Air Product and Chemical Report Task2

DOE/PC/89865-T7
(DE93013075)
DistributionCategory UC-108
SYNTHESIS OF PIMETHYL ETHER AND ALTERNATIVE FUELS IN THE

LIQUID PHASE FROM COAL-DERIVED SYNTHESIS GAS
Topical Report
Task 3.2: Screen Novel Catalyst Systems

Task 3.3: Evaluation of the Preferred Catalyst System
Contractor
AIR PRODUCTS AND CHEMICALS, INC.

Allentown, PA 18195-1501
Richard P. Underwood
January, 1993
Prepared for the United States Department of Energy

Under Contract No. DE-AC22-90PC89865
Contract Period December 1989--February1993
Contents
List of Figures ........................................................................................................... i
List of Tables .......................................................................................................... ii
Executive Summary ...................................................................................................... iii
1.0 BACKGROUND ................................................................................................... 1

1.1 One-Step, Slurry-Phase Syngas Conversion to Hydrocarbons
or Methanol/Hydrocarbon Mixtures .............................................................. 1
1.2 Slurry-Phase Conversion of Syngas to Mixed Alcohols ................................. 2
1.3 One-Step, Slurry-Phase Syngas Conversion to Mixed Ethers ........................ 4
2.0 EXPERIMENTAL ................................................................................................ 5

2.1 Apparatus ...................................................................................................... 5
2.2 Catalyst Materials ......................................................................................... 5
3.0 RESULTS AND DISCUSSION ............................................................................ 9

or Methanol/Hydrocarbon Mixtures .............................................................. 9
3.1.1 Reaction Liquid Studies ..................................................................... 9
3.1.2 Surface-Passivation of HZSM-5 ...................................................... 12
3.1.3 Slurry-Phase Methanol Conversion to Hydrocarbons ....................... 12
3.1.4 One-Step Syngas Conversion over Cu/ZnO/A1203-HZSM-5
Mixture ............................................................................................ 15
3.2 Slurry-Phase Conversion of Syngas to Mixed Alcohols ............................... 17
3.2.1 Cu/ZnO/A1203 and Cesium-promoted Cu/ZnO/A1203 ................... 17
3.2.2 Lurgi Octamix Mixed Alcohols Catalyst .......................................... 35
3.2.3 Cu-Co Mixed Alcohols Catalyst ...................................................... 40
3.2.4 Two-Component Catalyst Systems .................................................. 52
3.2.5 Comparison of Mixed Alcohols Catalysts ........................................ 55
3.3 Slurry-Phase Conversion of Syngas to Mixed Ethers via Mixed Alcohols ... 57
3.3.1 Product Identification ...................................................................... 57
3.3.2 Dehydration of Three-component Mixed Alcohols Streams ............. 58
3.3.3 One-Step Conversion of Syngas to Mixed Ethers ............................. 64
4.0 SUMMARY AND RECOMMENDATIONS ....................................................... 73

or Methanol/Hydrocarbon Mixtures ............................................................ 73
4.2 Slurry-Phase Conversion of Syngas to Mixed Alcohols ............................... 75
4.3 Slurry-Phase Conversion of Syngas to Mixed Ethers via Mixed Alcohols ... 76
REFERENCES ........................................................................................................ 77
List of Figures
Figure Title Page
2-1 Flow Schematic of Micro-Autoclave Reactor ...................................................... 6

3-1 Comparison of Liquid Stability ......................................................................... 10
3-2 Comparison of Liquid Stability ......................................................................... 11
3-3 Comparison of Decalin Stability for HZSM-5 and Surface-Passivated HZSM-5 13
3-4 Slurry Phase Methanol Conversion to Hydrocarbons ........................................ 14
3-5 Slurry Phase Methanol Conversion to Hydrocarbons ........................................ 16
3-6 Effect of GHSV on Product Rates ..................................................................... 18
3-8 Effect of GHSV on Alcohol Product Distribution ............................................. 21
3-14 Effect of Temperature on Product Rates ............................................................ 29
3-16 Effect of Temperature on Alcohol Product Distribution ............................ ,....... 32
3-17 Effect of Temperature on Alcohol Product Distribution .................................... 33
3-18 Effect of On-Stream Time on Product'Rates ..................................................... 36
3-20 Effect of Temperature on Product Selectivities ................................................. 38
3-21 Alcohol Product Distribution ............................................................................ 39
3-23 Effect of Pressure on Product Selectivities ........................................................ 42
3-24 Effect of Syngas Composition on Product Rates ............................................... 43
3-25 Effect of Syngas Composition on Product Selectivities ..................................... 44
3-26 Effect of On-Stream Time on Product Rates ..................................................... 45
3-27 Effect of GHSV on Product Rates and Selectivities .......................................... 46
3-28 Alcohol Product Distribution ............................................................................ 48
3-29 Effect of GHSV on Product Rates and Selectivities .......................................... 49
3-30 Effect of Temperature on Product Rates and Selectivities ................................. 50
3-31 Effect of Pressure on Product Rates and Selectivities ........................................ 51
3-32 Comparison of Performance of Two-Component Catalyst Systems ................... 53
3-33 Comparison of Alcohols Product Distribution for Cu/ZnO/A1203 and
Cu/ZnO/AI203 + 5% Rh/La203 ...........................................................................................................................
54
3-34 Correlation of FID Response Factors for Ethers and Paraffins ......................... 59
3-35 Effect of AI_O3 Fraction on Product Rates ........................................................ 65
3-36 Effect of AI203 Fraction on Product Selectivities .............................................. 66
3-37 Proposed Reaction Scheme for Synthesis of DME and C3,-Ethers ..................... 67
3-38 Measured and Predicted Ether Product Distributions ......................................... 69
List of Tables
Table Title Page
1-1 Optimal Ranges of Operating Conditions for Gas-to-Gasoline Process ................ 2

1-2 Average Blended Octane Numbers for Selected Alcohols ................................... 3
1-3 Heats of Reaction for Synthesis of Selected Alcohols from CO and 1-12x
CO + 2xI_ = CxH2_.tOH + (x-1)I-I20 ................................................................... 3
3-1 Slurry-Phase Syngas Conversion to Methanol/Hydrocarbons ............................ 15
3-2 Composition of Shell and Texaco Syngas ......................................................... 17
3-3 Methanol/Cosolvent Alcohols Product Distribution for Cs-eu]ZnO/A1203 ................ 28
3-a Effect of Feed Addition of Methanol and Ethanol for CtffZnO/A1203............................... 31
3-5 Effect of Feed Addition of Methanol and Ethanol for Cu/ZnO/A1203 ............................... 34
3-6 Comparison of Measured Product Rates for Cs-Cu/ZnO/A1203, Lurgi Octamix,
and Cu-Co Catalysts ......................................................................................... 55
3-7 Comparison of Measured Product Rates for Cs-Cu/ZnO/A1203, Lurgi Octamix,
and Cu-Co Catalysts ......................................................................................... 56
3-8 Expected Ether Products from Condensation of Methanol, Ethanol,
1-Propanol, 1-Butanol, and Isobutanol .............................................................. 57
3-9 Composition of Alcohol Mixtures Used in Alcohol Dehydration Experiments .. 58
3-10 Expected Ether Products from Direct, Intermolecular Condensation of
Alcohol Mixtures
3-11 Conversion and Selectivity for Reaction of Alcohol Mixture 11168-71 ............. 61
3-12 Conversion and Selectivity for Reaction of Alcohol Mixture 11168-73 ............. 61
3-13 Ether Product Distribution for Reaction of'Alcohol Mixture 11168-71 ............. 62
3-14 Ether Product Distribution for Reaction of Alcohol Mixture 11168-73 ............. 63
3-15 Effect of Reaction Time on Major Product Rates .............................................. 71
Executive Summary
As part of the DOE-sponsored contract "Synthesis of Dimethyl Ether and Alternative Fuels in the
Liquid Phase from Coal-Derived Syngas" (Contract No. DE-AC22-90PC89865), experimental
evaluations of the one-step synthesis of alternative fuels were carried out. The objective of this
work was to develop novel processes for converting coal-derived syngas to fuels or fuel additives.
Building on a technology base acquired during the development of the Liquid Phase Methanol
(LPMEOH) process, this work focused on the development of slurry reactor based processes.
The experimental investigations, which involved bench-scale reactor studies, focused primarily on
three areas:
1. One-step, slurry-phase syngas conversion to hydrocarbons or methanol/hydrocarbon mixtures

using a mixture of methanol synthesis catalyst and methanol conversion catalyst in the same
slurry reactor.
2. Slurry-phase conversion of syngas to mixed alcohols using various catalysts.
3. One-step, slurry-phase syngas conversion to mixed ethers using a mixture of mixed alcohols
synthesis catalyst and dehydration catalyst in the same slurry reactor.
The experimental results indicate that, of the three types of processes investigated, slurry phase
conversion of syngas to mixed alcohols shows the most promise for further process development.
Evaluations of various mixed alcofiols catalysts show that a cesium-promoted Cu/ZnO/A1203
methanol synthesis catalyst, developed in Air Products' laboratories, has the highest performance in
terms of rate and selectivity for Cz.-alcohols. In fact, once-through conversion at industrially
practical reaction conditions yielded a mixed alcohols product potentially suitable for direct gasoline
blending. Moreover, an additional attractive aspect of this catalyst is its high selectivity for
branched alcohols, potential precursors to iso-olefins for use in etherification.
iii
1.0 BACKGROUND
The objective of this task was to experimentally evaluate novel processes for converting coal-
derived synthesis gas to fuel oxygenates. Building on a technology base acquired during the
development of the LPMEOH process, the present work focused on developing slurry reactor based
processes.
Tile experimental investigations focused primarily in three areas:
1. One-Step, Slurry-Phase Syngas Conversion to Hydrocarbons or Methanol/Hydrocarbon

Mixtures
2. Slurry-Phase Conversion of Syngas to Mixed Alcohols
3. One-Step, Slurry-Phase Syngas Conversion to Mixed Ethers
1.1 One-Step, Slurry-Phase Syngas Conversion to Hydrocarbons or

Methanol/Hydrocarbon Mixtures
.._
The New Zealand Synthetic Fuels Corporation currently converts syngas, derived from natural gas
reforming, to gasoline via intermediate methanol:
CO + 1-12 -_ CI-I3OH
CI-I3OH _ gasoline.
In this process, the overall conversion is done in three steps in three separate reactors: (1) syngas
conversion to methanol using a Cu/ZnO/A1203 catalyst; (2) methanol dehydration to a mixture of
methanol and dimethyl ether using an A1203catalyst; and (3) conversion of the methanol/dimethyl
ether mixture to gasoline over HZSM-5 zeolite. 1 All three steps are done using packed bed reactors.
The focus of the present work was to evaluate the possibility of combining these reaction steps in
one slurry reactor by using a mixed catalyst system consisting of Cu/ZnO/A1203 methanol synthesis
catalyst and HZSM-5. Combining the reaction steps in this manner has the potential to save
considerable capital costs by reducing the number of reactors required for the overall conversion. In
addition, the overall conversion of syngas to gasoline releases a large quantity of heat:
approximately 2800 j/(g methanol) for methanol synthesis and 1250-2000 j/(g product) for
methanol conversion. The highly exothermic nature of the overall conversion makes this reaction
scheme well suited for a slurry reactor, which affords excellent heat management capabilities. One-
step conversion in a packed bed reactor probably would not be feasible because of the high heat
release.
The proposed process is a way of converting coal-derived syngas to gasoline in one step.
Alternatively, the process could be operated to produce mixtures of methanol and gasoline-range
hydrocarbons which may also be useful as a transportation fuel. The possibility exists that
hydrocarbons present in methanol fuel may enhance the properties of the methanol fuel (e.g., better
cold-starting, flame luminosity, etc.).
There are two key challenges in making the proposed one-step process economically viable. First,
since selectivity and productivity for each reaction step involved in the overall conversion depend
uniquely on reaction conditions, the reaction steps optimally operate at different temperatures and
pressures. Table 1-1 shows typical operating temperatures and pressures for the three reaction steps
in the gas-to-gasoline process. 2_
TABLE 1-1
Optimal Ranges of Operating Conditions for Gas-to-Gasoline Process
Temperature Pressure
Reaction Step _ (°C) (atm)
methanol synthesis 250-300 50-100
methanol dehydration 300-420 15-25
gasoline synthesis 350--420 15-25
In view of Table 1-1, operation of ali three reaction steps at the same conditions would necessarily
entail operation at a condition which is not ideal for ali three reactions, thus requiring a compromise.
However, a synergism is anticipated if ali three reactions are done concurrently. Specifically, in-situ
reaction of methanol to hydrocarbons will alleviate the constraint that thermodynamic equilibrium
imposes on the extent of conversion of syngas to methanol. The net performance will depend on the
opposing effects of a compromise in reaction conditions and the advantages of the reaction
synergism.
The second key challenge in the development of this process is identifying a slurry liquid that is
compatible with the methanol synthesis catalyst and also stable in the presence of the highly acidic
zeolite. Previous studies of slurry liquids done during the development of the LPMEOH process
have shown that only certain types of slurry liquids are compatible with the Cu/ZnO/AI:O 3 methanol
synthesis catalyst/ The preferred liquids for the methanol synthesis process consist of saturated
hydrocarbons of paraffinic and/or naphthenic structure. However, such compounds are subject to
acid-catalyzed cracking in the presence of HZSM-5, which is a very effective cracking catalyst. The
extent to which some potential slurry liquids cracked in the presence of zeolite was investigated in
the present study. From these liquid stability studies, a preferred slurry liquid was identified and
methanol conversion to hydrocarbons over HZSM-5 was done in a slurry reactor. In addition, the
overall conversion of syngas was done using Cu/ZnO/AI:O 3and HZSM-5 in the same reactor.
1.2 Slurry-Phase Conversion of Syngas to Mixed Alcohols
Alcohols are known to be effective oxygenated gasoline components. Table 1-2, which shows the
average of the research and motor octane numbers for some alcohols, 5 indicates that CI-C 4alcohols
are good octane improvers.
- t _.....
TABLE 1-2
Average Blending Octane Numbers for Selected Alcohols
Blending Octane
Alcohol (R+M)/2
methanol 115
ethanol 113
1-propanol 105
isobutanol 101
Studies have also shown that the use of mixed alcohols in gasoline results in lower hydrocarbon and
CO tailpipe emissions. 6 However, a potential drawback is that alcohols in gasoline are sensitive to
phase separation in the presence of water, moisture is ubiquitous in the gasoline distribution system.
Alcohol blends with a high methanol content are particularly sensitive to this phase instability. For
the effective use of alcohol as a gasoline additive, a considerable fraction of C2+cosolvent alcohols
is necessary for phase stability in the presence of 1-120.Thus, a commercially viable process for the
production of mixed alcohols from syngas must have a relatively high selectivity to C2+cosolvent
alcohols. For example, the Environmental Protection Agency (EPA) waiver granted to Texas
Methanol Corporation for the Lurgi Octamix mixed alcohols products specified that the methanol to
cosolvent alcohol split be 2:1 or, in other terms, a mix of 67% methanol and 33% C2+-alcohols by
weight.
Existing proposed processes for the production of mixed alcohols from syngas are based on
conversion in packed bed reactors. 7,s However, the conversion of syngas to alcohols is highly
exothermic. Table 1-3 shows the heats of reaction for the synthesis of selected alcohols from CO
anti I-t2.
TABLE 1-3
Heats of Reaction for Synthesis of Selected Aichols from
CO and H2 x CO + 2xH 2 = C H2_+IOH + (x-l)H20
AH (@298),
C.I-I2_+t OH kcal/mole
methanol - 17
ethanol -53
1-propanol -85
isobutanol - 131
The heat of reaction per mole of product alcohol increases substantially with molecular weight.
Removal of this high reaction heat is difficult in packed bed reactors. Slurry reactors offer much
better heat management capabilities enabling a higher per-pass conversion, potentially better catalyst
stability through the elimination of "hot spots," and the ability to process unshifted synthesis gas.
Another potential advantage in the use of a slurry reactor is an enhancement in the selectivity to
higher alcohols induced by secondary conversion (see below reaction), as a result of reactor back
mixing.
lower alcohols -_ higher alcohols
"Iqaepurpose of this study was to investigate slurry-phase mixed alcohols synthesis on a lab scale. A
Cu/ZnO/A1203 methanol synthesis catalyst and the same catalyst promoted with cesium were
investigated under reaction conditions conducive for producing higher alcohols. The effects of
temperature, gas-hourly space velocity (GHSV), and feed composition were investigated. In
addition, a commercial alkali-promoted Cu/ZnO/Al20 s mixed alcohols catalyst and a Cu-Co based
mixed alcohols catalyst were evaluated in the slurry reactor. Other investigations involved the use
of Cu/ZnO/A1203 and another catalyst component in the same reactor in attempts to increase syngas
conversion to C2.-alcohols.
1.3 One-Step, Slurry-Phase Syngas Conversion to Mixed Ethers
Methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and tert-amyl methyl ether (TAME)
have emerged as the most important oxygenates for gasoline blending. Properties of these ethers
that make them good gasoline components include excellent miscibility with gasoline, high blending
octane number, relatively low blending vapor pressure, and a tendency to reduce tailpipe emissions.
Current production of ethers is based mainly on petroleum and natural gas feedstocks. MTBE,
ETBE, and TAME are currently produced by reaction of an iso-olefin with an alcohol. For
example, in the case of MTBE, isobutylene is selectively reacted with methanol in the presence of
an acidic ion exchange resin catalyst. A coal-based route to ethers is of considerable interest.
Besides the reaction of an olefin with an alcohol, ethers can also be produced by intermolecular
dehydration of alcohols:
R-OH + R'-OH -_ R-O-R', R-O-R, R'-O-R' + 1-120,
where R and R' are alkyl groups. In the absence "of any carbon-carbon bond rearrangement, the
structure of the ethers produced by this route will depend directly on the structure of the reactant
alcohol molecules. As indicated by the above stoichiometry, in the case where R and R' are
different alkyl groups, the formation of three different ethers is possible. In general, for direct
dehydration of a mixture of n different alcohols, the formation of n(n+ 1)/2 different ethers is
possible. In addition, side reactions, such as intramolecular dehydration of alcohols to olefins, are
possible. Thus, product selectivity is considered to be a major issue in developing such a process.
Some of the ethers produced by the above scheme may be useful as octane or cetane improvers in
transportation fuels.
This work focused on investigating the feasibility of converting mixed alcohols, generated in-situ
from syngas, to mixed ethers in a single slurry reactor. This study involved the use of a mixed
catalyst system consisting of a mixed alcohols synthesis catMyst and a dehydration catalyst in the
same reactor. The major portion of the work involved the use of mixtures of cesium-promoted Cu/
ZnO/A1203 and AI203. The effect of the proportion of the two catalysts on product selectivity and
productivity was investigated. In addition, some initial experiments involved the dehydration of a
vaporized stream of mixed alcohols over Al2Oy
2.0 EXPERIMENTAL
2.1 Apparatus
The reactions were carried out in two 50 ml micro-autoclave reactors (Autoclave Engineers
Microclaves). The reactors were connected to a feed gas manifold and were operated in a
continuous, once-through mode.
A simplified schematic of the flow system for one of the reactors is shown in Figure 2-1. The feed
gases were supplied from cylinders of premixed gases. Four feed gases were supplied to the
reactors: two types of synthesis gas, reduction gas, and nitrogen. The synthesis gases were purified
by passage through packed beds of activated carbon to remove any iron or nickel carbonyls present.
Vaporized liquid was added to the gas feed by a high-pressure syringe pump which injected liquid to
a feed preheater/vaporizer. The exit gases from the reactor passed through a gas-liquid separator
which refluxed the vaporized and entrained slurry liquid back to the reactor. Pressure in the reactor
was controlled by a back pressure regulator and reactor exit stream flow rate was measured using a
wet test meter. Ali lines downstream from the reactor were electrically heat-traced to prevent the
possible condensation of reaction products.
Analysis of the feed and product gas streams was done on-line by gas chromatography (GC). The
components of the synthesis gas (I-I2, CO, CO2, and N2) were quantified by a Hewlett-Packard 5890
GC equipped with dual TCD detectors and packed columns. Hydrogen analysis was done using N2
carder gas and a column packed with activated carbon at 50°C. Carbon monoxide and N2 were
separated on a 13X molecular sieve column at room temperature with He carder. Carbon dioxide
analysis was done using a Porapak Q column at 130°C with He carder. TCD data was acquired and
quantified by a Hewlett-Packard 5850 Chemstation.
Analysis of organic products was done by another Hewlett-Packard 5890 GC with a single FID
detector and a 0.53 mm I.D. capillary column with a 5 mm DB-1 film. FID data was acquired by a
Hewlett-Packard 3396A integrator.
2.2 Catalyst Materials
For the one-step syngas conversion to methanol/hydrocarbons study, the methanol synthesis catalyst
used was a powder form of BASF $3-86, which is a commercial Cu/ZnO/AI203 methanol synthesis
catalyst. The zeolites used, HZSM-5, was obtained from Zeochem.
A few different catalysts were used in the syngas to mixed alcohols investigations. Most of the
studies involved the use of a cesium-promoted BASF $3-86, a catalyst which was formulated at Air
Products. This catalyst was produced by incipient wetness impregnation of BASF $3-86 with an
aqueous solution of cesium formate to yield a cesium loading of 1.1 wt%. The impregnated catalyst
was further treated by calcination and was reduced to the active form in the reactor prior to mixed
alcohols synthesis studies. In some experiments a co-catalyst was used along with the cesium-
promoted BASF $3-86. One material, Rh supported on La203, was produced by impregnating
La203 with aqueous Rh(C1)3solution, followed by drying and calcination. Another co-catalyst,
lanthanum strontium manganite (Lao9Sro._MnO3),was obtained from HUA Associates. Another
alkali-promoted Cu/ZnO/A1203 mixed alcohols catalyst was obtained from the Lurgi Corporation.
This is the same catalyst formulation used in Lurgi's Octamix process, which is a packed-bed
process for producing mixed alcohols from syngas currently offered for license. Finally, a Cu-Co
based mixed alcohols catalyst, obtained from an external source under a confidentiality agreement,
was also investigated for use in a slurry reactor. A Cu-Co based catalyst is used in the mixed
alcohols production process developed by IFP (Institut Franqais du Petrole).
For the mixed ethers synthesis studies, the mixed alcohols catalyst component used was the cesium-
promoted BASF $3-86 catalyst described above. The A1203component was Catapal SB, a y-A1203
obtained from Vista Chemical.
I
|
8
3.0 RESULTS AND DISCUSSION
Methanol/HydrocarbonMixtures
3.1.1 Reaction Liquid Studies

