as steam cracking feed or as
fuel.

US 5960643
Demethanizer operation
The operating temperature of the demethanizer condenser is raised above -48°C by allowing
1-50% of the ethylene in the demethanizer feed to be removed in the overhead. This
potentially eliminates the need for a chill train and dedicated low temperature refrigeration
system. The ethylene rich overhead stream can be used in the production of ethylene
derivatives.
US 7132580 UOP May 13, 2003

Reduction in the amount of light olefins that are undesirably captured in a dimethylether
recycle stream and improved recovery of methanol are achieved when a portion of the
methanolic feed to the MTO reaction zone is used as the scrubbing solvent in a primary DME
absorption zone in order to recycle this DME oxygenate by-product to the MTO reactor.

PRODUCT RECOVERY
PATENT SUMMARY
Reference Earliest
US 6459009 UOP October 19, 2000
US 6403854
Quench system with improved heat recovery
A two-stage quench tower system is used to separate water, entrained catalyst fines and
heavy oxygenates from the reactor effluent. In the first tower, the reactor effluent is contacted
with an aqueous stream and with a neutralizing agent, which prevents the build up of
organic acids. The hydrocarbon vapor stream from the top of the first tower exchanges heat
with the reactor feed and enters a second quench tower, where additional water is removed.
Part of the water from the bottom of the second tower is recycled to the first quench
tower, while the remainder is sent to a stripper to produce purified water as a bottom stream.
The stripper overhead stream, containing recovered oxygenates, is combined with the
overhead vapor stream from the first quench tower, prior to heat exchange with the reactor
feed.
US 6444869 UOP October 4, 1999

US 6303841
Use of pressure swing adsorption
The combination of a pressure swing adsorption (PSA) process with the demethanizer
column results in the elimination of cryogenic ethylene-based separation from the product
recovery section. After the conventional steps of compression, washing, caustic removal of
CO2, and drying, the crude olefin product is fed to a demethanizer for separation of the light
hydrocarbons. Instead of the typical temperature of -95°C, the demethanizer condenser is
maintained at about ñ45°C, allowing some ethylene and ethane to be present in the
overhead along with hydrogen and methane. This overhead stream is then passed to an
adsorption zone containing at least two adsorption beds, which operate on a cyclic basis to
adsorb and desorb ethylene. On adsorption, the beds produce an effluent stream containing
hydrogen and methane. On desorption, the beds produce an ethylene and ethane product
stream, which is at least partially recycled to the demethanizer feed.

PRODUCT RECOVERY
PATENT SUMMARY
Reference Earliest
US 5811621 Van Dijk, C. P. August 9, 1996
Demethanizer operation
Similar to US 5960643 (ExxonMobil). The operating temperature of the demethanizer
condenser is raised above -40°C by allowing some ethylene in the demethanizer feed to be
removed in the overhead. Preferably, the molar ratio of ethylene to methane in the overhead
product is at least 3:1 and condensation occurs by vapor recompression. This potentially
eliminates the need for a chill train and dedicated low temperature refrigeration system.
The ethylene rich overhead stream can be used in the production of ethylene derivatives.

Table A.5
OTHER CATALYSTS / PROCESS INTEGRATION
PATENT SUMMARY
Reference Earliest
Polypropylene from Intermediate grade propylene
Using an intermediate grade propylene stream, recovered form the olefin product of an
oxygenate to olefins reaction process with low dimethyl ether content, as feed to a
polypropylene forming reaction system.
US 7078364 University of Southern California April 22, 2002

Use of Ship-in-a-bottle catalysts
Utilizing a catalyst system in which the catalytic structure is tailormade at the nanometer
scale using a ship-in-a-bottle synthesis techniques in heterogeneous catalysis that have a
microporous structure defined by nanocages. Examples include zeolites and SAPOs
materials that have the controlled pore dimensions and hydrothermal stability required for
MTO processes.
US 7161051 ExxonMobil Chemical March 3, 2003

Integration of methanol and MTO processes
An integrated methanol synthesis/MTO reaction system implements a shared separation
system for separating oxygenate components from the respective methanol synthesis system
and MTO reaction system. The number of separation units in the integrated system may be
advantageously reduced through a shared separation system.

Use of modified chabazite-type molecular sieve
Methanol is converted to olefins in the presence of an aluminosilicate catalyst with chabazite
framework and high silica to alumina molar ratio. By optimizing acidity and pore size, the
catalyst performance in the conversion of methanol to olefins is similar to that for SAPO-34
catalysts. In an example, methanol is converted at 500°C, 40 psia and WHSV of 100 h-1. At
10% methanol conversion, the selectivities to ethylene and propylene are 37.61 wt% and
36.04 wt%, respectively.

PATENT SUMMARY
Reference Earliest
Integration of syngas, methanol, synfuel, and MTO processes
Similar to US 6486219. The unreacted syngas from the methanol reactor is directed to a
hydrocarbon synthesis (synfuel) reactor. This eliminates the need for syngas recycling in the
methanol reactor and leads to additional cost saving.

