Seminar Material
Seminar Material
Seminar Material
SB Jones JE Holladay
C Valkenburg DJ Stevens
C Walton C Kinchin
DC Elliott S Czernik
February 2009
PNNL-18284 Rev. 1
SB Jones1 JE Holladay1
C Valkenburg1 DJ Stevens1
C Walton1 C Kinchin2
DC Elliott1 S Czernik2
February 2009
Prepared for
the U.S. Department of Energy
under Contract DE-AC05-76RL01830
1
Pacific Northwest National Laboratory
2
National Renewable Energy Laboratory
Executive Summary
The President has established a goal to supply 35 billion gallons per year of renewable and alternative
fuels by 2017. This goal is addressed in part by the U.S. Department of Energy (DOE) Office of Biomass
Program‟s (OBP‟s) Thermochemical Platform multiyear program plan to “convert biomass to fuels,
chemicals and power via thermal and chemical processes such as gasification, pyrolysis and other non-
biochemical processes” (DOE 2008).
In recent years, the Biomass Program completed technoeconomic evaluations of both biological and
thermochemical pathways for converting biomass to ethanol. These “design case” studies provided a
detailed basis for understanding the current state of various conversion technologies for producing fuel
ethanol. The studies also helped identify technical barriers for which research and development could
potentially lead to significant cost improvements. Consistent assumptions for items such as plant
lifetimes, rates of return, and other factors were used in all cases so the various processes could be
compared.
The purpose of this design case study is to evaluate a processing pathway for converting biomass into
infrastructure-compatible hydrocarbon biofuels. This design case investigates production of fast pyrolysis
oil from biomass and the upgrading of that bio-oil as a means for generating infrastructure-ready
renewable gasoline and diesel fuels. Other options for pyrolytic processes and upgrading steps exist, but
they were not evaluated in this study. Likewise, gasification pathways that could be used to produce
hydrocarbons are not addressed here. This study has been conducted using similar methodology and
underlying basis assumptions as the previous design cases for ethanol.
The overall concept and specific processing steps were selected because significant data on this
approach exists in the public literature. The analysis evaluates technology that has been demonstrated at
the laboratory scale or is in early stages of commercialization. The fast pyrolysis of biomass is already at
an early stage of commercialization, while upgrading bio-oil to transportation fuels has only been
demonstrated in the laboratory and at small engineering development scale. Advanced methods of
pyrolysis, which are under development, are not evaluated in this study. These, may be the subject of
subsequent analysis by OBP.
The plant is designed to use 2000 dry metric tons/day of hybrid poplar wood chips to produce
76 million gallons/year of gasoline and diesel. The processing steps include:
1. Feed drying and size reduction
2. Fast pyrolysis to a highly oxygenated liquid product
3. Hydrotreating of the fast pyrolysis oil to a stable hydrocarbon oil with less than 2% oxygen
4. Hydrocracking of the heavy portion of the stable hydrocarbon oil
iii
5. Distillation of the hydrotreated and hydrocracked oil into gasoline and diesel fuel blendstocks
6. Hydrogen production to support the hydrotreater reactors.
Note that the Idaho National Laboratory (INL) is working on feedstock logistics that will eliminate the
need for drying and size reduction at the plant. That is, the “as received” feedstock to the pyrolysis plant
will be “reactor ready”. This development will likely further decrease the cost of producing the fuel.
The capital cost for a standalone “nth” plant is $303 million (2007 basis). At a 10% return on
investment (ROI), the minimum fuels (gasoline + diesel) selling price is $2.04/gal ($1.34/gal ethanol
equivalent basis).
An important sensitivity is the possibility of co-locating the plant with an existing refinery. In this
case, the plant consists only of the first three steps: feed prep, fast pyrolysis, and upgrading. Stabilized,
upgraded pyrolysis oil is transferred to the refinery for separation and finishing into motor fuels. The off-
gas from the hydrotreaters is also transferred to the refinery, and in return the refinery provides lower-cost
hydrogen for the hydrotreaters. This reduces the capital investment to $188 million and the minimum
fuel selling price to $1.74/gal ($1.14/gal ethanol equivalent basis).
Production costs near $2/gal (in 2007 dollars) and petroleum industry infrastructure-ready products
make the production and upgrading of pyrolysis oil to hydrocarbon fuels an economically attractive
source of renewable fuels. The study also identifies technical areas where additional research can
potentially lead to further cost improvements.
iv
Acronyms and Abbreviations
AR As received
Btu British thermal units
CFB circulating fluid beds
DOE U.S. Department of Energy
gal gallon
HDS hydrodesulfurized
HTS high temperature shift
LHV lower heating value
MFSP minimum fuel product selling price
MM Million
mm millimeter(s)
mtpd metric tons per day
MWth megawatts thermal
OBP Office of the Biomass Program
PSA pressure swing adsorption
ROI return on investment
tpd tons per day
TPEC total purchased equipment cost
v
Contents
vii
Figures
Tables
viii
1.0 Introduction
The President has established a goal to supply 35 billion gallons per year of renewable and alternative
fuels by 2017 (White House 2007). This goal is addressed in part by the U.S. Department of Energy
(DOE) Office of the Biomass Program‟s (OBP‟s) Thermochemical Platform multiyear program plan to
“convert biomass to fuels, chemicals and power via thermal and chemical processes such as gasification,
pyrolysis, and other non-biochemical processes” (DOE 2008).
In recent years, the Biomass Program completed technoeconomic evaluations of both biological and
thermochemical pathways for converting biomass to ethanol. These “design case” studies provided a
detailed basis for understanding the current state of various conversion technologies for producing fuel
ethanol. The studies also helped identify technical barriers where research and development could
potentially lead to significant cost improvements. Consistent assumptions for items such as plant
lifetimes, rates of return, and other factors were used in all cases so the various processes could be
compared.
The purpose of this design case study is to evaluate a processing pathway for converting biomass into
infrastructure-compatible hydrocarbon biofuels.
This design case investigates fast pyrolysis oil production from biomass and the upgrading of that
bio-oil as a means for generating infrastructure-ready renewable gasoline and diesel fuels. The overall
concept and specific processing steps were selected because significant data on this approach exist in the
public literature. Other options for pyrolytic processes and upgrading steps exist, but they were not
evaluated in this study. One example of alternative processing options is hydrothermal pyrolysis
followed by other upgrading steps. Likewise, gasification pathways can be used to produce
hydrocarbons, but those are also not addressed here. These and other options may be addressed in future
studies.
The design case presented here represents a goal case targeting performance potentially available
between now and 2015. This analysis evaluates technology that has been demonstrated at the laboratory
scale or is in early stages of commercialization. The fast pyrolysis of biomass is already at an early stage
of commercialization, while the upgrading of the bio-oil to transportation fuels has only been
demonstrated in the laboratory and at small engineering development scale. As such, the analysis does
not reflect the current state of commercially-available technology but includes advancements that are
potentially achievable by 2015.
The study has been conducted using similar methodology and underlying basis assumptions as the
previous design cases for ethanol. It allows a basis for comparison with other research and development
projects targeting the DOE objectives and lastly, provides a benchmark for the status of the pyrolysis
program.
1.1
2.0 Analysis Approach
The approach used is similar to that employed in previous conceptual process designs and associated
design reports (Aden et al. 2002, Spath et al. 2005, Phillips et al. 2007). Process flow diagrams are based
on literature information and research results; these data were then used to build a process model in
CHEMCAD©, a commercial process flow sheeting software tool. The capital costs were taken from
literature sources or were obtained from Aspen ICARUSTM software after being sized using the
CHEMCAD© heat and material balances. The capital and operating costs were assembled in a Microsoft
Excel© spreadsheet. A discounted cash flow method was used to determine the minimum product selling
price.
2.1
3.0 Feedstock and Plant Size
The feedstock is hybrid poplar wood chips delivered at 50 wt% moisture. The feedstock cost is
assumed to be $50.7/bone dry metric ton, delivered. This report takes a conservative approach and
assumes the same moisture level as was used in previous studies (Aden et al. 2002, Spath et al. 2005,
Phillips et al. 2007) and that feedstock grinding and drying occur at the plant.
The plant capacity is 2000 metric tons/day (mtpd) of bone dry wood. The plant is assumed to be an
established (“nth”) plant design, rather than a first of its kind.
3.1
4.0 Process Overview
A simplified block diagram of the overall design is given in Figure 4.1. The processing steps include:
1. Feed drying and size reduction
2. Fast pyrolysis to a highly oxygenated liquid product
3. Hydrotreating of the fast pyrolysis oil to a stable hydrocarbon oil with less than 2% oxygen
4. Hydrocracking of the heavy portion of the stable hydrocarbon oil
5. Distillation of the hydrotreated and hydrocracked oil into gasoline and diesel fuel blendstocks
6. Steam reforming of the process off-gas and supplemental natural gas to produce hydrogen for the
hydrotreating and hydrocracking steps.
Feed Handling and Preparation: The biomass feedstock is dried from its as-received moisture
level to less than 10% to minimize water in the fast pyrolysis product liquid. It is then ground to 2-6 mm
particle size to yield sufficiently small particles, ensuring rapid reaction in the pyrolysis reactor.
Fast Pyrolysis: Pyrolysis is the thermal decomposition of carbonaceous material in the absence of
oxygen to produce char, gas, and a liquid product rich in oxygenated hydrocarbons. In general, pyrolysis
is performed using a range of temperatures and residence times to optimize the desired product.
Figure 4.2 illustrates the approximate yields from different modes of pyrolysis (Bridgewater 2007).
Fast pyrolysis is assumed in this work. The biomass is heated to approximately 500°C in less than 1
second, and then rapidly cooled to stop the reaction. The liquid product, known as bio-oil, is obtained in
yields up to 75% by weight on a dry feed basis. It can also be upgraded to lower the oxygen content and
transported using the same trillion-dollar infrastructure used by the oil industry. In addition to being
transported and stored at a lower cost than solid biomass, bio-oil and upgraded oil can be used in
applications ranging from value-added chemicals to transportation fuels.
