Biomass and Coal Integration To Produce Liquid Fuels

Contents
Summary ....................................................................................................................................................... 3

1
Introduction ................................................................................................................................................... 4
Conclusion .................................................................................................................................................... 4
Project Premises .......................................................................................................................................... 5
Process Flow Diagrams................................................................................................................................. 6
Streams Attributes Table............................................................................................................................... 8
Process description...................................................................................................................................... 12
Safety .......................................................................................................................................................... 13
Environment................................................................................................................................................ 13
Utility Summary.......................................................................................................................................... 13
Operating Costs........................................................................................................................................... 14
Equipment Information Summary .............................................................................................................. 17
Capital Cost................................................................................................................................................. 19
Economic analysis ...................................................................................................................................... 22
Innovation and Optimization ...................................................................................................................... 27
References ................................................................................................................................................... 27
Engineering Calculations ............................................................................................................................ 29
Computer Programs .................................................................................................................................... 36
Computer Process Simulations ................................................................................................................... 36

2
Summary

The project scope was to design a biomass pyrolysis plant with an additional coal gasifier
unit. Upgrading the collected oil and syngas to transportation fuels was also included in the
design to maximize profits. This married process was then compared to a direct process as the
base case.
The plant was intended to be built in the gulf coast region due to transportation and labor
considerations. The time frame for building the plant was considered 1.5 years. The breakeven
point for the married process is 7 years when the cost of transportation fuel was not changed.
Extending the plant life for twenty years is also recommended since the need for transportation
fuel will still be present.
After considering the increased costs for the married process against the increased
revenue, building a plant with the married process is strongly recommended.

Married Process Direct Process

Feed (lbs/hr) Feed (lbs/hr)
Corn Stover 183335 Corn Stover 183335
Coal 272632 Coal 0
Water 272632 Water 0
Oxygen 111724 Oxygen 0
Hydrogen 0 Hydrogen 2970
Products Products 0
lpg 8466 lpg 0
naptha 37634 naptha 17132
middle distilate 2732 middle distilate 0
diesel 23891 diesel 17132
wax 1353 wax 0
bio-oil derived fuel 47781 bio-oil production 34263
syngas derived fuel 26294 syngas derived fuel 0
Total production 74075 Total production 34263

Married Process Direct Process

Capital Cost $ 57,479,725 Capital Cost $ 30,290,000
Labor Cost $ 11,214,000 Labor Cost $ 6,678,000
Raw Materials $ 11,871,326 Raw Materials $ 1,860,496
Utilities $ 41,656,701 Utilities $ 27,610,000

Revenue $ 202,240,764 Revenue $ 93,545,062

Figure 1 - Production Summary For Married and Direct Process

3
Introduction

Coal and biomass are sources of renewable energy that represent an alternative to
petroleum energy products. Biomass fuel is mainly derived from organic materials such as forest
debris and organic waste residues, coal is a combustible organic rock composed mainly of
carbon, oxygen and hydrogen. In addition to being sustainable, reliable and environmentally
friendly energy sources, coal and biomass play a major role in reducing dependency on
petroleum products and define a reliable way of being energy self-sufficient. Coal and biomass
are used to produce bio-oil which can be upgraded to biofuel which is a reliable source of
renewable energy obtained through a process of biological carbon fixation; this process reduces
emissions of greenhouse gases such as carbon dioxide which represents a major threat to global
warming.
Coal and biomass have been subject to several processes and technologies aiming to
produce bio-oils. These processes include Fischer-Tropsch coal conversion to liquid fuels which
consists mainly of gasification of coal to produce a mixture of hydrogen, carbon dioxide and
carbon monoxide, purification, separation and upgrade of the products. Another process involves
the direct pyrolysis of biomass to produce bio-oil and a third process involves marrying biomass
pyrolysis to coal gasification which is expected to reduce the costs and maximize the profits ,
this process is mainly based on using coal gasification products as a heating source for the
biomass pyrolysis process.
This project studies and evaluates all three processes in order to determine the optimal
case that will provide minimal costs and maximal profits in producing biofuel.

Conclusion

Renewable energy is the focus of research due to many advantages it brings to the
industry offering reliability with efficiency and accessibility. The objective of this project was to
study and evaluate alternative processes of producing bio-oil and bio-fuel in order to determine
the most cost effective, profitable and flexible process.
Using energy and mass balances, economic analysis and safety considerations, it was
determined that the best and most optimal case would be marrying the direct process of
producing bio-oil via biomass fast pyrolysis with coal gasification to produce synthesis gas that
would be used as a heating source for the pyrolysis. Furthermore, to address capacity constraints
that this married process may impose, it was suggested to introduce Fisher Tropsch process as an
additional way to produce bio-oil from the gasification synthesis gas. Upgrading bio-oil to bio-
fuel was also evaluated in this project and determined to be beneficial to the overall plant
economics.
Recommendation
Due to the sharing of resources, the married process is much more cost efficient.
However, the married process produces a major process constraint. The syngas is used as the
heating medium which forces a capacity constraint on the amount of syngas that can be
produced. This can be fixed by splitting the syngas. Some can go to the biomass pyrolysis for
heating while the other goes straight to gas treatment. This is the long term fix when the
production team wants to increase capacity of fuel from the FT reactors.
Upgrading oil into fuel is very expensive. However, it benefits from economies of scale.
Literature suggests that increasing the plant capacity provides economic advantages.

4
 This project was designed as a once through system as a preliminary estimate. When
more consideration is needed, recycle streams on all reactors is necessary. This will decrease
heating costs and increase material efficiency.
The final recommendation is to complete another aspen simulation with actual kinetic
data. This project was limited to potential yields at specific process conditions. This constricted
the design team from optimizing the process choosing more ideal temperatures, pressures, etc.

Project Premises

Achieving energy self-sufficiency requires an independency from petroleum products; this

will require more research and investment in the development of new processes and technologies
to produce biofuel which will a sustainable and secure source of renewable energy. In that
context this project will study three different processes associated with the production of bio-
fuels using coal and biomass. The direct process of producing bio-oil via biomass pyrolysis will
be based on a literature case study. This process will then be compared to a married process that
uses coal gasification as heat source for biomass pyrolysis, and to a direct process that uses
Fischer-Tropsch coal conversion to bio-oil which will be upgraded to bio-fuel.
Feed calculations for the married and for the Fischer-Tropsch processes will be determined
from energy and mass balances calculations based on the direct biomass pyrolysis case study
available in the literature.
Economic evaluation will determine the equipment cost, raw materials cost and the
capital investment required financing each case. Cash flow analysis studies will then determine
the optimal process of producing bio-fuel with the minimal associated cost and the maximal
return on investment. Based on these results the final recommendations will be made with
respect to this project.
Safety and Hazop studies will also be evaluated and taken into account in making the final
recommendations for this project.