Integration of syngas, methanol, synfuel, and MTO processes
A syngas stream from a steam reformer is combined with a syngas stream from an oxidation
reformer to form an optimal feed composition for a methanol synthesis reactor. Capital and
operating cost savings result from integrating fuels, heating and cooling requirements, and
the elimination or reduction of waste streams.
WO 0198237 JGC June 23, 2000

Production of olefins from methanol-DME mixture
A methanol-DME mixture is produced from syngas at milder reaction conditions (such as
lower pressure) than those in the reaction to form only methanol. Unreacted CO and H2 are
recovered by gas-liquid separation at high pressure and are partly recycled to the synthesis
reactor. The remaining offgas, also containing carbon dioxide and some DME, is cooled to a
temperature range of -40 to -30°C and sent to a membrane separation unit for DME recovery.
The liquid methanol-DME mixture from the high-pressure gas-liquid separator is combined
with recovered DME, and the mixture is expanded and heated. Finally, the vapor methanol-
DME stream is fed to a reactor containing a SAPO-34 or ZSM-5 catalyst to produce light
olefins. The presence of DME in the reactor feed reduces the total amount of exothermic heat
released in the conversion reaction.

PATENT SUMMARY
Reference Earliest
US 6303839 UOP July 22, 1997
US 5914433
Combination of methanol conversion and catalytic cracking of higher olefins
A secondary fluidized reaction zone is used to convert butylenes and heavier olefins from the
MTO process into additional ethylene and propylene. The yield of butylene (and heavier) to
propylene from this combined process is reduced to less than 0.15 wt%. The cracking
reaction is carried out at temperatures between 580 and 650°C, preferably in a separate
fluidized bed reactor using regenerated SAPO-34 catalyst. The catalyst to oil (mixed butylene
and heavier stream) ratio is maintained below 10. In order to minimize the by-production of
methane, the feed to the secondary reaction zone is first selectively hydrogenated to remove
diolefins.
US 5990369 UOP August 10, 1995

Combination of methanol conversion and olefins metathesis
A metathesis process is used to change the equilibrium distribution of olefins from the
methanol conversion process, providing more flexibility in the ratio of ethylene/propylene
produced. The metathesis reaction is carried out at temperatures ranging from 150 to 350°C
in the presence of a molybdenum oxide or tungsten oxide catalyst. Different process
alternatives include: metathesizing a fraction of the crude olefins stream; separating the
olefins and metathesizing ethylene and butylene into propylene; or separating the olefins and
metathesizing propylene into ethylene and butylene.
US 5714662 UOP August 10, 1995

Integration of methanol plant with methanol conversion plant
Crude methanol from the methanol plant is sent directly to the oxygenate conversion
process, without removal of water or higher alcohols. The integration of the two plants
provides capital and operating savings in the methanol distillation train and allows extended
operation of the carbon oxide conversion catalyst. In addition, the by-product water produced
in the methanol conversion reaction can be recycled to the syngas production zone, without
further treatment to remove hydrocarbons or oxygenates.

Appendix B
DESIGN AND COST BASES
DESIGN AND COST BASES
DESIGN CONDITIONS
Design and cost calculations are based on an assumed plant location along the U.S. Gulf
Coast at Houston‚ Texas. Particular temperature assumptions are:
Dry bulb air temperature 38°C (100°F)
Wet bulb air temperature 27°C (80°F)
Groundwater temperature 27°C (80°F)
Cooling water temperature 29°C (85°F)
Cooling water range 11°C (20°F)
The usual definitions of terms relating to yield are used in this report. They are as follows:
Conversion Ratio of material reacted to material fed‚ stated in percent or fraction
Selectivity Ratio of product desired to material reacted‚ stated in percent or fraction
of material reacted
Yield per pass Ratio of product desired to material fed‚ stated in percent or fraction of
material fed = Conversion x Selectivity
COST BASES
Below‚ we outline the criteria for calculating capital investment and production costs‚ and the
effect of the operating level on production costs.
Capital Investment
Equipment costs are estimated primarily from correlations developed by PEP and
supplemented occasionally by vendors’ estimates. If an equipment item is specialized or
contributes substantially to the cost of the facility‚ a vendors’ quote has been obtained if possible.
When necessary‚ the costs are corrected to a mid-2006 PEP Cost Index of 718.
Direct installation costs are estimated by a modular method developed by PEP; the details
are described in PEP Report 145‚ Battery Limits Cost Estimating (April 1982). The indirect costs
in capital investment are estimated by adding allowances for engineering‚ field expenses‚
overhead‚ purchasing‚ and contractor’s profit. The bases for the estimation of these allowances
are detailed in Section 7 of PEP Report 162‚ Computer Program for Estimating Plant Investment
(March 1985). These indirect cost estimates are then added to the direct investment (fob costs
plus direct installation costs) to get the overall installed costs. Allowance for fringe benefits, an
effective construction labor rate of $38.5 per hour has been incorporated into our installed cost
calculations for certain equipment categories.
Investment in utilities is computed for the entire plant and allocated to each major operation
according to use. Indirect costs for utilities and off-site tankage (generally raw material and
product storage) are assumed to be 20% of the direct utilities investment.
© SRI Consulting B-3 PEP Report 261