4.1
Typical Product Yields
90
Figure 4.2. Typical Product Yields from Different Modes of Wood Pyrolysis
There are many types of pyrolysis reactor configurations, each with different advantages and
disadvantages. The following paragraphs summarize the various reactor types:
Ablative pyrolysis: Mechanical pressure is used to press carbonaceous material (usually wood)
against a heated reactor wall. Material in contact with the wall essentially “melts” and, as it is moved
away, the residual oil evaporates as pyrolysis vapors. There is no requirement for inert gas in this
configuration, so processing equipment (on demonstration scales) can be smaller and potentially less
expensive. The other advantage to this configuration is that feed materials do not require extensive
grinding to achieve particle sizes sufficient for high heating rates. Conversely, this configuration is
surface-area controlled so scaling is a linear function of the heat-transfer area and does not benefit
from the same economies of scale as the other systems. The system is also slightly more complex due
to the mechanical nature of the process. There is currently a 50 tpd demonstration plant using this
technology in Germany. (Bridgewater 2007)
Moving Bed or Auger Pyrolysis: This reactor utilizes a screw to mix hot sand and biomass. While it
provides good control of residence times and does not dilute the products with fluidizing gas, the sand
must be reheated separately, which leads to mechanical reliability issues. There are currently no
large-scale commercial plants. (Bridgewater 2007)
Entrained Flow Pyrolysis: This reactor configuration is popular for studies of thermochemical
conversion kinetics and investigations of the effects of pressure. Feed material is typically fed into the
top of the reactor, co-current with a gas stream. The flow through this configuration is assumed to
approximate plug flow, with the residence time controlled by the length of the heated zone. Char
buildup can be a troublesome trade-off for these simple and inexpensive reactors. Liquid yields are
usually lower than fluid bed systems. (Bridgewater 2007)
Rotating Cone: This reactor combines biomass and hot sand at the top of the vessel. The solids are
mixed by a rotating cone inside the vessel. Hot pyrolysis oil vapors leave near the bottom of the
reactor, while hot sand and char exit the reactor from the bottom of the cone. No carrier gas is
needed, resulting in smaller downstream equipment. A 2 mtpd plant operating on palm oil empty fruit
bunches was commissioned in Malaysia in 2006. (BTG 2009)
Bubbling Fluidized Bed Pyrolysis: Here, biomass is introduced to hot sand fluidized by recirculated
product gas. This technology is well understood, simple to construct and operate (on large scales),
and very efficient in transferring heat to the biomass, resulting in high liquid yields. Small biomass
4.2
particle sizes are required for this method in order to obtain high heating rates. Dynamotive currently
operates two plants, one 100 mtpd and one 200 mtpd, in Canada. (Bridgewater 2007, Dynamotive
2007)
Circulating Fluidized Bed Pyrolysis: Similar to bubbling fluidized beds, these configurations circulate
hot sand between the pyrolysis reactor and a sand re-heater. Char or product gas and char are burned
to provide heat to the sand re-heater. Circulating fluid beds (CFBs) are widely used at very high
throughputs in the petroleum industry and are potentially suitable for large biomass throughputs as
well. Ensyn operates a 100 tpd (200 tpd green wood) plant in Canada. (Bridgewater 2007, Ensyn
2009)
Both fluidized bed configurations allow for greater control of vapor residence time, an important
consideration for optimization of the high liquid yield associated with fast pyrolysis. A circulating
fluidized bed was chosen, as this design is the most likely to be scalable to the 2000 mtpd feed rate
assumed in this report.
The upgrading step involves contacting the bio-oil with hydrogen under pressure and at moderate
temperatures (<400°C or 750°F) over fixed bed reactors. Single stage-hydrotreating has proved to be
difficult, producing a heavy, tar-like product. Dual-stage processing, where mild hydrotreating is
followed by more severe hydrotreating has been found to overcome the reactivity of the bio-oil (Elliot
2007). Overall, the pyrolysis oil is almost completely deoxygenated by a combination of
hydrodeoxygenation and decarboxylation:
Catalyst / 3H2
Cn COOH Cn+1 + 2H2O Hydrodeoxygenation
Catalyst / H2
Cn COOH Cn + CO2 Decarboxylation
Less than 2% oxygen remains in the treated, stable oil. Water and off-gas are produced as
byproducts. The water phase contains some dissolved organics, while the off-gas contains light
hydrocarbons, excess hydrogen, and carbon dioxide.
Once stabilized oil is produced it can be further processed into conventional fuels or sent to a
refinery. Both options are considered in this report.
4.3
5.0 Process Design
The design case assumes a standalone unit that combines feed pretreatment, fast pyrolysis,
hydrotreating and hydrocracking of pyrolysis oil and separation to gasoline and diesel fuel blendstocks,
and hydrogen generation.
Non-
CFB Pyrolysis Vapor
Pre-treatment Cyclone Quench Condensables
Biomass (nominal 500°C
(drying, grinding)
or 930°F)
Liquid &
Residual
Sand/Char Solids
Filter
Bio-Oil
Heated
Solids
Hot Sand
Combustor
Combustor
Exhaust Gas to Combustor
Fluidizing Gas
Table 5.1 summarizes the as received feedstock characteristics and feed requirements.
The dried, finely ground biomass is fed to a circulating fluidized pyrolysis reactor operating at 520°C.
Sand is used as the fluidizing medium and the residence time is less than a second. The biomass is
converted into a mixture of gases, bio-oil, and char. A cyclone separates the sand and char from the gases
and liquids. The hot bio-oil vapor is rapidly quenched with cooled bio-oil and then separated from the
remaining vapors (Solantausta 2003, Freel and Graham 1995). High temperature heat recovery is not
included due to the likelihood of severe fouling in the recuperators (Johnson et al. 2006). Most of the
gases are recycled back to the pyrolysis reactor to assist fluidization. The char and a portion of the gas
are burned to heat the circulating sand. The cooled pyrolysis oil contains about 20-25% associated water.
5.4
Table 5.2 shows the product characterization. Note that the bio-oil yield is near the high end of
the references. This choice is based on the assumption that improvements in bio-oil yield can be achieved
by the 2015 time-frame.
5.5
The detailed model flowsheet diagram and associated heat and material balance for the fast pyrolysis
section can be found in Appendix A.
H2 Natural
Gas
H2
Steam
Vapor
PSA Off-Gas Reforming
Bio Oil
from
Pyrolysis
Hydrotreater
Unit Preheater
(2 stages) Oil Light
Distillation
Stable Oil
Pressurization
To
Wastewater
Treatment Heavy Stable
Oil to
Hydrocracker
The filtered bio-oil product from the pyrolysis unit is pumped to high pressure, then combined with
compressed hydrogen and preheated with reactor effluent. Two catalytic reaction stages are used. The
first stage catalytic reactor serves to stabilize the bio-oil by mild hydrotreatment over cobalt molybdenum
(CoMo) hydrotreating catalyst (Elliott 2007). The product oil is further processed in the second-stage
hydrotreater. The second stage hydrotreater operates at higher temperature and lower space velocity than
the first stage. CoMo catalyst is also used in this reactor. Reactor effluent and a fired heater provide feed
preheat for the second stage. The second-stage product is separated into product oil, wastewater, and off-
gas streams.
The off-gas from the hydrotreaters is sent to a Pressure Swing Adsorption (PSA) system for recovery
of the hydrogen gas. The recovered hydrogen is recycled back to the reactors. The low pressure PSA tail
gas stream, which is rich in byproduct light hydrocarbons, is sent to the steam reformer for hydrogen
production. A small portion of this off-gas is used in the fired heater that preheats feed for the second-
stage hydrotreater.
Anaerobic digestion can be used to treat the less than 2% organics in the wastewater.
The processing conditions are listed in Table 5.3. The product oil is a mixture of hydrocarbons with a
low level (~2%) of oxygen, as shown in Table 5.4. Data from Beckman et al. (1990) and Elliot (2007)
were used to estimate the product slate.
5.6
Table 5.3. Hydrotreating Conditions
1st Stage(a) 2nd Stage(a)
Temperature, °F (°C) 465 (240) 700 (370)
Pressure, psig 2500 2015
LHSV, v/h/v 1 0.14
(a) Beckman et al 1990
5.7
Natural
Gas
H2 To
Steam
Off-Gas from Reforming Hydrotreaters
Hydrotreaters
Off-gas Off-gas
Upgraded Heavy
Distillation
Stable Oil
Stable Oil
Hydrocracker
Light
Stable Oil
Gasoline
Distillation
Diesel
The product is a mixture of liquids spanning the gasoline and diesel range and some byproduct gas.
The gasoline and diesel range products are separated by distillation. These products are suitable for
blending into finished fuel. The hydrocracking conditions and product yields are shown in Table 5.5.
5.8
Figure 5.4. Block Diagram of Hydrogen Production
Saturated and superheated steam are generated by recuperating heat from the reformer exhaust and
during syngas cooling. The steam is used to provide steam to the reformer and heat for process heaters
and distillation column reboilers. A steam export credit is taken for the small amount of excess steam not
used by the process. The heat and material balance for the steam reformer can be found in Appendix A.
5.9
5.6 Process Yields and Consumptions
The yield of product fuel from wood is shown in Table 5.7. The unadjusted yield, shown in the first
row of Table 5.7, does not take into account the natural gas used in steam reforming for hydrogen
production. It is of interest to know what the yield of fuel products would be if only renewable feedstocks
were used. In the base case, hydrogen for the upgrading reactors is generated in a conventional steam
reformer using offgas from the upgrading reactors plus natural gas. This hydrogen could also be derived
from renewable resources, for example by 1) gasifying biomass, then shifting the syngas to hydrogen or
by 2) steam reforming a portion of the fast pyrolysis oil. It is estimated that if the natural gas used to
generate hydrogen was replaced by biomass or bio-oil, approximately one third of the biomass feedstock
would be needed for hydrogen generation. The yield of fuel products on a 100% renewable basis is
shown in the second row of Table 5.7. The third row of Table 5.7 shows the 100% renewable yield on an
ethanol equivalent basis (lower heating value (LHV) adjusted). Table 5.7 also summarizes water, power
and NG consumption.
Table 5.8 shows the carbon balance. More than half of the carbon in the combined biomass plus
natural gas feed is converted into fuel products.
The heat and material balance for the Stand-Alone Design Case is located in Appendix A.
5.10
6.0 Process Economics
Existing pyrolysis units process 200 tpd of biomass or less, and capital cost data is limited. This
report used data from Ringer et al. 2006, scaled to 2000 tpd. Costs associated with feed handling,
pyrolysis reactor, quench, and product recovery were included. Heat recovery and power generation were
excluded. The 35% equipment contingency used in Ringer et al. 2006 was retained. As seen in Table
6.1, these costs are within the average of the data shown.
Most of the equipment for this section were sized using CHEMCAD© and costed using ASPEN
IcarusTM or taken from vendor budgetary quotes. The cost of a small hydrocracker system processing
hydrotreated bio-oil has been estimated by UOP (Marker et al. 2005). The large-diameter, high-pressure
hydrotreater vessels are likely to be manufactured outside of the United States. A 15% equipment
contingency was added to account for uncertainty in the fabrication and hydrocracker unit costs.
6.1
6.1.3 Hydrogen Generation
Hydrogen generation by steam reforming of natural gas is a well-known, mature process; therefore no
equipment contingency was added. The SRI Yearbook (SRI International 2007) and Foster Wheeler
(Gulf 2006, Meyer 2004) have published capital and operating data for plants of various capacities.
Storage capacity and cooling tower capital were estimated with ASPEN Icarus. Wastewater
treatment costs are from Beckman et al. 1990. A 15% process contingency was added.
Table 6.2 and Table 6.3 list the stand-alone design case installed equipment capital costs and the
factors used to determine the total project investment, respectively. The factors in Table 6.2 are from
Peters et al (2003).
Table 6.2. Total Project Investment Cost for the Design Case Stand-Alone Plant
2007 MMUSD % Contribution
Fast Pyrolysis 92 30%
Hydrotreating 81 27%
Hydrocracking and Separations 29 10%
Hydrogen Generation 86 28%
Utilities, etc. 14 5%
303* 100
* Summation higher due to rounding
6.2
6.2 Operating Costs
Table 6.4 lists the assumptions used to calculate the operating costs. Catalyst costs were escalated
with the average Producer Price Index for 2007.
