Bio Plant in Michigan

Wayne State University
Department of Chemical Engineering and Material Sciences
Strategic Planning of
Biodiesel Production
in Michigan
Process Design, Modification, and Sustainability Assessment
Jonathan Zatkoff, Archana Manoharan, Tadewos Woldemariam
4/26/2010
Table of Contents
Executive Summary .................................................................................................................................... 4
Introduction ................................................................................................................................................ 7
Alkali-catalyzed Process Using Methanol or Ethanol ............................................................................... 10
Unmodified Analysis of Production Rates ............................................................................................ 11
Modification of 8,000 ton/yr Production ............................................................................................... 14
Sale of Trisodium Phosphate and Heat Exchanger Network Modification ....................................... 14
Choline Chloride - Urea Mixture Modification ................................................................................. 16
Choline Chloride - Urea Mixture and Heat Exchanger Network Modification ................................. 18
Alkali-catalyzed Process Using Ethanol ................................................................................................... 19
Production Rate of Biodiesel - 8,400 tons/yr ........................................................................................ 20
Ethanol Recovery Modification ............................................................................................................ 20
Non-catalytic Process Operated at Supercritical Condition of Methanol .................................................. 21
Production Rate of Biodiesel - 9,696 tons/yr ........................................................................................ 22
Modifications ........................................................................................................................................ 22
Water Heat Exchanger Network ....................................................................................................... 22
Replacing Heat Exchanger Network With Heater and Cooler Modification ..................................... 23
Sustainability ............................................................................................................................................ 24
Economic Sustainability ....................................................................................................................... 24
Environmental Sustainability ................................................................................................................ 25
Inherent Safety Analysis ....................................................................................................................... 29
IChemE Sustainability Assessment ....................................................................................................... 31
Overall Sustainability............................................................................................................................ 32
Geographical Analysis of Biodiesel Demand and Production in Michigan ............................................... 35
Upper Peninsula .................................................................................................................................... 35
Northern Lower Peninsula .................................................................................................................... 37
Southern Lower Peninsula .................................................................................................................... 37
Conclusions .............................................................................................................................................. 40
Recommendations ..................................................................................................................................... 42
References ................................................................................................................................................ 43
Appendix A - Full Stream Data and Large Process Images ...................................................................... 46
Appendix B - Raw Data ............................................................................................................................ 64
Economic .............................................................................................................................................. 64
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Environmental....................................................................................................................................... 67
Inherent Safety ...................................................................................................................................... 67
IChemE Evaluation ............................................................................................................................... 68
Appendix C – MSDS ................................................................................................................................ 76
Appendix D - Workload Partitioning ........................................................................................................ 79
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Executive Summary
The Goal
The project requires a three part analysis of the biodiesel production process. Starting with
equipment modifications to improve quantity and quality of biodiesel, the project moves towards
evaluating the Michigan biodiesel industry in particular. A through sustainability analysis for
each process design examining net profits, social and environmental aspects is examined. The
three processes studied here are:
1. Alkali-catalyzed Biodiesel Production Process Using Methanol

2. Alkali-catalyzed Biodiesel Production Process Using Ethanol
3. Non-catalytic Biodiesel Production Process Operated at Supercritical Condition of
Methanol
Results of Unmodified Process Design
Biodiesel production using alkali catalyzed methanol was found to be the most efficient both in
the quality of biodiesel obtained and the time to reach breakeven point. Ethanol is easier to
recycle and recover in comparison to methanol but, the overall biodiesel production using alkali
catalyzed ethanol is not as profitable. Of the three processes mentioned above biodiesel
production at supercritical conditions using methanol was the least efficient and profitable.
Design Modifications
All three processes studied in the report were modified. The following modifications were
performed for the listed processes:
1. Alkali-catalyzed Process Using Methanol

a. Sale of Trisodium Phosphate and Heat Exchanger Network Modification
b. Choline Chloride - Urea Mixture Modification
c. Choline Chloride - Urea Mixture and Heat Exchanger Network
Modification
2. Alkali-catalyzed Process Using Ethanol
a. Ethanol Recovery Modification
3. Non-catalytic Process Operated at Supercritical Condition of Methanol
a. Water Heat Exchanger Network
b. Replacing Heat Exchanger Network With Heat and Cooler
Sustainability Assessment
To provide justification for the proposal on biodiesel manufacturing a through sustainability

assessment was conducted. The following sustainability metrics were used Net Annual Profit
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After Taxes (NAPAT), Potential Environmental Impact (EPA approach), Total Inherent Safety
(TIS), and IChemE. All modified processes have higher NAPAT and required lower time to reach
breakeven point compared to unmodified processes. Based on the EPA WAR algorithm
approach the unmodified processes had the worst impact on environment compared to the
modified processes. Biodiesel production at supercritical conditions with methanol has the most
detrimental impact on environment both in modified and unmodified processes. Same trend of
modified processes performing better than unmodified processes is followed in the total inherent
safety and IChemE analysis. In all the metrics the modified process of biodiesel production
using alkali catalyzed methanol performed the better than the other two.
Michigan’s Biodiesel Demand Strategic Planning Recommendation
The best strategy for biodiesel production in Michigan based on the process design and
sustainability analysis is developed. Michigan is divided into three parts Upper Peninsula,
Northwestern Michigan and Southeastern Michigan. A total of nine plants are recommended to
meet the 50,000 tons/yr biodiesel demand. The criteria used to determine the location and
capacity of these plants is based on population density, raw material production and
transportation costs. Southeast Michigan is expected to have the highest demand for biodiesel
due to high population densities and low transportation costs. It is also expected to have high
raw material costs due to lack of rural farm land. Upper Peninsula is predicted to have the lowest
demand and highest transportation costs.
A comprehensive look at the suggested plant locations and capacity is presented. Probable
advantages are presented along with constraints and possible solutions.
Advantages:
The suggested proposal offers many advantages for Michigan. From the obvious economic
growth to the multiple social advantages are examined. Some are listed below:
 Job creation and the resulting economic activity.

 Reduction in the dependency on fossil fuel along with the creation of new markets for
fuel industry.
 Possibilities for Urban Reclamation in the cities of Detroit and Flint would reduce
biodiesel production cost.
 Rural Economic Development through energy crops and biodiesel production through
ethanol.
 Biodiesel is better for the environment than gasoline.
Constraints:
Analysis conducted in this report assumes a predetermined demand for biodiesel. This might not
be the case in the real world, demand could fluctuate depending on several factors. An attempt
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has been made to not only examine economic and process design constraints but overall social
hurdles. Some of these are listed below:
 Initial establishment of biodiesel plants – guarantee of biodiesel demand.

 Lack of consumer awareness and incentives: Convincing consumers to successfully
switch to biodiesel could be a tremendous challenge.
 Lack of Funding/Research: Lack of incentives for the biodiesel manufactures and the
consumer is another problem.
 Gel temperature of biodiesel and effectiveness in cold weather.
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Introduction
Dependency on fossil fuel is not only a socio-economic problem but a deeply global political
issue. From the everyday act of filling up a gas tank to the far and wide reaching use of plastics,
the affect of hydrocarbons is undeniable. With the ever increasing monopoly of oil companies,
the question of an effective alternative to gasoline is required. One area where the use of fossil
fuel can be reduced is as fuel for automotives. This report tries to justify biodiesel as the efficient
alternative to fossil fuel. The project does rigorous analysis of equipment modification and
design in producing high purification biodiesel also analyzing sustainability of this process.
Examining ways to decrease equipment and manufacturing costs while increasing quality and
quantity of biodiesel.
Design modification is vital but not enough for an industry to survive and prosper. There are
more factors that affect the sustainability of a company. For example, just because biodiesel
supply exists it does not imply consumer demand. Therefore a through and multifaceted study of
the biodiesel industry in Michigan is required. This involves social, environmental and economic
assessments.
To successfully recommend process optimizations for biodiesel production a comprehensive

understanding of the reaction chemistry is required. Transesterification is the reaction that
ultimately produces biodiesel, it is represented in Figure 1. Vegetable oil reacts with methanol to
form biodiesel and glycerol. The reaction takes place at 60°C yields a 95% conversion. As seen
from Figure 3, a catalyst is used to improve this reaction. Sodium hydroxide is the most
common catalyst used. Possible advantages of replacing the catalyst are considered as a process
modification and presented later in the report. Some of the benefits of methoxide catalyst is
reduction in reaction temperature and higher conversion.
Figure 1 - Transesterification with Methanol
Transesterification is not limited to methanol alone, Figure 2 below shows the use of ethanol
over methanol. These two figures represent the reactions of two processes assigned, alkali-
catalyzed biodiesel production using methanol and ethanol.
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Figure 2 - Transesterification with Ethanol
Another major reaction in biodiesel production using a catalyst is the neutralization reaction.
This reaction is primarily how the catalyst is removed from the process to give pure product
biodiesel. Sodium Hydroxide used in the process is neutralized by reacting with an acid and the
product is collected as a byproduct. The first reaction in Figure 3 shows the neutralization
reaction and second reaction shows the formation of the methoxide ion when using a methoxide
catalyst instead of a hydroxide catalyst.
Figure 3 - Catalyst Recovery and Methoxide Catalysts
Some of the major concerns in biodiesel industry are the problem faced by side reactions that
result in soap formation. Effects of catalyst used on soap formation and yield are studies to
provide optimum product.
The following biodiesel production processes were examined. After analyzing the process and
conducting sustainability analysis on these modifications are recommended.
 Alkali-catalyzed Process Using Methanol