5
Process Flow Diagrams

Figure 2 - PFD For the Direct Case's Pyrolysis Section

P3 FC CT
I-17 I-14

Pyrolysis Reactor
Biomass Slurry P2
P1 P3 Cyclone
R1 E-12
V-2
Chopper E-14 I-19P-17
I-22
FT FC
Dryer I-11 I-10 Quench S3 Syngas
V-5
Tower
Separator
TT
I-25
V-3

S2 – Char / Ash E-16

FC CT C2 - Syngas FC
I-18 S-6
I-6 I-26
S-6 Bio-oil

Coal Slurry FC FT
I-24 I-23
S4 – Bio-oil S5 Bio-oil
C1
V-1 V-7

Chopper

Gazifier

Figure 3 - Married Cases’ Pyrolysis. Gasification and Bio-oil Separation Section

6
 S-7
FC CT
I-17 I-14
FC CT
I-17 I-6 Re-former
Pre-reformer
U2 - CH4
U1 H2
U3
CH2

V-1 V-2

S5 - Bio-oil U4

FC CT FC CT
I-17 I-6 I-17 I-6

U6 - Transportation Fuel

U5 V-1 V-1

Hydrotreater Hydrocracker

Figure 4 - Upgrading Section

F3
Water Gas Shift Reactor

FT
F2 F5 F6
S3 – Syngas

Acid Gas Removal FT Reactor

P-42 F4 – Carrier Fluid
FC

P-40
FT

F1 – Added Water

Figure 5 - FT Synthesis Section

7
Streams Attributes Table
Table 1 - Coal Gasification and Integrated Biomass Pyrolysis Stream Table

Stream Name P1 P2 P3 C1 C2 P4 R1
Removed
Syngas And
Water From Coal
Gasifier Biomass Pyrolysis
Chopper Dryer Dryer - Sent Slurry
Outlet - Combined Reactor
Outlet Outlet To Water Gas Chopper
Syngas in Pyrolysis Outlet
Shift Reactor Outlet
Reactor
Description And Tankage
Temperature (F) 77.00 212.00 212.00 77.00 2499.80 897.08 897.08
Pressure (psi) 14.69 14.69 14.69 14.69 14.69 14.69 14.69
Mass Flow Rate
(lb/hr)
Biomass 183335 183335 0 0 0 183335 0
Water 61112 13519 47593 272632 17807 31326 37607
Ash/Char 0 0 0 0 0 0 30049
Bio-oil 0 0 0 0 0 0 109818
Hydrogen 0 0 0 0 3210 3210 4288
CO 0 0 0 0 61526 61526 73552
CO2 0 0 0 0 31417 31417 41354
Methane 0 0 0 0 0 0 64
Ethane 0 0 0 0 0 0 260
Propane 0 0 0 0 0 0 279
Ammonia 0 0 0 0 0 0 22
Coal 0 0 0 272632 0 0 0
Oxygen 0 0 0 111724 0 0 0
carbon dioxide,
0 0 0 0 0 0 0
lights
lpg 0 0 0 0 0 0 0
naphtha 0 0 0 0 0 0 0
middle distillate/
0 0 0 0 0 0 0
diesel
wax 0 0 0 0 0 0 0
8
 Table 2 - Bio-oil Separation Stream Table

Stream Name S1 S2 S3 S4 S5

Pyrolysis Syngas
Char/Ash
Vapor Recovered Quench Bio-oil
From
From From Tower Product
Cyclone
Cyclone Separation
Description
Temperature (F) 897.08 897.08 77.00 302.00 115.34
Pressure (psi) 14.69 14.69 21.76 14.69 14.69
Mass Flow Rate
(lb/hr)
Biomass 0 0 0 0 0
Water 0 37607 1987 37607 35620
Ash/Char 30049 0 0 0 0
Bio-oil 0 109818 6321 109818 103497
Hydrogen 0 4288 4289 4288 0
CO 0 73552 73501 73552 52
CO2 0 41354 41025 41354 329
Methane 0 64 64 64 0
Ethane 0 260 256 260 3
Propane 0 279 264 279 14
Ammonia 0 22 15 22 6
Coal 0 0 0 0 0
Oxygen 0 0 0 0 0
carbon dioxide,
0 0 0 0 0
lights
lpg 0 0 0 0 0
naphtha 0 0 0 0 0
middle distillate/
0 0 0 0 0
diesel
wax 0 0 0 0 0

9
 Table 3 - Water Gas Shift and FT Liquid Synthesis Stream Table

Stream Name F1 F2 F3 F5 F6
Added Water
For the Water Water Gas Acid Gas FT Liquid
Scrubber
Gas Shift Shift Removal Synthesis
Product
Reaction Reactor Impurities Product
Stream
From Outlet Stream Stream
Tankage
Description
Temperature (F) 77.00 77.00 264.20 264.20 500.00
Pressure (psi) 14.69 298.78 291.53 291.53 336.49
Mass Flow Rate
(lb/hr)
Biomass 0 0 0 0 0
Water 4173 0 0 0 16739
Ash/Char 0 0 0 0 0
Bio-oil 0 6321 0 6321 6321
Hydrogen 0 10449 0 10449 1860
CO 0 67341 0 67341 13468
CO2 0 47185 47185 0 0
Methane 0 64 0 64 1603
Ethane 0 256 0 256 256
Propane 0 264 0 264 264
Ammonia 0 15 0 15 15
Coal 0 0 0 0 0
Oxygen 0 0 0 0 0
carbon dioxide,
0 0 0 0 0
lights
lpg 0 0 0 0 8466
naphtha 0 0 0 0 13743
middle distillate/
0 0 0 0 2732
diesel
wax 0 0 0 0 1353

10
 Table 4 - Bio-oil Upgrading Stream Table

Stream Name U1 U5 U3 U4 U6

Bio-oil Bio-oil Split Hydrogen Hydrotreaing

CO2 From
Split To To From Product
Reforming
Reformer Hydrotreating Reformer Outlet

Description
Temperature (F) 114.80 114.80 346.10 347.00 285.26
Pressure (psi) 14.69 14.65 362.59 362.59 14.71
Mass Flow Rate
(lb/hr)
Biomass 0 0 0 0 0
Water 2493 33127 1 0 0
Ash/Char 0 0 0 0 0
Bio-oil 7245 96252 29 0 33692
Hydrogen 0 0 0 3971 0
CO 4 48 4 0 0
CO2 23 306 19383 0 0
Methane 0 0 0 0 0
Ethane 0 3 0 0 0
Propane 1 13 1 0 0
Ammonia 0 6 0 0 0
Coal 0 0 0 0 0
Oxygen 0 0 0 0 0
carbon dioxide,
0 0 0 0 71672
lights
lpg 0 0 0 0 0
naphtha 0 0 0 0 23891
middle distillate/
0 0 0 0 23891
diesel
wax 0 0 0 0 0

11
Process description

This project studies and evaluates three different process used to commercially produce
bio-oil using coal and biomass, furthermore, the produced bio-oil is upgraded to biofuel via
hydrotreating and hydrocracking.