General service facilities not directly associated with process operations are assumed to be
20% of the battery limits installed cost and utilities-plus-storage investment. An allowance for
waste treatment facilities is also made. These allowances are determined prior to the addition of
contingencies to the installed costs.
The total fixed capital for the facility includes total investment in battery limits‚ utilities and
tankage‚ general service facilities‚ and a contingency. Usually the contingency is taken as 25%
each of the battery limits investment and the off-site investment. All of the above investment
estimates have been calculated with the aid of SRI’s PEPCOST II computer program.
In comparing PEP’s estimates with actual plant costs or contractors’ estimates‚ the following
should be borne in mind:
• The processes may be the same generally but differ enough in detail to affect costs
significantly, a typical result of differing owner or contractor engineering standards.
• The estimates may not be strictly comparable because of omission of process sections
(for example‚ by-product recovery) in one or another of the designs.
• Actual plants are frequently overdesigned for reasons unique to the particular situations.
• During periods of rapid escalation of equipment costs‚ and when long delivery times are
anticipated‚ cost indexes probably are not an accurate reflection of actual costs.
• During periods of depression in chemical plant construction‚ equipment vendors and
engineering contractors will provide goods and services at little or no profit.
• Local costs associated with special site preparation requirements as well as
requirements for roads, transportation depots, and port facilities, in addition to local
environmental and safety regulations may have a major impact on the cost of a
grassroots facility.
• The local quality and availability of process water and cooling water can significantly
impact plant costs.
• Fluctuations in foreign currency exchange rates may have a major impact on the capital
cost of plants located outside of the United States but reported in U.S. dollars.
• 100% equity financing is generally assumed in PEP’s total fixed capital and production
cost estimates, and therefore the estimates do not reflect the capitalized cost of future
debt service that may be added to the reported purchased cost of plants financed with
borrowed funds.
Production Costs
The operating labor wages are based on estimated prevailing rates in Houston‚ Texas. The
base rate is derived from U.S. national average rates in industrial chemical plants‚ corrected to
the Houston area on a relative basis for production workers. With an allowance for fringe benefits
and a 10% shift overlap assumed‚ the effective total rate is $41.5 per hour. The operating labor
requirements have been estimated subjectively on the basis of the number of major equipment
items in the process. The number of men per shift includes the working foremen. The cost of staff
supervision—such as the assistant operating department manager‚ etc.—is assumed to be
included in our allowance for plant overhead.
Production costs, including prices of purchased materials, are generally intended to
represent mid-2006 cost factors at the U.S. Gulf Coast.

The total maintenance costs are estimated to be 4% of the battery limits investment. In each
case‚ we have assumed a 60-40 split between materials and labor.
Plant overhead has arbitrarily been assumed at 80% of total labor. It includes all staff
personnel located at the plant site‚ and services directly associated with plant operations and
maintenance.
G&A‚ sales‚ and research costs are assumed for each product by making allowances for the
stage of process development in estimating research expense‚ and for the character of marketing
channels and technical service requirements in estimating selling expense. These estimates are
customarily assigned a percentage of the sales value of the product‚ generally in the range of 3-
30%. When actual prices are unknown‚ we base the G&A‚ sales‚ and research expense on the
calculated product value (total production cost plus 25%/yr pretax return on fixed capital).
The cost of taxes and insurance is calculated at 2% of total fixed capital. Depreciation is
based on 10 %/yr of fixed capital.
Effect of Operating Level on Production Costs

Variations in production costs with plant capacity and with operating rate are based on the
following assumptions:
• The annual costs of process plant operating labor‚ control laboratory labor‚ and operating
materials are invariant with plant capacity. Also‚ the entire process plant labor force
remains on the payroll when the plant is operating at reduced capacity or is shut down.
• Investment-related items‚ including maintenance labor‚ maintenance materials‚ taxes‚ and
depreciation‚ are directly proportional to investment‚ and their annual cost remains
constant with reduced operating rate.
• Corporate overhead charges are constant to various plant capacities‚ and the annual
allocation is also constant‚ regardless of plant operating rate.
• Production costs generally do not include any allowance for packaging or shipping; i.e.‚
they represent bulk costs‚ fob plant.
• Working capital is not included in the fixed capital cost‚ nor are start-up costs. Interest on
working capital is not included in the production cost or in the product value.
• Royalties are not included in any of the estimates. Royalties for any given licensed
process may vary considerably‚ depending on terms of the agreement‚ geographic
location‚ etc. Initial payments or paid-up royalties may be substantial‚ and they should be
considered in specific estimates.
• Annual costs for raw materials and utilities are directly proportional to the annual plant
production.
In accordance with the last assumption‚ unit costs for raw materials and utility consumptions
do not change with either plant capacity or operating rate.
SAFETY AND HANDLING

Methanol is moderately toxic by inhalation or oral ingestion. Once introduced into the human
body, it is gradually metabolized and expelled. The maximum allowable concentration in air, for
an 8- hour exposure, is 0.02 vol%. A concentration of 5% for one or two hours can cause death.
There is no evidence that methanol is carcinogenic.