As mentioned previously, studiesof slurry liquids done during the development of the LPMEOH
process 4 indicate that only certain liquids are compatible with the Cu/ZnO/A1203 methanol synthesis
catalyst. One class of liquids which appears to be universally compatible with Cu/ZnO/A½03 is
fully-hydrogenated paraffinic or naphthenic compounds. Thus, in the screening of liquids, attention
was focused on this general class of compounds. However, a disadvantage to the use of paraffinic
or naphthenic compounds is that they are subject to acid-catalyzed cracking in the presence of
HZSM-5, which is an effective cracking catalyst.
Since most of the acid sites on HZSM-5 are inside the crystallites, the basic strategy used in liquid
selection was to identify a paraff'mic liquid composed of molecules large enough to have restricted
access to the pores. The expectation is that this restricted access would minimize cracking of the
paraffinic liquid molecules. The concept of using a slurry liquid composed of molecules larger than
the pores of the catalyst for slurry-phase conversion of methanol to hydrocarbons has been used
previously?
To test the above ideas, the stability of three reaction liquids in the presence of HZSM-5 was
measured. The liquids screened were Penreco Drakeol 10, Exxon Isopar V, and decalin.
Drakeol 10 is a food-grade mineral oil composed of a mixture of C16-C3gstraight-chain, branched-
chain, and naphthenic saturated hydrocarbons. This is the preferred liquid for use in the LPMEOH
process. Exxon Isopar V consists exclusively of C_4-Clsbranched-chain saturated hydrocarbons.
Decalin (decahydronaphthelene) is perhydrogenated naphthalene, a C10bicyclic, saturated structure:
Liquid stability was investigated using a 50 ml stirred autoclave reactor. The stability tests were
done by heating a slurry of 2 g of HZSM-5 and 20 g of liquid in flowing N2while analyzing the off-
gas for cracked hydrocarbons by the FID GC. The results of tests, conducted at a pressure of
5.3 MPa and temperatures of 250°C and 300°C, are shown in Figures 3-1 and 3-2, respectively. The
results obtained at either temperature indicate that stability decreases in the following order: decalin
> Isopar V > Drakeol 10.
The fact that Drakeol 10 exhibited the lowest stability to cracking is not surprisir g since a major
portion of this liquid consists of straight-chain paraffins which have relatively easy access to the
pore structure of HZSM-5. On the other hand, decalin, which is composed of the bulkiest
molecules, has the most restricted access to the internal pore structure of the zeolite, and is the most
stable.
FIGURE 3- 1
Comparison of Liquid Stability
Catalyst" HZSM-5
250°C, 5.3 MPa
N2 Flow: 5,000 std.lit./kg-hr
20
Drakeol 10 x:x)o_
_.XX)q
XXX._J
10 - _
xxx_
_,. XXX>G
-_ 20
.I3
Isopar V "
n,,
n0 _ _._<x..x>
I_. F/'_'._ __
"0
_, 20
o
o
Decalin
I,..
(D
10
0 -
1 2 5 4 5 6 7
Carbon Number
FIGURE 3-2
Comparison of Liquid Stability

Catalyst" HZSM-5
300°C, 5.3 MPa
N 2 Flow: 5,000 std.lit./kg-hr
100 - Drakeol 10 :_=_-_

-,(vAX ._,
50 ._v._
_ , 0 -----
_ 1O0 - Isopar V
rr"
50
0
I1)
-_
(a
1O0 - Decalin
o
¢.)
5O
1 2 3 4 5 6 7
Carbon Number
!!
The ease with which a molecule can enter the pore structure of a microporous material is determined
by how large the kinetic diameter of the molecule is compared to the size of the pores. 1° The
bicyclic decalin molecule has a larger kinetic diameter than either straight-chain or branched chain
paraffins. The kinetic diameter of decalin is estimated to be greater than that of cyclohexane, which
has a kinetic diameter of 6.0/I,.1o The pores of HZSM-5 are 5.4-5.6/_ in diameter. Thus, it is not
surprising that decalin was the most stable liquid since its access to the interior of the zeolite
crystallites is highly restricted.
3.1.2 Surface-Passivation of HZSM-5

In an attempt to further reduce cracking of decalin in the presence of HZSM-5, passivation of the
surface of the zeolite crystallites was investigated. This work was motivated by the fact that the
HZSM-5 powder used consisted of finely divided particles, probably in the 0.5-5 micron range.
Such particles have considerable external surface area. The possibility exists that the external
surface of the crystallites may contribute significant acid sites and therefore cracking activity. These
sites are readily accessible to ali liquid molecules, including decalin. The aim of the passivation was
to selectively deactivate the acid sites on the surface of the crystallites to achieve greater liquid
stability, while leaving the internal acid sites available for conversion of methanol.
Surface passivation was done using a silanation technique employed previously by Sivasanker and
Reddy. 11These authors used N,N-dimethyltrimethylsilylamine to selectively silanate the external
surface of HZSM-5. The use of this silylamine as a silica precursor is particularly advantageous
because the silylamine molecules are too large to enter the pores and the amine functionality
interacts strongly with the external acid sites, thereby anchoring the precursor to the surface prior to
calcination.
The results for thedecaiin stability test, along with the results obtained for unmodified HZSM-5, are
shown in Figure 3-3. lt is quite clear that surface passivation resulted in much greater decalin
stability since the rate of production of cracked products is much lower than that for unmodified
HZSM-5. Thus, surface passivation of HZSM-5 may be a viable means of enhancing liquid
stability.
3.1.3 Slurry-Phase Methanol Conversion to Hydrocarbons

Slurry-phase methanol conversion to hydrocarbons was investigated using HZSM-5 and surface-
passivated HZSM-5, with decalin as the reaction liquid. The experiments were done by vaporizing
methanol into N2carrier being fed to the 50 ml autoclave.
Figure 3-4 compares, for unmodified HZSM-5, the observed product rates obtained for N2 flow
alone and that obtained during methanol addition to the feed. The results for N2 flow 'alone are
included to indicate the proportion of observed products which are expected to be formed purely
from cracking of the decalin. As can be seen, considerable additional hydrocarbon products were
formed from 8 mol% methanol in N2,as compared to N2 alone, indicating that methanol was
converted to hydrocarbons. Besides hydrocarbons, the other major product observed was DME. lt
is noteworthy that maximum in the product distribution appears at C4, indicating a relatively low
selectivity to gasoline range hydrocarbons. This is probably due, at least in parx, to the low
temperature (300°C) used for methanol conversion. Recall from Table 1-1 that methanol conversion
is preferentially done at higher temperature (350-420°C).
FIGURE 3-3
Comparison of Decalin Stability for

HZSM-5 and Surface-Passivated HZSM-5
300°C, 5.3 MPa
N2 Flow" 5,000 std.lit./kg-hr
3O
HZSM-5
.lc
i 15
O_
v
0 v
30
-o
0
Surfoce-Passivated HZSM-5
CL
"0
_ 15
O
o 0-- --_ _==_----

1 2 3 4 5 6 7
Corbon Number
13
FIGURE 3-4
Slurry Phase Methanol Conversion to Hydrocarbons
Catalyst: HZSM-5
Liquid" Decalin
300°C, 5.3 MPa
N2 Flow-5,000 std.lit./kg-hr
60
100% N
2
._.
L.
30
t"
I _ <xxx
<xxx
K.XXX
KXXX
o 60
8_ MeOH/g2% N2
0
"0
0 KXX><
L
30 __xX_v_ xO<><X
D<X.>GXJ x_<O<_
_>0<_
Nx-x:xl _
1 2 3 4 5 6 7
Carbon Number
Figure 3-5 shows the product distributions observed for methanol conversion over HZSM-5 and
surface-passivated HZSM-5. The product distribufon obtained for surface-passivated HZSM-5 is
substantially different than that for the unmodified HZSM-5. The C2-C7product rate for the
surface-passivated sample is essentially equal to that expected from cracking of the decalin, thereby
indicating that methanol is not converted to these products. However, the methane produced is
much greater than that for the unmodified HZSM-5.
The reason for the high methane selectivity for the surface-par, sivated sample is not clear. However,
one possibility is that the surface silanation not only capped off acid sites on the external surface of
the crystallites, but also may have necked down the pore openings. Such a decrease in the size of
the pore openings may allow only small molecules (e.g. CH4), formed via methanol on internal sites,
to escape the zeolite structure. Further study would be necessary to determine the specific cause of
the change in product diswibution for the surface-passivated sample.
3.1.4 One-Step Syngas Conversion over Cu/ZnO/AI=O3-HZSM-5 Mixture

The slurry-phase conversion of simulated coal-derived syngas using a 50:50 (by weight) mixture of
Cu/ZnO/A1203 methanol synthesis catalyst and HZSM-5 in decalin was investigated. After in-situ
reduction of the Cu/ZnO/A1203 component, the autoclave was run at 250°C and 5.3 MPa using a
space velocity of 5,000 std. lit./kg-hr (based on total catalyst weight). The results of this experiment
are shown in Table 3-1.
TABLE 3-1
Slurry-Phase Syngas Conversion to Methanol/Hydrocarbons
Catalysts: Cu/ZnO/Al203 and HZSM-5

Liquid: Decalin
Feed Gas: 51% CO/35% I-t2/13% CO2/1% N2
Conditions: 250°C, 5.3 MPa, GHSV=5000 std. lit./kg-hr
Production Rate (g/kg-hr)

Time on
stream _C1-C3 _C4-C 7
(hr) hydrocarbons hydrocarbons DME MeOH

1.2 18.4 8.8 333 18.5
10.1 7.9 8.7 250 15.4
14.8 8.3 6.5 201 14.8
The major product was DME, while selectivity to hydrocarbons was quite low. However, the
production rate of hydrocarbons was significantly greater than that expected from the decalin
cracking. Though not shown in Table 3-1, CO conversion is a strong function of on-stream time,
but is greater than that observed for methanol synthesis alone at these conditions (Cu/ZnO/AI203
without HZSM-5 present). The CO conversion decreased from 28% at 1.2 hours to 18% at
14.8 hours. Thus, deactivation of the mixed catalyst system appears to be significant.
Selectivity to gasoline range hydrocarbons is disappointingly low for this experiment. This is
probably due to the fact that the reaction temperature used (250°C) was much lower than the optimal
temperature range for methanol conversion to gasoline (350-420°C, see Table 1-1).
FIGURE 3-5
Slurry Phase Methanol Conversion to Hydrocarbons
Liquid" Decalin
300°C, 5.3 MPa
Feed" 8% MeOH/92% N2
N2 Flow: 5,000 std.lit./kg-hr
60
HZSM-5
_(xxx]
_.... _- -- -.- _.,
r ,_xxxl
_xx_
c_
60
__ Surface-Passivated HZSM-5
0
"0
0
o_ 3 0 - _v_
_YX
XXXVA
_XM v
vvvv
_XX v
KXO4X
_xxx
1 2 3 4 5 6 7
Carbon Number
16
3.2.1 Cu/ZnO/AI=O_ and Cesium-promoted Cu/ZnO/AI=O 3
3.2.1.1 Effect of Gas Composition and Gas.Hourly Space Velocity on Productivity and Product
Distribution
Two syngas feeds of different composition were investigated. One feed was representative of the
product gas from a Texaco coal gasifier, while the other simulated a Shell coal gasifier product gas.
The nominal compositions are shown in Table 3-2. Shell gas has a much lower 1-12/COratio (0.45)
than Texaco gas (0.69), and a lower CO2content (3% for Shell vs. 13% for Texaco).
TABLE 3-2
Composition of Shell and Texaco Syngas
Nominal Composition (_mol%)