o Modifications
 Trisodium Phosphate Sale and Heat Exchanger Network
 Choline Chloride/Urea Extraction and KOCH3 Catalyst
 Choline Chloride/Urea Extraction, KOCH3 Catalyst, and Heat Exchanger
Network
 Alkali-catalyzed Process Using Ethanol
o Modification
 Ethanol Recovery
 Non-catalytic Process Operated at Supercritical Condition of Methanol
o Modifications
 Water Heat Exchanger Network
 Heat and Cooler Substituted for Heat Exchanger Network
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The alkali-catalyzed process using methanol has inexpensive raw material costs. However,
methanol is a non renewable resource. The alkali-catalyzed process using ethanol has higher raw
material costs, but ethanol is also a renewable resource. Lastly, the non-catalytic process
operated at supercritical conditions of methanol creates no solid waste, but is energy intensive.
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Alkali-catalyzed Process Using Methanol or Ethanol
All the major sub processes involved in biodiesel production are presented below. Starting with
triolein and methanol as the raw materials this process uses the sodium hydroxide as the alkali
catalyst. The goal is to produce the best quality biodiesel and effectively recover methanol. The
process consists of seven sub-processes, each of which is described below Zhang et. al.[3] Details
of input, output and major intermediate streams for each process studied can be found in
Appendix A.
1. Transesterification: The reaction that takes place in the reactor R-101 at 60 °C and 400
kPa. The feed sent to the reactor conations virgin vegetable oil, methanol, and sodium
hydroxide. Vegetable oil stream is preheated to 60°C in heat exchanger E-101. Fresh
methanol and anhydrous sodium hydroxide are mixed and pumped into the reactor. A
95% conversion of oil is assumed in the reactor giving biodiesel and glycerol as the
products.
2. Methanol Recovery: Using vacuum distillation methanol is separated from other

components in T-201 using five theoretical stages and a reflux ratio of 2. Pure methanol
(stream 201) is recycled back to mixer (MIX-102). Bottom stream 202 is sent to T-301 a
washing column after being cooled in exchanger E-201.
3. Water Washing: Biodiesel is separated from glycerol, methanol and catalyst in the water
washing tower (T-301). A water flow rate of 11kg/h at 25 ° C is utilized. The resulting
streams 303 and 301A contain water, methanol and catalyst, and biodiesel respectively.
4. Biodiesel Purification: A four theoretical distillation T-401 with reflux ratio of 2 is used
to obtain a product stream containing FAME above 99.7%. To avoid degradation of
FAME this process is carried out in vacuum. Stream 301A is forwarded to T-401 after
the gravity separator X-301. Water and methanol are removed as vent gases in stream
401A after T-401; the FAME product is obtained in stream 401 as a liquid distillate (194
°C and 10 kPa).
5. Alkali Removal: To effectively remove the alkali catalyst NaOH a neutralization reactor
(R-201) is used in stream 303 by adding H3PO4. A gravity separator is used to further
remove the resulting Na3PO4.
6. Glycerol Purification: After alkali removal the main component of stream 305 is
glycerol. Distillation column T-501 with four theoretical stages and a reflux ratio of 2 is
used to remove water and methanol in order to obtain glycerol in a high grade. Bottom
stream of T-501 can have glycerol with 98% purity.
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7. Waste Treatment: Hazardous gas and liquid waste streams 401A and 501 with small
flow rates are obtained.
Unmodified Analysis of Production Rates
Figure 4 - Alkali-catalyzed Process Using Methanol
Production Rate of Biodiesel - 4,000 tons/yr

Table 1 - Important Stream Data for Alkali-catalyzed Process Using Methanol at 4,000 tons/yr
Unit 106 203 301 302 502 401

Temperature C 60 60 60 60 263.3066 196.3723
Pressure kPa 395 120 110 120 50 10
Mass Flow kg/h 701.6695 590.485 531.9334 64.09128 52.54935 500
Triolein 0.037541 0.04461 0.049456 0.000537 0.000033 0
Methanol 0.164611 0.007313 0.004818 0.027389 0 0.000218
M-Oleate 0.716532 0.851451 0.945169 0.000028 0.000659 0.999721
Glycerol 0.07419 0.088159 0 0.812228 0.99069 0
Sodium Hydroxide* 0.007125 0.008467 0 0.078008 0.004757 0
H2O 0 0 0.000557 0.081811 0.000007 0.000062
Phosphoric acid* 0 0 0 0 0.003854 0
Trisodium phosphate* 0 0 0 0 0 0
The unmodified process without any modification is analyzed for a production rate of 4,000
tons/yr. HYSYS was sued to simulate the seven sub processes mentioned above, the process is
shown in Figure 4. Triolein is used to represent virgin vegetable oil and methyl oleate (M-
Oleate) represents biodiesel. The NRTL VLE fluid package setting was used to model the
thermodynamic behavior. The transesterification reaction occurs in reactor R-101. Biodiesel of
99.9% purity is obtained in stream 401 at 196 °C and 10 kPa. Glycerol of 99.1% purity is
obtained in stream 502 at 60 °C and 120 kPa.
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Though high purity biodiesel is obtained from this process, it is found be an inefficient in energy
usage at this production rate. Glycerol obtained is of high purity thus it would not require
purification before possible selling. Modifications to improve this basic design are presented
later in the report.

Unit 106 203 301 302 502 401

Temperature C 60 60 59.21506 60.00062 263.3396 185.1412
Pressure kPa 395 120 110 120 50 10
Mass Flow kg/h 1292.138 1180.959 1063.202 128.8359 157.7756 1000.001
Triolein 0.040772 0.044611 0.049427 0.001027 0.000063 0
Methanol 0.092718 0.007304 0.003856 0.035124 0 0.00024
M-Oleate 0.778197 0.851459 0.945744 0.000155 0.001384 0.999612
Glycerol 0.080575 0.08816 0 0.808108 0.989948 0
H2O 0 0 0.000972 0.077972 0.000001 0.000148
The above table shows the information pertaining to some important streams for the unmodified
alkali-catalyzed process using methanol at a production rate of 8000 tons/yr. Similar to the
earlier process the NRTL VLE fluid package setting was used to model the thermodynamic
behavior. Biodiesel of 99.9% purity is obtained in stream 401 at 185 °C and 10 kPa. Glycerol of
99.0% purity is obtained in stream 502 at 60 °C and 120 kPa.
The production rate is the varying factor among these unmodified processes. Glycerol and
biodiesel is obtained are obtained in high purity. System with these given conditions is not a
very effective process.

Unit 106 203 301 302 502 401

Temperature C 60 60 59.21492 60.00018 263.3396 160.9465
Pressure kPa 395 120 110 120 50 10
Mass Flow kg/h 1882.606 1771.39 1594.783 193.2267 157.7756 1499.998
Triolein 0.041976 0.044612 0.049428 0.001022 0.000063 0
Methanol 0.065922 0.007277 0.003844 0.034985 0 0.000432
M-Oleate 0.80118 0.851482 0.945757 0.000155 0.001384 0.999309
Glycerol 0.082954 0.088162 0 0.808222 0.989948 0
H2O 0 0 0.000971 0.077993 0.000001 0.000259
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Above the unmodified alkali-catalyzed methanol system is examined at a production rate of
12,000 tons/yr. Biodiesel of 99.9% purity is obtained in stream 401 at 160°C and 10 kPa.
Glycerol of 99.0% purity is obtained in stream 502 at 60 °C and 120 kPa. This process is similar
to all the above mentioned unmodified processes and requires modifications to become efficient.
The transesterification reaction occurs in R-101 and the NRTL VLE was used to model the
thermodynamic behavior.

Unit 106 203 301 302 502 401

Temperature C 60 60 59.21504 59.99969 263.3375 134.5357
Pressure kPa 395 120 110 120 50 10
Mass Flow kg/h 2473.075 2361.87 2126.384 257.6448 208.566 1999.977
Triolein 0.042605 0.044611 0.049428 0.001024 0.000063 0
Methanol 0.051922 0.007283 0.003847 0.03502 0 0.000875
M-Oleate 0.813188 0.851476 0.945754 0.000155 0.001398 0.998655
Glycerol 0.084198 0.088162 0 0.808193 0.998499 0
H2O 0 0 0.000971 0.077988 0.000002 0.00047
Phosphoric acid* 0 0 0 0 0 0
The unmodified system is examined at a production rate of 16,000 tons/yr. Biodiesel of 99.8%
purity is obtained in stream 401 at 134 °C and 10 kPa. Glycerol of 99.8% purity is obtained in
stream 502 at 60 °C and 120 kPa. This is the highest production rate studied for alkali-catalyst
with methanol.
Different production rates were examined to determine the minimum operating production rate
of biodiesel for this design to breakeven. This analysis is presented in the economic
sustainability portion of this report. For all of these unmodified processes the energy
consumption is directly proportional to the production rates.
Page 13 of 80
Modification of 8,000 ton/yr Production
Sale of Trisodium Phosphate and Heat Exchanger Network Modification
Figure 5 - Alkali-catalyzed Process Using Methanol with Cooler and HEN Modification
Table 5 - Important Stream Data for Sale of Trisodium Phosphate and Heat Exchanger Network Modifications
Unit 106 203 301 302 502 401 306S