Utilities
Natural Gas, $/1000scf (1000 Btu/scf) 7.68(d)
Electricity, ¢/kwh 6.36(d)
Labor
Operating labor, $/hr burdened & 10% shift overlap 37.66(c)
Maintenance and overhead 95% of labor & supervision(e)
Materials
Maintenance 2% of total project
investment(e)
Local taxes & insurance 2% of total project investmente)
(a) Phillips et al. 2007
(b) Holmgren et al. 2007
(c) SRI International 2007
(d) Energy Information Agency 2007
(e) Phillips et al. 2007
6.3
blendstock), they are combined and referred to as a “fuel product” for simplicity. All MFSP calculations
are performed and reported on a combined product basis. Table 6.5 gives the economic parameters used
to calculate the MFSP. A sensitivity analysis was conducted to determine the effect of different financial
and operating assumptions on the MFSP.
The variable operating costs were determined from the heat and material balances and checked
against published data for the hydrocracker and steam reformer. These and the fixed operating costs are
shown in Table 6.6.
6.4
Table 6.6. Project Economics for the Stand-Alone Design Case Plant
$/gal product Contribution
Feedstock 0.48 23%
Natural Gas 0.32 16%
Catalysts & Chemicals 0.15 7%
Waste Disposal 0.01 0%
Utilities (Cooling Water, Electricity, Steam) 0.17 8%
Fixed Costs (Labor, Operating Supplies, etc.) 0.22 11%
The 2007 average refiner prices for gasoline and diesel were $2.18 and $2.20 respectively (Energy
Information Agency 2007). Thus, at $2.04/gal fuel product price, there is incentive to pursue motor fuels
from biomass.
6.5
7.0 Economic and Technical Sensitivities
The design case describes a single operating point for a stand-alone processing unit. This section
investigates the production cost sensitivities to technical, financial, and market issues. These include
plant size, ROI, feedstock costs, reactor conditions and product yields. Because hydrocarbon fuels are the
final product, an important sensitivity is the possibility of co-locating the pyrolysis and upgrading facility
with an existing refinery.
Figure 7.1. Block Diagram of Pyrolysis and Upgrading Plant Co-located with a Refinery
VTT and partners (Solantuasta 2006) and UOP (Marker et al 2005, Holmgren et al 2007) are
separately pursuing producing bioproducts compatible with existing refinery infrastructure. This will
lessen the initial investment; however, direct use of stable oil in a refinery requires complete
deoxygenation and a low acid number to prevent corrosion. As an alternative, a finishing deoxygenation
unit and/or a separate hydrotreating/hydrocracking operation using dedicated stainless steel equipment
may be needed. The finishing hydrotreating unit may result in saturating aromatic compounds, in which
case the light naphtha portion may need to be reformed in the refinery into aromatics before blending into
gasoline.
7.1
Table 7.1 compares the stand-alone and integrated economics. The capital cost calculations assume
that the refinery equipment is fully depreciated and only operating costs apply to the refinery side. This
greatly reduces the capital investment. A hydrogen transfer price of $0.56/lb (Holmgren et al 2007)
assumes that all operating costs (including feedstock and fuel) to the hydrogen generation unit within the
refinery are accounted for in that price. A credit is taken for the fuel gas sent from the upgrading unit to
the refinery. The transfer price for the fuel gas to the refinery is determined by adjusting the current price
of natural gas for the Btu value of the fuel gas. The product costs are significantly lower than those for
the stand-alone plant due to reduced capital investment and the net cost difference between hydrogen and
fuel gas.
Sensitivities to project contingency, capital investment, scale and ROI were determined for the stand-
alone case. Reducing the project contingency to three percent of the total capital project, (similar to that
used in Phillips et al. 2007), reduces the selling price by about $0.22/gal. The accuracy of the capital
estimate is in the range of -10% to +40%, and gives an MFSP range of $1.79/gal to $2.22/gal or a
difference of -0.22/gal to +$0.20/gal.
The base plant assumes a 90% stream factor. This may be optimistic with single reactors for fast
pyrolysis and upgrading. The equipment spare sensitivity determines the product cost increase if both the
pyrolysis unit and upgrading units had 3 reactors at 50% capacity each. This increases the selling price
by about $0.21/gal.
The cost of a single small pyrolysis with an upgrading unit at 500 tpd increases the selling price to
almost $2.68/gal. Four 500 tpd units feeding a single upgrading unit is more cost effective, assuming the
feedstock cost is the same for both cases. The cost of transporting biomass feedstock is a limiting factor
7.2
in the size of a biomass processing plant. It is possible that small, distributed pyrolysis plants can take
advantage of lower feedstock costs and produce an easily transported product that can then be upgraded to
fuel in a large, centralized facility. Further analysis is needed to look at the tradeoff between pyrolysis
plant size and feedstock cost, and the transportation costs to a centralized upgrading plant.
Integrated: $0.56/lb H2
Integrated w Capital
Upgrades
Integrated: $0.75/lb H2
Integrated: $1.25/lb H2
0% Project Contingency
3% Project Contingency
Total Project Investment
+40%
Total Project Investment -
10%
Plant Size at 5000 tpd
Equipment Spares
0% ROI
1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10
MFSP ($/gallon fuel)
30% ROI
2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80
The base case assumes a 10% ROI. A 30% return (shown on a separate scale to prevent making the
other sensitivities illegible) nearly doubles the baseline estimated selling price. The 0% return represents
the plant gate costs.
The base case assumes that the two stage hydrotreaters described in Section 5.2 sufficiently
deoxygenate the stable oil, and only the heavy tail end requires hydrocracking. If this is not sufficient,
7.3
and the entire stable oil stream is sent to the hydrocracker, the size of the hydrocracker increases
significantly. Hydrocracking the entire stable oil stream adds $0.10/gal to price of the fuel.
$80/ton Feedstock
$35/ton Feedstock
0.3 LHSV
0.1 LHSV
$100/lb Hydrotreater
Catalyst
$30/lb Hydrotreater
Catalyst
Hydrocrack Entire Stable
Oil Stream
1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10
MFSP ($/gallon fuel)
7.4
8.0 Conclusions and Recommendations
This analysis suggests that production of hydrocarbon motor fuels from biomass via the pyrolysis
route is potentially economically attractive. The cost becomes even more favorable if the facility can be
closely associated with an existing petroleum refinery to leverage that infrastructure. Both the stand-
alone plant that combines fast pyrolysis with hydrotreating, upgrading and hydrocracking to fuels and the
refinery-integrated plant fit with the existing infrastructure in terms of products and processing methods.
Developing partnerships with industry suppliers and refiners is important for production development and
product acceptance.
The pyrolysis pathway for producing hydrocarbon fuels is economically competitive with either the
biological or thermochemical pathways for production of ethanol fuels. On an energy-equivalent basis, as
shown in Table 7.1, the costs of either hydrocarbon or alcohol fuels are essentially the same when
consistent analysis methodologies and underlying financial assumptions are used.
As indicated previously, other pyrolytic processes exist, and the economics of those processes may be
different from the one analyzed here. This analysis suggests that cost-effective processing routes to
hydrocarbon fuels exist, but does not attempt to compare this approach with others. If other pyrolytic
processing routes have lower costs, the production of hydrocarbon fuels will be even more attractive.
The analysis describes a system with performance projected to be available in 2015. Further research
and development is needed to understand the limitations of the process and where improvements can be
made. The sensitivity analysis (Figure 7.3) suggests that the biggest impacts of technical improvements
are in the area of catalysis as it relates to bio-oil upgrading. Catalyst lifetimes and performance are
essential to the process and need additional development and testing. Pyrolytic processing of the biomass
is a relatively small percentage of the overall cost, and changes to the pyrolysis process will have little
direct impact on the fuel cost. However, research on pyrolytic processing that leads to a better quality
bio-oil requiring less upgrading could also potentially reduce product costs.
The analysis (Figure 7.2) also shows the fuel costs are highly sensitive to plant size and ROI. The
close coupling of the upgrading steps with a petroleum refinery helps leverage the economies of scale in
the fuel production steps. The pyrolysis step to produce bio-oil is less sensitive to scale and can
potentially be decoupled from the fuel upgrading step. This analysis uses figures for ROI that are
consistent with previous biofuels analyses produced by DOE and allow comparison with other technology
options. Industries attempting to build actual facilities may use different assumptions, and the costs for
the resulting fuels would change accordingly.
To achieve the potential for producing hydrocarbon fuels from biomass, additional research and
development are needed. A summary of needs includes the following:
Understand the trade-off between the size of the pyrolysis oil plant and feedstock and transportation
costs to a centralized upgrading facility.
Incorporate the reductions in feed preprocessing (grinding and drying) by using a reactor ready feed.
Understand pyrolysis reactor and upgrading reactor scale-up limitations if any.
Improve the quality and consistency of bio-oil.
8.1
Determine detailed characterization of upgraded oil and products, for example:
– boiling point curves and densities
– compound types (% aromatics, naphthenes, olefins, iso and normal) within the gasoline, diesel
and heavy fraction ranges
– acid number.
Conduct catalyst life studies for the pyrolysis oil upgrading catalysts.
Develop better understanding of reactor limitations and opportunities by developing a predictive
pyrolysis-oil production model and upgrading the reactor model to replace the stoichiometric models
used in this study.
Determine stable oil and product fuel specifications for oil refinery acceptance.
In addition, there are new initiatives for an advanced pyrolysis process for biomass, the details of
which fall outside this base-case study. Incorporation of those new concepts into economic assessments
of future cases for biomass pyrolysis should be the next stage of analysis. Advanced pyrolysis processes
may include:
new reactor system engineering involving improved heat transfer mechanisms
pyrolysis including in-situ catalysis
pyrolysis including in-situ chemical processing
post pyrolysis processing to improve product bio-oil properties
in-process separation systems to produce bio-oil fractions with useful properties
post-process separations and subsequent treatment to produce improved products
higher efficiency integrated systems with improved heat utilization.
8.2
9.0 References
Aden A, M Ruth, K Ibsen, J Jechura, K Neeves, J Sheehan, B Wallace, L Montague, A Slayton, and J
Lukas. 2002. Lignocellulosic Biomass to Ethanol Process Design and Economics Utilizing Co-Current
Dilute Acid Prehydrolysis and Enzymatic Hydrolysis for Corn Stover. NREL/TP-510-32438, National
Renewable Energy Laboratory, Golden, Colorado. http://www.nrel.gov/docs/fy02osti/32438.pdf
Couper JR, WR Pennery, JR Fair, and SM Walas. 2005. Chemical Process Equipment Selection and
Design. 2nd ed. Elsevier, Amsterdam.