Syngas CO H2 CO2 Nz
Texaco 51 35 13 1
Shell 66 30 3 1
The results for the CulZnO/AI203 will be discussed fit'st. Figures 3-6 and 3-7 show the major
product alcohol rates as a function of GHSV for Cu/ZnO/A1203 for Texaco and Shell gas feeds,
respectively. These data were obtained at a temperature of 300°C and a total preffsure of 7.0 MPa.
The major products for each catalyst are alcohols, accounting for greater than 90% by weight of the
total organic products. The minor side-products were largely low molecular weight paraffins and
esters.
Figures 3-6 and 3-7 show that the synthesis rate of ali products increases with increasing GHSV, but
the relative sensitivity to GHSV is product specific. The methanol rate increases linearly with
GHSV, for both feed gases, across the range of GHSV investigated here. Moreover, the reactor exit
methanol concentration shows little variation with GHSV. This indicates that the methanol
synthesis reaction is close to equilibrium at these conditions. Thermodynamic equilibrium
calculations, which incorporate the approximate reactor exit gas composition, support this
contention. The methanol synthesis rate for Texaco gas was higher than for Shell gas across the
GHSV range. This observation is consistent with thermodynamic equilibrium considerations; the
higher I-t2/CO ratio of the Texaco gas favors conversion to methanol. The EC_-C6 alcohols rate
EC2-C6 alcohols rate is not constrained by thermodynamic equilibrium limitations at these

i conditions, but rather the with
increases monotonically rate GHSV,
is governed by the the
but unlike intrinsic
result reaction kinetics.
for methanol, the The
rate EC2-C+alcohols
is non-linear. The
rate is higher for Shell gas than Texaco gas across the range of GHSV examined.
i The effect of GHSV on the synthesis rate of the individual higher alcohol products is quite
interesting. For both feed gases, the increase in ethanol rate with GHSV is approximately linear.
i rate curve is fairly

By contrast, fiat, especially
the dependence of thetoward the upper
isobutanol rate onlimits
GHSV of GHSV
is not asinvestigated. Consequently,
strong. In fact, the isobutanol
isobutanol is the major C2+-alcohol product at low GHSV(<5000 std. lit./kg-hr ), while ethanol is the
major product at high GHSV. This behavior can be rationalized in terms of the probable reaction
mechanism by which the higher alcohol products are formed, as proposed by published studies of
17
,.
FIGURE 3-6
Effect of GHSV on Product Rates
Catalyst: Cu/ZnO/AI20 _
Run No.' 11472-39
ii
FIGURE 3-7
Catalyst: Cu/ZnO/AI203
Run No." 11#72-39
300°C, 7.0 MPa, Shell Gas

800 - , i , i , _ _ i , l , 140
0 Methanol
700 • Ethanol 120 "-'L_
v 1-Propanol .c:
_- _ Isobutanol I
c- O_
I
O_ 600 @ _-C2-C s Alcohols • _ 100_
"_ 0 ' O_
500
o_ 80 _0
" (D "_
_ .+.., 400 o
ffl
5 5oo -5
¢... ..c
r- 200 __o
100
0 L ,_, , , , , ' 0
0 2 4 6 8 10 12
GHSV (10 3 std. lit./kg-hr)
19
alcohol synthesis on Cu/ZnO/Al203-based catalysts, t1'12These studies indicate that higher alcohols
are produced in a chain growth scheme by addition of primarily C t units to the ct- or _-carbon of a
lower alcohol:
C1 C1 C1
CO/I-I2 or methanol -_ ethanol _ 1-propanol -_ isobutanol
Formation of 1-propanol occurs by Ct addition to ethanol, and _sobutanol is formed from C1 addition
to 1-propanol. In such a sequential mechanism, the expectation is that low GHSV (longer residence
time) would favor formation of higher molecular weight alcohols. Thus, low GHSV favors
formation of isobutanol over ethanol.
Figures 3-8 and 3-9 show the effect of GHSV on the alcohol product selectivity for the Cu/ZnO/
A1203catalyst for Texaco and Shell feed gases, respectively. The selectivities are based on the
organic products only and do not consider CO that has been converted to CO2. The major alcohols
products are primary alcohols, that is, they are of the structare R-CH2-GH (where R is an alkyl
group). In addition, among the C,_ alcohols products, branched products, in particular the "2-
methyl-" isomers, dominate over linear products. This high selectivity to branched C,_ products is
well known for Ctt/ZnO/A1203-based catalysts _'_2and can be understood in terms of the reaction
mechanism mentioned above. The predominance of branched products is expected if [3-addition
dominates over ct-addition in the chain growth scheme.
As indicated in Figures 3-8 and 3-9, the extent to which the branched products prevail over the
linear isomers is greater at the lower space velocity. This is reasonable considering that long
residence time (low GHSV) favors secondary reaction, such as [3-addition, to the linear alcohols
resulting in formation of the "2-methyl-" isomers of the linear alcohols. Not surprisingly, the total
t
selectivity to EC2-C6alcohols is higher at low GHSV for both feed gases. Moreover, the selectivity
to Y.C2-C6 alcohols is higher for Shell gas as compared to Texaco gas. The selectivity to EC2-C6
alcohols increases from 9.8 wt% at 10,022 std. lit./kg-hr to 16.7 wt% at 1739 std. lit./kg-hr for
Texaco gas. For Shell gas, the selectivity increases from 15.8 wt% at 10,022 std. lit./kg-hr to
24.3 wt% at 1509 std. lit./kg-hr.
Next, the results for the Cs-promoted Cu/ZnO/A1203 catalyst will be discussed. Figures 3-10 and
3-11 show the major product alcohol rates as a function of GHSV for Cs-Cu/ZnO/A1203 for Texaco
and Shell gas feeds, respectively. The data were obtained at 300°C and 7.0 MPa, the same
temperature and pressure used for the results on the unpromoted catalyst (Figures 3-6 through 3-9).
In agreement with the results for the unpromoted Cu/ZnO/AI203, the methanol rate increases nearly
linearly with increasing GHSV for both feed gases, reflecting the constraint that thermodynamic
equilibrium imposes on the extent of conversion of syngas to methanol at these conditions. The
5"C2-C6 alcohols rate increases monotonically with GHSV for both feed gases. The effect of GHSV
on the individual rates for ethanol, 1-propanol, and isobutanol shows the same basic trend as that
observed for the unpromoted Cu/ZnO/A1203 catalyst. Interestingly, the isobutanol rate measured for
Texaco feed gas appears to go through a weak maximum as GHSV is increased.
As also observed for the unpromoted Cu/ZnO/A1203 catalyst, the ZC2-C6alcohols rate is higher for
Shell gas than Texaco gas across the range of GHSV. The relative degree to which the rate for Shell
gas is higher than Texaco gas is greater for the Cs-Cu/ZnO/A1203 than the unpromoted Cu/ZnO/
2O
FIGURE 3-8
Effect of GHSV on Alcohol Product Distribution
Run No." 11472-39
300°C, 7.0 MPa, Texaco Gas
90
GHSV=1739 std.lit./kg-hr
80
70 //4
//4
7"A ,
60//
r/_
. r/ii
10 ,/A
,/,4
I///I
- I//,4
o Nm - I/,/1 _ _ ,-,-_ I_ _ FT/I...-- 'I

>_ 90
7771
> //A GHSV=10022 std.lit./kg-hr
///I
•- 80 - //`4
///I
0 ;. /lA
0 70 - //,4
(1.) /
U') 60,/ ,,
/ ./-" /
" K//
Ii"//'1
10 - K//]
0 -
0 0 0 0 0 0 0 0 0
c c c c c c c t-- c
0 0 0 t_ 0 0 0 _ 0
t- c" r_ _ -_ .+-, --_ _ X
"_ _ 0 :3 _ :3 C C Q)
0 bJ !- .ta m ...13 o _ .-r=
"5 n.. o I I _ Q" I
l 10_ ,_. ,== l l
1
>_
•_ =_
(_
E
) E
c_ l
21
....................................................................................................
,...........
,,.,.,.,,.,,,,
,,.,,,..,,,,.,,
,,,.
,,,,,_
,,,,
.,,,,
,,.,,,,,,.,i,.,)_,_,,,,,_._r_m.,
n.lmi,_
_,_.nm..
)n._,r,_eii,i_p_,.vlmwl"
,,,llml'_imlll!ImlM.ll|Pl_q_IlUll_!ll_lll_ll
_'
l_Mllq'_
_l||llll_'l_ql'
_IIIIII_I_III_IIIIIPIIIIII_III_II_P
_ll_#lill_l_lll
_llllllM_IIlllll_qlnll"_l_ll)IllH_llllllH
rllllll_
,IIII
_I1811111
lq'l_l_ll
FIGURE 3-9
Catalyst" Cu/ZnO/AI203
Run No • 11472-59
9o t
80
70
60,/
/ V,._I /
o r,
TA
_ 0 ' " _
>', 90
_ GHSV=10022 sid lit./kg-hr
> I::
•--
.+_
80 - z-_
0 fj'j
0 70 - ,..,
f_f
(D fiJ
f/# ,, /
Or) 60//
fj'#
f/#'
10 - ""'i
0 "-"
0 0 0 0 0 0 0 0 0
C c- t'- C C C C r- _-
o 0 0 0 0 0 0 0 0
32 r- Q. _ _ ._ _ -_ x
"4" "_ 0 Z] ZJ :3 _= C (I)
Ld L.. JO O_ .0 _ _) 7-
I _ _- _ I I ,._
-- I
4--_. C-
O
EI E
e_ I
C4
22
FIGURE 3-I0
Catalyst: Cs-Cu/ZnO/AI203
Run No." 11168-76

800 , i , i , I , 1 , i , 140
0 Methanol
700 II Ethanol 120 "'_-

v 1-Propanol c-
_" • isobutanol I
c- (3n
I 600 ® EC2-C e Alcohols 100 ,z
500 _'_
v 80
.,., 400 o
n,- 60
-6 300 -6
c- c-
o 40 o
200
0
100
0_ _ __ 20 (.3
I+
0 , I , 1 , I , 1 , 1 , 0
0 2 4 6 8 10 12
GHSV (10 _ std. lit./kg-hr)
__e
i 23
FIGURE 3-1 1
Run No.: 11168-76

800 ' I ' I ' 1 ' 1 ' I ' 140
0 Methanol
0---->
700 II Ethanol / L_
• 1-Propanol / 120 ""
_c: • Isobutanol _ I
I
_3_ 600 tl :[:C2-C e Alcohols / 100 --_
E_
v 80 oo
-_ 400 -_
E)
_ 500 /li _____0 0
_'_
300 --_
0
g 40
1oo 20 o +
0 0
0 2 4 6 8 10 12
GHSV (10 3 std. lit./kg-hr)

AI203 catalyst. For example, at a GHSV of 10,000 std. lit./kg-hr for both feed gases, the EC2-C6
alcohols rate for Shell gas is 80% higher than that for Texaco gas for the Cs-Cu/ZnO/AI203 catalyst.
By contrast, at a GHSV of 10,000 std. lit./kg-hr for both feed gases, the EC2-C6 alcohols rate for
Shell gas is 43% higher than that for Texaco gas for the Cu/ZnO/A1203 catalyst.
Comparison of the alcohol rates of the two catalysts at constant feed gas composition indicates that,
in general, the XC2-C6 alcohols rate is significantly higher for the Cs-Cu/ZnO/AI203 than the
unpromoted Cu/ZnO/A1203 catalyst. However, one exception is that the XC2-C6 alcohols rate using
Texaco gas at a GHSV of 10,000 std. lit./kg-hr is nearly the same for both catalysts, while the XC2-
C6 alcohols rate at lower values of GHSV for this gas is consistently higher for the Cs-Cu/ZnO/
A1203catalyst. For both feed gases, the isobutanol rate is higher for the Cs-Cu/ZnO/A1203 catalyst
than the unpromoted catalyst, across the range of GHSV investigated. Interestingly, the relative
enhancement in isobutanol rate resulting from promotion of the catalyst with cesium is more
pronounced in the case of the Shell gas feed in comparison to Texaco gas.
Figures 3-12 and 3-13 show the influence of GHSV on the alcohol product distribution for the Cs-
Cu/ZnO/AI203 catalyst for Texaco and Shell feed gas, respectively. In agreement with results for
the unpromoted catalyst, low GHSV results in an enhancement in the selectivity to higher alcohols
for both feed gases• Particularly noteworthy is the increased selectivity to branched products, such
as isobutanol, at the low GHSV. Also, comparison of Figures 3-12 and 3-13 indicates that the
selectivity to C2.-alcohols is considerably higher for Shell gas than Texaco gas, in agreement with
the unpromoted Cu/ZnO/AI203 results•
The alcohol product obtained in this work will now be considered in light of what is technically
acceptable for fuel use. For a mixed alcohols product to be potentially useful as a gasoline additive,
it must contain a significant fraction of C2.-alcohols as cosolvents for the methanol. For example,
the EPA waiver granted to Texas Methanol Corporation for the Lurgi Octamix mixed alcohols
products specified that the methanol to cosolvent alcohol split be 2:1 or, in other terms, a mix of
67% methanol and 33% C2.-alcohols by weight. For this waiver, certain restrictions were also
placed on composition of the cosolvent mix; for example, the ethanol, propanols, and butanols must
comprise at least 60% by weight of the cosolvent alcohols. This waiver provides some guidelines
on product composition acceptable for gasoline blending.
The product mixes obtained for the Cs-Cu/ZnO/AI203 catalyst will now be considered in view of the
above mentioned EPA waiver. Table 3-3 shows the distribution of methanol and cosolvent alcohols
obtained for the Cs-CwZnO/A1203 for both syngas feeds at low and high GHSV. As shown, the
split between methanol and higher alcohols is more favorable for the Shell gas feed. For Shell gas
at a GHSV of 2028 std. lit./kg-hr, the product alcohol composition is essentially acceptable
according to the EPA waiver for Octamix. Moreover, for ali of the cases considered in Table 3-3,
the cosolvent alcohols are comprised of at least 70 wt% ethanol, propanols, and butanols•
25
FIGURE 3-12
Catalyst" Cs-Cu/ZnO/AI203
Run No." 11168-76

90
80
fJ_
70 - .,,_
fJ_
f/,_ /
60//
f/_
- f/J
10 ""
f//
r_ . F//
- f//
_ f J/
0 ' _,7_ 17"_!.-.-.. F7_ .-.-_

>_ 90
•_ ,/_ GHSV=10028 std.lit./kg-hr

•-
.._
80 - f//
f/J
70 - "'"
f/J
rf/
(_ rf/
/// /
09 60// ,/
frj
- frj
10 - ""
f/J
- fJJ
frj
#'//
. l'//
f/J
t'// FT'7"s _ ,,, _ ,,,
0 0 0 0 0 0 0 0 0
C C C C C C C C C
0 0 0 0 0 0 0 0 0
c- c- n _ _ _ _ _ X
"_ "4" 0 :3 ::3 ::3 C C (_
Q) ILl __ .O m .O ¢) Q) "l-
m o I I n _ I
i m __ ,_ I I __
•-- _1 "- i
.4_, r"
Ill -_
lD
EI E
C,4
i
I 26
FIGURE 3-13
Run No." 11168-76
9O
8O
7O
60tl
10 --
N .
oF _'7__'_..-._PYJ,-,-,_.
>_ 90
GI/ISV= 1 0018 std.lit./kg-hr
>
•- 80
° N
/
(1) 70 -
U3 60//
/ _'/1 /
. //._
10 - //_
- //t
- //1
0 "" NNN
-
f/.,
x/,,
/z_,
_ _ _ 177-2
-6 -5 "5 -5 -6 "6 -5 -6 -5
C C C C C C C C C
0 0 0 0 0 0 0 0
c- _ _ 4., .4-, ._ -+.., ._ X
"_ "_ O _ _ _ C C
W L_ .0 n7 .13 _ _ 7-
:_ o_ o I I o_ a. I
I __ _- .- I I __
•-- _I _- I
_c
._ J_.
Q)
EI E
t'N
27
TABLE 3-3
Methanol/Cosolvent Alcohols Product Distribution for Cs-Cu/ZnO/AI_O 3
Selectivity Among Total Alcohols

(wt%)
GHSV
Feed Gas Type (std. lit./kg-hr) Methanol ECz-C6 alcohols
Texaco 1518 77 23
Texaco 5000 84 16
Texaco 10028 90 10
Shell 2028 67 33
Shell 5000 73 27
Shell 10018 79 21
The results shown in Table 3-3 indicate that potentially useful alcohol product mixes can be
obtained, especially for Shell gas operating at low GHSV, using the Cs-promoted Cu/ZnO/AI203
catalyst in a slurry reactor. The fact that the product distributions shown were obtained on a once-
through basis, that is, no recycle of methanol or syngas, is significant. This once-through mode of
operation is particularly well-suited to a CGCC environment. Recycle of product methanol, ethanol,
or propanol may also be a viable means of obtaining acceptable product distributions at higher
GHSV. Results obtained for alcohol addition to the feed will be presented later.
32.1.2 Effect of Temperature on Product Rates and Selectivity:

The effect of temperature on the performance of the anpromoted CufZnO/AI203 and Cs-Cu/ZnO/
A1203catalysts was investigated using Shell gas at a pressure of 7.0 MPa and a GHSV of
5000 std. lit./kg-l_'. Figures 3-14 and 3-15 show the influence of varying the reaction temperature
between 280°C and 320°C on the synthesis rates for the major product alcohols for Cu/ZnO/A1203
and Cs-Cu/ZnO/AI203, respectively.
For both catalysts, the methanol rate decreases monotonically with temperature, reflecting the
constraint that thermodynamic equilibrium imposes on the synthesis of methanol in the investigated
temperature range. The EC2-C6 alcohols rate is less influenced by temperature over this same
temperature range for both catalysts. For each catalyst, there appears to be a maximum in the EC2-
C6alcohols rate in the vicinity of 300°C.
The influence of temperature on the rate of synthesis of the major C2 -alcohol products, ethanol,
1-propanol, and isobutanol, is interesting. The ethanol rate decreases with temperature across the
range, while the isobutanol rate increases, for both catalysts. The rate for 1-propanol decreases
slightly with temperature, but the decrease is not as strong as that for ethanol. Unlike the methanol
synthesis reaction, syngas conversion to ethanol and 1-propanol at these reaction conditions is not
constrained by thermodynamic equilibrium; across this range of temperature, the rates for ethanol
and 1-propanol are quite far from the equilibrium values. Thus, the decrease in rate with
temperature, as observed for ethanol and 1-propanol, must be attributed to some other phenomenon.
The increase in isobutanol rate which accompanies the decrease in ethanol and 1-propanol rate with
increasing temperature suggests that secondary conversion of ethanol and 1-propanol to higher
products, such as isobutanol, occurs at a faster rate than ethanol and 1-propanol formation and this
28
i
FIGURE 3-1 4
Effect of Temperoture on Product Rates
Catalyst" Cu/ZnO/AI203
Run No.: 11472-39
7.0 MPa, Shell Gas, GHSV=5000 std.lit./kg-hr
0 Methanol
l Ethanol
T 1-Propanol
Isobutanol
• TC2-C _ Alcohols
400 ' 1 ' I ' I ' I ' I ' ,, 90
Q . 80
L.
,_, r"
L 70 I
I 300 _
60
"J 50 (D
200 o
o 40 rY
rY cn
-6 30 o
C r-
O
0
r- 100 20
_ I+
0 , I i I , I J I , j I ' 0
270 280 290 300 310 320 3 30
Tempereture (°C)
29
FIGURE 3-1 5
Effect of Temperature on Product Rates
Run No.' 11168-76
0 Methanol
I Ethanol
w 1-Propanol
• Isobutanol
@ ZC2-C 8 Alcohols
400 ' I ' I ' 1 ' I ' _ ' 90
rC' 7o
i: 300
60
50
200 _-"
40 O3
100 °O
-:_--_i____> lo +
0 , i , I , I , I L I
-- -- 0
o
270 280 290 300 310 320 330
Temperature (°C)
i 30
becomes more significant at higher temperature. This hypothesis is consistent with the above
mentioned mechanism for the synthesis of higher alcohols in which higher alcohol products are
formed primarily from oc-or 13-addition of C 1units to lower alcohols. 1_,t2
Figures 3-16 and 3-17 show how temperature influences the distribution of alcohol products for Cu/
ZnO/AI203 and Cs-Cu/ZnO/AI203, respectively. Obviously, for both catalysts, increased
temperature results in a higher selectivity to C2-C6alcohols. Also, the Cs-promoted sample has a
higher selectivity to C2+-alcohols than the unpromoted Cu/ZnO/A1203, at both temperatures
considered. The branched chain alcohols show a particularly large increase in selectivity with
increased temperature for both catalysts. At 320°C, the selectivity to isobutanol for Cs-Cu/ZnO/
A1203catalyst was 14.3 wt%. For this same catalyst at 320°C, the methanol/_C2-C 6alcohols split
was 65/35 by weight, a split which is within the range for gasoline addition.
3.2.1.3 Methanol and Ethanol Addition to Feed Gas

One method of increasing product selectivity to higher alcohols during mixed alcohols synthesis is
by recycle of lower alcohols products. To determine the effectiveness of each catalyst at converting
methanol and ethanol to higher alcohols products, methanol and ethanol were injected into the
syngas feed for each catalyst. The results of these experiments are shown in Tables 3-4 and 3-5 for
unpromoted Cu/ZnO/A1203 and Cs-promoted Cu/ZnO/AI203, respectively. Both alcohols were
injected at a rate of 380 g/kg-hr, which corresponds to a reactor feed concentration of 5 mol%
methanol or 3.5 mol% ethanol. Also shown in Tables 3-4 and 3-5, for comparison, are the results
obtained for no alcohol addition for each catalyst.
The results in Tables 3-4 and 3-5 indicate that methanol addition increased the synthesis rates of
higher alcohols for both catalysts. The most significant effect was on the ethanol rate, which
increased by 40% for both catalysts. A portion of the added methanol was unreacted as indicated by
the increase in the methanol effluent rate over the case for no methanol addition. Effluent gas
analysis indicates that a large portion of the added methanol was converted to CO and I-I2,
presumably by the reverse of the methanol synthesis reaction. Methanol addition resulted in a
modest increase in the EC3-C6 alcohols rate for each catalyst; the rate increased by 18% and 21% for
Cu/ZnO/AI203 and Cs-Cu/ZnO/AI203, respectively. In summary, the effect of methanol addition to
the feed appears to be comparable for both catalysts.
-.
TABLE 3-4
Effect of Feed Addition of Methanol and Ethanol for Cu/ZnO/AI203
Methanol or Ethanol Injection Rate-380 g/kg-hr

300°C, 7.0 MPa, Syngas GHSV=5000 std. lit./kg-hr
Reactor Effluent Rate (g/kg-hr)

I2C3-C6
Feed Gas Methanol Ethanol 1-Propanol Isobutanol alcohols
Shell 258 15 9 15 45
Shell + 5 mol% methanol 379 21 12 16 53
Shell + 3.5 mol% ethanol 262 124 21 18 69
31
FIGURE 3-16
Effect of Temperature on Alcohol Product Distribution
Run No." 11472-39
9O
: ,.---_ T=280°C
80 - ,...,
. #'JA
- #" f .#I
70 - """
fJA
fJ.#l
ff.,A
60//
- _"4,
_ 10 - _
;¢;;
p'j_ _
N . ,_:_, ]
_-_
>_
0
9O
- rJ_
;_ _ IT/-APT-_ ,-,-_.-r_ ,-,-_ 1

e--
> . T=320°C
•-
..i-a
80
,O
© 70 -
frj
IfJJ
O0 60/, ""
fJJ
fJJ
10 - """
frj
fJJ
frj
fiJ
fJJ
f/J
1_11 _ _
0 0 0 0 0 0 0 0 0
C C C C t- C C C C
0 0 0 0 0 0 0 0 0
t" ¢" 13. _ _ _ -+-' _ X
ILl __ .0 133 -13 _ ¢) "l-

h o l I a... a. I
I _ ,-- ,--, I I ,_
/
0
EI E
eJ I
cy
32
FIGURE 3-17
Effect of Temperature on Alcohol Product Distribution
Catalyst" Cs-Cu/ZnO/AI203
Run No." 1116B-76
9O
T=280°C
80 "-"
r/M
70 Y_
60 ' _ /
/ "/11
f/./I
//A
//A
i//1
//11
•_
>_ 90 T=320°C 1
--- 80
o
_ 70
(1) /
U_ 60 ," rT_
//i //F
. fj-j JJF
I / I ///
1 0 I ...
frj ///
_
_ f.fJ /// ]
/// ///
" /// ///
0 ""
-
//,#
,,,,_
til [_ N'- _//
_'//i
I/li FT"A N ® _ 17771
"6 -'6 3 3 -6 -5 -6 -6 -6
¢- E r- E r_. E E E. ¢"
0 0 0 O 0 O 0 0 0
r- r" O. "_ "4-I ._ -_ _ x
"_ "_ 0 :3 :3 :3 t- E (D
Q) ILl I.. 33 m 33 _) _ -r"
:_ n 0 I I {:L a. I
I _"_ ,.- _- I I ,__
,-- __1 "" I

.4, t-
EI E
t_
33
The results for ethanol addition are considerably different than those for methanol addition.
Tables 3-4 and 3-5 show that ethanol addition at 3.5 mol% increased the synthesis rate of C3+-
alcohols significantly more than that observed for methanol addition at 5 mol%. For the
unpromoted Cu/ZnO/AI203 catalyst, ethanol addition resulted in a 53% increase in the EC3-Cs
alcohols rate over the case for no ethanol addition. For this same catalyst, the 1-propanol rate
increased by a factor of 2.3 while the isobutanol rate increased by 20%.
TABLE 3-5
Effect of Feed Addition of Methanol and Ethanol for Cs-Cu/ZnO/Ai203
Methanol or Ethanol Injection Rate=380 g/kg-hr

300°C, 7.0 MPa, Syngas GHSV=5000 std. lit./kg-hr
Reactor Effluent Rate (g/kg-hr!

Y_C3-C 6
Feed Gas Methanol Ethanol 1-Propanol Isobutanol alcohols
Shell 243 15 15 26 63
Shell + 5 mol% methanol 361 21 20 29 76
Shell + 3.5 mol% ethanol 241 116 64 55 162
For the Cs-promoted Cu/ZnO/Al203 catalyst, the influence of ethanol addition on the product
distribution was much more dramatic. Ethanol addition increased the _C3-C6 alcohols rate by a
factor of 2.6, an increase which is significantly more than the 53% increase observed for the
unpromoted catalyst. The 1-propanol rate and isobutanol rate increased by factors of 4.3 and 2.1,
respectively, upon ethanol addition.
Since other investigators have studied alcohol addition to syngas feed over Cu/ZnO-based catalysts,
it is worthwhile to compare their results with those in the present work. Nunan et al., 11in their
studies of Cs-doped Cu/ZnO, injected ethanol to I-I2/CO=1:1 feed and observed the effect on the
alcohol distribution at 300°C and 7.6 MPa. In agreement with the present results, their experiments
showed that ethanol injection did not effect the methanol rate, but significantly increased the rates
for 1-propanol and isobutanol. Kiennemann et al., 13studied the mechanism of higher alcohols
formation on Cu/ZnO/A1203 catalysts by using probe molecules such as methanol. In contrast to the
present work, they observed a much greater relative increase in the formation of ethanol,
1-propanol, and isobutanol, upon addition of methanol to CO/I-_=1:2 feed gas, than that observed in
this study. Recall that in the present work only an 18-21% increase in C3-C 6 alcohols was observed
upon addition of 5 mol% methanol. However, it is noteworthy that the reaction conditions
employed by Kiennemann et al. in their tests were much different than those used in the present
work. In their experiments, a reaction temperature of 215°C and reaction pressure of 1 atm were
used. Under these conditions, the formation of ethanol, 1-propanol, and isobutanol was not detected
prior to methanol addition.
The results in Tables 3-4 and 3-5 indicate that recycle of methanol and, in particular, ethanol is a
viable means of increasing the rate and selectivity to higher alcohols over these catalysts in a slurry
reactor. However, the Cs-promoted catalyst is much more effective at converting added ethanol to
higher products than the unpromoted catalyst. This is perhaps not surprising since the cesium
component is believed to provide an active center upon which key steps in the chain growth process
occur. 1_
34
3.2.2 Lurgi Octamix Mixed Alcohols Catalyst
The Lurgi Octamix mixed alcoholscatalyst is an alkali-promoted Cu/ZnO-basedmixed alcohols
catalyst that was developed for use in a modification of Lurgi's low-pressure methanol synthesis
process. Lurgi's powder catalyst was used directly in the micro-autoclave reactors to evaluate its
use in a slurry reactor based process. The fast two experimental runs with this catalyst showed an
anomalous activity instability with on-stream time. Later inspection of the micro-autoclave internals
indicated that a partial clog had developed in the impeller draft tube. After clearing the tube, a
successful retest of the catalyst was done, the results of which are reported here.
3.2.2.1 Effect of time on stream

The catalyst was reduced in situ using 2% 1-12in N2 by ramping the temperature from 100°C to
200°C at 10°C/hour, followed by a hold at 200°C for 8 hours.
Figure 3-18 shows the synthesis rate for the major products as a function of total time on syngas.
The major products were methanol, higher alcohols (grouped together as ZC2-C6 alcohols), and
dimethyl ether (DME). The relatively high rate of production of DME is surprising for this catalyst.
As shown in Figure 3-18, the methanol rate first increases, then decreases slightly with time on
stream. The DME ,ate also decreases slightly with time. Of the major products, the higher alcohols
rate shows the greatest decline with time. The Z;C_-C6alcohols rate approaches a reasonably level
value after about 130 hours, following which time process variable studies were done.
3.2.2.2 Effect of Reaction Temperature

The influence of temperature on rate and selectivity was investigated in the range of 250°C to 280°C
using the Shell gas feed at a pressure of 7.0 MPa and a GHSV of 50130std. lit./kg-hr. The guidelines
for operation of the catalyst, supplied by Lurgi, indicated that reaction temperatures in excess of
285°C should be avoided. The effect of temperature on rate and selectivity for the major products is
shown in Figures 3-19 and 3-20, respectively. For the range of temperature investigated, the DME
and ZC2-C6 alcohols rates increase dramatically with increasing temperature. By contrast, the
methanol rate is approximately constant between 250°C and 265°C, while showing a decrease upon
further increase in temperature to 280°C.
Figure 3-20 shows that increasing temperature dramatically increases selectivity to higher alcohols
and DME, accompanied by a corresponding decrease in selectivity to methanol. The maximum
selectivity to ZC_-C6 alcohols was 7.2%, the value measured at 280°C. The 4 wt% selectivity to
DME at this temperature is surprisingly high.
Figure 3-21 shows the alcohol product distribution obtained at 280°C, 7.0 MPa, and a GHSV of
5000 std. lit./kg-hr. Similar to the case for the cesium-promoted Cu/ZnO/A1203 catalyst, the
selectivity to "2-t_lethyl-" alcohol isomers is significant. The reason why the "2-methyl-" isomers
are formed in significant quantities was discussed earlier. At these reaction conditions, selectivity to
the various alcohols decreases with increasing carbon number. The methanol/EC2-C 6 alcohols split
at 280°C was 92/8, a split not favorable for direct gasoline addition. However, it is noteworthy that
Lurgi's packed bed-based Octamix process incorporates methanol recycle to achieve a suitable
alcohol product composition.
35
...........................
,..............
.,,,,,,w,,_
.........
m.,ew,,m,_,,,,,,
e_,m,,,
,,,,n,,,,,
...........
,,,1,qp,,,nmlmliIlmm
mlllllw,,ii,
p,,,,_lmlqp
,,WlP,,,,_,n,_,,,,,,,
Iqaf_q,llql_PHPq,_
,,mare,,
,._,_
i,,.
PIH,Ilnqq_,,I_PlIIBll
_IqnlI_RIII'_IRFIPlIIIP
PlPI'IrqI_IIH
PlIPIIIHi
'll'l_lqlR'llllll
IlIIllqlllq_
IRIHIRn
IqlllIIIImlllllVl
_l_lln,nIIllfllIl_lllHqll_
HqlllPllllRil_lll_llqlllllql_ll_llllllilp_lHIll_lllll_flqlllll
I_lll!llllllHUlqllq
I_l_lli_lililllll_
_IRII
__oI_IIHI
_lq
I_NI_II_IIIIIII
_lllnl
_lllllnp_
qnqlll_ll_
i_lllIIlir_
illlllqlllllllflN
lqlllliMil
_1
FIGURE 3-18
Effect of On-Streom Time on Product Rates
Catalyst" Octamix
Run No." 12200-31
250°C, 7.0 MPa, Shell Gas, 5000 GHSV
O Methonol
• ZC2-C 6 Alcohols
A Dimethyl ether
500 .... I .... J .... I ' , , ,--_ 25
<----o-----o
--0-------
400 20
L. L_
.__ e-
l I
U_' 300 - 1 50_
"<" - _x:::
ao 200 - _ 10 0
0 _ [3
02 A Of
100 _ 5
0 150 1 O0 1 50 200
Time on streGm (hr)
3d
FIGURE 3-19
Effect of Temperature on Product Rotes
Catalyst: Octamix
Run No." 12200-31
7.0 MPa, Shell Gas, GHSV=5000 std. lit./kg-hr
0 Methanol
@ ZC2-C 8 Alcohols
A Dimethyl ether
500 .... ,, ,,, i .... , .... I .... ,50
400 40
c- e-
l
300 i/" 3o I
CD . IED
CD CD
_J 200 20 "-I
4-_ 4_J
cK rx
1000 I ..... I,,,, J .... j,,,, I .... 10