Temperature C 60 60 59.21462 60.00023 262.409 185.164 25
Pressure kPa 395 200 110 120 50 10 100
Mass Flow kg/h 1292.1 1180.954 1063.2 128.8333 105.2056 999.9995 12.97858
Triolein 0.0407 0.044611 0.049427 0.001027 0.000063 0 0
Methanol 0.0927 0.0073 0.003855 0.035104 0 0.00024 0
M-Oleate 0.7781 0.851462 0.945746 0.000155 0.00139 0.999612 0
Glycerol 0.0805 0.08816 0 0.808125 0.989742 0 0
Sodium 0.0077 0.008467 0 0.077614 0.004752 0 0
H2O
Hydroxide* 0 0 0.000972 0.077975 0.000203 0.000148 0
Phosphoric acid* 0 0 0 0 0.00385 0 0
Trisodium 0 0 0 0 0 0 1
phosphate*
This process combines two modifications:
Solidification of Na3PO4 and HEN
Pure trisodium phosphate Na3PO4 is obtained as a waste byproduct in stream 306. Input stream
303 is subjected to the gravity separator X-302 to obtain this byproduct. Stream 303 contains
12.97 kg/h of trisodium phosphate at 60 °C and 110 kPa. At this temperature trisodium
phosphate is recovered as a liquid. Assigned modification for this process required this by-
product to be recovered as a solid fertilizer. To induce this phase change, a simple cooler is
Page 14 of 80
introduced to bring the temperature and pressure of this stream to 25 °C and 100 kPa.
Conventionally trisodium phosphate has been used an effective cleaning agent.
Adding the cooler essentially provides the energy required to make this phase conversion; thus,
making it easier to compare the possible revenue of a fertilizer by-product to the costs of
solidification. Various practical and efficient ways of solidifying this steam are available. A
simple cooling water system can be utilized to cheaply and efficiently convert the hot liquid
trisodium phosphate in stream 303 into a solid by-product in 307. Advantages of using a cooling
water system are that it is completely reusable and does not require extensive equipment
installation. Also, no additional waste products would originate from this design.
Production of industrial grade trisodium phosphate fertilizer is the goal of this modification.
Phosphate fertilizers release orthophosphates (H2PO4-) that are helpful for soil phosphate levels.
The ion is the desired phosphate released in the soil.
From an economic prospective investing in this waste by-product is beneficial. This process
produces 12.97 kg/hr, which is 19,700 gal/yr. Possible annual revenue from the sale of the solid
industrial grade trisodium phosphate is around $270,000. This easily justifies the equipment and
manufacturing costs of the cooler unit required to solidify the waste stream.
This modification is effective in both economic and social aspects but, due to the adverse effects
of trisodium phosphate on the natural ecosystems this facet of the process is not environmentally
friendly.
Heat Exchanger Network (HEN)
A simple heat exchanger network was introduced to eliminate a feed stream pre-heater and
reduce the amount of cooling water required in stream 202. Feed stream requires to be heated to
60 °C before entering in the reactor R-101, and stream 202 requires to be cooled to 60°C before
entering the liquid-liquid extractor. In the unmodified design a separate heater and cooler unit
achieved these temperatures. By introducing the HEN, equipment costs are reduced by
eliminating a heater unit.
Page 15 of 80
Choline Chloride - Urea Mixture Modification
Figure 6 - Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea and KOCH3 Modification
Table 6 - Important Stream Data for Choline Chloride - Urea Mixture Modification
Unit 106 202B 301 302 402

Temperature C 50 50 40 50 263.403
Pressure kPa 100 200 110 120 50
Mass Flow kg/h 1311.279 1177.181 1052.676 127.0049 107.9997
Triolein 0.008007 0.00892 0.00298 0.016535 0.019444
M-Oleate 0.79638 0.887099 0.99702 0 0
Glycerol 0.08242 0.091809 0 0.85096 0.980556
Methanol 0.095496 0.012168 0 0.112782 0
Choline Chloride/ Urea* 0 0 0 0.019684 0
KOCH3* 0.017696 0.000004 0 0.000038 0
Replacing NaOH with KOCH3
All the above mentioned unmodified processes turn out to be ineffective in energy consumption
and product formation. After examining the environmental effects of trisodium phosphate,
possible replacements for the catalyst were researched. This modification involves replacing the
NaOH catalyst with KOCH3 based on the studies conducted by Singh et al. As a result of this
study it was found that the effects of potassium methoxide on biodiesel production are far
superior to sodium hydroxide.
The following trend was observed for soap formation:
NaOCH3 > NaOH > KOCH3 >> KOH
Soap Formation
Page 16 of 80
Using potassium methoxide as a catalyst reduces soap formation when compared to using
sodium hydroxide. One of the major issues with biodiesel production is the side reactions that
result in soap formation.
It was shown in this study that, “…KOH was found to have a significantly higher level of soap
formation than the other three and was the worst catalyst in terms of soap formation.” [23]
Soap formation causes severe equipment damage and highly reduces product yield. For these
reasons KOH is not a recommended catalyst for transesterification reaction.
Another major aspect of the study dealt with the effects of catalyst on the product yield. The
following trend was observed:
KOCH3 > NaOCH3 > KOH >> NaOH
Product Yield
KOCH3 is the best catalyst to increase biodiesel product yield it converts 99% reactants to
products. By replacing the catalyst the biodiesel yield is greatly increased; subsequently,
increasing the profits. Clearly, potassium methoxide is a better choice when compared to any of
the other three catalysts.
The reaction temperature is lowered to 50 °C and a 4.5:1 feed molar ratio is used. The catalyst at
a concentration of 0.2 mol/mol is utilized. The unmodified process temperature was 60 °C and a
6:1 feed molar feed ratio was used.
Another advantage of using potassium methoxide it can be completely removed from the process
without catalyst neutralization reactor. This is possible because of the similarities between the
methoxide functional group and methanol. When the catalyst is completely recycled back no
additional raw materials are required thus greatly reducing costs.
Deep Eutectic Solvents (DES)
A 2:1 molar ratio of Choline Chloride and Urea is used to create a deep Eutectic solvent. The
unique property of these solvents is their ability to have drastically lower melting point [21] than
either of the two components individually, Table 7.
Table 7 - DES Melting Point
Chemical Melting Point (°C)

Choline Chloride 302
Urea 133
2:1 Molar Ratio 12
Page 17 of 80
The goal of this modification is to eliminate additional biodiesel purification via distillation.
Using DES in HYSYS simulation the biodiesel purification distillation column was eliminated.
The distillation column is the most energy intensive and expensive unit. Even without the
distillation column the product biodiesel was 99.7% pure thus, proving that the DES
modification works. This combination results in a system that runs much more efficiently, with a
high affinity for hydrogen bonding. Lastly, DES is inexpensive, non-toxic and environmentally
benign solvent system[22]. The choline chloride liquid chemical name is determined to be 3,5,5-
triamino-4,6-dihydroxy-1,2,2-trimethylhexahydropyrimidin-1-ium chloride, a high molecular
weight solvent. The density of this salt is determined to be 1.14 g/ml making it easily separable
and recycled, reducing raw materials.
This modification is expected to be extremely successful in rural areas of Michigan. Choline

chloride also called chicken‟s feet is very inexpensive compound used in farming. Urea the
other component of the DES used in this modification is also a inexpensive material used largely
in farming. Mixing these two chemicals to create a 2:1 molar ratio and operating it for
purification is far less cumbersome than installing and running a distillation column.
Choline Chloride - Urea Mixture and Heat Exchanger Network Modification
Figure 7 - Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea, KOCH3, and HEN Modification
Table 8 - Important Stream Data for Choline Chloride - Urea Mixture and Heat Exchanger Network Modification
Unit 106 202B 301 302 402

Temperature C 50 50 40 50 263.3865
Pressure kPa 100 200 110 120 50
Mass Flow kg/h 1311.186 1176.981 1052.676 126.805 110.1762
Triolein 0.008008 0.008921 0.00798 0.016561 0.01906
M-Oleate 0.796436 0.88725 0.99202 0 0
Glycerol 0.082426 0.091825 0 0.852301 0.980939
Methanol 0.095432 0.012 0 0.111384 0.000001
Choline Chloride/ Urea* 0 0 0 0.019715 0
KOCH3* 0.017698 0.000004 0 0.000038 0
Page 18 of 80
The above analysis is on a system with the DES and HEN modification. The assigned
modification of creating solid waste product in stream 306 is not considered here. The reason for
this is to quantify and justify that each modification is profitable and successful in HYSYS.
The HEN modification involves introducing a heat exchanger and getting rid of a heater and
cooler. Equipment reduction is key, as it reduces not only the investment costs but also the
maintenance and operation costs. System E-100 is introduced taking away heater E-101 and
cooler E-201.
The combination of the DES with the HEN is considered separately to quantify the applicability
and profitability of each modification. Thus, proving that each modification works and is
successful in creating profits either combined or individually.
Alkali-catalyzed Process Using Ethanol
Ethanol can be substituted to create a process that is more sustainable because ethanol is a
renewable resource. The process in Figure 8 was adapted from Santana et al[2].
Figure 8 - Alkali-catalyzed Process Using Ethanol
Page 19 of 80
Table 9 - Important Stream Data for Alkali-catalyzed Process Using Ethanol
Unit 1a 4 14 11
Temperature C 25 70 295.26 30
Pressure kPa 101.3 101.3 101 101
Mass Flow kg/h 312.9 1610.388 109 1052.091
CetylC1cryla 0 0.653212 0 0.999842
Triolein 0 0.000103 0 0.000158
Ethanol 1 0.27596 0 0
NaOH 0 0.006148 0.090825 0
H2O 0 0 0 0
Glycerol 0 0.064577 0.909175 0
This process utilizes a CSTR reactor, which requires a kinetic reaction to be simulated in
HYSYS. NRTL VLE was used to simulate the thermodynamic properties of this process. The
sodium hydroxide catalyst reacts at 70 °C. The ethanol is then partially recycled in a distillation
column. The bottoms product is cooled and the biodiesel, represented by CetylC1cryla, is
purified using gravity separation. The final distillation column purifies the glycerol co-product.
The glycerol is 91% pure, because this process does not utilize any catalyst neutralization and
removal systems. However, the glycerol can still be sold as an additive to improve the durability
of asphalt.
Ethanol Recovery Modification
Figure 9 - Alkali-catalyzed Process Using Ethanol Recovery Modification
Page 20 of 80
Table 10 - Important Stream Data for Ethanol Recovery Modification
Unit 1a 4 14 11 13a 13b