Direct Fast Pyrolysis

The first evaluated process is the direct conversion of biomass to bio-oil via fast
pyrolysis. This process is available in literature and is used in this study for comparison
purposes. The process starts with biomass pretreatment as it is dried from 25 per cent moisture
content to 7 per cent moisture. Biomass is then fed to a fluid bed reactor operating at atmospheric
pressure and 480 degrees. The product vapors from the pyrolysis reactor are then condensed to
produce liquid bio-oil. The produced bio-oil is finally subject to upgrading to bio-fuel via
hydrotreating and hydrocracking.
The upgrading process starts with separating pyrolysis lignin from water soluble compounds. A
pre-reformer is then used to convert aqueous phase oil mixed with steam to synthesis gas which
is then fed into a reformer with methane to produce hydrogen. The hydrogen along with
pyrolysis lignin are then injected to a hydrotreater where the oxygen found in bio-oil is converted
to water and carbon dioxide molecules. The product from the hydrotreater is finally fed to a
hydrocracker where long carbon chain hydrocarbons are processed.
In this process the heat for the biomass pyrolysis is generated from uncondensable pyrolysis
product vapors recycled to the reactor, and from the combustion of pyrolysis solid products
separated from the vapors via cyclones.

Coal-Biomass Married Case

The second process evaluated in this study is a biomass coal married case to produce
bio-oil. This case assumes the same conditions and equipment for biomass pyrolysis, but
considers using coal gasification synthesis gas as a heating source for the biomass pyrolysis.
Coil is introduced, grounded and mixed with 50 % water to produce coal water slurry. Along
with oxygen and steam, the slurry is fed to the gasifier operating at a high temperature of 1500
degrees where it is converted to synthesis gas. After leaving the gasifier, the syngas temperature
is adjusted using a heat exchanger and the product is used as a heating source for the biomass
pyrolysis process described in the direct fast pyrolysis case.

Fisher Tropsch Coal Gasification

Fisher Tropsch Coal gasification is also evaluated in this project as a way of using direct
gasification of coal to produce bio-oil. This process is based on reacting hydrogen and carbon
monoxide from syngas using a catalyst to produce the desired bio-oil product. As described
before, Coal slurry is introduced to a gasifier operating at a high temperature of 1500 degrees
along with oxygen and steam. The produced synthesis gas which is mainly composed of
hydrogen, carbon dioxide and carbon monoxide is then purified from sulfur compounds, mercury
compounds and other impurities. The resulting concentrated stream of carbon dioxide is then fed
to a Fisher Tropsch reactor where it is converted to hydrocarbons via catalytic reactions. The
hydrocarbons are then separated and furthermore treated to produce naphtha and diesel fuel.

12
Safety
Syngas from gasification process is very hot and combustible (Pytler); therefore, a
leaking from this process can cause explosion and fires. Syngas is usually poisonous, causing
health hazard problem to workers if they are exposed to it. Since syngas leaking could impact the
health and economic cost to the biomass plant, a gas detector can be used to help detect the leak,
and the repair activities can be carried on as soon as possible. Moreover, regular maintenance
and check on the gasification process could also minimize the probability of leaking. In addition,
produced syngas from gasification could contain several contaminants, which can cause catalyst
poisoning, erosion, emission and clogging of filters. These contaminants include ash, char,
sodium and potassium compounds, nitrogen compound (NH3 and HCN), tars, H2S and HCL
(Pytler). A wet scrubbing should be required to help removed these contaminant; however, the
wet scrubbing can cause wastewater stream, which can affect the environment. During the
combustion reaction in the pyrolysis process, by-product of CO and PAH could be released
(Furnssin). CO could be oxidized and become CO2, and it doesn’t cost much to get rid of it,
while most of PAH is carcinogenic chemicals, which cause health risk to the workers who are
exposed to. As a result, there should be a very low limit for CO and PAH in the pyrolysis plant,
reducing the health hazard issue.

Environment
The industry also needs to have a strict regulation of the fugitive emission which could be
released through the leak of pressurized equipment, causes pollution to the environment and
long-term health risk to workers. VOCs can be released through a furnace in the control
equipment, and it can cause pollution in groundwater and soil; therefore, strict operation and
regular maintenance on the furnace is required to minimize the VOC emissions. Wastewater
could be greatly produced during the gasification process, and contained several chemicals
(Furnssin), which could damage to the environment and ground water; therefore, the treatment of
wastewater is required in the pyrolysis plant. According to the biomass CHP Harboore in
Denmark, a separate combustion system could be used to treat the waste water from the gasifier
(Furnssin).

Utility Summary
Since this project is only a preliminary design, heat integration and recovery methods
were not looked into. Alongside this, the majority of the project was done via hand calculations
and excel spreadsheets. With that, the utility costs were mainly estimated using engineering
judgment.

13
 Table 5 - Utility Summary For Married Process

Married Process
Unit Steam Water Fuel
Gasifier& FT $ 2,000,000.00 $ 50,000.00 $ 3,000,000.00
Pyrolysis
Combustion $ 31,377,171.97
Upgrading $ 4,183,622.93 $ 1,045,905.73
Total $ 41,656,700.63
Table 6 - Utility Summary For Direct Process

Direct Process
Unit Steam Water Fuel
Gasifier& FT n/a n/a n/a
Pyrolysis $ 60,000.00 $ 50,000.00 $ 10,000,000.00
Combustion $ 15,000,000.00
Upgrading $ 2,000,000.00 $ 500,000.00
Total $ 27,610,000.00

Operating Costs

Labor
Typical labor requirements for process equipment were recommended by Timmerhaus in
his book Plant Design and Economics for Chemical Engineers. His references as wells as the
team’s engineering judgment were used to estimate the required amount of labor and cost. The
necessary amount of labor needed to run the units was calculated by considering the major
process equipment for the plant. Timmerhaus’s values were then used to estimate the amount of
labor per unit per shift. The hourly rate for any given operator was assumed to be 30 $/hour. This
value was chosen as a reasonable rate for operators in the gulf coast region of the United States.
Each shift was assumed to be 12 hours and 2 shifts were necessary for every day. No overtime
was factored into this calculation. Any unforeseen additional costs will be lumped in with the
contingencies when the total plant cost is calculated. The operations of the plant were assumed
24 hours and 350 days in the year. This accounts for roughly 2 weeks of down time due to
planned and unplanned maintenance. Turnarounds were not considered in this preliminary study.
The required cost for maintenance and electricians is also factored in when calculating the fixed
capital investment (FCI).
The Married Process required labor and Direct Process required labor are compared
against each other in tables7 and 8. The Direct Process needs 33 operators per shift to run the
plant. The cost for 33 operators is 8.3 million per year. For the Married Process, 45 operators are
needed per shift. The cost for that much labor is around 11.3 million per year. Again, the Married
Process is more costly. However, this is to be expected due to the introduction of additional units
was needed to upgrade the Direct Process into the Married Process. The cost benefits and
consequences to increase the amount of necessary labor will be discussed in the economic
evaluation section of this report.