0
240 250 260 270 280 290
Temperature (°C)
i 37
!
FIGURE 3-20
Effect of Temperature on Product Selectivities
Catalyst: Octamix
Run No." 12200-31
7.0 MPa, Shell Gas, GHSV=5000 std. lit./kg-hr
0 Methonol
@ ZC2-C B Alcohols
A Dimethyl ether
100 .... I .... I'' " ,' I .... I .... 10
8O 8
60 6
• >,,
>_ 4--,
,--
t_ 40 4 -_
0
0 C)
C) (D
@ (23
O0
20 2
0 .... I , , , , I , , , , I .... 1 , , , , 0
240 250 260 270 280 290
Temperature (°C)
FIGURE 3-21
Alcohol Product Distribution
Catalyst: Octamix
Shell Gas, 280°C, 7.0 MPa, GHSV=5000 std. lit./kg-hr
90
0
c-
0
c-
E
85
/ z.,,
fft
e,'//
O_ frj
/'//
rf1
f/J
80 - ,,-,
/ z// /
/f -- 0 /"
0 t" /
4-_ / ,,,t _ 0 -
> 10 .... o -,.-,
. ,,,, -- o i I
. ,./ _ o o o _1 or_ I --o
-- c"
"" .' _ 13. C C
.c_ 0
Lr) 5 - ',-, _- o o _ -_ o
C _ X
" li., m I I
Iii
.79
3.2.2.3 Effect of Pressure
Figures 3-22 and 3-23 show the effect of reaction pressure on rate and selectivity, respectively. For
these experiments, reaction pressures of 5.3 MPa, 7.0 MPa, and 9.7 MPa were investigated using
Shell gas feed at 280°C and a GHSV of 5000 std. lit./kg-hr. Figure 3-22 shows that increasing
pressure from 5.3 MPa to 7.0 MPa resulted in an increased synthesis rate for methanol, _C2-C 6
alcohols, and DME. However, further increase in pressure from 7.0 MPa to 9.7 MPa had only a
slight effect on the rate; the methanol and DME rates were almost invariant in this range, while the
EC2-C6 alcohols rate decreased slightly. Since the effect of pressure on the rate for each of the
major products is of a comparable magnitude, the selectivity shows little variation with pressure
across this range, as illustrated in Figure 3-23.
3.2.2.4 Effect of Feed Gas Composition

The influence of syngas composition on the performance of the Octamix catalyst was investigated
by comparing the Texaco and Shell feed gases. Figure 3-24 shows the methanol and EC2-C6
'alcohols rates as a function of GHSV for both feed gases, while Figure 3-25 shows the
corresponding selectivity data. These data were obtained at 280°C and 7.0 MPa using GHSVs of
5000 and 10,000 std. lit./kg-hr. As observed for the cesium-promoted Cu/ZnO/A1203 catalyst, the
EC2-C6 alcohols rate and selectivity is much higher for Shell gas. Not surprisingly, selectivity to
EC2-C6 alcohols decreases with increasing GHSV.
3.2.3 Cu-Co Mixed Alcohols Catalyst

A Cu-Co based mixed alcohols catalyst was evaluated for use in a slurry reactor. This catalyst
sample was obtained under a confidentiality agreement from an external source. A sample of this
material was slurried with Drakeol 10 mineral oil and activated in-situ using a stream of 2% Hz in
N2. Following activation, the feed was changed to Shell gas at 5000 std. lit./kg-hr and the reaction
conditions adjusted to 250°C and 7.0 MPa. The temperature was maintained at 250°C for 48 hours,
after which the effect of temperature, pressure, GHSV, and syngas type were investigated.
3.2.3.1 Effect of Time on Stream

During the course of the investigation of various process variables, the reactor was periodically run
at a fixed set of conditions to measure the catalyst stability. The results for periodic runs at 280°C,
7.0 MPa, and 5000 std. lit./kg-hr of Shell gas feed are shown in Figure 3-26. The major products
were identified and grouped as methanol, ZC2-C6 alcohols, and )_Cl-C 6 hydrocarbons. These
products account for 97 wt% of the total products observed; a very small selectivity low molecular
weight esters accounts for the balance. No ether products were observed. The ZC2-C6 alcohols and
EC_-C6 hydrocarbons rates decrease monotonically with on-stream time, while the methanol rate
first increases then decreases with time. The rates appear to level off after approximately 150 hours
on stream.
3.2.3.2 Effect of Gas-Hourly Space Velocity

Figure 3-27 shows the effect of GHSV on the synthesis rates of the major products at 290°C and
7.0 MPa using the Shell feed gas. As shown, the methanol rate increases with GHSV, ranging from
20 g/kg-hr at 3000 std. lit./kg-hr to 32 g/kg-hr at 10,000 std. lit./kg-hr. Interestingly, the ECI-C 6
hydrocarbons rate increases slightly between 3000 std. lit./kg-hr and 5000 std. lit./kg-hr, but
decreases upon further increase in GHSV to 10,000 std. lit./kg-hr. The ZC2-C6 alcohols rate also
increases slightly from 3000 std. lit./kg-hr to 5000 std. lit./kg-hr, but appears to be approximately
constant at higher GHSV.
'' IV i
FIGURE 3-22
Effect of Temperature on Product Rates
Catalyst" Octamix
Run No." 12200-31
280°C, Shell Gas, GHSV=5000 std. lit./kg-hr
0 Methanol
• EC2-C 8 Alcohols
A Dimethyl ether
500 .... i .... i .... I' , ,, I .... 50
400 40
c- e-
l 300 ____) 30 I
E_ E_
E_ E_
_J 200 - _A 20
(D /A _ (1)
4-, / .4.-.,
C_ A rv
100 10
0 , , ___ i , , ___ i , , , , I , , , , I .... 0

5 6 7 8 9 10
Pressure (MPG)
41
FIGURE 3-23
Effect of Pressure on Product Selectivities
Catalyst" Octamix
Run No.' 12200-31
280°C, Shell Gas, GHSV=5000 std. lit./kg-hr
0 Methanol
A Dimethyl ether
100 .... i,,,, i,,,, I .... i .... 120
0 0 0
80 <------
_-_ _15
60 v
>_ >_
e_
10-,-,
o_
.> >
o 40 _ _ o
__o 4-------
(/3 .A 5 Or)
20 • ---_--A-
0 , , , , I , , , , I , I , ' I , , , , I ' ' ' _ 0

5 6 7 8 9 0
Pressure (MPo)
I 42
FIGURE 3-24
Effect of Syngas Composition on Product Rates
Catalyst: Octamix
Run No." 12200-31
280°C, 7.0 MPa
• Texaco Ges (51_ C0/35_ H2/13_ C02/1_N 2)

0 Shell Gas (66_ C0/30_H2/3_ 002/1_ N2)
1000 , , , 'l , ' ' 50 ' ' ' ' ' ' ' /
Methanol _-C2 Cs Alcohols
800 • 40
0 _-
¢- ¢-
I
cn 600 I
cn 30
cn cn
"_ "-_ 20
400 ¢_
o
n,- o
n,"
200 10
0 l , , 1 , , , 0 , _,___, 1 , i ,
4000 8000 12000 4000 8000 12000
GHSV (std. lit./kg-hr) GHSV (sta. lit./kg-hr)
43
I
i i i ,
FIGURE 3-25
Effect of Syngas Composition on Product Selectivities
Catalyst: Octamix
Run No.' 12200-31
280°C, 7.0 MPa
@ Texaco Gas (51_ C0/35_ H2/13_ C02/1_ N2)

0 Shell Gas (66_ C0/,30_ H2/3_ C02/1_ N2)
100 , , , , , , .,.... 10 , , , , , , ,
__----e - TC -C Alcohols
• _0 2 6
0__--- _
80 8 -
Methanol -
60 _ 6 O_
>, >,
"1"-II ,m
°_
"-> :_ \0
o 40 o 4
o _ -
-$ o
co co
20 2 _
0 , , , I , , ' 0 , , , I ,
4000 8000 12000 4000 8000 12000

GHSV (std. lit./kg-hr) GHSV (std. lit./kg-hr)
44
J
FIGURE 3-26
Effect of On-Stream Time on Product Rates
Catalyst" Cu-Co
Run No." 12071-14
Shell Gas, 280°C, 7.0 MPa, GHSV=5000 std. lit./kg-hr
0 Methanol
• TC2-C 8 Alcohols
EC1-C s Hydrocarbons
25 .... , .... , ,, , ' , ' "" ' I .... , .... I
20
1 15
Cn
"_" 10 _ _.
(tj ___.
0 i R , , I .... I,, , , I , ,,, I l,, , 1, ,,

o so loo 1so 200 2so _oo
Time on Syngos (hr)
4#
FIGURE 3-27
Effect of GHSV on Product Rates end Selectivities
Catalyst: Cu-.Co
Shell Gas, 290°C, 7.0 MPa
0 Methanol
• TC2-C 8 Alcohols
ECI-C 8 Hydrocarbons
40,,, I'', , ' ' ' 60 ,'' i',' J ' ' '
0 50 _0
_L. _. 4-0
__ 20 ....
_' 50 _'-'_-_
°_
v
_ A _ U
o- v---v-_ • 20
•
10
10
0 4000 8000 12000 0 4000 8000 12000
45
The selectivity plot in Figure 3-27 shows that the selectivity to C2.-alcohols is a weak function of
GHSV, decreasing slightly with increasing GHSV. The increase in selectivity to methanol with
increasing GHSV occurs at the expense of a corresponding decrease in selectivity to hydrocarbons.
As can be seen, at low GHSV, the selectivity to hydrocarbons is approximately equal to the
selectivity to ZC2-C6 alcohols.
The alcohol product composition is in the acceptable range for direct gasoline blending. The
methanol/_C2-C 6 alcohols weight ratio is a strong function of GHSV, ranging from 56/44 at
3000 std. lit./kg-hr to 66/34 at 10,000 std. lit./kg-hr.
Figure 3-28 shows the alcohol product distribution obtained for this Cu-Co catalyst using the Shell
feed gas. Selectivity values in Figure 3-28 are based on total organic products, including
hydrocarbons and esters. Selectivity to the individual alcohols decreases with increasing molecular
weight. In addition, the alcohol products are exclusively primary alcohols. In contrast to the case
for the Cu/ZnO/A1203-based catalysts discussed earlier, the selectivity to linear primary alcohols is
greater than the selectivity to branched primary alcohols. The high selectivity to linear alcohol
products has been reported to be a characteristic of the Cu-Co based catalysts. _4
Figure 3-29 shows the effect of GHSV on the rate and selectivity for the Texaco feed gas. The
effect of GHSV on the product rates is similar to that observed for Shell gas, but the rates and
relative proportions of the various products are different. Comparison with Figure 3-27 for Shell
gas indicates that methanol and ZC2-C6 alcohols rates are lower for Texaco gas, while the ZC_-C6
hydrocarbons rate is higher for Texaco gas, across the GHSV range investigated. In fact, the
selectivity to hydrocarbons for the Texaco feed gas is considerably higher than the selectivity to C2+-
alcohols. The overall performance of the catalyst, in terms of productivity and selectivity for
alcohols, is considerably better for the Shell feed gas in comparison to the Texaco feed gas.
3.2.3.3 Effect of Temperature

Figure 3-30 shows the measured effect of temperature, between 260°C and 300°C, on the rates and
selectivities for the major products. These experiments were done at a reaction pressure of 7.0 MPa
using the Shell gas feed at a GHSV of 5000 std. lit./kg-hr. The production rate for ali products
increases with temperature. The rate of increase in methanol rate with temperature is not as great as
the increase in ZC_-C6hydrocarbons rate. The result of this is that, as temperature is increased, the
selectivity to methanol decreases at the expense of an increase in the selectivity to hydrocarbons.
The selectivity to ZC2-C6 alcohols shows little variance with temperature, remaining approximately
constant at 30 wt% across the range of temperature investigated here. In summary, selectivity to
total alcohols is enhanced by operation at low temperature, but this comes at the expense of
decreased prc,ductivity.
3.2.3.4 Effect of Pressure

Figure 3-31 shows the effect of total pressure on the rates and selectivities for the major products.
For these experiments, the pressure was varied between 5.2 MPa and 9.8 MPa at a reaction
temperature of 290°C using the Shell gas feed at a GHSV of 5000 std. lit./kg-hr. The production
rates of methanol, ZC2-C6 alcohols, and ZC1-C6 hydrocarbons increase monotonically with pressure
across the range examined. The extent to which pressure influences the rate is similar for ali
products, resulting in little variation in selectivity as a function of pressure.
47
FIGURE 3-28
Alcohol Product Distribution
Catalyst: Cu-Co
Shell Ges, 290°C, 7.0 MPe, OHSV=5000 std. lit./kg-hr
60
50 o
N E
_ f/_
/// 0
40 7 ... c /
o _ _ /,
// _ o c Z
20 / --- c 0
> •
///
///
• 0
• /// z/z _ 0
• /// ,., _ __ I I
-- I// z / / 0 0 _ --
" /// ''' _ -- c I 0 --
/// _ _ 0 0 -- C --I 0
10 - ---
///
---
///
I c _ _ o _ c0
/// I-// _ • 0 0 •
/// ... 0 _ I I I I
0 ,.. i" ir771 _ _ --
48
FIGURE 3-29
Effect of GHSV on Product Rates and Selectivities
Catalyst: Cu-Co
Texaco Gas, 290°C, 7.0 MPa
0 Methanol
v TC1-Ce Hydrocarbons
40 ,,, i,,, i _ , , 60 ,,, i, _, i , , ,
50
30
r'-
_ v
4.,
°
_7
"_ 20 -_, 30
O --
_ 20
a: _ m
10
10 -
0 , , , I , , , I , , , 0 , , , 1 , , m 1 , , ,
0 4000 8000 12000 0 4000 8000 12000
GHSV (std. lit./kg-hr) GHSV (std. lit.//kg-hr)
49
FIGURE 3-30
Effect of Temperature on Product Rates and Selectivities
Catalyst: Cu-Co
Shell Gas, 7.0 MPa, GHSV=5000 std. lit./kg-hr
0 Methonol
V TC1-C8 Hydrocarbons
40 , i,, , l,, , i , 60 , i,,, i".,, i,--
_0 °--_o_ °
k.
30 / %
20 ._ 30
_-, .__
0 --
_ 20
o 10
o
10
0 , 1 • __ , I L , , I , 0 , I , , _ I , , , 1 ,
260 280 300 260 280 300
Temperature (°C) Temperature (°C)
5o
FIGURE 3-31
Effect of Pressure on Product Rates and Selectivities
Catalyst: CJ-Co
Shell Gas, 290QC, GHSV=5000 std. lit./kg-hr
0 Methanol
@ EC2-C 8 Alcohols
_7 EC1-C s Hydrocarbons
40 ,,,, .... j,,_,, .... ,.... 60 L.... '"""""_""""'J

r
5O
30 _0 0 -------------°
20 _ 30
v _ .
o V-_-------V__V
o
Pf © 20
60 -
10
10
.j
l
0 j,, ,1 .... I .... I .... I .... 0 .... I .... I,j, , I .... I, ,,
5 6 7 8 9 10 5 6 7 8 9 10
Pressure (MPa) Pret_sure (MPa)
51
3.2.4 Two-Component Catalyst Systems
The goal here was to investigate two-component catalyst systems for the conversion of syngas to
mixed alcohols. Studies of the reaction mechanism for the formation of mixed alcohols indicate that
higher molecular weight alcohols are formed from lower molecular weight alcohols via a sequential
mechanism. The focus was to investigate the use of certain co-catalysts together with Cu/ZnO/
AI203 in the same reactor to enhance the conversion of lower alcohols to higher alcohols. Two
reaction concepts were envisioned: (1) methanol formed on the Cu/'ZnO/A1203 component could be
further reacted/homologated to higher alcohols over the co-catalyst, or (2) ethanol and/or C2-
oxygenates, formed over the co-catalyst at a greater rate than that for Ctt/ZnO/A1203, could enter the
reaction sequence to form C3+-alcohols.
In this investigation, two type of catalysts were used as co-catalysts with BASF $3-86, a Cu/ZnO/
A1203methanol synthesis catalyst. This catalyst was promoted with Cs in the studies discussed
previously. One material, lanthanum strontium manganite (La0.gSr0._MnO3),is of the class of
compounds known as perovskites. This material contains cations of high basicity (La3., Sr2+);basic
cations are known to enhance selectivity to higher alcohols. In addition, this material contains
manganese, a metal present in many catalysts developed for synthesizing mixed alcohols. The other
material used as a co-catalyst was rhodium supported on La.203. Rhodium on basic oxide supports,
such as La203, is known to be selective for the synthesis of C2-oxygenates, particularly ethanol and
acetaldehyde, from syngas. Two Rh/La203 catalysts, differing only in Rh loading (0.5% and 5.0%
by weight), were investigated. In ali three cases, the co-catalyst was used together with Cu/ZnO/
A1203in a 50:50 mixture by weight.
Figure 3-32 shows the results obtained for 100% Cu/ZnO/AI203 and 50:50 mixtures of Cu/ZnO/
A1203with 0.5% Rh/La203, 5.0% Rh/La203, and La0.gSr0._MnO3.The performance results are shown
as the measured production rates for methanol and EC:-C_ alcohols versus GHSV obtained at 300°C
and 7.0 MPa using Shell gas feed. Only a single GHSV was investigated in the case of the
La0.9Sr0.1MnO 3 catalyst, lt is important to note that the rate and GHSV are calculated based on the
total weight of catalyst in the reactor, including the co-catalyst for the cases where co-catalyst was
used.
For methanol synthesis, the rate is comparable for each catalyst system except the 5.0% Rh/La203 +
Cu/ZnO/AI203 mixture. The rate for this particular system is lower than that for the other catalysts
at the higher space velocities of 5000-10,000 std. lit./kg-hr. Much larger differences between the
catalysts were observed for the ZC2-C6alcohols rate. None of the two-component catalyst systems
performed better than the Cu/ZnO/AI203 operating alone with no co-catalyst. For the two Rh/La203
+ Cu/ZnO/A1203 systems, the 0.5% Rh/La203 co-catalyst performed much better than 5.0% Rh/
La203 co-catalyst. Among the two-component systems, the La0.gSr0.1MnO 3 + Cu/ZnO/AI203 mixture
showed the best performance in terms of _C2-C6 alcohols rate, at least at a GHSV of 5000 std. lit./
kg-hr.
For the La0.9Sr0.tMnO3 + Cu/ZnO/AI203 and 0.5% Rh/La203 + Cu/ZnO/A1203 systems, the use of the
co-catalyst had only a minor effect on the distribution of alcohol products among the C2+-alcohols.
The most significant effect on product distribution was observed for the 5.0% Rh/La203 + Cu/ZnO/
A1203mixture. A comparison of the alcohol product distributions obtained for the 5.0% Rh/La203 +
Cu/ZnO/Ai203 mixture and Cu/ZnO/AI203 alone is showll in Figure 3-33. As shown, the selectivity
-| to ethanol is slightly higher for the mixture, while the selectivity to products higher than ethanol is
" Ill
FIGURE 3-32
Comparison of Performance of Two-Component