GENERAL EQUIPMENT SIZING AND PROCESS SIMULATION METHODOLOGIES
The sizing of miscellaneous process equipment items was primarily based on design
guidelines and calculation methodologies described by Walas. Vendors were consulted on the
design of reactors and some of the larger, critical process equipment items.
Aspen Plus 2006 was used to develop integrated whole-plant process simulation models
within battery limits. Vapor-liquid equilibrium calculation methods were based on RK-ASPEN.
Thermophysical property routes were selected to help assure proper calculation of three phase
separation and aqueous-phase heat capacities. The Nested Broyden convergence method was
used in the simulation of fractionation columns via RadFrac models. Equilibrium reactor models
were used for the DME reactor. The predicted reaction equilibria were selectively spot-checked
and partially validated against available literature data.

Appendix C
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transformation into hydrocarbons on the HZSM-5 zeolite. Chemical
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spectroscopic investigation of the conversion of methanol to olefins on
silicoaluminophosphates SAPO-34 and SAPO-18 under continuous flow
conditions Catal.Lett., 74, 1/2, 61-68, 2001.
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methylnaphthalenes in HSAPO-34 cages and their function as reaction
centers in methanol-to-olefin catalysis. J. Phys. Chem. B., 105, 51,
12839 - 12843, 2001.

Accession Number
261A064 Weiguo Song, John B. Nicholas, and James F. Haw. A persistent
carbenium ion on the methanol-to-olefin catalyst HSAPO-34: acetone
shows the way. J. Phys. Chem. B., 105, 19, 4317 - 4323, 2001.
261A065 Bjrnar Arstad and Stein Kolboe. The reactivity of molecules trapped
within the SAPO-34 cavities in the methanol-to-hydrocarbons reaction
J.Am.Chem.Soc., 123, 33, 8137 – 8138, 2001.
261A066 Weiguo Song, Hui Fu, and James F. Haw. Supramolecular origins of
product selectivity for methanol-to-olefin catalysis on HSAPO-34.
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261A067 Xianchun Wu and R. G. Anthony. Effect of feed composition on
methanol conversion to light olefins over SAPO-34. Appl.Catal. A:
General, 218, 1/2, 241-250, 2001.
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olefins (MTO) process in a circulating fluidized bed reactor. Fuel, 80, 8,
1187-1197, 2001.
261A069 Hui Fu, Weiguo Song, James F. Haw. Polycyclic aromatics formation in
HSAPO-34 during methanol-to-olefin catalysis: ex situ characterization
after cryogenic grinding. Catal.Lett., 76, 1/2, 89-94, 2001.
261A070 Bjørnar Arstad, Stein Kolboe. Methanol-to-hydrocarbons reaction over
SAPO-34. Molecules confined in the catalyst cavities at short time on
stream. Catal.Lett., 71, 3/4, 209-212, 2001.
261A071 M.G. Abraha, X.Wu, R.G.Anthony. Effects of particle size and modified
SAPO-34 on conversion of methanol to light olefins and dimethyl ether
Reaction Kinetics and the Development and Operation of Catalytic
Processes, Eds.G.F. Froment, K.C. Waugh,, Amsterdam e.a., Elsevier,
Stud.Surf.Sci.Catal., v.133, 211-220, 2001.
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Français des Zéolithes, 2001.
261A073 D. Chen, H. P. Rebo, A. Grønvold, K. Moljord and A. Holmen Methanol
conversion to light olefins over SAPO-34: kinetic modeling of coke
formation Micropor.Mesopor.Mater., 35/36, 121-135, 2000.
261A074 Marie-Ange Djieugoue, A. M. Prakash, and Larry Kevan Catalytic study
of methanol-to-olefins conversion in four small-pore
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261A075 Misook Kang Methanol conversion on metal-incorporated SAPO-34s
(MeAPSO-34s). J.Molec.Catal. A: Chemical, 160, 2, 437-444, 2000.