14
 Table 7 - Married Process Labor Requirements

Married Process
Labor (workers/unit/shift)
Unit Description
Pyrolysis biomass feed handling 1
biomass feed prep 1
pyrolysis reactor 1
chopper 2
dryer 0
grinder 0
magnetic separator 0
steam blower 0
Combustion Heater 2
combustion gas blower 1
combustor cyclones 1
water treatment 1
dearator 0
bfw pump 0
char/ash feeder 1
Upgrading liquid/gas separation 2
pumps 0
reforming system 2
cooler 2
hydrogen handling 2
adsorber 1
hydrotreater 3
flue gas blower 1
flue gas combustor 1
Gasifier coal feed handling 1
coal-water slurry prep 1
Gasifier 2
Gas Clean Up 3
Oxidant Compression 1
Heat Recovery Steam
1
Generator
F-T Liquid Synthesis 3
Storage fuel, oil, water storage 3
tankage pumps 1
Utilities Cooling Water Tower 2
Totals: 45
Total Labor Cost $ 11,340,000.00

15
 Table 8 - Direct Process Labor Requirements

Direct Process
Labor (workers/unit/shift)
Unit Description
Pyrolysis biomass feed handling 1
biomass feed prep 1
pyrolysis reactor 1
chopper 2
dryer 0
grinder 0
magnetic separator 0
steam blower 0
Combustion Heater 2
combustion gas blower 1
combustor cyclones 1
water treatment 1
dearator 0
bfw pump 0
char/ash feeder 1
Upgrading liquid/gas separation 2
pumps 0
reforming system 2
cooler 2
hydrogen handling 2
adsorber 1
hydrotreater 3
flue gas blower 1
flue gas combustor 1
--- --- ---
--- --- ---
--- --- ---
--- --- ---
--- --- ---
--- --- ---
--- --- ---
Storage fuel, oil, water storage 3
tankage pumps 1
Utilities Cooling Water Tower 2
Totals: 33
$ 8,316,000.00

16
Raw Materials
The list of raw materials and their respective costs are shown on Table 9. They are
compared with the Direct Process raw material Costs. The biomass cost remained the same due
to the nature of the project. Therefore the cost remained constant. The oxygen is only needed in
the gasification of coal and was not present in the Direct Process, only the Married Process. The
cost of oxygen was estimated using Ackerson to establish a ballpark amount. This is the same
with the coal and catalyst cost. The amount of water was directly calculated via the stream tables
and a reference cost from Timmerhaus. The catalyst used in the hydroprocessing section is
nickel-molybdenum catalyst. There is also a sacrificial catalyst used in a guard bed. The specific
type of catalyst was not named, but the total cost of the catalyst was stated in the reference.
Catalyst for the FT synthesis was not named either but the total cost was specified. Replacement
of catalyst was estimated to be once a year by engineering judgment.
From the table below, it can be seen that the raw material cost for the Married Process is
greatly more so that the raw material cost for the Direct Process. Again, the feasibility of this
price increase will be assed in the economic section of this report.

Table 9 - Raw Material Costs For Married And Direct Process

Raw Materials $/year Raw Materials $/year

Biomass $ 58,100.00 Biomass $ 58,100.00
Oxygen $ 2,132,920.77 Oxygen
Water $ 2,994.53 Water $ 2,395.62
Coal $ 5,777,311.00 Coal
Catalyst (bio-oil Catalyst (bio-oil
upgrading) $ 1,800,000.00 upgrading) $ 1,800,000.00
Catalyst (FT) $ 2,100,000.00 Catalyst (FT) -
Total $ 11,871,326.30 Total $ 1,860,495.62

Equipment Information Summary

Table 10 - Married Case Biomass Pyrolysis Information Summary

Equipment / Unit Description

biomass feed handling
pyrolysis reactor
chopper and grinder
The delivered feedstock is transported in by truck.
The feed is weighed on scales and sent through a conveyor system
to the grinder.
A bubbling fluidized bed reactor is very flexible when dealing with
heating mediums.
Sand or syngas can be used.
The biomass needs to be reduced to the size range of 2.5 mm to 250
micron.
This allows the bio-oil yields in the pyrolysis reactor in increase.

17
 The incoming corn stover feedstock is dried to a certain amount
before reaching the pyrolysis reactor.
Water removal is necessary b/c it will act as a heat sink in the
reactor. Any heat that vaporizes the water will be considered
dryer wasted energy.
Any unwanted fines are removed immediately after the feedstock is
placed on the conveyor system
Any residual metals in the feedstock will be found in the char after
pyrolysis. Char and ash are unwanted products and need to be
magnetic separator minimized.
steam blower This blows steam out of the dryer
Char and ash developed in the pyrolysis reactor is removed through
a.
Ideally, the char and ash are removed while the rest of the stream is
still in a vapor form for better particle collection.
Any particles below 2-3 microns will be unable to leave the vapor
stream.
Any char in the recycle stream can catalyze vapor cracking. This is
char/ash cyclone an unwanted side reaction and needs to be minimized.
This heater is used takes the char and ash removed via pyrolysis
heater cyclones and heats up gasification instead of the pyrolysis reactor.
combustion gas blower This blower sends fuel gas as well as char and ash to the heater.
Excess water is present in FT synthesis, biomass pyrolysis, gas
clean up and hydrotreating. The residual water needs to be cleaned
of H2S as well as any sludge and bio-oil that were not properly
water treatment separated.
This device removes oxygen and other dissolved gasses from water
holding systems.
Any dissolved oxygen or other gasses in the water can lead to
major corrosion in the walls of piping due to the formation of
dearator oxides.

Table 11 - Married Case Gasification Information Summary

Equipment / Unit Description

Coal feed handling The coal needs to be grinded in order to increase syngas yield
Gasifier can run along the range of 1250 – 1600 oC.
The syngas exits the gasifier at 1300 oC.
Gasifier The Gasifier in this project is modeled after the Texaco Gasifier.
CO2 and H2S are removed through adsorbers.
H2S is an environmental concern and CO2 is generally an inert
Gas Clean U[p component taking up space in the process.
FT Liquid Synthesis was modeled after Sasol’s system.
Operating conditions follow higher temperature FT (HTFT)
FT Liquid Synthesis Product yields are also taken from Sasol’s reports.

18
 Table 12 - Married Case Upgrading Process Information Summary

Equipment/ Unit Description

Bio-oil needs to be separated from the syngas and water prior to
liquid/gas separation hydrotreating
Methane from the pyrolysis stream was separated and sent to the
reformer.
CO2 was scrubbed out and the hydrogen was sent back to upgrade
reforming system the bio oil
The bio-oil was sent through upgrading units to produce
hydrotreater transportation fuels.

Capital Cost

The cost of the equipment was based on recommended values from Syngas. The Power
Factor Applied to Capacity Ratio Method was used to estimate the equipment cost of the married
process. This method takes into account the new size of certain units due to marrying the process
streams. The Power Factor for these calculations was X = 0.65. This number was determined via
Plant Design and Economics for Chemical Engineers by Timmerhaus. The recommended power
factor for hydrotreating, reforming and cracking are 0.65, 0.60, and 0.70. These three
descriptions are incorporated into the process, and an average was taken to accommodate for the
differences.
The results are shown on Table 13. Both the calculated married process values are
presented with the direct process cost estimation to show what components were included and
excluded due to the marrying the process.
The equipment cost for the Married Process totaled 57 million dollars while the
Direct Process totaled 36 million dollars. Some of the notable discrepancies between the two are:
the equipment in the married process is generally bigger which would result in more costly
equipment and the inclusion of gasification and FT synthesis. The Married Process is 58% more
costly than the Direct Process. However, the Married Process does have a larger output of
product. This will be discussed more thoroughly in the economics section of the report. The
additional revenue from the extra units and the savings costs from the Married Process will be
weighed against the higher capital costs.
Some notable additions in the Married Process include the Gasifier section, Gas Clean
Up, FT Liquid Synthesis and extra Tankage. There are also some units that are shared by both
with results in a net savings due to the absence of redundancy. These omitted equipments are
shown in Table 15. The total savings from omitted items totals 4 million. That is a 7% saving.