Catalyst Systems
Shell Gas, 300°C, 7.0 MPa
m Cu/ZnO/AI203
@ 0.5_ Rh/La203 + Cu/ZnO/AI203
v 5.0_ Rh/La203 + Cu/ZnO/AI203
Lao.9Sro.lMnO 3 + Cu/ZnO/AI203
600 ,,, i''' i ' ' ' 120 ,,, J,,, I ' ' '
Methanol TC2-C 6 Alcohols
500 100 m
_- 400 _. 80
..E e-
l I _"°3
.--Y. LOo 9Sro IMnO3
"_ 300 x_ _ 60
v
"_
o 200 _o 40
r'Y rv"
100 / 20 - 1
0 , , , 1 , , I I , , , 0 I I 1 I _ , I I , , '
0 4000 8000 12000 0 4000 8000 12000
FIGURE 3-33
Comparison of Alcohols Product Distributions for

Cu/ZnO/AI2O 3 and Cu/ZnO//AI2Oz, + 5,% Rh/La20 _
300°C, 7.0 MPa, GHSV=5000 std. lit./kg-hr, Shell Gas
Cu/ZnO/Ai203 5% Rh/La203-Cu/ZnO/AI203
85 85
less for the mixture. The reason for the suppression in higher products is not clear and, to gain
understanding, would require further investigation.
In summary, none of the mixed catalyst systems investigated here performed better than Cu/ZnO/
AI203. Obviously, further work is necessary to identify or develop viable co-catalysts.
3.2.5 Comparison of Mixed Alcohols Catalysts

In summary, several catalysts were investigated for use in a slurry reactor;, these were single-
component catalysts, as well as two-component systems which involved the use of a co-catalyst with
Cu/ZnO/A1203. The use of the particular co-catalysts that were investigated, in physical mixtures
with Cu/ZnO/A1203, apparently did not provide any performance advantage over the use of Cu/ZnO/
A1203alone. More work is needed to identify or develop suitable co-catalysts. However, it is
worthwhile to compare the performance of the four single component catalysts that were
investigated: (1) a Cu/ZnO/A1203 methanol synthesis catalyst, (2) a Cs-promoted Cu/ZnO/AI203
methanol synthesis catalyst, (3) Lurgi's Octamix catalyst, which is also an alkali-promoted Cu/ZnO-
based material, and (4) a Cu-Co based mixed alcohols catalyst.
Comparisons of the performance of the four catalysts, at a common set of reaction conditions, are
shown in Tables 3-6 and 3-7. Table 3-6 shows a comparison of the production rates of methanol,
ZC2-C6alcohols, and ZC_-C6 hydrocarbons at 280°C, 7.0 MPa, and 5000 std. lit./kg-hr of Shell feed
gas. Table 3-7 shows the corresponding product selectivities obtained at these same reaction
conditions.
TABLE 3-6
Comparison of Measured Product Rates for
Cs-Cu/ZnO/Ai203, Lurgi Octamix, and Cu-Co Catalysts
Reaction Conditions: Shell gas, 280°C, 7.0 MPa, GHSV=5000 std. lit./kg-hr
Production Rate (g//kg-hr)

EC2-C 6 _CI-C 6
Catal_,st Run No. Methanol alcohols hydrocarbons

Cu/ZnO/A1203 11472-39 361 57.1 5.1
Lurgi Octamix 12200-31 368 31.4 3.0
Cu-Co 12071-14 16 9.6 7.3
Cs-Cu/ZnO/AI203 I 1168-75 357 68.5 5.7
.... _r .... _ .......

55 IIr ' lit II JP '
TABLE 3-7
Comparison of Measured Product Rates for
Cs-Cu/ZnO/AI203, Lurgi Octamix, and Cu-Co Catalysts
Reaction Conditions: Shell gas, 280°C, 7.0 MPa, GHSV=5000 std. lit./kg-hr
Production Rate (g//kg-hr)

_"_C2-C6 __,Cl -C6
Catalyst Run No. Methanol alcohol s hydrocarbons

Cu/ZnO/AI203 11472-39 83.7 13.3 1.2
Lurgi Octamix 12200-31 84.6 7.2 0.7
Cu-Co 12071-14 48.5 28.6 21.6
Cs-Cu/ZnO/AI203 11168-75 81.6 15.7 1.3
When producing mixed alcohols for blending into gasoline, the goal is to achieve a high selectivity
for C2+-alcohols, which are cosolvents for the methanol product. In addition, a high total alcohols
synthesis rate is desirable, since this will increase reactor productivity. Non-selective conversion of
syngas to products other than alcohols, e. g., light hydrocarbons, is undesirable.
Using the above criteria as a guide, comparisons of the four catalysts (Tables 3-6 and 3-7, and much
of the other process variable studies done on these catalysts) indicate that the Cs-Cu/ZnO/AI203
catalysts showed the best overall performance. The EC2-C6 alcohols rate was higher for this catalyst
than the others. Although the Cu-Co catalyst had the highest selectivity to C2+-alcohols, the rate was
significantly less than either of the other two catalysts. Moreover, the Cu-Co catalyst had the
highest rate and selectivity to hydrocarbons.
The present results indicate that Cs-Cu/ZnO/AI203 is a viable catalyst for the slurry-phase synthesis
of mixed alcohols from syngas. Further work on this catalyst, including some longer-term life tests,
is necessary to determine its viability in a commercial process.
It is noteworthy that a potentially attractive characteristic of the Cs-Cu/ZnO/A1203 catalyst is its

ability to produce a relatively high selectivity to branched-chain alcohols, particularly the
"2-methyl-" isomers. Notable branched-chain product alcohols from this catalyst include isobutanol
(2-methyl-l-propanol) and 2-methyl- 1-butanol. These products are of particular interest because
they can be dehydrated to useful olefins. The products of direct, intramolecular dehydration of
isobutanol and 2-methyl-1-butanol are isobutylene and isoamylene, respectively. Isobutylene and
isoamylene can be reacted with an alcohol, particularly methanol, to produce methyl tert-butyl ether
(MTBE) and tert-amyl methyl ether (TAME), respectively. Both ethers are, of course, known to be
outstanding oxygenated gasoline additives. Thus, alcohols produced from coal-derived syngas using
Cs-Cu/ZnO/A1203 represent a viable, alternative source of iso-olefins for use in etherification.
3.3 Slurry-Phase Conversion of Syngas to Mixed Ethers via Mixed
Alcohols
3.3.1 Product Identification

As mentioned previously, the dehydration of mixt_es of alcohols is likely to yield a variety of
products. The most prevalent products are expected to be mixed ethers, formed from intermolecular
condensation of alcohols. In addition, olefins, which are formed from intramolecular dehydration of
alcohols, are an expected side product. Ethers are the desirable products. The goal is to produce
mixed ethers from product of a mixed alcohols synthesis catalyst.
A variety of ether products are expected from the condensation of a mixture of alcohols.
Statistically, n(n+ 1)/2 different ethers can be formed from direct, intermolecular condensation of n
different alcohols, assuming no rearrangement of the carbon backbone structure of the reactant
alcohols. The major alcohol products from syngas conversion to mixed alcohols are C_-C4primary
alcohols: methanol, ethanol, 1-propanol, 1-butanol, and isobutanol (2-methyl-l-propanol). Thus,
considering only these alcohol products, the number of different ethers that could be formed, by the
above formula, is 5(5+1)/2=15.
Table 3-8 lists the possible ether products from condensation of C_-C4 primary alcohols. Also
shown in the table are the structures of these ethers and their boiling points. Several of the ethers
listed are not commercially available and must be synthesized for gas chromatographic identification
and quantification purposes. For the purposes of the present investigation, none of the ethers were
synthesized, but small samples of several of the commercially available ethers were purchased.
Table 3-8 also indicates whether each ether was purchased as a pure sample for identification and
quantification purposes.
TABLE 3-8
Expected Ether Products from Condensation of
Methanol, Ethanol, 1.Propanol, l-Butanol, and Isobutanol
Boiling Obtah_ed
Point Sample?
Ether Structure (°C) (Y/N)
dimethyl CH;O-CI_ -24.9 Y
methyl ethyl CI-t3-O-CI-tzCI-t
3 7.3 N
diethyl CI-I3CI-Iz-O-CI-I2Ct_ 34.5 Y
methyl n-propyl CI-I3-O-CI-I2CI-I2CH 3 38.9 N
methyl isobutyl CI-I3-O-CI-I2CH(CI-13)CI _ 58 N
ethyl n-propyl CH3CH2-O-CI-_CI-_CH 3 63.6 N
di-n-propyl CH3CI-_CH2-O-CI-_CH2CI-_ 68.3 Y
methyl n-butyl CI-I3-O- CH2CI-IzCI-I2CI-t
3 71 Y
ethyl isobutyl CI-13CI-I2-
O- CINCH (CI-I3)CI-I3 81 Y
ethyl n-butyl CI--I3
CI-I2-O-CI-I2CH2CI-t2CH 3 92.2 Y
n-propyl isobutyl CI-I3CI-12CI-Iz-
O- CI-12CH(CI-13)CI-I
3 105 N
n-propyl n-butyl CH_CI-I2Ct-_-O- CI-_CH2CI-tzCH3 117.1 N
diisobutyl CI-t3CH(CI-I3)CI_-O-CI-t2CH(CI-I3)CI _ 122 N
n-butyl isobutyl CH3CH2CI-I2CI-I2-O-CH2CH(CH3)CH 3 N/A N
di-n-butyl CI-I3CI-t2CI-IzCI-Iz-
O- CH;_CI-I2CI-I2CH3 142.4 N
57
Reaction product peak identification on the FID gas chromatograph was done in the following way.
Gas chromatographic retention times were determined for ali of the ethers that were obtained as pure
samples. Identification of ether products for which pure samples were not available was done by
considering their boiling points with respect to the other ethers, as well as by consideration of which
products were expected. In addition, retention times for C_-C8alcohols, CI-C8 hydrocarbons, and
some esters were determined. Many possible products, besides ethers, could be eliminated by those
determinations. Also, two studies involving dehydration of three-component alcohol mixtures of
different and known composition, the results of which are presented later, assisted in the
identification of gas chromatographic peaks.
Quantification of pure ether products was done by making liquid calibration mixtures of known
composition and calibrating the gas chromatograph using a standard procedure. This resulted in the
determination of response factors for these available ethers. Calibration for the unavailable ethers
was more challenging. For these ethers, the response factors for the pure samples were used as a
guide, along with the response factors for paraffins of similar structure. A correlation was made of
ether response factor to the response factor of a paraffin with the same number of carbon atoms.
Using this correlation, the response factors for ethers which were not available as pure samples, such
as methyl ethyl ether and methyl propyl ether, could be calculated. The method used also assumed
that response factors were independent of the location of the -O- linkage in the molecule or the
degree of branching within the alkyl groups. So, for example, methyl n-propyl ether and diethyl
ether were assumed to have the same response factor, both having four carbon atoms. Likewise,
methyl isobutyl ether was assumed to have the same response factor as methyl n-butyl ether. The
method used here is subject to some error; the response factors determined are probably only
accurate to within 10%.
Figure 3-34 shows the correlation developed between the ether response factor and the paraffin
response factor from which some ether response factors were determined. The response factor
(denoted RF) is defined as the molar concentration per unit peak area. As can be seen, the ratio
RF(ether)/RF(paraffin) decreases with increasing carbon number. For methyl ethyl ether, which is
the only ether with three carbon atoms, the response factor was necessarily determined by
interpolation. This interpolation was done by fitting the data with the curve shown in Figure 3-34.
3.3.2 Dehydration of Three-component Mixed Alcohols Streams

Two different, three-component alcohol taixtures were prepared. The composition of these mixtures
is shown in Table 3-9.
TABLE 3-9
Composition of Alcohol Mixtures Used in Alcohol Dehydration Experiments
Concentration in Mixture
(wt%/mol%)
Mixture Number Methanol Ethanol 1-Propanol Isobutanol
11168-71 64.4/73.6 25.5/20.3 10.1/6.1 --
11168-73 77.3/87.3 13.8/8.3 -- 8.9/4.4
FIGURE 3-34
Correlation of FID Response Factors

for Ethers and Paraffins
2,0 I 1 i I I -
1.9
1.8 '
c-
,-,-- 1.7
13_
1 6
I,
rx 1.5
1.4
c-
"" 1.3
rY 1.2
1.1
1.0 i i I i
2 3 4 5 6
No. of C Atoms
The proportions of methanol, ethanol, and 1-propanol in mixture 11168-71 were chosen to simulate
the composition of the mixed alcohols produced over a Cu-Co based catalyst. The Cu-Co catalyst
does not produce significant quantities of isobutanol, so it was not included in the mixture. The
other mixture, 11168-73, includes proportions of methanol, ethanol, and isobutanol which simulate
the product from an alkali-promoted Cu/ZnO/AI203 catalyst, such as that used in Lurgi's Octamix
process. Typically, for the product from this type of catalyst, isobutanol production exceeds
propanol production. For this reason, 1-propanol was omitted from this mixture. The absence of
isobutanol in mixture 11168-71 and 1-propanol in mixture 11168-73 results in different product
spectrums upon dehydration. This aided in identifying the ether products on the gas chromatogram
for which no standard was available. Six different ethers are possible by direct condensation
without C backbone rearrangement. Table 3-10 shows the expected ether products for each alcohols
mixture.
TABLE 3-I0
Expected Ether Products from Direct, Intermolecular Condensation of Alcohol Mixtures
Mixture Number Expected Ether Products

11168-71 dimethyl methyl methyl diethyl ethyl di-n-
ethyl n-propyl n-propyl propyl
11168-73 dimethyl methyl methyl diethyl ethyl diiso-

ethyl isobutyl isobutyl butyl
For the alcohol dehydration studies, these alcohol mixtures were vaporized into flowing N2
immediately upstream of the reactor. The flow rates of N2and alcohol mixture were adjusted to
yield 10 mol% alcohols and 90 mol% N2at a combined GHSV of 5000 std. lit./kg-hr. The reaction
pressure for the experiments was 5.3 MPa. The catalyst, Catapal SB y-A1203in powder form, was
combined with Drakeol 10 mineral oil, the slurry liquid. Experiments done using N2 flow alone
showed that the Drakeol 10 oil did not break down or crack at temperatures up to 300°C.
Tables 3-11 and 3-12 show results for the reaction of alcohol mixtures 11168-71 and 11168-73,
respectively. These data are for reaction at 300°C. As shown in Tables 3-11 and 3-12, alcohol
conversion was quite high, greater than 76% for both alcohol mixtures. Conversions of the
individual alcohols were comparable, ranging from 76% to 85%. In addition, conversion shows
little variation with on stream time, at least for the time scale of the experiment.
TABLE 3-11
Conversion and Selectivity for Reaction of Alcohol Mixture 11168.71
Run No: 11168-72

Reaction Conditions: 300°C, 5.3 MPa, GHSV=5000 std. lit./kg-hr
Catalyst: Catapal SB y-Al203
Selectivity Selectivity Feed C

Time on Methanol Ethanol 1-Propanol to to Ct-C,, Atom
Stream Conversion Conversion Conversion Ethers Hydrocar- Recovery
(hr) (%) (%) (%) (C%) bons (C%) (%)
3.2 77 84 85 67 6.5 79
3.8 77 83 84 67 5.1 78
4.3 77 84 85 63 4.6 74
The selectivities reported in Tables 3-11 and 3-12, expressed as C%, were calculated by the
following:
C% Selectivity for product(s) i = 100% x (C converted to product i)/(total feed C converted)..
The major products besides ethers were hydrocarbons. However, the GC method employed did not
separate paraffins from olefins, so no distinction could be made. Presumably, the major type of
hydrocarbon product formed was olefin from intramolecular dehydration of the feed alcohols. As
can be seen in Tables 3-11 and 3-12, the selectivity to hydrocarbons is quite low, at least a factor of
10 lower than the selectivity to ethers for both alcohol mixtures.
'FABLE 3-12
Conversion and Selectivity for Reaction of Alcohol Mixture 11168-73
Run No: 11168-74