Accession Number
261A076 J. M. Campelo, F. Lafont, J. M. Marinas and M. Ojeda Studies of catalyst
deactivation in methanol conversion with high, medium and small pore
silicoaluminophosphates Appl.Catal. A: General, 192, 1, 85-96, 2000.
261A077 Weiguo Song, James F. Haw, John B. Nicholas, and Catherine S.
Heneghan Methylbenzenes are the organic reaction centers for
methanol-to-olefin catalysis on HSAPO-34 J.Am.Chem.Soc., 122, 43,
10726 - 10727, 2000.
261A078 Ana G. Gayubo, Andrés T. Aguayo, Ana E. Sánchez del Campo, Ana M.
Tarrío, and Javier Bilbao Kinetic modeling of methanol transformation
into olefins on a SAPO-34 catalyst Ind. Eng. Chem. Res., 39, 2, 292 –
300, 2000.
261A079 Andrés T Aguayo , Ana G Gayubo, Alaitz Atutxa, Martin Olazar, Javier
Bilbao. Regeneration of a catalyst based on a SAPO-34 used in the
transformation of methanol into olefins J. Chem.Technol. Biotechnol.,
74, 11, 1082-1088, 1999.
261A080 Andrés T Aguayo, Ana E Sánchez del Campo, Ana G Gayubo , Ana
Tarrío, Javier Bilbao. Deactivation by coke of a catalyst based on a
SAPO-34 in the transformation of methanol into olefins J.
Chem.Technol. Biotechnol., 74, 4, 315-321, 1999.
261A081 Misook Kang and Chul-Tae Lee. Synthesis of Ga-incorporated SAPO-
34s (GaAPSO-34) and their catalytic performance on methanol
conversion. J.Molec.Catal. A: Chemical, 150, 1/2, 213-222, 1999.
261A082 Misook Kang. Synthesis and catalytic performance on methanol
conversion of NiAPSO-34 crystals (II): catalytic performance under
various reaction conditions. J.Molec.Catal. A: Chemical, 150, 1/2, 205-
212, 1999.
261A083 Misook Kang, Myeong-Heon Um and Jong-Yul Park. Synthesis and
catalytic performance on methanol conversion of NiAPSO-34 crystals (I):
effect of preparation factors on the gel formation. J.Molec.Catal. A:
Chemical, 150, 1/2, 195-203, 1999.
261A084 Misook Kang and Tomoyuki Inui. Synthesis of NiAPSO-34 catalysts
containing a larger concentration of Ni and effect of its sulfidation on
methanol conversion. J.Molec.Catal. A: Chemical, 144, 2, 329-335,
1999.
261A085 Misook Kang and Tomoyuki Inui. Dynamic reaction characteristics
affected by water molecules during the methanol to olefin conversion on
NiAPSO-34 catalysts. J.Molec.Catal. A: Chemical, 140, 1, 55-63, 1999.
261A086 De Chen, Kjell Moljord, Terje Fuglerud and Anders Holmen. The effect
of crystal size of SAPO-34 on the selectivity and deactivation of the MTO
reaction. Micropor.Mesopor.Mater., 29, 1/2, 191-203, 1999.
261A087 Stephen Wilson and Paul Barger. The characteristics of SAPO-34 which
influence the conversion of methanol to light olefins. Micropor. Mesopor.
Mater., 29, 1/2, 117-126, 1999.

Accession Number
261A088 Masashi Inoue, Pongtorn Dhupatemiya, Suphot Phatanasri and
Tomoyuki Inui. Synthesis course of the Ni-SAPO-34 catalyst for
methanol-to-olefin conversion. Micropor. Mesopor. Mater., 28, 1, 19-24,
1999.
261A089 De Chen, Hans Petter Rebo and Anders Holmen. Diffusion and
deactivation during methanol conversion over SAPO-34: a percolation
approach. Chem.Eng.Sci., 54, 15/16, 3465-3473, 1999.
261A090 D. Chen, H. P. Rebo, K. Moljord, and A. Holmen. Methanol conversion
to light olefins over SAPO-34. Sorption, diffusion, and catalytic reactions.
Ind.Eng.Chem.Res., 38, 11, 4241 – 4249, 1999.
261A091 A.G. Gayubo et al. The role of water on the attenuation of coke
deactivation of a SAPO-34 catalyst in the transformation of methanol
into olefins. Catalyst Deactivation 1999, Eds.B. Delmon, G.F. Froment,
Amsterdam e.a., Elsevier, Stud.Surf.Sci.Catal., v.126, 1999.
261A092 Stocker, M. Methanol-to-hydrocarbons: catalytic materials and their
behaviour. Microporous Mesoporous Materials, 29, 3-48, 1999.
261A093 Keil, F.J., Methanol-to Hydrocarbons: Process Technology, Microporous
nd Mesoprous Materials, vol. 29, 49-66, 1999.
261A094 T.Inui, M.Kang, Y.Nomura. Significant roles of substituted iron-group
metal ions in SAPOs for exhibiting high catalytic performance of
th
selective olefin synthesis from methanol. Proc. 12 Intern.Zeolite Conf.,
Eds.M.M.J.Treacy e.a., MRS, Warrendale, v.2, 1345-1350, 1999.
261A095 M. Popova, Ch. Minchev and V. Kanazirev. Methanol conversion to light
alkenes over SAPO-34 molecular sieves synthesized using various
sources of silicon and aluminium. Appl.Catal. A: General, 169, 2, 227-
235, 1998.
261A096 Ana E. Sánchez del Campo, Ana G. Gayubo, Andrés T. Aguayo, Ana
Tarrío, and Javier Bilbao. Acidity, surface species, and mechanism of
methanol transformation into olefins on a SAPO-34. Ind.Eng.Chem.Res.,
37, 6, 2336 - 2340, 1998.
261A097 Andreas Philippou, Fathollah Salehirad, Donat-Pierre Luigi, Michael W.
Anderson. Investigation of surface methoxy groups on SAPO-34. A
combined magic-angle turning NMR experimental approach with
theoretical studies. JCS Faraday Trans., 94, 18, 2851-2856, 1998.
261A098 Tajima, N.; Tsuneda, T.; Toyama, F.; Hirao, K. A new mechanism for the
first carbon-carbon bond formation in the MTG process: A theoretical
study. J. Am. Chem. Soc., 120, 8222-8229, 1998.
261A099 T. Inui and M. Kang. Reliable procedure for the synthesis of Ni-SAPO-34
as a highly selective catalyst for methanol to ethylene conversion.
Appl.Catal. A: General, 164, 1/2, 211-223, 1997