Temperature C 25 70 295.25979 30 78.090801 276.00524
Pressure kPa 101.3 101 101 101 101 101
Mass Flow kg/h 156.1708 1610.31833 109 1052.091 156.69801 4.900494
CetylC1cryla 0 0.653241 0 0.999842 0 0
Triolein 0 0.000103 0 0.000158 0 0
Ethanol 1 0.275929 0 0 1 0.001291
NaOH 0 0.006148 0.090826 0 0 0
H2O 0 0 0 0 0 0
Glycerol 0 0.06458 0.909174 0 0 0.998709
Due to the price of ethanol is extremely important to recycle as much as possible. The motivation
for making this modification is reduce, reuse, and recycle. Recycling ethanol from waste streams
lowers raw material costs. An additional distillation column was installed and 156 kg/hr of
ethanol was able to be recovered. This modification reduced the amount of ethanol in the feed
stream by half. The installed distillation column also creates 100% pure glycerol, with can be
sold at a high price in the soap industry.
Non-catalytic Process Operated at Supercritical Condition of Methanol
Figure 10 - Non-catalytic Process Operated at Supercritical Condition of Methanol
Page 21 of 80
Table 11 - Important Stream Data for Non-catalytic Process Operated at Supercritical Condition of Methanol
Unit 202 206 401 502 603 608

Temperature C 250.59369 66.50435 179.52149 176.22760 360 278.6878
Pressure kPa 2000
4 10 16 22 5000 5000
4
Mass Flow kg/h 3229.8259 3229.8259 1212.2570 120.40002 7920 7920
Liquid Volume m3/h 3.847395
66 3.847395
66 1.382485
3 0.095496
7 10.80902 10.80902
Triolein
Flow 0.018077 0.018077 0 0 05 05
Methanol 0.561929 0.561929 0.000084 0 0 0
M-Oleate 0.380589 0.380589 0.999916 0 0 0
Glycerol 0.039405 0.039405 0 1 0 0
n-Decane 0 0 0 0 1 1
The non-catalytic process[1] offers interesting opportunities for the production for biodiesel, but
the process is extremely energy intensive. Triolein is used to represent virgin vegetable oil and
methyl oleate represents biodiesel. The UNIQAUC VLE was used to model the thermodynamic
behavior, and the high pressure behavior was correlated using Aspen RK EOS. The
transesterification reaction occurs in a PFR, which requires the use of a kinetic reaction. An
activation energy of approximately 68,000 J/mol was used because the single pass reaction
conversion was less than 100%. This process uses a heat exchanger network to heat the reactor
inlet and cool the reactor outlet, n-decane was used to approximate heating oil. The process
utilizes three valves to decrease the pressure, in order to purify the biodiesel. The purification
process is simpler than the alkali-catalyzed process because to reactor is necessary for catalyst
removal. This process is very effective producing 99.9% pure biodiesel and 100% Glycerol,
which can be used to produce high quality soaps or filler in asphalt. Additionally this process can
be improved to enhance sustainability.
Modifications
Water Heat Exchanger Network
Figure 11 - Non-catalytic Process Operated at Supercritical Condition of Methanol with Water HEN Modification
Table 12 - Important Stream Data for Water Heat Exchanger Network Modification
Page 22 of 80
Unit 202 206 401 502 603 607
Temperature C 250.5941 66.50517 187.3731 176.2276 320 235.4331
Pressure kPa 2000 10 1 2 5000 5000
Mass Flow kg/h 3229.864 3229.864 1212.2 120.4 1150 1150
Triolein 0.018078 0.018078 0 0 0 0
Methanol 0.561935 0.561935 0.000046 0 0 0
M-Oleate 0.380584 0.380584 0.999954 0 0 0
Glycerol 0.039404 0.039404 0 1 0 0
H2O 0 0 0 0 1 1
The n-decane used in the heat exchanger network is very harsh environmentally and financially
expensive. A water HEN was substituted to lower costs, enhance inherent safety, and reduce
environmental impact. A modification that could further improve this HEN would be to recycle
the effluent stream, creating an internal loop. Again this process creates high quality biodiesel
and glycerol.
Replacing Heat Exchanger Network With Heater and Cooler Modification
Figure 12 - Non-catalytic Process Operated at Supercritical Condition of Methanol with Heater/Cooler Modification
Table 13 - Important Stream Data for Heater and Cooler Modification
Unit 202 206 401 502

Temperature C 250.6075 66.50428 179.498 176.2276
Pressure kPa 2000 10 1 2
Mass Flow kg/h 3229.826 3229.826 1212.2 120.4
Triolein 0.018079 0.018079 0 0
Methanol 0.561929 0.561929 0.000084 0
M-Oleate 0.380587 0.380587 0.999916 0
Glycerol 0.039404 0.039404 0 1
This modification replaces the HEN with a heater and cooler, which internally recycles the
utilities. The goal of this modification is to reduce the amount of raw materials required for the
process, reducing the total manufacturing cost. Again this process creates high quality biodiesel
and glycerol.
Page 23 of 80
Sustainability
Economic Sustainability
In order to determine the economic viability of each process a net annual profit after taxes (NAPAT) was
used to determine the number of years necessary to recoup the total investment. Table XX shows the
calculated total production cost, NAPAT, break even time, and biodiesel production per year.
Table 14 - Economic Analysis of All Processes using NAPAT
Total Break Even Biodiesel Production

Process Production Point (years) (tons/yr)
Cost ($) NAPAT ($)
Alkali-catalyzed
Methanol
4,000 ton/yr 4,963,683.86 -250,257.93 N/A 4,000
8,000 ton/yr 8,001,526.05 462,804.98 17.29 8,000
12,000 ton/yr 11,138,391.44 1,125,972.28 9.89 12,000
16,000 ton/yr 14,288,388.93 1,785,085.53 8.00 16,000
Modifications
Sale of Na3PO4/HEN 8,060,140.20 488,805.90 16.49 8,000
KOCH3/Choline Cl- 7,373,539.76 957,230.12 7.70 8,400
KOCH3/Choline Cl-/HEN 7,332,727.74 977,636.13 7.50 8,400
Alkali-catalyzed 9,277,575.65 5,212.18 1,779.98 8,400

Ethanol
Ethanol Recovery 8,150,174.92 588,512.54 13.85 8,400
Non-catalytic
Supercritical Methanol
Oil HEN 37,351,531.85 -13,301,053.93 N/A 9,696
Water HEN 11,903,355.05 -576,965.52 N/A 9,696
Heater/Cooler 9,944,270.02 402,576.99 24.70 9,696
From an economic standpoint, the alkali-catalyzed process using methanol with choline
chloride/urea, KOCH3, and HEN modification offers the best opportunity to have a viable
process.
Based on a study conducted by Iowa State University an average plant cost for 30,000 gal/year
production of biodiesel was $17 million. This production rate is approximately 50 tons/yr.
Therefore, calculations of $4 million to $14 million are reasonable, for the production rates
studied.
Page 24 of 80
Since the alkali-catalyzed process-using methanol did not earn profit after taxes at all production
rates, it would be advisable to know the minimum flow rate, which this process must operate at
to break even.
2.00E+06
1.50E+06
Net Profit After Taxes ($)
1.00E+06
5.00E+05
0.00E+00
4,000 6,000 8,000 10,000 12,000 14,000 16,000
-5.00E+05
Biodiesel Production Rate (tons/year)
Figure 13 - Break Even Production Rate
As shown by Figure 13, the minimum production rate is approximately 5,500 tons per year.
Environmental Sustainability
Environmental impact of a process design is important aspect that needs be addressed during
design proposal. To understand the impact of the processes the Waste Reduction Algorithm
(WAR) developed by Environmental Protection Agency (EPA) was used. The Potential
Environmental Impact (PEI) of the Alkali-Catalyzed Process using Methanol, Alkali-Catalyzed
Process using Ethanol and Non-Catalytic Process Operated at Super Critical Condition of
Methanol were calculated.
Based on the waste output and energy consumption of each process, the algorithm is used to
determine the process with the most Potential Environmental Impact (PEI). Two distinct
analyses can be performed using WAR algorithm, product and non-product analysis depending
on the product stream of biodiesel. The overall PEI of a given chemical is determined by taking
the summation of the specific PEI of that chemical‟s overall possible impact categories.
k   l kl (Eq. 1)
l
Where, kl is every impact category of a chemical,  l is the weighing factor.
Page 25 of 80
The weighing factor of a given chemical is used to emphasize the particular areas of concern
whether it is global atmospheric or local toxicological concerns. Each of the two areas of concern
has its own four categories as shown below.
Global Atmospheric Impacts Toxicological Impacts
 Global Warming Potential (GWP)  Human Toxicity Potential by Ingestion (HIPI)