Catalyst: Catapal SB y-A1203
Selectivity Selectivity Feed C

Time on Methanol Ethanol 1-Propanol to to CI-C4 Atom
Stream Conversion Conversion Conversion Ethers Hydrocar- Recovery
(hr) ,, (%) (%) (%) (C%) bons (C%) (%)
3.9 77 80 77 74 4.4 84
4.4 76 79 77 73 4.0 83
5.0 76 80 77 72 3.8 82
Feed C recovery, the percentage of feed carbon accountable in measured products, was 74-79% for
alcohol mixture 11168-71 and 82-84% for alcohol mixture 11168-73. These values were lower than
expected. Other products besides ethers and hydrocarbons were detected but not quantified in the
61
| i i ,, ,u
chromatograms. The total of these unknowns is not sufficient to make up for the "missing" C, but
does account for a portion of it. There are two other possible reasons for the low recovery values.
First, a change in the color of the y-A1203catalyst from white before reaction to gray after reaction
indicates some carbon may have been deposited, perhaps as coke, and is not accounted for in the exit
stream. Second, the feed flow rate of alcohols may have been lower than expected because of error
in the syringe pump used for the injection. The extent to which each of these phenomena
contributes to the low C recovery is not clear.
Tables 3-13 and 3-14 show the ether product distributions obtained for dehydration of alcohol
mixtures 11168-71 and 11168-73, respectively. The product distribution is expressed in terms of the
reactor exit product molar concentration for each ether normalized to the dimethyl ether product
molar concentration. Thus, the values in Tables 3-13 and 3-14 are the ether product concentrations
relative to the concentration of product dimethyl ether. Also shown is the calculated product
distribution based simply on the probability of the various bimolecular reactions between the feed
alcohols. In these calculations, the probability of formation of each product is assumed to depend
on the (multiplicative) product of the molar concentration of each reactant alcohol in the feed.
Thus, the probabilistic normalized ether product concentration (PNEPC) for an ether formed by
condensation of alcohol (i) and alcohol (j) is calculated for each ether (ij) by:
PNEPCij =(Yi)(Yj)/(Yraa3H)
2,
where Yiand yj are the feed molar concentrations of reactant alcohols i and j, respectively, and YM,,oH
is the feed molar concentration of methanol.
TABLE 3-13
Ether Product Distribution for Reaction of Alcohol Mixture I1168-71
Run No.: 11168-72

Catalyst: Catapal SB y-Al203
Time Normalized Ether Product Concentration

on Stream Methyl Methyl Ethyl Di-n-
(hr) Dimethyl Ethyl n-Propyl Diethyl n-Propyl Propyl
3.2 1.000 0.280 0.087 0.023 <0.011 0.005
3.8 1.000 0.292 0.088 0.029 <0.016 0.005
4.3 1.000 0.295 0.089 0.029 <0.016 0.005
Probability of biomolecular 1.000 0.275 0.084 0.076 0.023 0.007

reaction based on feed
concentrations of alcohols
(PNEPC)
62
TABLE 3.14
Ether Product Distribution for Reaction of Alcohol Mixture 11168-73
Run No.: 11168-74

Catalyst: Catapal SB y-AlzO3
Time Normalized Ether Product Concentration

on Stream Methyl Methyl Ethyl
(hr) Dimethyl Ethyl Isobutyl D.iethyl Isobutyl Diisobutyl
3.9 1.000 0.121 0.047 0.004 0.005 <0.001
4.4 . 1.000 0.121 0.045 0.004 0.005 <0.001
5.0 1.000 0.119 0.045 0.004 0.005 <0.001
Probability ofbiomolecular 1.000 0.095 0.050 0.009 0.005 0.002

reaction based on feed
concentrations of alcohols
(PNEPC)
The retention times of ethyl n-propyl ether and diisobutyl ether could not be determined
unequivocally, since pure component standards for these ethers were not available. So, the results
shown in the tables indicate the maximum value of the concentration of ethyl n-propyl ether or
diisobutyl ether based on the largest peak in the general vicinity of their expected retention time,
For both alcohol mixtures, the major product ether was dimethyl ether. This is perhaps not
surprising since methanol is present in the highest concentration of both alcohol mixtures. In fact,
for both alcohol mixtures, ethers with at least one met_,yl group attached to the -O- linkage
dominate. For alcohol mixture 11168-71, the second and third most prevalent ether products are
methyl ethyl ether and methyl n-propyl ether, respectively. Likewise, for alcohol mixture 11168-73,
methyl ethyl ether and methyl isobutyl ether are the second and third most prevalent products, lt is
noteworthy that the distribution of these "methyl" ethers agrees with what would be predicted based
on the simple probability of bimolecular reaction. However, the formation rate of the other ethers,
those resulting from the bimolecular reaction of alcohols higher than methanol, is lower than that
predicted based on simple probability. The reason for this is not clear. One possibility is that steric
hindrances, caused by the bulkiness of the alcohols higher than methanol, may retard the formation
of these ethers, resulting in production rates lower than those expected based on simple probability.
The results for dehydration of these simple mixtures of alcohols indicate that mixed ethers can be
formed at high conversion and good selectivity over the y-Al203 catalyst. Moreover, these favorable
results can be obtained at 300°C and 5.3 MPa, a temperature and pressure which are also favorable
for producing mixed alcohols from syngas. This compatibility in terms of reaction conditions
suggests the possibility of combining the two reaction steps in one reactor. In this scenario, mixed
alcohols produced from syngas over a mixed alcohols catalyst could be reacted in-situ over a
y-AlzO3catalyst to mixed ethers. Experimental results obtained for combination of these reaction
steps in a single slurry reactor, using a mixed catalyst system, are presented in the next section.
63
3.3.3 One-Step Conversion of Syngas to Mixed Ethers
These experiments involved the use of mixtures of two catalysts, a mixed alcohols synthesis catalyst
and an alcohol dehydration catalyst, in the same autoclave reactor. The mixed alcohols catalyst was
Cs-promoted Cu/ZnO/A1203, the same material used in the syngas to mixed alcohols studies
discussed earlier. The dehydration component was Catapal SB y-AI203, which was used in the
alcohol dehydration studies discussed above. These two catalysts were slurried together in various
proportions using Drakeol 10 mineral oil. The Cs-Cu/ZnO/A1203 component was reduced in the
reactor using the same procedure as that used in the mixed alcohols synthesis studies. Peak
assignment and quantification were somewhat more difficult for these studies because of the large
number of products typ :ally present in the reactor exit stream. Some minor products could not be
identified.
3.3.3.1 Effect of Al20 J in the Mixed Catalyst System:

Figure 3-35 shows the influence of AI203 content on the rate oi syn_esis of the various products.
The C3.-ether products consist largely of methyl ethyl, methyl n-propyl, methyl isobutyl, diethyl,
and di-n-propyl ethers. In the case of the Cs-Cu/ZnO/A1203 catalyst alone (0% A1203in Figure
3-35), the ether production rate is close to zero. As the A1203frz.ctxonincreases, the methanol and
EC2-C6alcohols rates decrease rapidly and monotonically. The decrease in alcohols rate is
accompanied by a corresponding monotonic increase in the rate of production of dimethyl ether, at
least across the range of A1203 content investigated. However, the dimethyl ether rate is expected to
return to zero as the A1203 content approaches 100%, since A1203is essentially inactive for methanol
synthesis and methanol is required to produce dimethyl ether.
The influence of A1203 content on the rate of synthesis of C3+-ethers is quite interesting. The
C3.-ethers rate passes through a sharp maximum as AI_O3content is increased. The location of the
maximum C3.-ethers rate is at only approximately 5 wt% AI203.
The influence of the A1203content on product selectivity is shown in Figure 3-36. The major
product is dimethyl ether for AI203 content below approximately 4 wt%. Above approximately
10 wt% AI203, methanol and dimethyl ether are essentially the only products. The selectivity to
C3,-ethers is maximized at 5 wt% A1203. However, the maximum selectivity to C3+-ethers is quite
low, only 10 wt% of the total organic products.
The reason why the C3.-ethers rate goes through a maximum and the dimethyl ether rate increases
dramatically with increasing A1203 content is not immediately clear, but some speculation is
worthwhile. The proposed reaction scheme for formation of the various products shown in
Figure 3-37 provides some insight. Figure 3-37 shows that methanol, formed by syngas, can
undergo subsequent reaction along two different major pathways in this mixed catalyst system. Path
I consists of A1203-catalyzed dehydration of methanol to dimethyl ether. Path II represents the path
along which methanol is converted to higher alcohol products. Once the higher alcohols products
are formed, they can be dehydrated over AI203 to form C3.-ethers. Thus, if the dehydration activity
of the catalyst system is high, as in the case for high A1203 content, then Path I could plausibly
dominate, thereby suppressing the production of higher alcohols. In this case, the formation of
C3.-ethers would also be suppressed because higher alcohols are necessary precursors. On the other
hand, too little dehydration activity wr-,aldcause alcohols to dominate, being formed by Path II but
not reacting further to C3.-ethers. Obviously, a compromise in dehydration activity is required to
achieve a balance between Paths I and II. This balance occurs at a very low (5 wt%) AI203 content
l
_ for the present system at the given reaction conditions.
[ 64
. , III til
FIGURE 3-35
Effect of AI 2 0 3 Fraction on Product Rotes
Cotalyst Mixture" Cs-Cu/ZnO/AI203 + AIzO3

300°C, 7.0 MPa, GHSV=5000 std. lit./kg-hr, Shell gas
FIGURE 3-36
Effect of AI203 Fraction on Product Selectivities
Catalyst Mixture' Cs-Cu/ZnO/AI203 + AI203
300°C, 7.0 MPa, GHSV=5000 std. lit./kg-hr, Shell gas
0 Methanol
• _-C2-C6 Alcohols
A Dimethyl Ether
0 £C 3+ -Ethers
100 ' ' ' ' I ' ' ' ' l ' "" ' ' 1 .... I ' ' ' '
-A
80
_ 60
4-, A
I_ "
20
0
0 10 20 30 40 50
AI203 Fraction (wtr)
66
FIGURE 3-37
Proposed Reaction Scheme for

Synthesis of Dimethyl Ether and "_3+ -Ethers
CH3-O-CH 3 (Dimethyl Ether)
-H
hl
CO/H 2 , _ CH30H
._ Path II
+CO CnH OH, -H20

2n+l _ CnH2n+I-O-CmH2m+I
C mH 2m+1 OH
(C3+-ethers)
(C2+-alcohols)
67
3.3.3.2 Ether Product Distribution for 5% AI203 + 95% Cs-Cu/ZnO/AlzO J
Figure 3-38 shows the distribution of ether products obtained for the 5% A1203mixed catalyst
system at 300°C, 7.0 MPa, and a GHSV of 5000 std. lit./kg-hr of Shell gas. The distribution is
expressed as tile concentration of the various products normalized to the dimethyl ether
concentration, the same notation used above in the discussion of mixed alcohols dehydration.
Considering the distribution of alcohol products formed over Cs-CufZnO/Al203 at these conditions,
the ether product distribution is consistent with expectations. The major ether products have methyl
groups attached to the -O- linkage; not surprising since methanol is the major alcohol product.
Also shown in Figure 3-38 is the product distribution calculated based on simple probability of
bimolecular reaction, similar to the case above, only this time the calculation is based on the
expected alcohol product concentrations which would be produced if the Cs-Cu/ZnO/AI203 catalyst
was operating alone. Interestingly, the methyl ethyl ether and methyl n-propyl ether normalized
concentrations are close to the values predicted by simple probability. By contrast, the measured
methyl isobutyl ether normalized concentration is significantly less than that predicted by
probability. This is perhaps reasonable in view of the expectation that less isobutanol may be
formed in the mixed system since its precursor, 1-propanol, can also be reacted away to form ethers
such as methyl n-propyl ether and di-n-propyl ether. Surprisingly, the diethyl ether and di-n-propyl
ether measured normalized concentrations are significantly higher than that predicted by probability.
The reason for the latter phenomenon is not understood and its resolution requires further
investigation.
3.3.3.3 Effect of GHSV for 5 wt%AlzO 3 + 95 wt% Cs-Cu/ZnO/AlzO J

The effect of GHSV on the major product rates is shown in Figure 3-39 for the 5 wt% A1203case
operating at 300°C and 7.0 MPa with the Shell gas feed. The synthesis rates for ali products
increase with increasing GHSV over the range of GHSV investigated. However, the degree to
which GHSV 'affects the rate depends on the type of product. Alcohol products show a steeper rise
in rate with increasing GHSV than ether products. Obviously, high selectivity to ethers is favored at
low GHSV (long reactor residence time), while high selectivity to alcohols is favored at high
GHSV. This phenomenon is consistent with the reaction pathways, since the formation of ethers
occurs by sequential reaction of intermediate product alcohols. The CO conversion for these
experiments decreases with increasing GHSV. The CO conversion ranged from 32% at
3000 std. lit./kg-hr to 18% at 10,000 std. lit./kg-hr.
3.3.3.4 Effect of On-Stream Time for Mixed Catalyst System

None of the mixed A1203 + Cs-Cu/ZnO/AI203 systems were run for more than two days, so long
term activity maintenance data was not available. Table 3-15 shows the effect of on stream time, up
to 50.5 hours, on the major product rates and CO conversion for the 5 wt% A1203case. As shown,
the CO conversion decreased from 26% at 25 hours to 22% at 50.5 hours, indicating a deactivation
of the total catalyst system. Interestingly, the methanol and EC2-C 6 alcohols rates increased
significantly with time on stream. In contrast, the ether rates, including the dimethyl ether and
C3+-ethers, decreased substantially with time. Apparently, the dehydration component, A1203, had a
faster rate of deactivation than the alcohol synthesis component, Cs-Cu/ZnO/AI203. The result is
that, as the deactivation progressed, the intermediate alcohols were not consumed as rapidly to form
ethers, resulting in higher alcohols production rate.
68
i, 'Ill
FIGURE 3-38
Measured and Predicted Ether Product Distributions
Catalyst Mixture" 95_ Cs-Cu/ZnO/AI203 + 5_ AI203

Run No." 11472-51
300°C, 7.0 MPa, Shell Gas, GHSV=5000 std.lit./kg-hr
Measured
1.00 - 777_
////1
///,4
////1
c 0.95 - "'/'_
J/fm
o "/lA
L.O // / /
•+-, / /
r-
c _ 0.10 -
0 U
r"
0 0
_ 0 05 -
c
0
..,
W
0.00 [7"77_ 17-/-/'21
(..)
o ¢"
• Predicted Based on
.,-, a
E 1 O0 - Probability of Bimolecular
o Reaction
0
0 _ 0 " 95 - ///.4
L. _ ////1
13. _ "/ ///_
.N_ / /
0 / ////
E 0 " 10 .- z/z/
l/li
k.. _ I JJJ
0 l/l/
lilt
z 0 05 - ////
////
////
///i
0.00 --'- J//i ....
L. k.- k.. k- k-- ll,.

eh eh eh eh eh
JC r" r- L-- JC Jt:
eh eh eh eh 0
t- r O. "_-t t"
4-J 13.
eh _eh 0
_- _3 _ 0
L_
E o. o "-
4-m
eh -- >_ I
_
t- t-
+_ .--
70
eh E
E
69
FIGURE 3- 39
Catalyst Mixture" 95_; Cs-Cu/ZnO/AI203 + 5_ AI203

Run No." 11472-51
0 Methanol
li TC2-C e Alcohols
A Dimethyl Ether
0 :[:Ca+ Ethers
400 , , , _ , , , i , ¢t ,
A
300
t---
"_
_
200
A
/
n,"
100
0 , ,, i I J ' i I , L ,
0 4000 8000 12000
GHSV (std. lit./kg-hr
70
TABLE 3-15
Effect of Reaction Time on Major Product Rates
Catalyst Mixture: 5% A120a + 95% Cs-CuffZnO/Al203

Reaction Conditions: 300°C, 7.0 MPa, GHSV=5000 std. lit./kg-hr, Shell gas
Production Rate (g/kg-hr) CO

Time on stream _C2-C 6 Dimethyl Conversion
(br) Methanol alcohols ether C:+-ethers (%)
25 153 37 255 55 26
50.5 184 49 158 38 22
Several reasons could be envisioned for the deactivation of the dehydration component, but no
evidence was provided to suggest a particular mechanism in the present study. Further work is
necessary to investigate this phenomenon in more detail.
71
r, plrlIIr,1rr' ,,I,r
I
! 72
,u '_1_
4.0 SUMMARY AND RECOMMENDATIONS