Accession Number
261A100 D. Chen et al. The role of coke deposition in the conversion of methanol
to olefins over SAPO-34. Catalyst Deactivation 1997, Eds.C.H.
Bartholomew, G.A. Fuentes, Amsterdam e.a., Elsevier,
Stud.Surf.Sci.Catal., v.111, 159-168, 1997.
261A101 Blaszkowski, S. R.; van Santen, R. A. Theoretical study of C-C bond
formation in the methanol-to-gasoline process. J. Am. Chem. Soc., 119,
5020-5027, 1997.
261A102 J. W. Wilson. Fluid catalytic cracking technology and operation.
PennWell Publishing Company, 1997.
261A103 M. J. Van Niekerk, J. C. Q. Fletcher and C. T. O'Connor. Effect of
catalyst modification on the conversion of methanol to light olefins over
SAPO-34. Appl.Catal. A: General, 138, 1, 135-145, 1996.
261A104 Fathollah Salehirad and Michael W. Anderson. Solid-state13C MAS NMR
study of methanol-to-hydrocarbon chemistry over H-SAPO-34. J.Catal.,
164, 2, 301-314, 1996.
261A105 Ivar M. Dahl and Stein Kolboe. On the reaction mechanism for
hydrocarbon formation from methanol over SAPO-34: 2. Isotopic
labeling studies of the co-reaction of propene and methanol. J.Catal.,
161, 1, 304-309, 1996.
261A106 L.Smith, A.K.Cheetham e.a. A quantitative description of the active sites
in the dehydrated acid catalyst HSAPO-34 for the conversion of
methanol to olefins. Catal.Let, 41, 1/2, 13, 1996.
261A107 Benito, P. L.; Gayubo, A. G.; Aguayo, A. T.; Olazar, M.; Bilbao, J.
Concentration-Dependent Kinetic Model for Catalyst Deactivation in the
MTG process. Ind. Eng. Chem. Res., 35, 81, 1996.
261A108 A. N. Rene Bos, Peter J. J. Tromp, and Henk N. Akse. Conversion of
methanol to lower olefins. Kinetic modeling, reactor simulation, and
selection. Ind.Eng.Chem.Res., 34, 11, 3808 - 3816, 1995.
261A109 I.M. Dahl and S.Kolboe. On the reaction mechanism for hydrocarbon
formation from methanol over SAPO-34 : I. Isotopic labeling studies of
the co-reaction of ethene and methanol. J.Catal., 149, 2, 458-464, 1994.
261A110 J.Chen, P.A.Wright, S.Natarajan, J.M.Thomas. Understanding the
Broensted acidity of SAPO-5, 17, 18, 34 and their catalytic performance
for CH3OH conversion to hydrocarbons. Zeolites and Related
Microporous Materials: State of the Art 1994, Stud.Surf. Sci. Catal., 84C,
Eds.J.Weitkamp e.a., 1731-1738, Amsterdam e.a., Elsevier, 1994.
261A111 S. Hocevar, J. Batista and V.Kaučič. Acidity and catalytic activity of
MeAPSO-44 (Me = Co, Mn, Cr, Zn, Mg), SAPO-44, AIPO4-5, and AIPO4-
14 molecular sieves in methanol dehydration. J.Catal., 139, 2, 351-361,
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© SRI Consulting C - 10 PEP Report 261

Accession Number
261A112 S.Hocevar, J.Levec. Acidity and catalytic activity of MeAPSO-34 (Me =
Co, Mn, Cr), SAPO-34, and H-ZSM-5 molecular sieves in methanol
dehydration. J.Catal., 135, 2, 518-532, 1992.
261A113 S.Hocevar, J. Batista, V.Kaučič. Selectivity of transition metal substituted
MeAPSO-34 and MeAPSO-44 (Me = Mg, Cr, Mn, Co, Zn) molecular
sieves in methanol dehydration reaction. Ninth Intern.Zeolite Conf.,
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Heinemann, 1992.
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alkenes on SAPO molecular sieves. Appl.Catal., 71, 1, 139-152, 1991.
261A115 Dehertog, W.J.H., and G.F. Froment. "Production of Light Alkenes from
Methanol on ZSM-5 Catalysts." Applied Catalysis. Vol. 71: 1, 153-165,
1991.
261A116 J.Chen, J.M.Thomas. Synthesis of SAPO-41 and SAPO-44 and their
performance as acidic catalysts in the conversion of methanol to
hydrocarbons. Catal.Lett., 11, 2, 199-208, 1991.
261A117 J. M. Thomas, Y. Xu, C. R. A. Catlow, and J. W. Couves. Synthesis and
characterization of a catalytically active nickel silicoaluminophosphate
catalyst for the conversion of methanol to ethane. Chem.Mater., 3, 4,
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Klinowski. In situ solid-state NMR studies of the catalytic conversion of
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- 2734, 1990.
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and Muliang Ying. Characteristics and performance of SAPO-34 catalyst
for methanol-to-olefin conversion. Appl.Catal. 64, 1/2, 31-40, 1990.
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binding of CH3OH prior to carbon-carbon bond formation during the
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conversion of methanol to hydrocarbons over a SAPO-34 catalyst using
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Preparation of silico-alumino-phosphates by the rapid crystallization
method and their catalytic performance in the conversion of methanol to
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from methanol on a novel nickel-silicoaluminophosphate catalyst. JCS
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Accession Number
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Methanol Conversion to Olefins, Ind. Eng. Chem. Process Des. DeV.,
22, 532, 1983.
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(Total No. 120), Oct. 2005.