Diebold JP. 2000. A Review of the Chemical and Physical Mechanisms of the Storage Stability of Fast
Pyrolysis Bio-Oils. NREL/SR-570-27613, Golden, Colorado.
http://www.nrel.gov/docs/fy00osti/27613.pdf
U.S. Department of Energy. 2008. Biomass Multi-Year Program Plan. Office of the Biomass Program,
Energy Efficiency and Renewable Energy, U.S. Department of Energy, Washington D.C.
http://www1.eere.energy.gov/biomass/pdfs/biomass_program_mypp.pdf
Energy Information Agency. Industrial Electricity and Natural Gas Prices Jan-Nov 2007 average. Retail
Gasoline and Diesel Prices Jan-Sept. 2007. Available at http://www.eia.doe.gov/
Elliott, DC. 2007. “Historical Developments in Hydroprocessing Bio-oil.” Energy & Fuels 21:1792-1815.
Freel B and R Graham. 1995. “Method and Apparatus for a Circulating Bed Transport Fast Pyrolysis
Reactor System.” US Patent 5,792,340. Ensyn Technologies Inc.
Gulf Publishing Co. 2006. Hydrocarbon Processing; Refining Processes 2006. Gulf Publishing Co.,
Houston, Texas.
9.1
Johnson WL, GH Yavari, and D St A G Radelin. 2006. “Apparatus for Separating Fouling Contaminants
from Non-Condensable Gases at the End of a Pyrolysis/Thermolysis of Biomass Process.” US Patent
7,004,999 B2. Dynamotive Energy Systems.
Meyers RA. 2004. Handbook of Petroleum Refining Processes. 3rd ed. McGraw-Hill, New York.
Mohan D, C Pittman, and P Steele. 2006. “Pyrolysis of Wood/Biomass for Bio-oil: A Critical Review.”
Energy & Fuels 20:848-889.
Oasmaa A and E Kuoppala. 2003. “Fast Pyrolysis of Forestry Residue. 3. Stability of Liquid Fuel.”
Energy & Fuels 17:1075-1084.
Perry RH, DW Green, and JO Maloney. 1984. Perry’s Chemical Engineers’ Handbook. 6th ed. McGraw-
Hill, New York.
Peters MS, KD Timmerhaus, and RE West. 2003. Plant Design and Economics for Chemical Engineers.
5th ed, McGraw-Hill, New York.
Phillips S, A Aden, and J Jechura, D Dayton, and T Eggman 2007. Thermochemical Ethanol via Indirect
Gasification and Mixed Alcohol Synthesis of Lignocellulosic Biomass. NREL/TP-510-41168. National
Renewable Energy Laboratory, Golden, Colorado. http://www.nrel.gov/docs/fy07osti/41168.pdf
Phyllis Database for Biomass and Waste. “Hybrid Poplar.” Version 4.13. Energy Research Center of the
Netherlands. http://www.ecn.nl/phyllis
Ringer M, V Putsche, and J Scahill. 2006. Large-Scale Pyrolysis Oil Production: A Technology
Assessment and Economic Analysis. NREL/TP-510-37779. National Renewable Energy Laboratory,
Golden, Colorado.
Solantausta Y. 2003. Techno-Economic Assessment, the Finnish Case Study. COMBIO Project NNE5-
CT-00604, VTT Technical Research Centre of Finland, http://www.combio-project.com/economics.htm
Spath P, A Aden, T Eggeman, M Ringer, B Wallace, and J Jechura. 2005. Biomass to Hydrogen
Production Detailed Design and Economics Utilizing the Battelle Columbus Laboratory Indirectly-
Heated Gasifier. NREL/TP-510-37408, National Renewable Energy Laboratory, Golden, Colorado.
http://www.nrel.gov/docs/fy05osti/37408.pdf
SRI International. 2007. “Hydrogen Production from Natural Gas.” PEP Yearbook International, Vol 1E,
SRI International, Menlo Park, California.
9.2
White House Office of Communications. 2007. Twenty in Ten: Strengthening America’s Energy Security.
White House Office of Communications, Washington D.C. Available at
http://www.energy.gov/media/20in10FactSheet.pdf
9.3
Appendix A
A.4
Recycle
145 Gas
140 Demister
146
Flue 144
Gas 138
126
1810 CWR
Exhaust 130 CWS
1811
105 Pyrolyzer Trim
Cooler
100 137
111
Dryer
106 Sand 131
Heater 139 150
116 113 Char and 133 Pyrolysis
Sand
A.1
Sand Oil
Recycle to
Intermediate
Storage
Fluidizing Quench
Gas Water
Ash Quench
Wet
148 161 Ash
147 Fuel
Gas
Air 120
0 0
Acetic Acid 0 0
Formaldehyde 0 0
2-5-Xylenol 0 0
N-Heptane 0 0
1-ts-35-3C1CycC6 0 0
3-3-5-TriMth-C7 0 0
N-PropylCyc-C6 0 0
1-2-3-Mesitylene 0 0
N-ButylCycHexane 0 0
1-2-DiC1-3C2-Bz 0 0
Cis-Decalin 0 0
Dimethyl-C11 0 0
1-2-4-triethylbe 0 0
1-1-Bicyclohexyl 0 0
Diphenyl 0 0
diamantane 0 0
Phenanthrene 0 0
N-C15-CycloC5 0 0
Hexatriacontane 0 0
Ca 0 0
Sulphur 0 0
Calcium Chloride 0 0
Sand 0 0
258
C-253 a,b,c
Pyrolysis Oil From
Intermediate 250 Hydrogen From H2
Storage Plant
200 253
R-205 225
220 208
A.5
240
207
CWS V-225
Low Pressure
1820 Flash
213
205 E-206
E-221
212
221 Steam
223
V-222
226
736
CWR High Pressure
1821 Flash E-226
To De-butanizer
738 227
230
Waste Water
Condensate
Stream No. 200 202 203 205 207 208 212 213 215 220 221
Temp F 110.6798 174.8342 430 465.5045 470 700 484.8971 481.4931 319.3935 150 110
Pres psig 1 2500 2495 2495 2490 2475 2475 2470 710.3041 705.3041 700.3041
Enth MMBtu/h -579.38 -572.13 -533.75 -533.75 -532.53 -493.17 -493.17 -494.39 -532.77 -560.91 -566.01
Vapor mass fraction 0 0.062243 0.15953 0.24881 0.25969 0.52647 0.6898 0.67505 0.22969 0.12881 0.12332
Total lb/h 151607.6 161371 161371 161371 161371 161371 161371 161374.8 161374.8 161374.8 161374.8
Flowrates in lb/h
Water 32161.65 32161.64 32161.64 44375.22 44375.22 44375.22 71936 71936 71936 71936 71936
Hydrogen 0 9763.431 9763.431 8474.411 8474.411 8474.411 3839.811 3843.556 3843.557 3843.557 3843.557
Carbon Dioxide 0 0 0 1000 1000 1000 9000.002 9000.002 9000.003 9000.003 9000.004
Methane 0 0 0 50 50 50 3350 3350 3350 3350 3350
Ethane 0 0 0 6.9 6.9 6.9 2006.899 2006.9 2006.9 2006.9 2006.9
Propane 0 0 0 5.1 5.1 5.1 1705.1 1705.101 1705.101 1705.101 1705.101
I-Butane 0 0 0 4.4 4.4 4.4 1504.4 1504.4 1504.4 1504.4 1504.4
Pyro-lignin 64305.6 64305.58 64305.58 54819.78 54819.78 54819.79 0 0 0 0 0
Cellobiose 23313.63 23313.62 23313.62 13988.17 13988.17 13988.17 0.0037 0.0051 0.0051 0.0051 0.0051
Levoglucosan 5674.065 5674.063 5674.063 2724.021 2724.021 2724.021 0.001 0.0014 0.0014 0.0014 0.0014
Furfural 11633.4 11633.4 11633.4 0 0 0 0 0 0 0 0
HydroxyAcetone 6044.922 6044.922 6044.922 4835.938 4835.938 4835.938 0 0 0 0 0
Acetic Acid 8474.371 8474.367 8474.367 5084.619 5084.619 5084.619 0 0 0 0 0
2-5-Xylenol 0 0 0 26002.45 26002.45 26002.45 8000.004 8000.002 8000.001 8000.001 8000.001
N-Heptane 0 0 0 0 0 0 3275.653 3275.653 3275.654 3275.654 3275.655
1-ts-35-3C1CycC6 0 0 0 0 0 0 4892.768 4892.769 4892.768 4892.768 4892.769
3-3-5-TriMth-C7 0 0 0 0 0 0 1994.707 1994.707 1994.707 1994.707 1994.707
N-PropylCyc-C6 0 0 0 0 0 0 4892.767 4892.769 4892.769 4892.769 4892.77
1-2-3-Mesitylene 0 0 0 0 0 0 642.0663 642.0664 642.0664 642.0664 642.0665
N-ButylCycHexane 0 0 0 0 0 0 234.2028 234.2029 234.2029 234.2029 234.2029
1-2-DiC1-3C2-Bz 0 0 0 0 0 0 1593.217 1593.217 1593.217 1593.217 1593.217
Cis-Decalin 0 0 0 0 0 0 3186.433 3186.433 3186.433 3186.433 3186.433
Dimethyl-C11 0 0 0 0 0 0 8635.319 8635.321 8635.321 8635.321 8635.322
1-2-4-triethylbe 0 0 0 0 0 0 3186.432 3186.434 3186.434 3186.434 3186.433
1-1-Bicyclohexyl 0 0 0 0 0 0 238.9825 238.9825 238.9825 238.9825 238.9825
Diphenyl 0 0 0 0 0 0 4383.289 4383.289 4383.289 4383.289 4383.289