19
 Table 13 - Equipment Cost Estimation For The Married Process

Married Process
Unit Description Cost
Pyrolysis biomass feed handling $ 1,262,123.62
biomass feed prep $ 2,524,247.25
pyrolysis reactor $ 1,514,548.35
chopper $ 378,637.09
dryer $ 631,061.81
grinder $ 378,637.09
magnetic separator $ 25,242.47
steam blower $ 883,486.54
char/ash cyclone $ 1,514,548.35
Combustion Heater $ 6,310,618.12
combustion gas blower $ 75,727.42
combustor cyclones $ 1,262,123.62
water treatment $ 2,524,247.25
dearator $ 252,424.72
bfw pump $ 164,076.07
feed system $ 1,893,185.44
Upgrading liquid/gas separation $ 757,274.17
bio-oil separation vessel $ 252,424.72
pumps $ 252,424.72
reforming system $ 2,019,397.80
cooler $ 883,486.54
hydrogen handling $ 7,572,741.75
adsorber $ 100,969.89
hydrotreater $ 631,061.81
flue gas blower $ 378,637.09
flue gas combustor $ 3,786,370.87
Gasifier coal feed handling $ 1,000,000.00
coal-water slurry prep $ 1,000,000.00
Gasifier $ 3,500,000.00
Gas Clean Up $ 2,000,000.00
Oxidant Compression $ 1,500,000.00
Heat Recovery Steam
Generator $ 1,000,000.00
F-T Liquid Synthesis $ 4,000,000.00
Storage fuel, oil, water storage $ 1,500,000.00
tankage pumps $ 750,000.00
Utilities Cooling Water Tower $ 3,000,000.00
Totals: $ 57,479,724.58

20
 Table 14 - Capital Cost Estimate For Direct Process For Comparison

Direct Process (values from Syngas)

Unit Description Cost
Pyrolysis biomass feed handling $ 1,000,000.00
biomass feed prep $ 2,000,000.00
pyrolysis reactor $ 1,200,000.00
chopper $ 300,000.00
dryer $ 500,000.00
grinder $ 300,000.00
magnetic separator $ 20,000.00
steam blower $ 700,000.00
char/ash cyclone $ 1,200,000.00
Combustion Heater $ 5,000,000.00
combustion gas blower $ 60,000.00
combustor cyclones $ 1,000,000.00
water treatment $ 2,000,000.00
dearator $ 200,000.00
bfw pump $ 130,000.00
feed system $ 1,500,000.00
Upgrading liquid/gas separation $ 600,000.00
bio-oil separation vessel $ 200,000.00
pumps $ 200,000.00
reforming system $ 1,600,000.00
cooler $ 700,000.00
hydrogen handling $ 6,000,000.00
adsorber $ 80,000.00
hydrotreater $ 500,000.00
flue gas blower $ 300,000.00
flue gas combustor $ 3,000,000.00
--- --- ---
--- --- ---
--- --- ---
--- --- ---
--- --- ---
--- --- ---
--- --- ---
Storage fuel, oil, water storage $ 1,500,000.00
tankage pumps $ 750,000.00
Utilities Cooling Water Tower $ 3,000,000.00
$ 35,540,000.00

21
 Table 15 - Items Omitted From Married Process Costing Due To Redundancy

Items Omitted Justification Savings

Gasification combustion turbine
generator shared with married process $ 23,000.00
Steam Turbine Generator shared with married process $ 20,000.00
Cooling Water System shared with married process $ 3,000,000.00
Ash Handling System shared with married process $ 18,000.00
Buildings and Structures contingency
cooling is unnecessary b/c
syngas is the heating medium
syngas cooling for pyrolysis $ 31,000.00
the same heater provides
Gasification heater energy to both systems $ 1,000,000.00
Total: $ 4,092,000.00

Economic analysis
Fixed Capital Investment (FCI) was estimated by using the study estimate method (Peters).
Equipment cost was calculated in earlier section, and used to estimate FCI by selected
percentage range. Figure16 showed that equipment cost was 24% of FCI.

Table 16 - Estimated of FCI for Direct Process

Percentage Cost
Components Selected Range Range
purchased equipment 24 0.24 30.29
purchased equipment
installation 10 0.10 12.62
instrumentation 8 0.08 10.10
piping 7 0.07 8.83
electrical 4 0.04 5.05
buildings 4 0.04 5.05
yard improvement 2 0.02 2.52
service facilities 12 0.12 15.15
land 0 0.00 0.00
engineering and supervision 8 0.08 10.10
construction expense 9 0.09 11.36
legal expense 2 0.02 2.52
contractor's fee 2 0.02 2.52
contingency 8 0.08 10.10
Total 100 1 126.21

22
 The working capital (WC) was assumed to be 15% of FCI, which was an average cost for
a chemical plant (Peters). The TCI was sum of FCI and WC, which was total of $145.15 million.
Total Product Cost (TPC)
The next major component of an economic analysis is the total product cost (TPC), which
including the two major costs: manufacturing costs and general expenses. The table below
was the estimation of the TPC by calculating each component in the TPC. Each component
cost was calculated by using the FCI, raw materials, utilities cost, and the operating labor
costs. The table below showed every component cost in the TPC. The percentage range was
chosen according to Plant Design book (Peters).

23
 Table 17 - Estimated TPC for married process
Default
Basis
factor, user Cost,
Item may
Basis cost,
million $/y
million $/y
change
Raw materials 11.871
Operating labor 11.214
Operating supervision 0.15 of operating labor 11.214 1.682
Utilities 41.657
Maintenance and repairs 0.06 of FCI 239.499 14.370
Operating supplies 0.15 of maintenance & repair
14.370 2.155
Laboratory charges 0.15 of operating labor 11.214 1.682
Royalties (if not on lump-sum basis) 0.01 of c o 126.255 1.263
Catalysts and solvents 0 -- 0.000
Variable cost = 85.894
Taxes (property) 0.02 of FCI 239.499 4.790
Financing (interest) 0 of FCI 239.499 0.000
Insurance 0.01 of FCI 239.499 2.395
Rent 0 of FCI 239.499 0.000
Depreciation Calculated separately
Fixed Charges = 7.185
Plant overhead, general 0.6 of labor, supervision27.266
and maintenance
16.360
Plant Overhead = 16.360
Manufacturing cost = 109.439
Administration 0.2 of labor, supervision27.266
and maintenance
5.453
Distribution & selling 0.05 of c o 126.255 6.313
Research & Development 0.04 of c o 126.255 5.050
General Expense = 16.816
TOTAL PRODUCT COST WITHOUT DEPRECIATION = co = 126.255

Cumulative Cash Position (CCP)