Appendix D
PROCESS FLOW DIAGRAMS
Figure 4.2 (Sheet 1 of 2)
METHANOL TO OLEFINS BY THE
UOP/HYDRO PROCESS
METHANOL CONVERSION SECTION
365 psia 10
38°C
Vent Gas
E-108 E-109 E-110 360 psia Vapor Stream
410°C 8
45 psia 600°C CW CW CW
to C-201
5 50 psia
3
V-102
7°C
6 K-102 K-102 K-102 90 psia
9 12
38°C
12 C-103
35 psia
R-101 R-102 1 LP
10
Steam
C-101 E-106 57°C E-111

E-105 LP C4+ Stream
Waste Water 11
1 CW Steam
Crude 143°C to C-206
153°C
Methanol 45°C BFW
80 psia
1
4 122°C E-104 V-101
15
48
LP Air 226°C
T-151 107°C
Steam 2 55 psia
E-103
A-F 7 13 C-102
116°C
E-101 E-102 50 psia K-101
125°C 1
LP
14
Steam
159°C E-107
T-151 A-F R-101 R-102 C-101 C-102 V-102 C-103

Crude Methanol Fluidized Reactor Regenerator Quench Tower Water Stripper Phase Separator Condensate
Tanks Stripper
K-101 E-104 K-102
Air Compressor Air-Cooled Product Compressor
Exchanger (Stages 1-3)
PEP Report 261

2007
D-3
METHANOL TO OLEFINS BY THE
UOP/HYDRO PROCESS
PRODUCT SEPARATION SECTION
Tail Gas
to Fuel
E-209
-61°C
-4°C 5°C 455 psia E-207 Ethylene
24
475 psia E-204 -12°C C3H6 Product
22 450 psia Refr.
LP C2H4
K-102 -100°C
Steam Refr.
(4th Stage) E-205 97 V-203
80°C E-206
20 V-202
C3H6
T-251 A-C Regeneration Refr.
Gas C-205
20 R-201 -20°C
C-204 23
Process E-208 E-202 1
Water
C3H6
-28°C E-208 1
Refr.
Aqueous 38°C 85°C
-23°C C3H6 Vapor
Caustic Soda 355 psia Refr.
17 350 psia -11°C E-210
12°C Ethane
16 30 25
36
V-201 By-Product
C-201 C-202 50°C

A&B 300 psia
10°C C-203 E-214
E-211
1 CW
Vapor Stream C3H6 E-201 1 LP 58°C
8 Refr. Steam
CW V-205
from V-102 350 psia
22°C V-204 190 Propylene
95 29
E-203 44
18 Product
27
19 67°C
Spent NaOH to C-206
21 26 C-207 A C-207 B
Waste Treatment
11 1 LP
Steam
C4+ Stream 1 LP 96
126°C E-212 Steam
from C-103
E-213 28 C4+ 59°C E-215

CW By-Product Propane
30
By-Product
C-201 C-202 A&B C-203 R-201 C-204 C-205

Caustic Scrubber Gas Dryers Deethanizer Acetylene Demethanizer C2 Splitter
Converter
T-251 A-C C-207 A&B
C-206
Aqueous Caustic C3 Splitter
Depropanizer
Soda Tanks
PEP Report 261

2007
D-5
METHANOL TO PROPYLENE BY THE LURGI
MTP PROCESS
METHANOL CONVERSION
6
Methanol E-101 E-102 E-103 O
O O
85 C 105 C 260 C
1 40OC
P-106 470OC
Waste Water R-101 To Train 2

R-102
To Offsites O
75 C
P-105
H-101
14 3
2
O
300 C
18.7 psig
115OC 240OC 9
21.6 psig
7
From Train 2 Fuel Air
4
C-101 10
85OC
1 E-104
10
LP 452OC
Steam O
390 C
E-105
128OC
HP
16 Steam
K-101
42OC
1.2 psig
80OC
80OC 101.3 psig
10 28.8 psig
12 13 E-110 E-111 LP Steam
E-108 E-109 cw E-112
C-102 cw cw
H6C3 NNF
cw Ref To C-203
15OC
E-107 333.3 psig
To C-206 1
From C-206 15 V-103 V-104 V-105
Light Recycles From
C-203 & C-205 O 18 20 22 21 To C-203
48 C
5 O
41 C
E-106 P-104
19 To C-203
O
95 C P-103
11 17 To C-203
P-101 P-102
C-101 C-102 R-101 V-103 K-101 V-104 V-105 R-102 H-101