diamantane 0 0 0 0 0 0 8635.319 8635.321 8635.321 8635.321 8635.322
Phenanthrene 0 0 0 0 0 0 6087.9 6087.901 6087.901 6087.901 6087.902
N-C15-CycloC5 0 0 0 0 0 0 291.442 291.4421 291.442 291.442 291.442
Hexatriacontane 0 0 0 0 0 0 0 0 0 0 0
Chrysene 0 0 0 0 0 0 6120.283 6120.284 6120.283 6120.283 6120.283
Cyclopentane 0 0 0 0 0 0 0 0 0 0 0
N-Pentadecane 0 0 0 0 0 0 0 0 0 0 0
N-Octadecane 0 0 0 0 0 0 0 0 0 0 0
Tetralin 0 0 0 0 0 0 0 0 0 0 0
Ethylbenzene 0 0 0 0 0 0 0 0 0 0 0
Benzene 0 0 0 0 0 0 0 0 0 0 0
N-Butane 0 0 0 0 0 0 0 0 0 0 0
Toluene 0 0 0 0 0 0 0 0 0 0 0
1-3-5-Mesitylene 0 0 0 0 0 0 0 0 0 0 0
P-Xylene 0 0 0 0 0 0 1738.065 1738.064 1738.064 1738.064 1738.065
N-Propylbenzene 0 0 0 0 0 0 0.0131 0.0102 0.0102 0.0102 0.0102
A.6
Table A.2. (contd)
Stream No. 223 225 226 227 230 240 242 245 250 253 258
Temp F 100 99.9329 99.9329 200 100 100 44.3597 100 77 84.6947 303.1303
Pres psig 700.3041 35.3041 35.3041 35.3041 700.3041 700.3041 35 300 300 300 2500
Enth MMBtu/h -33.374 -0.07606 -33.298 -30.008 -487.88 -46.01 -45.02 -0.20059 -0.90996 -1.1106 6.2841
Vapor mass fraction 0 1 0 0.000449 0 1 0.99656 1 1 1 1
Total lb/h 69520.25 25.2322 69495.02 69495.01 72156.03 19698.48 16435.05 3263.436 6500 9763.431 9763.431
Flowrates in lb/h
Water 242.2865 0.2879 241.9986 241.9986 71621.36 72.3108 72.3111 0 0 0 0
Hydrogen 0.4663 0.455 0.0113 0.0113 3.7543 3839.336 575.9001 3263.436 6500 9763.431 9763.431
Carbon Dioxide 31.1286 17.3243 13.8043 13.8043 250.624 8718.251 8718.251 0 0 0 0
Methane 0.6464 0.6206 0.0258 0.0258 5.2046 3344.148 3344.149 0 0 0 0
Ethane 0.5571 0.5241 0.0331 0.0331 0.0423 2006.3 2006.3 0 0 0 0
Propane 730.0195 3.4583 726.5612 726.5612 17.2753 957.8062 957.8062 0 0 0 0
I-Butane 889.0693 2.1131 886.9562 886.9562 6.5343 608.7963 608.7963 0 0 0 0
Pyro-lignin 0 0 0 0 0 0 0 0 0 0 0
Cellobiose 0 0 0 0 0.0051 0 0 0 0 0 0
Levoglucosan 0 0 0 0 0.0014 0 0 0 0 0 0
Furfural 0 0 0 0 0 0 0 0 0 0 0
HydroxyAcetone 0 0 0 0 0 0 0 0 0 0 0
Acetic Acid 0 0 0 0 0 0 0 0 0 0 0
2-5-Xylenol 7748.411 0.0064 7748.406 7748.406 249.3144 2.2761 2.2761 0 0 0 0
N-Heptane 3193.759 0.2507 3193.508 3193.508 0.7128 81.1817 81.1817 0 0 0 0
1-ts-35-3C1CycC6 4857.789 0.0991 4857.69 4857.689 0.1593 34.8195 34.8196 0 0 0 0
3-3-5-TriMth-C7 1987.447 0.0195 1987.427 1987.427 0.015 7.2457 7.2457 0 0 0 0
N-PropylCyc-C6 4878.879 0.0392 4878.839 4878.839 0.1611 13.7284 13.7284 0 0 0 0
1-2-3-Mesitylene 641.6517 0.001 641.6508 641.6508 0.0785 0.3363 0.3363 0 0 0 0
N-ButylCycHexane 233.9581 0.0007 233.9575 233.9575 0.0024 0.2423 0.2423 0 0 0 0
1-2-DiC1-3C2-Bz 1592.735 0.0012 1592.733 1592.733 0.0573 0.4248 0.4248 0 0 0 0
Cis-Decalin 3184.489 0.0052 3184.483 3184.483 0.0499 1.8948 1.8948 0 0 0 0
Dimethyl-C11 8633.4 0.0045 8633.395 8633.395 0.0018 1.9188 1.9189 0 0 0 0
1-2-4-triethylbe 3186.106 0.0008 3186.105 3186.105 0.0099 0.3178 0.3178 0 0 0 0
1-1-Bicyclohexyl 238.9565 0.0001 238.9565 238.9565 0.0004 0.0256 0.0256 0 0 0 0
Diphenyl 4383.134 0.0003 4383.133 4383.133 0.0454 0.1092 0.1092 0 0 0 0
diamantane 8633.234 0.0054 8633.229 8633.229 0.0045 2.0826 2.0826 0 0 0 0
Phenanthrene 6087.885 0 6087.884 6087.884 0.0107 0.0052 0.0052 0 0 0 0
N-C15-CycloC5 291.442 0 291.442 291.442 0 0.0001 0.0001 0 0 0 0
Hexatriacontane 0 0 0 0 0 0 0 0 0 0 0
Chrysene 6120.283 0 6120.283 6120.283 0.0003 0 0 0 0 0 0
Cyclopentane 0 0 0 0 0 0 0 0 0 0 0
N-Pentadecane 0 0 0 0 0 0 0 0 0 0 0
N-Octadecane 0 0 0 0 0 0 0 0 0 0 0
Tetralin 0 0 0 0 0 0 0 0 0 0 0
Ethylbenzene 0 0 0 0 0 0 0 0 0 0 0
Benzene 0 0 0 0 0 0 0 0 0 0 0
N-Butane 0 0 0 0 0 0 0 0 0 0 0
Toluene 0 0 0 0 0 0 0 0 0 0 0
1-3-5-Mesitylene 0 0 0 0 0 0 0 0 0 0 0
P-Xylene 1732.51 0.015 1732.494 1732.494 0.6275 4.927 4.927 0 0 0 0
N-Propylbenzene 0.0102 0 0.0102 0.0102 0 0 0 0 0 0 0
A.7
Table A.2. (contd)
Methane 3344.769 0 0 0 0
Ethane 2006.824 0 0 0 0
Propane 961.2645 0 0 0 0
I-Butane 610.9094 0 0 0 0
Pyro-lignin 0 0 0 0 0
Cellobiose 0 0 0 0 0
Levoglucosan 0 0 0 0 0
Furfural 0 0 0 0 0
HydroxyAcetone 0 0 0 0 0
Acetic Acid 0 0 0 0 0
2-5-Xylenol 2.2824 0 0 0 0
N-Heptane 81.4324 0 0 0 0
1-ts-35-3C1CycC6 34.9186 0 0 0 0
3-3-5-TriMth-C7 7.2652 0 0 0 0
N-PropylCyc-C6 13.7676 0 0 0 0
1-2-3-Mesitylene 0.3373 0 0 0 0
N-ButylCycHexane 0.243 0 0 0 0
1-2-DiC1-3C2-Bz 0.426 0 0 0 0
Cis-Decalin 1.9 0 0 0 0
Dimethyl-C11 1.9233 0 0 0 0
1-2-4-triethylbe 0.3186 0 0 0 0
1-1-Bicyclohexyl 0.0257 0 0 0 0
Diphenyl 0.1094 0 0 0 0
diamantane 2.088 0 0 0 0
Phenanthrene 0.0052 0 0 0 0
N-C15-CycloC5 0.0001 0 0 0 0
Hexatriacontane 0 0 0 0 0
Chrysene 0 0 0 0 0
Cyclopentane 0 0 0 0 0
N-Pentadecane 0 0 0 0 0
N-Octadecane 0 0 0 0 0
Tetralin 0 0 0 0 0
Ethylbenzene 0 0 0 0 0
Benzene 0 0 0 0 0
N-Butane 0 0 0 0 0
Toluene 0 0 0 0 0
1-3-5-Mesitylene 0 0 0 0 0
P-Xylene 4.942 0 0 0 0
N-Propylbenzene 0 0 0 0 0
A.8
Fuel Gas
Fuel Gas to Reformers
To Reformer
601
526
523 Fuel Gas
CWS
To Heaters
1850 531
Hydrogen 602
515
302 Recycle
529
1851
Hydrogen From CWR
H2 Plant 508
To E-511
532 524 510
540
536
De-butanizer 511
305 Hydrotreating
Diesel Splitter
304
Product Splitter
Stable Oil
Condensate 306 309
737
From
Hydro-
510 treater
307
735 Diesel Pool
Steam 547
308
A.9
Table A.3. Hydrocracking and Product Separation Heat and Material Balance
Stream No. 227 302 304 305 306 307 308 309 310 500 508
Temp F 200 203.3611 457.477 308.4405 427.7641 470 734.4869 398.6693 398.8038 744.7188 366
Pres psig 35.3041 35.3041 35.3041 5 5 2 1 1 15 1300 1295
Enth MMBtu/h -30.008 -4.1857 -15.689 -12.8 -5.6145 -1.3824 5.6133 -10.415 -10.413 5.6658 5.651
Vapor mass fraction 0.000449 1 0 0 0 0.52048 0 0 0 0 0.20116
Total lb/h 69495.01 3466.51 66028.52 19360.17 46668.37 46668.38 8800.003 37868.36 37868.37 8800.005 11010
Flowrates in lb/h
Water 241.9986 241.9984 0 0 0 0 0 0 0 0 0
Hybrid Poplar Ch 0 0 0 0 0 0 0 0 0 0 0
Hydrogen 0.0113 0.0113 0 0 0 0 0 0 0 0 2129.363
Carbon Dioxide 13.8043 13.8043 0 0 0 0 0 0 0 0 0
Methane 0.0258 0.0258 0 0 0 0 0 0 0 0 0
Ethane 0.0331 0.0331 0 0 0 0 0 0 0 0 0
Propane 726.5612 726.5609 0 0 0 0 0 0 0 0 0
I-Butane 886.9562 886.956 0 0 0 0 0 0 0 0 0
2-5-Xylenol 7748.406 0.0001 7748.407 3162.434 4585.977 4585.977 0.0083 4585.968 4585.968 0.0083 0.0083
N-Heptane 3193.508 1596.752 1596.765 1596.766 0 0 0 0 0 0 0
1-ts-35-3C1CycC6 4857.689 0.0486 4857.643 4541.519 316.1233 316.1233 0.0016 316.1216 316.1216 0.0016 0.0016
3-3-5-TriMth-C7 1987.427 0.0002 1987.428 1856.982 130.4458 130.4458 0.0003 130.4456 130.4456 0.0003 0.0003
N-PropylCyc-C6 4878.839 0.0006 4878.839 3903.073 975.7652 975.7652 0.0087 975.7564 975.7565 0.0087 0.0087
1-2-3-Mesitylene 641.6508 0 641.6508 128.3304 513.3206 513.3206 0.0191 513.3015 513.3015 0.0191 0.0191
N-ButylCycHexane 233.9575 0 233.9575 125.987 107.9707 107.9707 0.0016 107.9691 107.9691 0.0016 0.0016
1-2-DiC1-3C2-Bz 1592.733 0 1592.733 135.2346 1457.499 1457.499 0.0871 1457.412 1457.412 0.0871 0.0871