 Ozone Depletion Potential (ODP)  Human Toxicity Potential by Exposure
 Acidification Potential (AP) (HTPE)
 Photochemical Oxidation Potential (PCOP)  Aquatic Toxicity Potential (ATP), and
 Terrestrial Toxicity Potential (TTP)
The total output rate of PEI (PEI/hr) allows one to compare an alternative processes in terms of
the potential effects on the environment. In other words, the total output rate of PEI is very
necessary in assessing if a given geographical location can accommodate a process plant. It can
also be used to determine how a given processes design with variable production rate impacts the
environment.
For production of biodiesel using alkali catalyzed with methanol, production rate biodiesel is
directly proportional to the impact on the environment. The HTPI and HTPE areas of concerns
are a little higher than the ones mentioned above. This is due to the corrosive nature of the strong
base sodium hydroxide in the feed stream and the distillation tower. Of all categories of
environmental concern AP (Acidification Potential) exhibits the highest environmental concern.
What this tells us is that geographical locations with frequent rain throughout the year most
likely are not encouraged to build biodiesel plants because of the possibility of acid rain. In
Figure 14, the AP category of the smallest production rate (500kg/hr) has a total output rate of
PEI 1.5 per hour while the AP for the production of biodiesel with the highest production of
biodiesel (2000 kg/hr) has a PEI of 5.2 per hour.
6.00E+01
5.00E+01
4.00E+01
PEI
3.00E+01
2.00E+01
1.00E+01
0.00E+00
HTPI HTPE TTP ATP GWP ODP PCOP AP
500 1000 1500 2000 1000HEN 1000HEN(DES)
Figure 14 - Total Output rate of PEI (PEI/hr)
Page 26 of 80
Also using the WAR algorithm comparisons of the total output rate of PEI (PEI/hr) for
production of 1000kg/hr production of biodiesel in the Alkali catalyzed Method using Methanol
was made. Figure 15, shows the unmodified process and suggested HEN modification. These
two have similar impact on the indicated categories. This is because the major change in the
design is the reduction of energy consumption. However, in the second modification of
potassium methoxide catalyst replacing sodium hydroxide, the potential impact is consistent and
comparable.
2.00E+00
1.80E+00
1.60E+00
1.40E+00
1.20E+00
PEI
1.00E+00
8.00E-01
6.00E-01
4.00E-01
2.00E-01
0.00E+00
1000kg/hr(unmodified) 1000(HEN)(modfied) 1000HEN(DES)(modified)
Figure 15 - Total Output rate of PEI for 1000kg/hr Production of Biodiesel
Figure 16 compares the total PEI leaving the system per kg of product. For the unmodified
process of alkali catalyzed with methanol, 0.045 PEI per kilogram of product is exhibited for
unmodified process is 0.00025 and 0.0078 PEI per kilogram is exhibited for first and second
modifications respectively.
Alkali-catalyst production using methanol impacts the environment in the acidification potential
(AP) category. This is the result of waste products which might produce or decompose
themselves into acidic gases generate acid rain.
Page 27 of 80
2.50E-02
2.00E-02
1.50E-02
PEI
1.00E-02
5.00E-03
0.00E+00
1000 1000HEN 1000HEN(DES)
Figure 16 - Total PEI per kg of product
In the following figure 17, the total output rate of PEI for the production of biodiesel at
supercritical condition indicates a higher impact in the category of Photochemical Oxidation
impact (PCOP) at about 122 PEI/hr. This could be due to the production of biodiesel by product
(glycerol) at highest temperature. Similarly, the Aquatic Potential Impact (A) for is significantly
higher (190 PEI/hr) than the other areas of categorical impacts. Modification to use water
instead of n-decane is responsible for this change.
In other words, the inlet of water used to heat the reaction to supercritical condition has to still
come out of the process at fairly high temperature. This stream must be cooled to an acceptable
aquatic temperature before it is lead to oceans.
1.40E+02
1.20E+02
1.00E+02
8.00E+01
PEI
6.00E+01
4.00E+01
2.00E+01
0.00E+00
1000-A(HEN) 1000-AHEN(DES)
1000-C (Eth.Recovery) 1000-F(modified)
Figure 17 - Total Output Rate of PEI Comparison
In Figure 18, a similar trend to the previous scenario is shown when comparing the three
modified chemical processes according to total output of PEI per kg of product. Refer to Figure
18.
Page 28 of 80
1.20E-01
1.00E-01
EPI/kg of Product
8.00E-02
6.00E-02
4.00E-02
2.00E-02
0.00E+00
1000-A HEN 1000-A HEN(DES)

1000-C (Eth.Recovery) 1000-F(modified)
Figure 18 - Total Output of PEI/kg of Product
EPA analysis justifies the suggested modifications.
Inherent Safety Analysis

A basic definition of inherent process safety includes five main components:
 Simpler Design
 Safer Design
 Smaller Processing Units
 Substitution of less dangerous chemicals
 Moderate Process
The factors considered are show in Table 15 were adopted from Inherent safety in process: An
index-based approach[5].
Page 29 of 80
Table 15 - Inherent Safety Factors
These metrics were used to analyze each process and summed to calculate Total Inherent Safety (TIS).
Complete calculations can be found in Appendix B.
Table 16 - Overall Inherent Safety Comparison
Process Total Inherent

Safety
Alkali-catalyzed Process Using Methanol 4,000 tons/yr 12
Alkali-catalyzed Process Using Methanol With Cooler and HEN Modification 12
Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea and KOCH3 11
Modification
Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea, KOCH3, and 11
HEN Modification
Alkali-catalyzed Process Using Ethanol 10
Alkali-catalyzed Process Using Ethanol Recovery Modification 9
Non-catalytic Process Operated at Supercritical Condition of Methanol 15
Non-catalytic Process Operated at Supercritical Condition of Methanol with Water 14
HEN Modification
Non-catalytic Process Operated at Supercritical Condition of Methanol with 14
Heater/Cooler Modification
Page 30 of 80
The alkali-catalyzed process using ethanol recovery offers the best overall safety, with a score of
9. However, this process is not the most economically viable. The alkali-catalyzed process using
methanol with choline chloride/urea, KOCH3, and HEN modification, received a middle score of
11, which is lower than the unmodified process due to lower reactor operating temperatures, 50
°C compared with 60 °C for the unmodified process. The non-catalytic process is least safe due
to high operating temperatures (350 °C) and pressures (2000 kPa), as well as requiring more
storage for raw materials in two of the processes.
In all the processes operating temperature and pressures contributed the most to raising the TIS
score. The highest temperatures occur in the bottoms of the distillation columns, these
temperatures ranged between 200 °C and 350 °C. The other factor which caused a TIS score to
increase was that with increased production there needed to be more storage for raw materials
and products. It was assumed that storage would take place on site.
The use of choline chloride and urea did not increase the TIS score because it biodegradable and
is internal to the process. Additionally, the potassium methoxide had negligible effect on the TIS
score because is internal to the process.
IChemE Sustainability Assessment
The IChemE Sustainable Development Progress Metrics[6] was used to assess sustainability for
all the processes listed in Table 17. To provide a fair and well rounded comparison both
modified and unmodified processes were evaluated. This allows for an unbiased comparison
between different modifications and the effect of these modifications on sustainability. The
IChemE metrics uses 49 detailed factors that are helpful in evaluating a company‟s progress
towards a more sustainable operation[5]. Eleven broad areas were considered in the metrics,
these are listed below:
 Energy  Aquatic Impacts
 Material (Fuel and water excluded)  Impacts to Land
 Water
 Profit, Value and Tax
 Land
 Investments
 Atmospheric Impacts
 Society  Workplace
This assessment is meant to be extremely through, for example comprehensive analysis of a

company‟s effect on its shareholders was examined while quantifying the impact on the
atmosphere, land and water resources. In general terms, energy evaluations deal with the
processes‟ energy use per the value of product produced, material analysis dealt with raw
material usage and hazard waste production. Water and land analysis evaluated the amount of
these resources used by the processes. Social impacts were also studied such as profit sharing,
investment and workplace dynamics.
Analyses for all processes examined are presented in Appendix B. In all categories, the
suggested modified processes fared better than the unmodified processes. As mentioned earlier
Page 31 of 80
several factors were considered in this analysis but, three specific factors are presented below as
an example. The above table shows the results for three best suggested modifications.
Table 17 - Notable IChemE Criteria
Indirect
Ozone Depletion per Community
Energy Usage (GJ) Value Added (tons/$) Impact ($/$)
Choline Chloride/Urea, KOCH3, and