MACRS of 6 year was used for depreciation calculation because it depreciated the equipment
more rapidly and helped to reduce the amount of tax paid in first five years and also generated
more cash flow, which was used to repaid the capital costs. Two processes, married and direct
were developed through an Aspen Simulation. Based on economic calculation, after ten years,
the married process was able to generate a total profit of $75 million, while the direct process
lost around $65.58 million; therefore, the married process was preferred due to the economic
profitability. For the purpose of increasing the project’s profit, a project life was extended out to
ten years. Figure 4 was the cash cumulative position graph, which indicated the capital cost was
totally repaid in between year 7th and 8th, and had a total of profit of $75 million.
24
 Table 18 - CCP For Direct Process
Year -2 -1 0 1 2 3 4 5 6 7 8 9 10
fix capital investment -18.93 -45.06 -65.65
working capital -19.45
total capital investment -18.93 -45.06 -85.10
Start-up cost -12.96
Operating Rate 0.50 0.90 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Annual Sale 46.77 84.19 93.55 93.55 93.55 93.55 93.55 93.55 93.55 93.55
annual factor 0.10 0.18 0.14 0.12 0.09 0.07 0.07 0.07 0.07 0.07
annual depreciation 12.96 23.34 18.67 14.93 11.95 9.55 8.49 8.49 8.50 8.49
annual total cost -48.87 -70.44 -77.10 -78.64 -80.21 -81.82 -83.46 -85.12 -86.83 -88.56
Annual Gross Profit -28.03 -9.58 -2.22 -0.03 1.38 2.17 1.60 -0.07 -1.79 -3.51
Annual Net Profit -28.03 -9.58 -2.22 -0.03 0.90 1.41 1.04 -0.07 -1.79 -3.51
Annual Operating Cash Flow -18.93 -45.06 -85.10 -15.06 13.75 16.45 14.90 12.85 10.97 9.53 8.42 6.72 4.98
Cummulative Cash Position -18.93 -63.99 -149.09 -164.15 -150.40 -133.95 -119.05 -106.20 -95.24 -85.70 -77.28 -70.57 -65.58

Table 19 - CCP For Married Process

Year -2 -1 0 1 2 3 4 5 6 7 8 9 10
0
2. Fixed Capital Investment -35.92 -85.50 -124.59
3. Working Capital -36.90 36.90
4. Salvage Value 0
5. Total Capital Investment -35.92 -85.50 -161.49
6. Annual Investment 0 0 0 0 0 0 0 0 0 0
7. Start-up cost -24.60
8. Operating rate 0.50 0.90 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
9. Annual sales 101.12 182.02 202.24 202.24 202.24 202.24 202.24 202.24 202.24 202.24
10. Annual Total Product Cost -88.41 -127.36 -139.40 -142.18 -145.03 -147.93 -150.89 -153.90 -156.98 -160.12
11. Annual depreciation factor 0.20 0.32 0.19 0.12 0.12 0.06
12. Annual depreciation 49.20 78.72 47.23 28.34 28.34 14.17
13. Annual Gross Profit -61.09 -24.07 15.61 31.72 28.87 40.14 51.35 48.34 45.26 42.12
14. Annual Net Profit -61.09 -24.07 10.15 20.62 18.77 26.09 33.38 31.42 29.42 27.38
15. Annual operating cash flow -11.89 54.65 57.38 48.96 47.11 40.26 33.38 31.42 29.42 27.38
16. Total annual cash flow -35.92 -85.50 -161.49 -11.89 54.65 57.38 48.96 47.11 40.26 33.38 31.42 29.42 27.38
17. Cumulative cash position -35.92 -121.43 -282.92 -294.80 -240.15 -182.77 -133.81 -86.71 -46.44 -13.06 18.36 47.77 75.15

25
 Figure 6 - Visual Representation of CCP for Married Process
Where:
T = V + W + Ax
T – Total capital investment (TCI)
V – Manufacturing Fixed capital investment (FCI)
Ax – Nonmanufacturing FCI
W – Working Capital Investment
Income Tax = (sj –coj –dj) φ
sj – total income or sale
coj – costs for operation
dj – depreciation charge
φ – tax rate
Gross Profit = sj –coj (before depreciation charge)
Net profit after tax = (sj –coj –dj) * (1-φ)
Net cash flow including depreciation charge = (sj –coj –dj) * (1-φ) + dj

26
Innovation and Optimization

The major point for innovation and optimization is the uniting of the syngas and biomass
processes. This type of integration needs number optimization strategies in order to
accommodate the two separate systems.
A standard biomass pyrolysis process can operate with many different types of reactors:
bubbling fluidized bed, circulating fluidizing bed, ablative pyrolysis, and vacuum pyrolysis and
rotating cone pyrolysis reactor. However, the introduction of syngas as the heating medium
possesses very interesting design considerations due to the vapor liquid contact requirement.
Rotating cone pyrolysis reactor is no longer valid since it was designed to operate without a
carrier gas and scaling up may not be applicable. Vacuum pyrolysis is slow and does not produce
enough liquid yields. The point of marrying the process is to produce more liquid product so
vacuum pyrolysis in no longer applicable. Ablative pyrolysis cannot be scaled to larger sizes.
The best reactor for the current process is a bubbling fluidized bed reactor. This design is very
reliable and common in the industry. Heat transfer can be used with sand or syngas.
Another unique change that occurs in the Married process is the absence of sand. The
syngas operates as the heating medium.
The married process also provides many optimizing opportunities. Hydrogen and water
are produced in numerous sections in the process and consumed as the limiting reactant in other
parts. Excess hydrogen from the FT synthesis section can be rerouted to hydrotreating in order to
remove pressure from the reformer. Excess water removed from the dryer can be sent to the
water gas shift reaction as well. This allows for more raw material consumption and reduces raw
material cost.

References
Ackerson, Dr. Michael D. Novel Methods For Converting Coal And Biomass To Liquid
Fuel. N.p.: n.p., n.d. Print.
Ringer, M., V. Putsche, and J. Scahill. Large-Scale Pyrolysis Oil Production: A
Technology Assessment And Economic Analysis. N.p., n.d. Web.
Syngas, Mark M., Justinus A. Satrio, and David D. Hsu. Techno-Economic Analysis of
Biomass Fast Pyrolysis to Transportation Fuels. N.p.: n.p., n.d. Print.
Hix, Andrew, and Kendall, Rachel. Process Design and Economic Analysis of Fischer-
Tropsch Reactions
"What Is Biomass? Biomass Is Fuel Developed from Organic Materials | ReEnergy
Holdings." (n.d.): n. pag. ReEnergy Holdings. Web. 04 May 2013.
"Biofuels : What Are They?" (n.d.): n. pag. Biofuels. Web. 04 May 2013.Pytlar,
Theodore S., Jr. "Status of Existing Biomass Gasification and Pyrolysis Facilities in North
America." (2010)
Furnsinn, Stefan, Ruedi Buhler, and Hermann Hofbauer, eds. "Health, Safety and
Environment of Biomass Gasification." (2005): 1-153
Peters, Max Stone, Klaus D. Timmerhaus, and Ronald E. West. Plant Design and
Economics for Chemical Engineers. New York: McGraw-Hill, 2003

27
 Leckel, Dieter. "Upgrading of Fischer-Tropsch Products To Produce Diesel." Sasol. Sasol
Technology Research and Development, n.d. Web.
Kreutz, Thomas G., Eric D. Larson, Guangjian Liu, and Robert H. Williams. Fischer-
Tropsh Fuels from Coal and Biomass. Princeton.Edu. Princeton Environmental Institute, n.d.
Web. <http://www.princeton.edu/pei/energy/publications/texts/Kreutz-et-al-PCC-2008-10-7-
08.pdf>.