Methanol Quench DME Stage 1 KO MPT Stage 2 KO Stage 3 KO MTP Reactors MTP Recycle
Stripper Tower Reactor Drum Effluent Drum Drum Heater
Compressor
PEP Report 261

2007
D-7
METHANOL TO PROPYLENE BY THE LURGI
MTP PROCESS
PROPYLENE RECOVERY
C4 - C6 Recycle
Recycle to 5 24 25 C1 - C2 Purge
E-106 E-225
C1 - C2 Recycle
cw
10OC
49OC
275 psig
V-213
160
Propylene
C-206 32
Product
P-209
1
Methanol
E-107
23
28
65OC Propane
33
By-Product
E-216 E-221
52OC
E-218 C3H6 Ref cw
E-222
49OC
30
V-207 O cw
-25 C V-209
333 psig 290 psig 58 psig
V-211
E-219
63
From V-105 21 70 35
P-206 P-207
From V-105
43
19 31 C4 - C6 Purge
From V-104 C-203 C-204 C-205
P-208
1 1 1
From V-103 17 LP LP
Steam Steam MP
E-220 Steam
E-217
E-223
109OC 132OC 149OC
E-224
45OC Gasoline
26 27 29
By-Product
cw
C-203 V-207 C-204 V-209 C-206 C-205 V-211 V-213

De-ethanizer De-ethanizer Depropanizer Depropanizer Propylene Dehexanizer Dehexanizer Propylene
Reflux Drum Column Reflux Drum Column Column Reflux Drum Reflux Drum
PEP Report 261

2007
D-9

Methanol To Olefin

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Abstract

Process Economics Program Report 261

© SRI Consulting PEP Report 261

A private report by the

SR I Menlo P ark, C alifornia 94025

1 INTRODUCTION ........................................................................................................ 1-1

2 SUMMARY ................................................................................................................. 2-1

GENERAL ASPECTS................................................................................................. 2-1

TECHNOLOGY ASPECTS......................................................................................... 2-2

Commercial Methanol to Olefins Technology ........................................................... 2-2

Analysis of Patents ..................................................................................................... 2-2

Process Design .......................................................................................................... 2-3

PROCESS ECONOMICS........................................................................................... 2-4

Methanol to Ethylene and Propylene ......................................................................... 2-4

Methanol to Propylene................................................................................................ 2-4

CONCLUSIONS ......................................................................................................... 2-6

3 INDUSTRY STATUS.................................................................................................. 3-1

ETHYLENE INDUSTRY ............................................................................................. 3-1

Ethylene Feedstock Considerations........................................................................... 3-4

Ethylene End Uses ..................................................................................................... 3-5

Ethylene Supply and Demand .................................................................................... 3-7

Ethylene Prices........................................................................................................... 3-8

PROPYLENE INDUSTRY .......................................................................................... 3-8

Propylene Transportation and Storage ...................................................................... 3-11

Propylene End Uses................................................................................................... 3-11

Supply and Demand of Propylene.............................................................................. 3-13

Propylene Prices ........................................................................................................ 3-14

Production of Primary Propylene................................................................................ 3-16

Propylene from Ethylene Plants ................................................................................. 3-18

Propylene from Refineries .......................................................................................... 3-19

© SRI Consulting iii PEP Report 261

Production of Secondary Propylene........................................................................... 3-20

Propane Dehydrogenation.......................................................................................... 3-21

Metathesis .................................................................................................................. 3-23

Methanol to Propylene................................................................................................ 3-26

METHANOL TO OLEFINS ......................................................................................... 3-28

Olefin Cracking ........................................................................................................... 3-29

R&D Activities by ExxonMobil .................................................................................... 3-30

DMTO Technology ..................................................................................................... 3-30

METHANOL AS FEEDSTOCK................................................................................... 3-31

Regional Capacity Trends .......................................................................................... 3-32

Methanol Prices .......................................................................................................... 3-35

Methanol Shipping...................................................................................................... 3-36

4 UOP/HYDRO MTO PROCESS .................................................................................. 4-1

INTRODUCTION ........................................................................................................ 4-1

COMMERCIAL DEVELOPMENTS ............................................................................ 4-1

Recent Advancements in UOP/Hydro MTO Technology ........................................... 4-3

TECHNOLOGY REVIEW ........................................................................................... 4-4

MTO Catalyst Development ....................................................................................... 4-4

MTO Reactor Design Consideration .......................................................................... 4-6

MTO Process Chemistry and Kinetics........................................................................ 4-12

© SRI Consulting iv PEP Report 261

Kinetic Models based on ZSM-5 .......................................................................... 4-12

Product Recovery ....................................................................................................... 4-15

METHANOL TO OLEFINS BY THE UOP/HYDRO PROCESS ................................. 4-15

Process Description.................................................................................................... 4-16

Process Discussion .................................................................................................... 4-29

COST ESTIMATES .................................................................................................... 4-32

Comparison With Other Technologies ....................................................................... 4-43