HEN Modification 5.251 0.033 2709.30
Ethanol Recovery Modification 10.339 0 2653.99
Supercritical Methanol with

Heater/Cooler Modification 76.039 0.014 2298.29
The modified non-catalytic process at supercritical condition of methanol is the least sustainable
when it comes energy usage. This is expected as this process functions at extremely high
temperature and pressures. Alkali-catalyzed process using ethanol recovery had the least ozone
depletion, this is consistent as ethanol is more environmentally friendly compared to methanol.
The indirect community impact of the three processes are in close range and do not differ too
much, proving that each process has a positive social impact.
The IChemE assessment reinstates the conclusions from the previous sustainability analysis, i.e.
the suggested modified processes are more sustainable compared to the unmodified processes.
Taking a closer look at the results shows that the alkali-catalyzed biodiesel production with
ethanol recovery has the highest sustainability followed closely by choline chloride/urea and
HEN modification of alkali-catalyzed biodiesel production with methanol. The non-catalytic
biodiesel production at super critical conditions of methanol is not very sustainable, the
suggested modifications for this process increase the sustainability but are not comparable to the
other two catalytic processes.
Overall Sustainability
Unlike product and profit analysis sustainability is very difficult to measure and quantify. Many
different kinds of sustainability need to be examined. The processes mention in Table 18
underwent economic, social, and environmental sustainability analysis. It is found that some
processes are better economic performers while having poor environmental impacts. On the
other hand, some other processes that have very less environmental impact did not perform well
economically. The following graph, Figure 19, is an attempt to understand the overall
sustainability performance of all the modified and unmodified processes. Table 18 shows the
Page 32 of 80
results from economic, inherent safety, and environmental sustainability analysis normalized for
all the processes.
Table 18 - 3 Dimensional Sustainability Process Reference and Normalized Scores
Economic Inherent Environmental

Process Index Sustainability Safety Sustainability
Alkali-catalyzed Methanol 4,000 tons/yr 1 0 6 8
Alkali-catalyzed Cooler and HEN 5 4 7 10
Alkali-catalyzed Choline Chloride/Urea 6 8 8 9
Alkali-catalyzed Choline Chloride/Urea, HEN 7 10 9 9
Modification
Alkali-catalyzed Process Ethanol 8 1 8 9
Alkali-catalyzed Process Ethanol Recovery 9 5 9 10
Non-catalytic Process Methanol 10 0 3 1
Non-catalytic Water HEN 11 0 4 1
Non-catalytic Heater/Cooler 12 3 4 2
Figure 19 - Three Dimensional Sustainability Analyses
Score Meaning
0 Not Viable
5 Average
10 Excellent
Page 33 of 80
In Figure 19, is a three dimensional plot, with economic sustainability on the x axis, inherent
safety on the y axis, and environmental sustainability on the z axis. This comparison gives each
process a 0 to 10 score for each metric, 0 being not viable and 10 being excellent sustainability.
Processes in the lower left are unsustainable in all three metrics and processes in the upper right
are very sustainable in all metrics. The processes break up into three groups. The first is
economically unsustainably with varies degrees of inherent safety and environmental
sustainability, e.g. 1, 8, 10, and 11. The next groups for processes are middle of the road, e.g. 2,
3, 4, 5, 9, and 12. A very interesting trend can be seen with the alkali-catalyzed methanol process
(2, 3, and 4); as production rate increase, economic sustainability increase, but the environmental
sustainability decreases. The last group has excellent scores in all categories, e.g. 6 and 7. These
processes utilize less energy, produce more biodiesel, use lower temperatures, and use
biodegradable materials; creating the best combination of all the processes.
Page 34 of 80
Geographical Analysis of Biodiesel Demand and Production in Michigan
Based on the process analysis and sustainability assessment conducted an effective solution to
the biodiesel deficit in Michigan is suggested. The total demand of biodiesel in Michigan is
assumed to be 50,000 tons/year. Michigan is divided into three geographical areas, Upper
Peninsula, Northwestern Michigan, and Southeastern Michigan. Figure 20 shows nine biodiesel
plants of varying capacities and geographical locations are recommended to fulfill the demand.
Population density, raw material production, and transportation are the factors evaluated to
determine the plant locations. Each plant has a functioning radius within which the raw
materials would be produced and product biodiesel distributed. It is important to mention that
this is a preliminary analysis and locations and capacities of the plants could change based on
various factors.
Figure 20 - Proposed Locations of Biodiesel Plants
Upper Peninsula
The Upper Peninsula (UP) is allotted two plants one in Marquette and the other in Sault Ste.
Marie. The population distribution in the UP is the lowest in the entire state averaging out to be
less than one per square mile according to the US census Figure 23. Based on studies conducted
by Michigan‟s Biomass Energy Program (MBEP) [9] area surrounding the Sault Ste. Marie plant
is most suitable for the production of energy crops. Thus it is recommended that this plant be an
alkali-catalyst ethanol plant. The idea here is to utilize the resources available locally, by
building an ethanol plant around a farm land which is able to produce high volumes of ethanol,
Page 35 of 80
sustainability is ensured. The effective radius of this plant covers all the high tourist spots
guaranteeing supply of biodiesel at high demand periods. It is estimated that the potential
biodiesel demand for this plant would be 3000 tons/year.
Depending on availability of raw materials the

Marquette plant could either be an ethanol or
methanol plant. This choice can be made based
on the socio-economic impact, for example if
incentives are provided for energy crops, an
ethanol plant would be built. Due to the lower
population density and geographical isolation
this plant is only expected to have a low
biodiesel demand of 2000 tons/year. For the
same reasons this plant is expected to have high
transportation costs also.
The Northwestern Michigan portion of the state

is allocated four varied capacity plants.
Northern portion of the state is covered by two
Figure 22 – Energy Crops
plants, one in Traverse City and another in

Alpena. Both these plants most likely will have
to use methanol as a raw material since MBEP
studies indicate no surrounding cropland highly
conducive for ethanol production. Traverse City
is a high tourist location (travel ref) and is
estimated to have a demand of 3500 tons/ year.
Effective radius of this plant is larger in
comparison and intersects with the coverage of
both the Alpena and Sault Ste. Marie plants.
This is intentional and is aimed to provide better
coverage. By creating a grid of plants that are
interconnected adequate support can be provided
during high peak tourist months. Also the grid
Figure 21 - Pasture Land
Page 36 of 80
ensures redundancy in case one plant faces production delays or fails to function. The plant in
Alpena is expected to have a demand of 1500 tons/yr of biodiesel. Combined the Northwestern
Michigan region would have a total biodiesel demand of 5000 tons/yr.
Northern Lower Peninsula
Western and Mid Michigan are included in the Northwestern Michigan region, plants in Grand
Rapids and Mt. Pleasant are recommended for these regions respectively. Both these plants
would excel at biodiesel production from ethanol. According to the MBEP study the radii
covered by these plants have the highest production of energy crops, thus ensuring low
transportation costs and ample raw material supply. Each of these plants is predicted to have a
total demand of 5000 ton of biodiesel per year. Due to the advantage of their location in farm
and rural area their production would possibly be higher than the demand. The plant in Mt.
Pleasant would possibly be able to support the Southern Michigan biodiesel demands. The
concept of redundancy and plant gird is again implemented in this region. This ensures supply is
kept up with possible changes in demand over the region.
Figure 23 - Population Density
Southern Lower Peninsula
The Southeastern Michigan region of state is the densest of all the regions both in population
density and transportation. Biodiesel is expected to be directly proportional to population
Page 37 of 80
density. Therefore, this region is predicted to have the highest demand in the state a total of
30,000 tons/yr. The transportation costs for this region are estimated to be lowest for the entire
state, as it is highly connected. Three plants are recommended for this region, they would be
centrally located in Detroit, Ann Arbor and Flint. These plants are expected to produce enough
biodiesel to support the entire Southeastern Michigan region. Detroit and Flint plant would be
methanol plants and Ann Arbor possibly an ethanol plant.
A highly connected grid is created by these three plants; they are estimated to produce 10,000
tons/yr of biodiesel. To effectively compete with gasoline in this area an active offensive
approach would be required. By overlapping the effective radius these plants redundant failsafe
system is created. As these plants are closer to each other more recharging stations can be
supported at low transportation costs while simultaneously increasing profits.
Of the nine plants recommended three plants would be alkali-catalyzed ethanol plants and six
would be run as alkali-catalyzed methanol plants. Based on the Total Inherent Safety conducted,
these plants offer tangible safety improvements. Additionally it is important to note that, the
choline chloride/urea extraction can be used for either methanol or ethanol transesterification.
All the above analysis is conducted on the assumption that there is a certain demand for
biodiesel. The truth however is that there is very low demand for biodiesel in Michigan today.
Hence the industry is facing severe crisis that threatens its very existence. Superior process
engineering is only one aspect of the solution; the plan is to propose a solution to completely
revive Michigan‟s biodiesel industry. This can only be achieved when a combined multi-aspect
solution is created.
One big problem faced by the biodiesel industry is that biodiesel is a new product that requires
customers to acclimate. Decades of using gasoline provide a certain level of convincing and
predictability. To overcome this barrier, incentives need to put in place either by the biodiesel
industry or the Michigan government. One suggestion is to make available either for a minimal
fee or free of charge engine convertors. Vehicle engines running on gasoline can be converted to
use biodiesel by simply installing these converters. By increasing the ease in switching to
biodiesel from gasoline the biodiesel industry will greatly benefit. Convertors are sold by the
local biodiesel producer Arbor Biofuels, located in Milan, Michigan this company has managed
to sustain and thrive by keeping their production process up to standards with new developments
in biodiesel production.
Advantages:
The suggested proposal offers many advantages for Michigan. The most vital benefit would be
job creation and the resulting economic activity. Technicians, engineers and general labor force
will be required for each plant. As a result biodiesel plants would help produce both direct and
indirect employment. The proposal also would benefit indirectly the rural farmers growing
energy crops for all the ethanol plants thus increasing rural economic development. A study
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conducted by the State of Michigan shows that, “100 million gallon ethanol plant could create
over 2,000 local jobs and much of the plant profits would be retained in the local community.”
Also the Corn Marketing Program of Michigan estimates that, “nearly 80% of the money
generated by an ethanol plant is spent within a 50 mile radius of the factory.” Another advantage
is the possible reduction in the dependency on fossil fuel along with the creation of a new fuel
industry. Taking advantage of urban reclamation the cities of Detroit and Flint would benefit
hugely from the biodiesel plants.
The environmental impact of using biodiesel as a fuel is also an advantage. Biodiesel is better
for the environment than gasoline. The modified process suggested in the report has an inherent
safety rating that is better in many folds when compared to unmodified processes.
Constraints and Potential Solutions:
Biodiesel gel temperature is a huge concern. Considering the winter temperatures in Michigan
the effective functioning of biodiesel is critical. The gel temperature of biodiesel ranges between
-10°C and 16°C[25]. To improve biodiesel performance several additives can be used. One way
of improving biodiesel performance in cold weather is to use branched-chain esters to reduce the
gel temperature of biodiesel[26]. The final biodiesel plant with additives will function even in
cold winters and sustain a demand year round. Plants can customize biodiesel to suit Michigan‟s
weather like winter and summer blends.
Initial establishment of biodiesel plants requires a guarantee of biodiesel demand. There has to
demand before the plants are built to capacity. It is easier to assume that just building the plant
will create demand but, unfortunately this could be a gross error. Uncertain markets and yields
could crumble the infrastructure of the entire biodiesel industry. Lack of consumer awareness
and incentives: Convincing consumers to successfully switch to biodiesel is a serious and
tremendous challenge. This requires immense amount of marketing and outreach to create an
environment where yearly increases in demand are possible. Lack of Funding/Research: Lack
of incentives for the biodiesel manufactures and the consumer is another problem.
Page 39 of 80
Conclusions
Three different processes of biodiesel production were examined. The benefits of using alkali
catalyzed production process were compared to a non-catalytic production process at
supercritical conditions. The advantages of using specific starting materials as in methanol and
ethanol were also studied. All the given processes were found to be energy intensive and
requiring optimization. These processes do not score well on the sustainability analysis either.
Comparing the unmodified process to each other, methanol proved to be more economically
sustainable than ethanol, and the processes need to have a minimum production rate to have a
NAPAT. The non-catalytic production process with methanol at supercritical conditions had the
most energy consumption and least safe.
The following modifications were applied to the processes:
 Alkali-catalyzed Process Using Methanol