Cis-Decalin 3184.483 0 3184.484 1024.104 2160.379 2160.379 0.0983 2160.281 2160.281 0.0983 0.0984
Dimethyl-C11 8633.395 0 8633.397 1406.676 7226.72 7226.72 0.0961 7226.625 7226.625 0.0961 0.0961
1-2-4-triethylbe 3186.105 0 3186.106 49.8727 3136.233 3136.233 0.2496 3135.983 3135.984 0.2496 0.2497
1-1-Bicyclohexyl 238.9565 0 238.9565 4.0338 234.9227 234.9227 0.035 234.8877 234.8877 0.035 0.035
Diphenyl 4383.133 0 4383.134 2.1702 4380.966 4380.966 6.4693 4374.497 4374.496 6.4693 6.4695
diamantane 8633.229 0 8633.231 174.8519 8458.38 8458.38 15.8027 8442.577 8442.577 15.8027 15.8052
Phenanthrene 6087.884 0 6087.887 0 6087.889 6087.889 2653.667 3434.22 3434.221 2653.668 2653.667
N-C15-CycloC5 291.442 0 291.442 0 291.4421 291.4421 3.1626 288.2794 288.2794 3.1626 3.1626
Chrysene 6120.283 0 6120.284 0 6120.288 6120.288 6120.288 0.0001 0.0001 6120.288 6120.286
1-Pentene 0 0 0 0 0 0 0 0 0 0 0
O-Xylene 0 0 0 0 0 0 0 0 0 0 0
Cyclopentane 0 0 0 0 0 0 0 0 0 0 0.0552
N-Pentadecane 0 0 0 0 0 0 0 0 0 0 0
N-Octadecane 0 0 0 0 0 0 0 0 0 0 0
Tetralin 0 0 0 0 0 0 0 0 0 0 0.0439
Ethylbenzene 0 0 0 0 0 0 0 0 0 0 0
Benzene 0 0 0 0 0 0 0 0 0 0 0
N-Butane 0 0 0 0 0 0 0 0 0 0 28.8114
Toluene 0 0 0 0 0 0 0 0 0 0 0
1-3-5-Mesitylene 0 0 0 0 0 0 0 0 0 0 0
P-Xylene 1732.494 0.3188 1732.176 1248.131 484.0454 484.0454 0.0088 484.0365 484.0366 0.0088 0.0088
N-Propylbenzene 0.0102 0 0.0102 0.0064 0.0038 0.0038 0 0.0038 0.0038 0 0
N-Butylbenzene 0 0 0 0 0 0 0 0 0 0 0
O-Ethyltoluene 0 0 0 0 0 0 0 0 0 0 0
C9H18 0 0 0 0 0 0 0 0 0 0 13.652
MthCyclohexane 0 0 0 0 0 0 0 0 0 0 38.0712
A.10
Table A.3. (contd)
Stream No. 510 511 515 523 524 526 529 531 532 536 540
Temp F 1247.858 402.8347 110 110 118.5025 110 110 109.9931 77 95 109.9931
Pres psig 1275 1275 1255 1255 1300 1255 1255 1 300 1300 1
Enth MMBtu/h 5.6979 -4.3021 -7.9143 -0.09247 -0.06215 -0.01709 -7.8047 -0.00062 -0.15399 -0.08641 -7.8041
Vapor mass fraction 1 0.6392 0.11945 1 1 1 0 1 1 1 0
Total lb/h 11010.12 11010.12 11010.12 1110 1110 205.1373 9694.978 0.9811 1100 1100 9694
Flowrates in lb/h
Water 0 0 0 0 0 0 0 0 0 0 0
Hybrid Poplar Ch 0 0 0 0 0 0 0 0 0 0 0
Hydrogen 1219.721 1219.721 1219.77 1029.363 1029.363 190.2349 0.172 0.1702 1100 1100 0.0018
Carbon Dioxide 0 0 0 0 0 0 0 0 0 0 0
Methane 0 0 0 0 0 0 0 0 0 0 0
Ethane 0 0 0 0 0 0 0 0 0 0 0
Propane 0 0 0 0 0 0 0 0 0 0 0
I-Butane 0 0 0 0 0 0 0 0 0 0 0
2-5-Xylenol 0.0083 0.0083 0.0083 0.0001 0.0001 0 0.0083 0 0 0 0.0083
N-Heptane 0 0 0 0 0 0 0 0 0 0 0
1-ts-35-3C1CycC6 0.0016 0.0016 0.0016 0 0 0 0.0016 0 0 0 0.0016
3-3-5-TriMth-C7 0.0003 0.0003 0.0003 0 0 0 0.0003 0 0 0 0.0003
N-PropylCyc-C6 0.0087 0.0087 0.0087 0 0 0 0.0087 0 0 0 0.0087
1-2-3-Mesitylene 0.0191 0.0191 0.0191 0 0 0 0.0191 0 0 0 0.0191
N-ButylCycHexane 0.0016 0.0016 0.0016 0 0 0 0.0016 0 0 0 0.0016
1-2-DiC1-3C2-Bz 0.0871 0.0871 0.0871 0 0 0 0.0871 0 0 0 0.0871
Cis-Decalin 0.0984 0.0984 0.0984 0 0 0 0.0983 0 0 0 0.0983
Dimethyl-C11 0.0961 0.0961 0.0961 0 0 0 0.0961 0 0 0 0.0961
1-2-4-triethylbe 0.2497 0.2497 0.2497 0 0 0 0.2496 0 0 0 0.2496
1-1-Bicyclohexyl 0.035 0.035 0.035 0 0 0 0.035 0 0 0 0.035
Diphenyl 6.4695 6.4695 6.4695 0.0002 0.0002 0 6.4693 0 0 0 6.4693
diamantane 15.8052 15.8052 15.8052 0.0026 0.0026 0.0005 15.8022 0 0 0 15.8022
Phenanthrene 0 0 0 0 0 0 0 0 0 0 0
N-C15-CycloC5 0.0032 0.0032 0.0032 0 0 0 0.0032 0 0 0 0.0032
Chrysene 0 0 0 0 0 0 0 0 0 0 0
1-Pentene 0 0 0 0 0 0 0 0 0 0 0
O-Xylene 0 0 0 0 0 0 0 0 0 0 0
Cyclopentane 0.8451 0.8451 0.845 0.0552 0.0552 0.0102 0.7796 0.0006 0 0 0.779
N-Pentadecane 2.3923 2.3923 2.3923 0 0 0 2.3923 0 0 0 2.3923
N-Octadecane 0 0 0 0 0 0 0 0 0 0 0
Tetralin 196.8838 196.8838 196.8838 0.0439 0.0439 0.0081 196.8318 0.0004 0 0 196.8314
Ethylbenzene 0 0 0 0 0 0 0 0 0 0 0
Benzene 0 0 0 0 0 0 0 0 0 0 0
N-Butane 115.3507 115.3507 115.3013 28.8121 28.8121 5.3247 81.1645 0.2964 0 0 80.8681
Toluene 0 0 0 0 0 0 0 0 0 0 0
1-3-5-Mesitylene 0 0 0 0 0 0 0 0 0 0 0
P-Xylene 0.0088 0.0088 0.0088 0 0 0 0.0088 0 0 0 0.0088
N-Propylbenzene 0 0 0 0 0 0 0 0 0 0 0
N-Butylbenzene 0 0 0 0 0 0 0 0 0 0 0
O-Ethyltoluene 0 0 0 0 0 0 0 0 0 0 0
C9H18 6782.503 6782.503 6782.505 13.652 13.652 2.523 6766.33 0.1299 0 0 6766.2
MthCyclohexane 2669.528 2669.528 2669.527 38.0711 38.0711 7.0359 2624.419 0.3836 0 0 2624.036
A.11
Table A.3. (contd)
Stream No. 544 547 601 602 735 737 1850 1851
Temp F 150 150 85.0536 85.0536 700.0002 496.55 90 105
Pres psig 1 15 35 35 645 645 45.3041 40.3041
Enth MMBtu/h -21.85 -15.53 -39.134 -10.149 -28.903 -33.135 -129.5 -129.21
Vapor mass fraction 0 0 0.98769 0.98769 1 1.00E-06 0 0
Total lb/h 28555.25 38367.25 15824.14 4103.631 5193.402 5193.402 19029.97 19029.96
Flowrates in lb/h
Water 0 0 249.8139 64.7836 5193.402 5193.402 19029.97 19029.96
Hybrid Poplar Ch 0 0 0 0 0 0 0 0
Hydrogen 0.0018 0 457.8133 118.7234 0 0 0 0
Carbon Dioxide 0 0 6947.662 1801.718 0 0 0 0
Methane 0 0 2656.017 688.7776 0 0 0 0
Ethane 0 0 1593.595 413.2626 0 0 0 0
Propane 0 0 1340.26 347.5659 0 0 0 0
I-Butane 0 0 1189.417 308.4483 0 0 0 0
2-5-Xylenol 3162.44 4585.968 1.8125 0.47 0 0 0 0
N-Heptane 1596.764 0 1332.604 345.5806 0 0 0 0
1-ts-35-3C1CycC6 4541.518 316.1217 27.7666 7.2006 0 0 0 0
3-3-5-TriMth-C7 1856.981 130.4455 5.7693 1.4961 0 0 0 0
N-PropylCyc-C6 3903.079 975.7582 10.933 2.8352 0 0 0 0
1-2-3-Mesitylene 128.3341 513.3166 0.2678 0.0695 0 0 0 0
N-ButylCycHexane 125.9872 107.9704 0.193 0.05 0 0 0 0
1-2-DiC1-3C2-Bz 135.2398 1457.493 0.3383 0.0877 0 0 0 0
Cis-Decalin 1024.112 2160.371 1.5088 0.3913 0 0 0 0
Dimethyl-C11 1406.674 7226.722 1.5272 0.3961 0 0 0 0
1-2-4-triethylbe 49.8727 3136.233 0.253 0.0656 0 0 0 0
1-1-Bicyclohexyl 4.0338 234.9227 0.0204 0.0053 0 0 0 0
Diphenyl 2.1701 4380.964 0.0869 0.0225 0 0 0 0
diamantane 174.8532 8458.38 1.6581 0.43 0 0 0 0
Phenanthrene 0 3434.22 0.0042 0.0011 0 0 0 0
N-C15-CycloC5 0 288.2826 0.0001 0 0 0 0 0
Chrysene 0 0.0001 0 0 0 0 0 0
1-Pentene 0 0 0 0 0 0 0 0
O-Xylene 0 0 0 0 0 0 0 0
Cyclopentane 0.779 0 0.0005 0.0001 0 0 0 0
N-Pentadecane 0 2.3923 0 0 0 0 0 0
N-Octadecane 0 0 0 0 0 0 0 0
Tetralin 4.8831 191.9483 0.0003 0.0001 0 0 0 0
Ethylbenzene 0 0 0 0 0 0 0 0
Benzene 0 0 0 0 0 0 0 0
N-Butane 80.868 0 0.2354 0.061 0 0 0 0
Toluene 0 0 0 0 0 0 0 0
1-3-5-Mesitylene 0 0 0 0 0 0 0 0
P-Xylene 1248.139 484.0367 4.1775 1.0833 0 0 0 0
N-Propylbenzene 0.0064 0.0038 0 0 0 0 0 0
N-Butylbenzene 0 0 0 0 0 0 0 0
O-Ethyltoluene 0 0 0 0 0 0 0 0
C9H18 6484.484 281.7122 0.1032 0.0268 0 0 0 0
MthCyclohexane 2624.033 0 0.3046 0.079 0 0 0 0
A.12
Exhaust
630
HP
526
Hydrogen
615
PSA Offgas
605
From V-710 612
505 Steam Drum
BFW
721 730
603
Steam
KO Reformer
Drum
725 502
LP Offgas
601 604 To V-710 610
Steam 734
Air H2 to
Drum Hydrotreaters
609
Hydro
To V-710 desulfurization
503 250
507 Steam
735 To E-311 520
Drum
736 To E-226 532
743
733 Export Steam PSA
508
High Temperature
Shift Reformer