28
Engineering Calculations

The compositions of the corn stover was determined via elemental wt% given by Syngas.
The distribution is shown on the table below.

Corn Stover
Element
Value (wt %)
Ash 6
Carbon 47.28
Hydrogen 5.06
Nitrogen 0.8
Chlorine 0
Sulfur 0.22
Oxygen 40.63
99.99

The coal composition was found in Ackerson. The distribution and total amount of coal by element is shown below.

coal composition wt%

normalized actual
data amount (kg)
carbon 69.71 0.80 98863.62267
hydrogen 4.8 0.05 6807.422017
nitrogen 1.4 0.02 1985.498088
sulphur 3.64 0.04 5162.29503
oxygen 7.83 0.09 11104.60717
87.38 1.00 123923.445

The coal water slurry is based on a 50/50 ratio. The amount of oxygen to weight of coal was 0.4098. The results of this calculation are shown below.

29
 amount of water for
slurry (kg) 123923.4
Oxygen (kg) 50783.83
coal (kg) 123923.4
The syngas composition out of the gasifier is based on the Texaco gasifier. The composition was based on table four from Ackerson

syngas
composition
syngas
composition wt% normalized kg/hr via aspen
h2 28.6 29% 1459.204
co 38.4 40% 27966.143
co2 12.6 13% 14280.586
h2o 17.4 18% 8094.067

The outlet of the pyrolysis reactor were based on kg/100 kg of dry biomass. These ratios were taken from Wright. The syngas present in the stream
are considered inert in pyrolysis. Pyrolysis was considered 100% conversion.

product
composition out of
reactor
composition syngas out bio oil out of
yeild based on excess due total out of of pyrolysis % ignoring of separators separators
kg/100 kg of 83334 kg to syngas in pyrolysis product ash (outlet via aspen via aspen
dry biomass biomass in kg kg reactor stream of cyclone) simulation simulation
carbon dioxide 5.42 4517 14281 18797 14% 0.15474 18648 150
carbon monoxide 6.56 5467 27966 33433 25% 0.27522 33410 23
methane 0.035 29 29 0% 0.00024 29 0
ethane 0.142 118 118 0% 0.00097 116 1
hydrogen 0.588 490 1459 1949 1% 0.01605 1950 0
propane 0.152 127 127 0% 0.00104 120 6
ammonia 0.0121 10 10 0% 0.00008 7 3
0 0 0% 0.00000
acetic acid 5.93 4942 4942 4% 0.04068 58 4884

30
propionic acid 7.31 6092 6092 5% 0.05015 6 6086
methoxyphenol
(guaiacol) 0.61 508 508 0% 0.00418 0 508
ethylphenol 3.8 3167 3167 2% 0.02607 0 3167
formic acid 3.41 2842 2842 2% 0.02339 157 2684
propyl-benzoate 16.36 13633 13633 10% 0.11223 0 13633
phenol 0.46 383 383 0% 0.00316 0 384
toluene 2.27 1892 1892 1% 0.01557 1631 261
furfural 18.98 15817 15817 12% 0.13021 433 15384
benzene 0.77 642 642 0% 0.00528 588 53
0 0 0% 0.00000
water 10.8 9000 8094 17094 13% 0.14072 903.202039 16191.1018
char/ash 16.39 13658 13658 10% --- 0 0

The bio-oil specified the streams section of the report are actually made up of multiple components. For simplicity’s sake, all those chemicals were
consolidated into one term, bio-oil. The actual bio-oil composition is shown below. These values are taken from Wright pg 8.

Composition of Bio-oil
acetic c acid 10%
propionic acid 12%
methoxyphenol
(guaiacol) 1%
ethylphenol 6%
formic acid 6%
propyl-benzoate 27%
phenol 1%
toluene 4%
furfural 32%
benzene 1%

The water gas shift reaction follows: H2O + CO > H2 + CO2

The stream components were varied until the H2/CO mol ratio was around 2. This specification will promote high liquid fuel yield. Before the water
gas shift reaction, the ratio was 0.82. After the reaction, the ratio was 2.2. Extra water was included in order to achieve satisfactory amounts of CO
and H2.
31
 syngas after Fischer -
water gas shift CO2 Scrubber CO2 Scrubber
separations change (stoic) Tropsch
(kg/hr)reaction outlet Product Stream
(kg/hr) Outlet
carbon dioxide 18648 2800 21448 21448 0 0
carbon monoxide 33410 2800 30610 30610 6122
methane 29 29 29 729
ethane 116 116 116 116
hydrogen 1950 2800 4750 4750 845
propane 120 120 120 120
ammonia 7 7 7 7

acetic acid 58 58 58 58
propionic acid 6 6 6 6
methoxyphenol
(guaiacol) 0 0 0 0
ethylphenol 0 0 0 0
formic acid 157 157 157 157
propyl-benzoate 0 0 0 0
phenol 0 0 0 0
toluene 1631 1631 1631 1631
furfural 433 433 433 433
benzene 588 588 588 588

water 2800 2800 0 0 7609

char/ash 0 0 0 0

lpg 0 0 0 0 0 3848
naphtha 0 0 0 0 0 6247
middle distillate 0 0 0 0 0 1242
wax 0 0 0 0 0 615
38505 30373
h2/co ratio (mol): 0.816968598 2.172345608
32
The Fischer-Tropsch reactor products were calculated using a combination of expected yields and stoichiometry. The expected product yields from
FT liquid synthesis according to Sasol are shown below. To determine the amount of product, 5% of the CO (which is considered the limiting
reagent) will be used the production of methane. 30% of CO will be calculated to produce LPG and so on. The conversion for one pass in FT reactors
according to literature is 80%.

The stoichiometric equations necessary for these calculations are also shown below. For simplifying the calculations, the number of carbons in
product oil is assumed an average amount. This allows the mol calculations to also be converted back to mass.

Stoichiometric Data and Assumptions Component wt%

Methane 3H2 + CO → CH4 + H2O Methane 5%
Liquid Propane Gas (LPG) (assume n=3) 7H2 + 3CO → C3H8 + 3H2O LPB 30%
Naphtha (assume n=7) 15H2 + 7CO → C7H16 + 7H2O Naptha 50%
Middle Distillate (assume n = 10) 21H2 + 10CO → C10H22 + 10H2O Middle Distillate 10%
Wax (assume n = 30) 61H2 + 30CO → C30H62 + 30H2O Wax 5%

With the above assumptions and expected yields, the FT reactor outlet composition calculations are shown below.