o Modifications
 Trisodium Phosphate Sale and Heat Exchanger Network
 Choline Chloride/Urea Extraction and KOCH3 Catalyst
 Choline Chloride/Urea Extraction, KOCH3 Catalyst, and Heat Exchanger
Network
 Alkali-catalyzed Process Using Ethanol
o Modification
 Ethanol Recovery
 Non-catalytic Process Operated at Supercritical Condition of Methanol
o Modifications
 Water Heat Exchanger Network
 Heat and Cooler Substituted for Heat Exchanger Network
Of the modified processes, the process using potassium methoxide and methanol is found to be
the most profitable and requiring the least amount of time to break even. Process using ethanol
with potassium methoxide as the catalyst was found to be the most safe and environmentally
friendly.
Michigan is divided into three geographical regions: Upper Peninsula, Northwestern Michigan
and Southeastern Michigan. The Upper Peninsula is expected to have the highest transportation
costs and a biodiesel production of 5,000 tons/yr. A total of nine plants with varying capacities
and geographical locations are recommended. Marquette and Sault Ste. Marie are the two
suggested plant locations for this region. The Northwestern Michigan region is assigned a total
of four plants and includes both Mid Michigan and Western Michigan. The plants would be
located at Traverse City, Alpena, Mt. Pleasant, and Grand Rapids. A total biodiesel demand of
Page 40 of 80
15,000 tons/yr is estimated for this region. These plants are expected to be ethanol based and
have lower transportation costs than UP plants. The densest region in terms of population and
demand for biodiesel is the Southeastern Michigan. The plants are suggested at Flint, Ann
Arbor, and Detroit. This region is expected to have the highest demand of 30,000 tons/yr and the
lowest transportation costs.
Advantages of the proposal include local job creation and economic activity. Rural economic
development is expected with all the energy crops created for ethanol production is another
advantage of the proposal. Dependence on fossil fuel is expected to decrease thus creating a
more sustaining and self reliant Michigan economy.
Some of the possible constraints could be the performance of biodiesel in cold weather.
Additives to final biodiesel product to reduce gel temperature of biodiesel would solve this
problem. Low biodiesel demand resulting from lack of consumer awareness is a possibility.
Incentives to provide awareness of biodiesel usage and benefits could help transition consumers
towards biodiesel and away from gasoline.
Page 41 of 80
Recommendations
Equipment recommendations:
For alkali-catalyzed processes replacing the catalyst with potassium methoxide is recommended
and extremely beneficial. Also a simple heat exchanger system replacing a heater and cooler
will help with the optimization of the process. Instead of using a distillation column to purify
biodiesel using a DES system of choline chloride and urea is suggested. For the process using
ethanol, ethanol recovery is suggested and for the non-catalytic process using methanol at super
critical conditions using heated water is more beneficial over the use of heated oil.
Economic Recommendations:
To minimize the raw material costs, plants located in the regions of energy crop production
should use ethanol for biodiesel production.
Lower number of equipment is always recommended in a process as long same or better results
are obtained. This reduces the equipment, instillation, operating and maintenance costs.
Inherent Safety Recommendation:
Non-catalytic process with methanol at super critical is the most unsafe of all the processes and
is not recommended for this reason. The operating temperatures and pressures of this process
require high safety review. The best recommendation for inherent safety is the modified process
using ethanol.
Michigan's Biodiesel Industry:
To compete effectively with gasoline the Michigan biodiesel industry would need to be spread
into three geographical regions, Upper Peninsula, Northwestern Michigan and Southeastern
Michigan. A total of nine plants is recommended to support the demand of the entire state.
Three of the plants would run on ethanol and 6 on methanol. To overcome possible failures and
hindrances in supply of biodiesel plants in high density regions are created to form a supply grid.
Plants should invest in biodiesel additives to improve performance in cold weather. Also to
improve customer awareness of biodiesel incentives such a cheap engine convertors and tax
breaks are recommended.
Page 42 of 80
References
HYSYS Simulations
[1] The problems in design and detailed analyses of energy consumption for biodiesel synthesis
at supercritical conditions (Process F), Glisic and Skala, 2009
[2] Simulation and cost estimate for biodiesel production using castor oil and ethanol (Process
C), Santana et al., 2009
[3] Biodiesel production from waste cooking oil: 1. Process design and technological
assessment (Process A), Zhang et al. - 1, 2003
Economic Analysis
[4] You et al., 2008, Economic Cost Analysis of Biodiesel Production: Case in Soybean Oil
(NAPAT)
Inherent Safety
[5] AnnaMari Heikkilä: Inherent safety in process plant design: An index-based approach
IChem E Analysis
[6] The Sustainability Metrics, Sustainable Development, Progress Metrics recommended for
use in the Process Industries
EPA WAR GUI:
[7] American Meteorological Society, A look at U.S. Air Pollution Laws and their Amendments,
http://www.ametsoc.org/ams/sloan/cleanair/ (18 July 2002).
[8] Ozone standards, United States, Environmental Protection Agency, Areas Violating the 8-
Hour Ozone Standard, http://www.epa.gov/ARD-R5/naaqs/8o3_nmap.htm (1 April
2001).
Ethanol crops
[9] Energy Crops and Their Potential Development in Michigan, Michigan Biomass Energy
Program, August, 2002
[10] National Directory of Federal and State Biomass Tax Incentives and Suhsidies, Gregory
Sanderson and Southeastern Regional Biomass Energy Program (1994).
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[11] United States, Department of Agriculture, 1997 National Resources Inventory, (1999), p.
20.
[12] Environmental Considerations in Energy Crop Production, J. W. Ranney and L. K. Mann,

Biomass & Bioenergy Vol. 6, No.3, (1994): p. 216.
[13] National Resources Inventory, pg. 7 & 61., United States, Department of Agriculture, 1997
[14] Environmental Law & Policy Center, Repowering the Midwest: The Clean Energy
Development Plan for the Heartland, (2001), p. 6.
[15] Western Regional Biomass Energy Program, “Environmental Issues,” p. 3; J. Cooper,

Policy Considerations for Biomass Commercialization and its Impact on the Chariton
Valley Biomass Project, (Madison: Bioenergy „98 Conference Proceedings), p. 31.
[16] National Renewable Energy Laboratory, Choices for a Brighter Future, p. 1.
Sustainability:
[17] Clean Fuels Development Coalition, Clean Fuels: Paving the Way for America‟s Future,
Bethesda: Clean Fuels Development Coalition, 1995
Incentives:
[18] United States, Department of Energy, State Alternative Fuel Laws and Incentives,
(Washington: Office of Energy Efficiency and Renewable Energy, 1994).
[19] United States, Environmental Protection Agency, Biomass Executive Order: Developing
and Promoting Biobased Products and Bioenergy,
http://www.epa.gov/g...leanenergy/biomoass/eo_biomass.html (29 September 2000)
[20] United States, Department of Energy, Renewable Energy Production Incentive,

http://www.eren.doe.gov/power/repi.html (18 October 2001).
Deep Eutectic Solvents
[21] Ionic Liquid Supported Acid/Base-Catalyzed Production of Biodiesel, Alexandre A. M.