BFW 615
706 513 Fuel Gas
To 509 512
V-710
Steam 754 514
Condensate
Drum
Collection
A.13
Table A.4. Hydrogen Generation by Steam Reforming Heat and Material Balance
Stream No. 250 532 500 501 502 503 505 507 508 509 512
Temp F 77 77 60 61.8717 700 700 1050 1562 549.1881 667.5483 150
Pres psig 300 300 400 400 399.5 399.5 389.5 359.5 354.5 344.5 329.5
Enth MMBtu/h -0.90996 -0.15399 -34.902 -34.892 -26.96 -26.96 -498.35 -367.68 -440.7 -440.7 -526.32
Vapor mass fraction 1 1 1 1 1 1 1 1 1 1 0.53835
Total lb/h 6500 1100 17196.06 17401.2 17401.2 17401.2 110098.3 110098.4 110098.4 110098.8 110098.8
Flowrates in lb/h
Water 0 0 0 0 0 0 88044.1 60993.9 60993.9 51908.3 51908.3
Hydrogen 6500.0 1100.0 0.0 190.2 190.2 190.2 327.6 7450.3 7450.3 8466.9 8466.9
Carbon 0 0 0 0 0 0 0 0 0 0 0
Carbon Monoxide 0 0 0 0 0 0 0 17026.3 17026.3 2899.8 2899.8
Carbon Dioxide 0 0 0 0 0 0 2084.2 21749.5 21749.5 43945.3 43945.3
Methane 0 0 17196.1 17196.1 17196.1 17196.1 17992.9 2878.1 2878.1 2878.1 2878.1
Ethylene 0 0 0 0 0 0 0 0 0 0 0
Ethane 0 0 0 0 0 0 478.0 0.1 0.1 0.1 0.1
Propylene 0 0 0 0 0 0 0 0 0 0 0
Propane 0 0 0 0 0 0 401.9 0 0 0 0
I-Butane 0 0 0 0 0 0 356.5 0 0 0 0
Formaldehyde 0 0 0 0 0 0 0 0.2 0.2 0.2 0.2
2-5-Xylenol 0 0 0 0 0 0 0.1 0 0 0 0
N-Heptane 0 0 0 0 0 0 385.5 0 0 0 0
1-ts-35-3C1CycC6 0 0 0 0 0 0 6.9 0 0 0 0
3-3-5-TriMth-C7 0 0 0 0 0 0 1.3 0 0 0 0
N-PropylCyc-C6 0 0 0 0 0 0 2.6 0 0 0 0
1-2-3-Mesitylene 0 0 0 0 0 0 0 0 0 0 0
N-ButylCycHexane 0 0 0 0 0 0 0 0 0 0 0
1-2-DiC1-3C2-Bz 0 0 0 0 0 0 0 0 0 0 0
Cis-Decalin 0 0 0 0 0 0 0.2 0 0 0 0
Dimethyl-C11 0 0 0 0 0 0 0.1 0 0 0 0
1-2-4-triethylbe 0 0 0 0 0 0 0 0 0 0 0
1-1-Bicyclohexyl 0 0 0 0 0 0 0 0 0 0 0
Diphenyl 0 0 0 0 0 0 0 0 0 0 0
diamantane 0 0 0 0 0 0 0.1 0 0 0 0
Phenanthrene 0 0 0 0 0 0 0 0 0 0 0
N-C15-CycloC5 0 0 0 0 0 0 0 0 0 0 0
Cyclopentane 0 0 0 0 0 0 0 0 0 0 0
N-Pentadecane 0 0 0 0 0 0 0 0 0 0 0
N-Octadecane 0 0 0 0 0 0 0 0 0 0 0
Tetralin 0 0 0 0 0 0 0 0 0 0 0
Ethylbenzene 0 0 0 0 0 0 0 0 0 0 0
Benzene 0 0 0 0 0 0 0 0 0 0 0
N-Butane 0 0 0 5.3 5.3 5.3 5.4 0 0 0 0
Toluene 0 0 0 0 0 0 0 0 0 0 0
1-3-5-Mesitylene 0 0 0 0 0 0 0 0 0 0 0
P-Xylene 0 0 0 0 0 0 1.1 0 0 0 0
C9H18 0 0 0 2.5 2.5 2.5 2.5 0 0 0 0
MthCyclohexane 0 0 0 7.0 7.0 7.0 7.1 0 0 0 0
A.14
Table A.4. (contd)
Stream No. 513 514 520 526 601 603 604 605 609 610 612
Temp F 150 150 150 110 85.0536 85.0536 85.0536 85.0536 256.2011 60 550
Pres psig 329.5 329.5 329.5 1255 35 35 35 35 400 0.001 2
Enth MMBtu/h -183.1 -343.22 1.9013 0.009921 -39.131 -38.37 -0.76068 -26.859 -11.172 -0.97388 26.657
Vapor mass fraction 1 0 1 1 0.98944 1 0 1 1 1 1
Total lb/h 59271.69 50827.07 7620.208 205.1373 15824.14 15657.06 167.0814 10959.94 4697.12 230000 230000
Flowrates in lb/h
Water 1081.2 50827.1 0 0 249.8 147.0 102.8 102.9 44.1 0 0
Hydrogen 8466.9 0 7620.2 190.2 457.8 457.8 0.0 320.5 137.3 0 0
Carbon 0.0 0 0 0 0 0 0 0 0 0 0
Carbon Monoxide 2899.8 0 0 0 0 0 0 0 0 0 0
Carbon Dioxide 43945.3 0 0 0 6947.7 6947.3 0.4 4863.1 2084.2 0 0
Methane 2878.1 0 0 0 2656.0 2656.0 0.0 1859.2 796.8 0 0
Ethylene 0 0 0 0 0 0 0 0 0 0 0
Ethane 0.1 0 0 0 1593.6 1593.4 0.1 1115.4 478.0 0 0
Propylene 0 0 0 0 0 0 0 0 0 0 0
Propane 0 0 0 0 1340.3 1339.8 0.4 937.9 401.9 0 0
I-Butane 0 0 0 0 1189.4 1188.5 1.0 831.9 356.5 0 0
Formaldehyde 0.2 0 0 0 0 0 0 0 0 0 0
2-5-Xylenol 0.0 0 0 0 1.8 0.4 1.4 0.3 0.1 0 0
N-Heptane 0 0 0 0 1332.6 1285.0 47.6 899.5 385.5 0 0
1-ts-35-3C1CycC6 0 0 0 0 27.8 23.1 4.7 16.1 6.9 0 0
3-3-5-TriMth-C7 0 0 0 0 5.8 4.3 1.5 3.0 1.3 0 0
N-PropylCyc-C6 0 0 0 0 10.9 8.7 2.3 6.1 2.6 0 0
1-2-3-Mesitylene 0 0 0 0 0.3 0.2 0.1 0.1 0 0 0
N-ButylCycHexane 0 0 0 0 0.2 0.1 0.1 0.1 0 0 0
1-2-DiC1-3C2-Bz 0 0 0 0 0.3 0.1 0.2 0.1 0 0 0
Cis-Decalin 0 0 0 0 1.5 0.7 0.8 0.5 0.2 0 0
Dimethyl-C11 0 0 0 0 1.5 0.2 1.3 0.1 0.1 0 0
1-2-4-triethylbe 0 0 0 0 0.3 0 0.2 0 0 0 0
1-1-Bicyclohexyl 0 0 0 0 0.0 0 0 0 0 0 0
Diphenyl 0 0 0 0 0.1 0 0.1 0 0 0 0
diamantane 0 0 0 0 1.7 0.3 1.4 0.2 0.1 0 0
Phenanthrene 0 0 0 0 0 0 0 0 0 0 0
N-C15-CycloC5 0 0 0 0 0 0 0 0 0 0 0
Cyclopentane 0 0 0 0 0 0 0 0 0 0 0
N-Pentadecane 0 0 0 0 0 0 0 0 0 0 0
N-Octadecane 0 0 0 0 0 0 0 0 0 0 0
Tetralin 0 0 0 0 0 0 0 0 0 0 0
Ethylbenzene 0 0 0 0 0 0 0 0 0 0 0
Benzene 0 0 0 0 0 0 0 0 0 0 0
N-Butane 0 0 0 5.3 0.2 0.2 0.0 0.2 0.1 0 0
Toluene 0 0 0 0 0 0 0 0 0 0 0
1-3-5-Mesitylene 0 0 0 0 0 0 0 0 0 0 0
P-Xylene 0 0 0 0 4.2 3.6 0.6 2.5 1.1 0 0
C9H18 0 0 0 2.5 0.1 0.1 0 0.1 0 0 0
MthCyclohexane 0 0 0 7.0 0.3 0.3 0 0.2 0.1 0 0
A.15
Table A.4. (contd)
Stream No. 615 630 706 707 721 725 730 733 734 735 736
Temp F 150 311.6723 276.468 276.468 497.3775 497.3795 497.3795 700.0002 700 700 700
Pres psig 329.5 1.5 670 670 650 650 650 645 645 645 645
Enth MMBtu/h -185.86 -447.3 -1133.3 -0.00703 -1371.1 -1316.6 -675.88 -121.47 -486.09 -28.903 -22.468
Vapor mass fraction 0.98557 1 0 0 0 0.355 1 1 1 1 1
Total lb/h 51651.48 292778.2 171067 1.0604 214800.3 214800 119221.6 21991.57 88000 5193 4037
Flowrates in lb/h
Water 1081.2 28603.1 171067.0 1.1 214800.3 214800.0 119221.6 21991.6 88000 5193.0 4037.0
Hydrogen 846.7 0 0 0 0 0 0 0 0 0 0
Carbon 0 0 0 0 0 0 0 0 0 0 0
Carbon Monoxide 2899.8 0 0 0 0 0 0 0 0 0 0
Carbon Dioxide 43945.3 78010.5 0 0 0 0 0 0 0 0 0
Methane 2878.1 0 0 0 0 0 0 0 0 0 0
Ethylene 0 0 0 0 0 0 0 0 0 0 0
Ethane 0.1 0 0 0 0 0 0 0 0 0 0
Propylene 0 0 0 0 0 0 0 0 0 0 0
Propane 0 0 0 0 0 0 0 0 0 0 0
I-Butane 0 0 0 0 0 0 0 0 0 0 0
Formaldehyde 0 0 0 0 0 0 0 0 0 0 0
2-5-Xylenol 0 0 0 0 0 0 0 0 0 0 0
N-Heptane 0 0 0 0 0 0 0 0 0 0 0
1-ts-35-3C1CycC6 0 0 0 0 0 0 0 0 0 0 0
3-3-5-TriMth-C7 0 0 0 0 0 0 0 0 0 0 0
N-PropylCyc-C6 0 0 0 0 0 0 0 0 0 0 0
1-2-3-Mesitylene 0 0 0 0 0 0 0 0 0 0 0
N-ButylCycHexane 0 0 0 0 0 0 0 0 0 0 0
1-2-DiC1-3C2-Bz 0 0 0 0 0 0 0 0 0 0 0
Cis-Decalin 0 0 0 0 0 0 0 0 0 0 0
Dimethyl-C11 0 0 0 0 0 0 0 0 0 0 0
1-2-4-triethylbe 0 0 0 0 0 0 0 0 0 0 0
1-1-Bicyclohexyl 0 0 0 0 0 0 0 0 0 0 0
Diphenyl 0 0 0 0 0 0 0 0 0 0 0
diamantane 0 0 0 0 0 0 0 0 0 0 0
Phenanthrene 0 0 0 0 0 0 0 0 0 0 0
N-C15-CycloC5 0 0 0 0 0 0 0 0 0 0 0
Cyclopentane 0 0 0 0 0 0 0 0 0 0 0
N-Pentadecane 0 0 0 0 0 0 0 0 0 0 0
N-Octadecane 0 0 0 0 0 0 0 0 0 0 0
Tetralin 0 0 0 0 0 0 0 0 0 0 0
Ethylbenzene 0 0 0 0 0 0 0 0 0 0 0
Benzene 0 0 0 0 0 0 0 0 0 0 0
N-Butane 0 0 0 0 0 0 0 0 0 0 0
Toluene 0 0 0 0 0 0 0 0 0 0 0
1-3-5-Mesitylene 0 0 0 0 0 0 0 0 0 0 0
P-Xylene 0 0 0 0 0 0 0 0 0 0 0
C9H18 0 0 0 0 0 0 0 0 0 0 0
MthCyclohexane 0 0 0 0 0 0 0 0 0 0 0
A.16
Table A.4. (contd)
A.17
765 To T-310 Reboiler
790
Blow Down 720
Boiler Feed
Water
707
Figure A.5. Flow Diagram for the Steam Reformer Steam Drum
A.18
Table A.5. Steam Reformer Steam Drum Heat and Material Balance
A.19
Vent
Superheated Steam
Condensate 768
A.20
Table A.6. Condensate Collection Heat and Material Balance
A.21
Appendix B
Table B.1 lists the equipment cost details. Table B.2 lists the specifications for the standard equipment.