FT reactor outlet
calculations
methane calc lpg calc naphtha calc mid calc wax calc
CO used mol: 43.727962 262.367772 437.27962 87.455924 43.72796
h2o mol 1093.19905 1049.471088 787.103316 349.823696 262.367772 218.6398

h2 mol 0.011224389 43.73918639 306.1069584 743.3865784 830.8425024 874.5705

methane mol 2374.806155 2243.622269 1632.30536 695.2588625 511.6014221 422.7025
lpg mol 1.819158288 45.54712029 0
naphtha mol 87.455924
middle distillate
mol 62.46851714
wax mol 8.7455924
1.457599
33
The calculations for the upgrading section are shown below. The primary component for bio oil is C10H12O2 (propyl benzoate). For the sake of the
stoichiometric calculations, the bio-oil properties will be assumed that of propyl benzoate. The chemical formula for bio-oil reforming is:
C10H12O2 + 18H2O → 10CO2 + 24H2
The product from the hydrotreater was not calculated via stoichiometric calculations. Expected yields via Wright were given.

Feed Wt %
Bio-oil 96%
Hydrogen 4%

Product
Light ends 15%
gasoline 29%
diesel 8%
water and carbon
dioxide 49%

The conversion for standard hydrotreating is 0.78.

34
 total
16 - Bio Oil 17 - Bio Oil total going Totals totals into outlets of
Split to Split to into out of upgrading upgrading
Reformer Upgrading Add Ins reformer reformer units units
kg/hr
Biomass 0 0 0 0 0
Water 1133 15058 5347 6480 0.377126 15058 0
Ash/Char 0 0 0 0 0 0 0
Bio-oil 3293 43751 3293 13.0959 43764 15315
Gas
Compounds
Hydrogen 0 0 845 845 1805 1805
CO 2 22 2 2 24
CO2 10 139 10 8810.476 8950
Methane 0 0 0 0 0
Ethane 0 1 0 0 1
Propane 0 6 0 0 6
Ammonia 0 3 0 0 3

water, lights,
co2 32578
naphtha range 10859
diesel range 10859

35
Computer Programs

No computer programs apart from Excel and Aspen Plus were used. All excel calculations are
shown in the Engineering Calculation Section of the report. All Aspen Plus results are shown in
the Computer Process Simulation Section of the report.

Computer Process Simulations

Figure 7 - Separation of Bio-oil and Syn gas

Figure 7 is the Flowsheet of an aspen simulation that determines how much syn gas is recovered
from the bio-oil after the pyrolysis and cyclone. The resulting stream values are then inserted into the
excel file for further calculations.

36
Table 20- Separation of Bio-oil and Syn Gas Aspen Results

CYCOUT OIL1 OIL2 OILPROD SYNGAS VAP

Temperature C 150 50 25 46.3 25 50

Pressure bar 1.013 1.013 1.5 1.013 1.5 1.013
Vapor Frac 1 0 0 0 1 1
Mole Flow
kmol/hr 4082.677 1151.474 254.452 1405.926 2676.751 2931.203
Mass Flow kg/hr 121475 56658.94 6760.192 63419.14 58055.86 64816.06
Volume Flow
cum/hr 141793.8 54.92 6.624 62.672 44236.3 77744.18
Enthalpy
MMkcal/hr -157.867 -84.214 -17.871 -102.085 -74.61 -89.361
Mass Flow kg/hr
CO2 18797.42 93.689 55.975 149.664 18647.75 18703.73
CO 33433.02 16.378 7.067 23.445 33409.57 33416.64
METHANE 29.155 0.033 0.015 0.048 29.107 29.122
ETHANE 117.833 0.942 0.538 1.48 116.353 116.891
PROPANE 126.337 3.922 2.436 6.358 119.978 122.414
AMMONIA 9.718 0.936 1.776 2.712 7.007 8.783
ACETIC 4941.702 4342.635 540.954 4883.589 58.112 599.067
PROPIONI 6092.093 5852.896 233.226 6086.122 5.971 239.197
METHOXY 507.776 506.702 1.073 507.775 0.001 1.074
ETHYLPHE 3166.917 3163.141 3.774 3166.915 0.002 3.776
FORMIC 2841.357 2154.533 529.691 2684.224 157.133 686.824
PROPYLBE 13633.41 13614.59 18.812 13633.4 0.011 18.824
PHENOL 383.869 377.843 5.919 383.762 0.107 6.026
TOLUENE 1891.404 244.572 16.242 260.813 1630.59 1646.832
FURFURAL 15817.58 13884.74 1499.719 15384.46 433.115 1932.834
BENZENE 641.401 47.404 5.761 53.165 588.236 593.997
WATER 17094.3 12353.92 3837.187 16191.1 903.202 4740.389
HYDROGEN 1949.713 0.074 0.026 0.1 1949.612 1949.638

37
 Figure 8 - Simulation to Determine Duty To Pyrolysis Reactors

Figure 8 shows the aspen simulation that determined how much heat duty and amount of syn
gas necessary to heat the biomass amount to 480 oC. The results are shown below.

Table 21 - Figure 8 Aspen Results

MOISTUR RXTINLE
BIOIN E T STOVER SYN25 SYN600 SYNGAS SYNOUT

Temperature C 79 100 480 100 25 600 1371 483.1

Pressure bar 1.013 1.013 1.013 1.013 1.013 1.013 1.013 1.013
Vapor Frac 0.472 0 0.51 0.481 0.846 1 1 1
Mole Flow 6932.20 6932.20 6591.10
kmol/hr 3 341.099 3 3 2496.05 2496.05 2496.05 2496.05
Mass Flow
kg/hr 89479 6145 89479 83334 51800 51800 51800 51800
Volume Flow 94562.5 218488. 97205.8 51677.9 178879. 336831. 154940.
cum/hr 7 6.692 6 2 5 2 4 4
Enthalpy
MMkcal/hr 477.539 -22.818 497.498 500.357 -86.823 -71.409 -53.893 -73.852
Mass Flow
kg/hr
CARBON 39407.9 0 39407.9 39407.9 0 0 0 0
4217.51 4217.51 4217.51 1459.20 1459.20 1459.20 1459.20
HYDROGEN 2 0 2 2 4 4 4 4
NITROGEN 666.8 0 666.8 666.8 0 0 0 0
CHLORINE 0 0 0 0 0 0 0 0
SULFUR 183.37 0 183.37 183.37 0 0 0 0
33865.1 33865.1 33865.1
OXYGEN 2 0 2 2 0 0 0 0
CALCIUM 2718.87 0 2718.87 2718.87 0 0 0 0

38
 8 8 8
1444.45 1444.45 1444.45
POTASSIU 6 0 6 6 0 0 0 0
MAGNESIU 450.09 0 450.09 450.09 0 0 0 0
S 83.35 0 83.35 83.35 0 0 0 0
P 151.697 0 151.697 151.697 0 0 0 0
MN 17.979 0 17.979 17.979 0 0 0 0
ZN 43.675 0 43.675 43.675 0 0 0 0
FE 33.34 0 33.34 33.34 0 0 0 0
AL 16.67 0 16.67 16.67 0 0 0 0
NA 7.502 0 7.502 7.502 0 0 0 0
SI 14.128 0 14.128 14.128 0 0 0 0
B 7.706 0 7.706 7.706 0 0 0 0
CU 3.834 0 3.834 3.834 0 0 0 0
8094.06 8094.06 8094.06 8094.06
H2O 6145 6145 6145 0 7 7 7 7
27966.1 27966.1 27966.1 27966.1
CO 0 0 0 0 4 4 4 4
14280.5 14280.5 14280.5 14280.5
CO2 0 0 0 0 9 9 9 9

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