Methanol/Hydrocarbon Mixtures
There are several key technical issues involved in the use of Cu/ZnO/AI203 methanol synthesis
catalyst and HZSM-5 methanol conversion catalyst in the same slurry reactor. The present study
addressed, to a limited extent, two key technical hurdles: (1) identifying a slurry liquid which is
stable in the presence of the acidic zeolite component but also compatible with the methanol
synthesis component; and (2) establishing conditions for reaction which allow both steps in the i
sequence to proceed at an economically attractive rate and selectivity.
Of the slurry liquids tested, which were ali of the type compatible with the methanol synthesis
catalyst, decalin (decahydronaphthalene) was found to be the most stable to cracking. A correlation
between stability and the inability of a liquid molecule to access the pore structure of the zeolite was
identified. However, even decalin, which consists of the bulkiest molecules of the liquids
investigated, cracked considerably at practical reaction temperatures. Surface silanation of the
zeolite decreased, but did not eliminate, cracking of the decalin. Moreover, the product distribution
during methanol conversion for the surface treated sample was very different from that for the
unmodified HZSM-5. The product distribution for the surface treated sample was characterized by
excessive production of methane. The high methane selectivity was probably caused by necking
down of the pore openings during the silanation treatment, which resulted in the inability of
molecules larger than methane to exit from the interior of the zeolite crystallites.
Despite the relatively high "background" production of hydrocarbons caused by cracking of the
decalin, syngas was converted to hydrocarbons using the mixed catalyst system. However, at a
reaction temperature of 250°C, a relatively high selectivity to dimethyl ether and light hydrocarbons
was observed, while the selectivity to gasoline-range hydrocarbons was very low. A significantly
higher reaction temperature, closer to the temperature range of 350-420°C used for methanol
conversion to hydrocarbons in the gas-to-gasoline process, is probably required to achieve a higher
selectivity to gasoline range hydrocarbons. In addition, GHSV must certainly play a role in the
product distribution and should be investigated in more detail.
Identification of a practical slurry liquid for use with the mixed catalyst system remains a key
challenge. Though decalin was the most stable of the liquids tested, its use in such a process,
especially at higher temperatures than those used in the present study, would not be economical.
Surface silanation was shown to decrease cracking of the decalin, but diffusion of decalin molecules
into the pore structure, though highly hindered, probably will still occur. The entrance of decalin
into the pore structure will be even more prevalent at higher reaction temperatures. After a thorough
investigation, a commercial source has not been identified for saturated hydrocarbon liquids
consisting of molecules that are bulkier than decalin.
Perhaps more detailed studies of other types of slurry liquids, besides saturated hydrocarbon types,
may be worthwhile. However, these liquids would necessarily have to be compatible with the Cu/
I ZnO/A1203 methanol synthesis catalyst. Unfortunately, one class of potential slurry liquids, silicone
p
73
oils, has been shown to be incompatible with the methanol synthesis catalyst. Though not
mentioned in the discussion section, one silicone oil, Syltherm, was found to break down in the
presence of reduced Cu/ZnO/Al203 catalyst.
One interesting possibility for a practical slurry liquid could involve the use of hydrocarbon
products of the HZSM-5 component as the slurry liquid. However, to be practical, these products
must have high boiling points to minimize liquid loss from the reactor. One product worth
investigating as a slurry liquid is durene, i.e., 1,2,4,5-tetramethyl benzene. This product is a solid at
room temperature and boils at 193°C, close to the boiling point for decalin (185-193°C). Since this
compound is aromatic, its compatibility with the methanol synthesis component is questionable, and
requires investigation. Another possiblity is that the Cu/ZnO/AI203 component could be modified to
produce a catalyst better able to tolerate unsaturated hydrocarbon liquids.
Surface silanation remains an area of worthwhile investigation for minimizing cracking. Only one
silanation technique was used in the present study and no attempt was made to optimize it. Other
silanation techniques, involving either impregnation or vapor deposition of silica precursors, may
not neck down pore openings as much as the one used here, thereby yielding a potentially better
product distribution for methanol conversion. Further work is required to address this speculation.
Besides the issue of slurry liquid stability, ot!_er technical issues regarding the proposed one-step
process will need to be addressed. One significant issue is the requirement that the HZSM-5
component be periodically regenerated. In the current methanol-to-gasoline process operated in
New Zealand, the conversion of methanol/dimethyl ether mixtures to gasoline is done in packed bed
reactors. Multiple reactors are required since each reactor must be periodically brought off-line to
burn off coke which has accumulated on the HZSM-5 catalyst. Presumably, the same regeneration
step would be required in a one-step process. Thus, two problems arise: (1) separation of the
catalyst from the slurry liquid, and (2) separation of the HZSM-5 component from the Cu/ZnO/
AI203 component, since the Cu/ZnO/A1203 would probably not survive the high temperature coke
burning procedure. Once separated, presumably the HZSM-5 could be regenerated in a fluidized
bed. At this point, a viable means of doing the separations, particularly the separation of the
HZSM-5 from the Cu/ZnO/A1203, is not apparent.
The above issues (regeneration of the HZSM-5 component and separation problems) indicate that a
more practical method for overall conversion of syngas to hydrocarbons might involve the use of
two separate slurry reactors in series. The first reactor would contain the Cu/ZnO/A1203 methanol
synthesis component and, optionally, a dehydration component such as AI203 to convert methanol to
dimethyl ether in-situ. The second slurry reactor would contain the HZSM-5 component. In this
case, the requirements for a viable slurry liquid are different, since the slurry liquid in the HZSM-5
would not have to be compatible with the Cu/ZnO/A1203 catalyst. Though the reaction steps would
then be separated, the use of a slurry reactor in the second reactor may still provide significant
advantage in heat management.
In conclusion, further research work is necessary to address key technical issues in developing an
industrially practical slurry reactor based process for converting syngas to hydrocarbons using Cu/
ZnO/A1203 and HZSM-5. Further work should focus on identification of viable slurry liquids and
perhaps involve zeolite catalyst surface passivation techniques.
74
Syngas conversion to mixed alcohols in a slurry reactor was successfully done on a laboratory scale.
Several catalysts were investigated, including a Cs-promoted Cu/ZnO/AI203 methanol synthesis
catalyst, an alkali-promoted Cu/ZnO/Al203-based catalyst from Lurgi, a Cu-Co formulation, and
two-component systems involving mixtures of Cu/ZnO/AI203 and a co-catalyst. The best
performing catalyst was the Cs-promoted Cu/ZnO/AI203 catalyst prepared in Air Products'
laboratory. This sample was prepared by a simple procedure involving impregnation of BASF $3-
86 methanol synthesis catalyst with aqueous cesium formate solution, followed by drying and
calcination.
For the Lurgi catalyst, the rate and selectivity to C2.-alcohols was substantially lower than that
measured for the Cs-promoted Cu/ZnO/A1203 catalyst.. Like the Cs-Cu/ZnO/AI203 catalyst, the
Lurgi catalyst produced significant amounts of branched alcohols, specifically the "2-methyl-"
isomers of primary linear alcohols. By contrast, in line with expectations, the Cu-Co catalyst
produced linear alcohols, almost exclusively. The performance of the Cu-Co catalyst was
characterized by higher selectivity to hydrocarbons and lower alcohol rates relative to the Cs-Cu/
ZnO/AI203 catalyst. The Cu-Co catalyst did, in fact, show the highest selectivity to C2.-alcohol of
any of the tested catalysts. None of the two-component catalyst mixtures investigated performed as
well as Ctt/ZnO/A½03 alone. However, the use of two-component catalyst systems is believed to be
a fruitful area for further research.
The effect of various process variables on the performance of the Cs-prom,..ted Cu/ZnO/AI203
catalyst was investigated in detail. Determinations were made of the effects of temperature, GHSV,
syngas composition, and co-feeding methanol and ethanol with the syngas. The results show that
selectivity to C2.-alcohols is favored at low GHSV, high temperature, and low 1-12/CO.In addition,
methanol and ethanol addition to the feed increased the rate of synthesis to higher alcohol products,
thus demonstrating the desirability of recycling those products to the reactor feed to enhance the
product slate.
It is noteworthy that the methanol/C2.-alcohols product distribution obtained for once-through

operation at industrially practical reaction conditions, using a feed syngas typical of the product of a
coal gasifier, was in the range suitable for blending into gasoline.
Preparation of the Cs-promoted catalyst should be optimized to attempt to improve its performance
even further. Variables such as cesium loading, cesium precursor composition, and Cu/ZnO/A1203
substrate type should have an impact on the ultimate performance. In addition, longer term activity
maintenance studies should be done to better ascertain the significance of catalyst deactivation.
As mentioned previously, a potentially attractive characteristic of the Cs-Cu/ZnO/A½03 catalyst is

its ability to produce a relatively high selectivity to branched-chain alcohols, particularly the
"2-methyl-" isomers. Notable branched-chain product alcohols from this catalyst include isobutanol
(2-methyl-1-propanol) and 2-methyl-1-butanol. These products are of particular interest because
they can be dehydrated to useful iso-olefins, such as isobutylene and isoamylene. Isobutylene and
isoamylene can be reacted with an alcohol, particularly methanol, to produce methyl tert-butyl ether
(MTBE) and tert-amyl methyl ether (TAME), respectively. Both ethers are, of course, known to be
75
outstanding oxygenated gasoline additives. Thus, alcohols produced from coal-derived syngas using
Cs-Cu/ZnO/AI203. besides representing a viable gasoline additive in their own right, may be an
alternative source of iso-olefins for use in etherification.
4.3 Slurry-Phase Conversion of Syngas to Mixed Ethers via Mixed

Alcohols
The present work has shown that mixed alcohols can be dehydrated selectively to mixtures of ethers
using an AI203 catalyst in a slurry reactor. Selectivity to olefins, the major side products, at
practical reaction conditions was an order of magnitude lower than the selectivity to ethers. The
measured ether product distribution was generally consistent with that expected based on simple
statistical probability of bimolecular reaction. However, the results indicate that the formation of
some ethers, particularly those with both alkyl groups larger than methyl, was somewhat suppressed
relative to probabilistic predictions. Thus, dehydration of two mixtures of alcohols, both of which
contained mostly methanol, produced mostly ethers with at least one methyl group attached to the -
O- linkage.
One-step, slurry-phase syngas conversion to mixed ethers using a mixed catalyst system of Cs-Cu/
ZnO/A1203 plus AI203 was also successfully done. In this system, mixed alcohols formed in-situ
over the Cs-Cu/ZnO/A1203 catalyst were dehydrated to mixed ethers. However, significant
quantities of C3+ethers, i.e. those larger than dimethyl ether, were formed only for a certain range of
A1203catalyst fraction in the reactor. For the reaction conditions used in the present study, the rate
and selectivity to C3+ethers was maximized for a catalyst mixture consisting of 95 wt% Cs-Cu/ZnO/
A1203and 5 wt% AI203. For catalyst mixtures with lower A1203fraction the product mix shifts
toward alcohols, while higher AI203 fraction yields almost exclusively dimethyl ether, lt is not
surprising that the ether product distribution for the optimum catalyst mixture showed a slight
deviation from that predicted based on simple probability of bimolecular reaction of the major
product alcohols of the Cs-Cu/ZnO/AI203 catalyst component. For example, the selectivity to
methyl isobutyl ether was slightly less than that predicted based on bimolecular reaction probability.
This phenomenon is thought to be a result of the sequential nature of the reaction mechanism by
which the higher alcohols, such as isobutanol, are formed.
For the one-step synthesis, short term activity maintenance results indicate a rapid deactivation of
the dehydration catalyst component. However, longer term studies are necessary to determine the
significance and cause of the deactivation. In addition, mixed catalyst systems involving the use of
other mixed alcohols synthesis components and other dehydration components should be
investigated.
Another key issue that needs to be addressed is the viability of using the ether products from
dehydration of mixed primary alcohols as fuels or fuel additives. For example, the characteristics
with respect to their use in gasoline must be investigated. Some important criteria for a gasoline
additive are the blending octane number and blending Reid vapor pressure (RVP). Octane testing
and RVP determinations of various ethers representative of the product of mixed alcohols
dehydration is the subject of ongoing work. The potential use of these product ethers in diesel fuel
must also be assessed.
76
REFERENCES
1. Maiden, C.J., "The New Zealand Gas-to-Gasoline Project," in Methane Conversion, Bibby,
D.M., C.D. Chang et al.(Eds.), Elsevier Science Publishers B.V., Amsterdam (1988).
2. Yurchak, S., "Development of Mobil's Fixed-Bed Methanol-to-Gasoline (MTG) Process," Ibid.
3. Chang, C.D., Catal. Rev.-Sci. Eng. 25, 1, 1 (1983).
4. Air Products and Chemicals, Inc., Topical Report, Task 3.1: Alternative Liquid Media Studies
for the Liquid Phase Methanol Process, DOE Contract DE-AC22-87PC90005, 1990.
5. F.W. Cox in Proceedings of the Third International Symposium on Alcohol Fuels Technology,
I1-22, pp. 1-14, U. S. Department of Energy, Asilomar, CA, 1979.
6. API Publication 4261, Alcohols and Ethers - A Technical Assessment of Their Application as
Fuels and Fuel Components, 2nd Edition, July 1988.
7. Courty, P., Chaumette, P., Raimbault, C., and Travers, P., Production of Methanol-Hieher
Alcohol Mixtures from Natural Gas via Syngas Chemistry, Revue de L'Institut Francais dh
Petrole 45(4), July-August 1990.
8. Uchiyama, S. and Kawata, N., Production of Mixed Alcohols from Synthesis Gas, Sekiyu
Gakkaishi 33( 1), 1-12, 1990.
9. Lewis, J.M.O., Chemical Conversion Process, U.S. Patent 4,814,541 assigned to UOP (March
21,1989).
10. Breck, D.W., Zeolite Molecular Sieves, John Wiley and Sons, New York (1974).
11. Nunan, J. G., Bogdan, C. E., Klier, K., Smith, K. J., Young, C.-W., and Herman, R. G., Higher
Alcohol and Oxygenate Synthesis over Cesium-Doped Cu/ZnO Catalysts Journal of Catalysis
116, 195-221, (1989).
12. Smith, K. J. and Anderson, R. B., A Chain Growth Scheme for the Higher Alcohols Synthesis
Journal of Catalysis 85,428-436 (1984).
13. Kiennemann, A., Idriss, H., Kieffer, R., Chaumette, P., and Durand, D., Study of the Mechanism
of Higher Alcohol Synthesis on Cu-ZnO-Al203 Catalysts by Catalytic Tests, Probe Molecules,
and Temperature Programmed Desorption Studies, Industrial and Engineering Chemistry
Research 30, 1130-1138, (1991).
14. Xiaoding, X., Doesburg, E. B. M., and Scholten, J. J. F., Synthesis of Higher Alcoho'lsfrom
Syngas - Recently Patented Catalysts and Tentative Ideas on the Mechanism, Catalysis Today 2,
125 (1987).
77
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DOE/PC/89865-T7

SYNTHESIS OF PIMETHYL ETHER AND ALTERNATIVE FUELS IN THE

Task 3.2: Screen Novel Catalyst Systems

AIR PRODUCTS AND CHEMICALS, INC.

Prepared for the United States Department of Energy

1.0 BACKGROUND ................................................................................................... 1

2.0 EXPERIMENTAL ................................................................................................ 5

3.0 RESULTS AND DISCUSSION ............................................................................ 9

4.0 SUMMARY AND RECOMMENDATIONS ....................................................... 73

2-1 Flow Schematic of Micro-Autoclave Reactor ...................................................... 6

1-1 Optimal Ranges of Operating Conditions for Gas-to-Gasoline Process ................ 2

1. One-step, slurry-phase syngas conversion to hydrocarbons or methanol/hydrocarbon mixtures

2. Slurry-phase conversion of syngas to mixed alcohols using various catalysts.

Tile experimental investigations focused primarily in three areas:

1. One-Step, Slurry-Phase Syngas Conversion to Hydrocarbons or Methanol/Hydrocarbon

1.1 One-Step, Slurry-Phase Syngas Conversion to Hydrocarbons or

1.2 Slurry-Phase Conversion of Syngas to Mixed Alcohols

1.3 One-Step, Slurry-Phase Syngas Conversion to Mixed Ethers

R-OH + R'-OH -_ R-O-R', R-O-R, R'-O-R' + 1-120,

2.2 Catalyst Materials

3.1.1 Reaction Liquid Studies

Comparison of Liquid Stability

N2 Flow: 5,000 std.lit./kg-hr

Comparison of Liquid Stability

300°C, 5.3 MPa

N 2 Flow: 5,000 std.lit./kg-hr

100 - Drakeol 10 :_=_-_

3.1.2 Surface-Passivation of HZSM-5

3.1.3 Slurry-Phase Methanol Conversion to Hydrocarbons

Comparison of Decalin Stability for

300°C, 5.3 MPa

N2 Flow" 5,000 std.lit./kg-hr

o 0-- --_ _==_----

Slurry Phase Methanol Conversion to Hydrocarbons

3.1.4 One-Step Syngas Conversion over Cu/ZnO/AI=O3-HZSM-5 Mixture

Catalysts: Cu/ZnO/Al203 and HZSM-5

Production Rate (g/kg-hr)

(hr) hydrocarbons hydrocarbons DME MeOH

Slurry Phase Methanol Conversion to Hydrocarbons

N2 Flow: 5,000 std.lit./kg-hr

3.2.1 Cu/ZnO/AI=O_ and Cesium-promoted Cu/ZnO/AI=O 3

Nominal Composition (_mol%)

EC2-C6 alcohols rate is not constrained by thermodynamic equilibrium limitations at these

i rate curve is fairly

Effect of GHSV on Product Rates

Effect of GHSV on Product Rates

300°C, 7.0 MPa, Shell Gas

GHSV (10 3 std. lit./kg-hr)

o Nm - I/,/1 _ _ ,-,-_ I_ _ FT/I...-- 'I

Effect of GHSV on Product Rates

300°C, 7.0 MPa, Texaco Gas

700 II Ethanol 120 "'_-

GHSV (10 _ std. lit./kg-hr)

Effect of GHSV on Product Rates

300°C, 7.0 MPa, Shell Gas

GHSV (10 3 std. lit./kg-hr)

300°C, 7.0 MPa, Texaco Gas

0 ' _,7_ 17"_!.-.-.. F7_ .-.-_

•_ ,/_ GHSV=10028 std.lit./kg-hr

t'// FT'7"s _ ,,, _ ,,,

0 , , _ i , , _ i , , , , I , , , , I .... 0