B.1
Table B.1. Equipment Capital Cost Detail
Original New Original Scaled and Equip
# Stream Stream Scaling Size Equip Cost Scaling Install Installed Cost Installed Cost Bare Equip Cost
Reqd Equipment Name Metric Metric Units Ratio (per unit) Base Year Exp Factor in Base Year in 2007$ cost in 2007$ Source
A100 Pyrolysis Oil
1 Feedstock Handling 500 2,000 tpd 4.00 $5,570,000 2003 0.7 2.47 14,699,318 19,212,106 $7,778,181 1
1 CFB Pyrolyzer 500 2,000 tpd 4.00 $3,392,000 2003 0.7 2.47 8,951,542 11,699,724 $4,736,731 1
1 Quench 500 2,000 tpd 4.00 $1,940,000 2003 0.7 2.47 5,119,691 6,691,470 $2,709,097 1
1 Heat recovery 500 0 tpd 0.00 $1,140,000 2003 0.7 2.47 0 0 $0 1
1 Product recovery and storage 500 2,000 tpd 4.00 $800,000 2003 0.7 2.47 2,111,213 2,759,369 $1,117,153 1
1 Recycle 500 2,000 tpd 4.00 $1,380,000 2003 0.7 2.47 3,641,842 4,759,911 $1,927,090 1
1 Steam and Power production 500 0 tpd 0.00 $3,160,000 2003 0.7 2.47 0 0 $0 1
1 Utilities 500 0 tpd 0.00 $3,130,000 2003 0.7 2.47 0 0 $0 1
$34,523,605 45,122,581 $18,268,251
Equipment Contingency 35% $15,792,903 $6,393,888
60,915,484 $24,662,139
Cost sources 1) Ringer et al. 2006
2 Feed Pump 1,000 2,000 tpd 2.00 $122,000 2004 0.65 2.47 945,706 1,118,617 $452,882 2
1 1st stage Reactor 2,038 1,959 liq scfh 0.96 $860,700 1Q 2007 0.65 2.47 2,125,929 2,120,904 $858,666 3
1 2nd stage Reactor 2,038 1,959 liq scfh 0.96 $9,018,000 1Q 2007 0.65 2.47 19,852,131 22,221,810 $8,996,684 3
2nd stage Three Phase
1 174,497 161,375 lb/h 0.92 $673,300 1Q 2005 0.65 2.47 1,663,113 1,777,236 $719,529 3
Separator
1st Feed/Product Heat
1 59.85 38.38 mmbtuh 0.64 $647,800 1Q 2005 0.65 2.47 1,628,026 1,347,791 $545,664 3
Exchanger
2nd Feed/Product Heat
1 33.30 1.22 mmbtuh 0.04 $622,200 1Q 2005 0.65 2.47 1,537,134 201,410 $81,542 3
Exchanger
1 Fired Heater 8.35 40.00 mmbtuh 8.18 $378,000 2004 0.65 2.47 933,660 3,057,432 $1,237,827 2
1 Air Cooler 40.38 28.10 mmbtuh 0.70 $228,000 1Q 2005 0.65 2.47 548,093 500,254 $202,532 3
1 Product Trim Cooler 8.35 8.35 mmbtuh 1.00 $128,700 1Q 2005 0.65 2.47 317,889 357,424 $144,706 3
mmscfd
1 PSA 10 15 1.50 $1,750,000 2004 0.65 2.47 4,838,004 2,694,155 $1,090,751 2
H2
1 Product Flash Drum 71,462 69,520 lb/h 0.97 $38,800 1Q 2005 0.65 2.47 95,836 105,842 $42,851 3
1 Product Pump 1,000 2,000 tpd 2.00 $39,000 2004 0.65 2.47 151,158 357,591 $144,774 2
1 Hydrogen Compressor 2,840 2,840 acfm 1.00 $3,869,400 1Q 2005 0.65 2.47 9,557,418 10,746,045 $4,350,625 3
Subtotal $43,497,310 $46,881,581 $18,980,397
Equipment Contingency 15% $7,032,237 $2,847,060
$53,913,818 $21,827,457
Cost sources 2) Vendor quote, 2004; 3) Aspen Icarus
Table B.1. (contd)
1 T-540 Reflux Drum 24 23 gpm 0.96 $11,500 1Q 2005 0.65 2.47 27,630 31,066 $12,577 3
1 Debutanizer Feed Preheater 6.66 3.29 mmbtuh 0.49 $29,000 1Q 2005 0.65 2.47 45,291 50,924 $20,617 3
1 T315 Feed Preheater 6.66 4.23 mmbtuh 0.64 $29,000 1Q 2005 0.65 2.47 53,328 59,961 $24,276 3
1 Hydrocracker Unit : 2,250 590 bpd fd 0.26 $30,000,000 1Q 2005 0.65 2.47 12,567,718 14,130,726 $5,720,942 4
H508 Fired heater Included in hydrocracker unit cost
R510 Hydrocracker Vessel Included in hydrocracker unit cost
E513 Feed/product exchanger Included in hydrocracker unit cost
E516 air cooler Included in hydrocracker unit cost
E517 trim cooler Included in hydrocracker unit cost
V520 HP flash Included in hydrocracker unit cost
V530 LP flash Included in hydrocracker unit cost
1 Naphtha Product Cooler 1.4 1.45 mmbtuh 1.04 $46,300 1Q 2005 0.65 2.47 116,999 131,550 $53,259 3
1 Diesel Product Cooler 3.1 4.93 mmbtuh 1.59 $44,600 1Q 2005 0.65 2.47 148,935 167,458 $67,797 3
16,819,896 6,809,675
Subtotal $2,522,984 $1,021,451
15% $19,342,881 $7,831,126
1 Field-Erected CTW w/pumps, etc 10,400 7,549 gpm 0.73 $352,000 1Q 2005 0.78 2.47 274,164 308,261 $124,802 3
1 Plant Air Compressor 2,000 2,000 tpd 1.00 $32,376 2002 0.34 2.47 79,969 106,212 $43,001 6
1 Hydraulic Truck Dump with Scale 2,000 2,000 tpd 1.00 $80,000 1998 0.6 2.47 197,600 266,553 $107,916 6
1 Firewater Pump 2,000 2,000 tpd 1.00 $18,400 1997 0.79 2.47 45,448 61,783 $25,013 6
1 Diesel Pump 2,000 2,000 tpd 1.00 $6,100 1997 0.79 2.47 15,067 20,482 $8,292 6
1 Instrument Air Dryer 2,000 2,000 tpd 1.00 $8,349 2002 0.6 2.47 20,622 27,389 $11,089 6
1 Plant Air Receiver 2,000 2,000 tpd 1.00 $7,003 2002 0.72 2.47 17,297 22,974 $9,301 6
1 Firewater Storage Tank 2,000 2,000 tpd 1.00 $166,100 1997 0.51 2.47 410,267 557,726 $225,800 6
1 Ammonia Pump included in Stream Reformer Cost
1 Hydrazine Pump included in Stream Reformer Cost
1 Ammonia Storage Tank included in Stream Reformer Cost
B.4
Cost sources 3) Aspen Icarus; 5) Beckman et al. 1990; 6) Phillips et al. 2007
Table B.1. (contd)
B.6
Table B.2. (contd)
E-305C Debutanizer Condenser 150 200 Air Fin Area, ft2 209 CS Tubes
Duty, MMBtu/h 1.5
E-310C Naphtha Splitter Condenser 150 200 Air Fin Area, ft2 503 CS Tubes
Duty, MMBtu/h 5.6
E-315C Diesel Splitter Condenser 150 300 Air Fin Area, ft2 670 CS Tubes
Duty, MMBtu/h 13.4
E-540C T-540 Condenser 150 400 Air Fin Area, ft2 1680 CS Tubes
Duty, MMBtu/h 2.7
D-305 Debutanizer Reflux Drum 15 250 Horizontal, 5 Diameter, ft 2 CS
min holdup Length, ft 6
D-310 Naphtha Splitter Reflux Drum 15 350 Horizontal, 5 Diameter, ft 4.8 CS
min holdup Length, ft 14.3
D-315 Diesel Splitter Reflux Drum 15 425 Horizontal, 5 Diameter, ft 4.5 CS
min holdup Length, ft 13.5
D-540 T-540 Reflux Drum 15 250 Horizontal, 5 Diameter, ft 3.4 CS
min holdup Length, ft 10.3
E-305 Debutanizer Feed Preheater 150 530 Pre-engineered Area, ft2 83 CS
Duty, MMBtu/h 3.33
E-311 Diesel Splitter Feed Preheater 150 Shell & tube Area, ft2 574 CS
floating head Duty, MMBtu/h 3.55
E-542 Naphtha Product Cooler 50 475 Air Fin Area, ft2 838 CS
Duty, MMBtu/h
E-543 Diesel Product Cooler 50 475 Air Fin Area, ft2 670 CS
Duty, MMBtu/h 3.1
B.7