Lapis, Dr., Luciane F. de Oliveira, Dr. , Brenno A. D. Neto, Prof. Dr. , Jairton Dupont,
Prof. Dr., Green Chem., 2007, 9, 868 - 872, DOI: 10.1039/b702833d
[22] Extraction of glycerol from biodiesel into a eutectic based ionic liquid, Andrew P. Abbott,
Paul M. Cullis, Manda J. Gibson, Robert C. Harris and Emma Raven, www.rsc.org
[23] An Alternative Nonvolatile Solvent to Dissolve Metals: The Mixture of Choline Chloride
and Urea. DORRA KRIDIS ( The Cooper Union for the Advancement of Sciences and
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Art, New York, NY10003) MARK FUHRMANN (Brookhaven National Laboratory,
Upton, NY 11973).
Catalysts
[24] Process optimization of biodiesel production using alkaline catalysts, A. Singh, B. He, J.
Thompson, J.Van Gerpen, Applied Engineering in Agriculture, American Society of
Agriculture and biological engineers Vol. 22(4): 587:600
Gel Temperature:
[25] Use of branched-chain esters to reduce the crystallization temperature of biodiesel,

Inmok Lee, Lawrence A. Johnson and Earl G. Hammond, Iowa State University,
50011 Ames, Iowa, 1995
[26] Improving the low temperature properties of biodiesel fuel, Purnanand Vishwanathrao
Bhale, Nishikant V. Deshpande and Shashikant B. Thombre
Other
[27] Biodiesel Production, Vernon R. Eidman, Journal of Agriculture and Applied Economics,
39,2 (August 2007)
[28] Technology Solutions: Biodiesel boom creates glut of glycerin, Erika Englehaupt, Environ.
Sci. Technol., 2007, 41 (15), p 5175 DOI: 10.1021/es0725910 Publication Date (Web):
August 1,2007
[29] Zero Waste Biodiesel: Using Glycerin And Biomass To Create Renewable Energy, Sean
Brady, Kawai Tam Coauthors: Gregory Leung, Christopher Salam. Department of
Chemical and Environmental Engineering University of California, Riverside
[30] Biodiesel Use in Engines, Vern Hofman, Dennis Wiesenborn, Michael Rosendahlm Jason
Webster, NSSU Extension Service, North Dakota State Univeristy, January 2006
Page 45 of 80
Appendix A - Full Stream Data and Large Process Images
Figure 24 - Alkali-catalyzed Process Using Methanol
Table 19 - Stream Data for Alkali-catalyzed Process Using Methanol Producing 500 kg/hr
Unit 101 103 101A 101B 102 105B 105A 105 v1 106 201
Temperature C 25 25 25.00067 25.13398 27.18548 60 26.94912 25 60 60 28.19579
Pressure kPa 100 100 100 400 395 400 400 100 395 395 20
Mass Flow kg/h 58.63668 4.999639 63.63632 63.63632 174.8375 526.8321 526.8321 526.8321 0 701.6695 111.1845
Triolein 0 0 0 0 0 1 1 1 0.037811 0.037541 0
Methanol 1 0 0.921434 0.921434 0.971404 0 0 0 0.165793 0.164611 1
M-Oleate 0 0 0 0 0 0 0 0 0.721674 0.716532 0
Glycerol 0 0 0 0 0 0 0 0 0.074722 0.07419 0
Sodium Hydroxide* 0 1 0.078566 0.078566 0.028596 0 0 0 0 0.007125 0
H2O 0 0 0 0 0 0 0 0 0 0 0
Phosphoric acid* 0 0 0 0 0 0 0 0 0 0 0
Trisodium phosphate* 0 0 0 0 0 0 0 0 0 0 0
Unit 202 201A 1201 202A 203 water 301 302 301A 301B 303
Temperature C 113.9852 28.37256 28.37256 114.0976 60 25 50 60 60 60 1.955671
Pressure kPa 30 395 395 200 120 110 110 120 110 120 120
Mass Flow kg/h 590.485 111.1845 111.2011 590.485 590.485 5.539643 531.9334 64.09128 531.9334 0 64.09128
Triolein 0.04461 0 0 0.04461 0.04461 0 0.049456 0.000537 0.049456 0 0.000537
Methanol 0.007313 1 1 0.007313 0.007313 0 0.004818 0.027389 0.004818 0 0.027389
M-Oleate 0.851451 0 0 0.851451 0.851451 0 0.945169 0.000028 0.945169 0 0.000028
Glycerol 0.088159 0 0 0.088159 0.088159 0 0 0.812228 0 1 0.812228
Sodium Hydroxide* 0.008467 0 0 0.008467 0.008467 0 0 0.078008 0 0 0.078008
H2O 0 0 0 0 0 1 0.000557 0.081811 0.000557 0 0.081811
Phosphoric acid* 0 0 0 0 0 0 0 0 0 0 0
Unit H3PO4 v2 304 305 306 501 502 401A 401 402
Temperature C 60 60 60 60 60 61.66437 263.3066 196.3723 196.3723 522.936
Pressure kPa 120 110 110 110 109 40 50 10 10 20
Mass Flow kg/h 4.0817 0 68.17274 61.68345 6.489292 9.134098 52.54935 5.62594 500 26.30748
Triolein 0 0 0.000025 0.000028 0 0 0.000033 0 0 0.999989
Methanol 0 0.901736 0.025697 0.0284 0 0.19179 0 0.436191 0.000218 0
M-Oleate 0 0 0.000508 0.000561 0 0 0.000659 0.516618 0.999721 0.000011
Glycerol 0 0.000096 0.76365 0.843988 0 0 0.99069 0 0 0
Sodium Hydroxide* 0 0 0.003667 0.004053 0 0 0.004757 0 0 0
H2O 0 0.098168 0.108293 0.119686 0 0.80821 0.000007 0.047192 0.000062 0
Phosphoric acid* 1 0 0.002971 0.003283 0 0 0.003854 0 0 0
Trisodium phosphate* 0 0 0.095189 0 1 0 0 0 0 0
Page 47 of 80
Unit 101 103 101A 101B 102 105B 105A 105 v1 106 201
Temperature C 25 25 25.00067 25.13398 26.6352 60 26.94912 25 60 60 28.19579
Pressure kPa 100 100 100 400 395 400 400 100 395 395 20
Mass Flow kg/h 117.2734 9.999277 127.2726 127.2726 238.4738 1053.664 1053.664 1053.664 0 1292.138 111.1789
Triolein 0 0 0 0 0 1 1 1 0 0.040772 0
Methanol 1 0 0.921434 0.921434 0.95807 0 0 0 0.999984 0.092718 1
M-Oleate 0 0 0 0 0 0 0 0 0.000006 0.778197 0
Glycerol 0 0 0 0 0 0 0 0 0.00001 0.080575 0
H2O 0 0 0 0 0 0 0 0 0 0 0
Phosphoric acid* 0 0 0 0 0 0 0 0 0 0 0
Unit 202 201A 1201 202A 203 water 301 302 301A 301B 303
Temperature C 114.0296 28.37256 28.37256 114.1424 60 25 59.21506 60.00062 60 60 60.00069
Pressure kPa 30 395 395 200 120 110 110 120 110 120 120
Mass Flow kg/h 1180.959 111.1789 111.2011 1180.959 1180.959 11.07929 1063.202 128.8359 1063.202 0 128.8359
Triolein 0.044611 0 0 0.044611 0.044611 0 0.049427 0.001027 0.049427 0 0.001027
Methanol 0.007304 1 1 0.007304 0.007304 0 0.003856 0.035124 0.003856 0 0.035124
M-Oleate 0.851459 0 0 0.851459 0.851459 0 0.945744 0.000155 0.945744 0 0.000155
Glycerol 0.08816 0 0 0.08816 0.08816 0 0 0.808108 0 1 0.808108
H2O 0 0 0 0 0 1 0.000972 0.077972 0.000972 0 0.077972
Phosphoric acid* 0 0 0 0 0 0 0 0 0 0 0
Unit H3PO4 v2 304 305 306 501 502 401A 401 402
Temperature C 60 60 60 60 60 59.56967 263.3458 185.1412 185.1412 360.6182
Pressure kPa 120 110 110 110 109 40 50 10 10 20
Mass Flow kg/h 8.1634 0 136.9988 124.0203 12.97858 18.83937 105.1809 7.819739 1000.001 55.38204
Triolein 0 0 0.000048 0.000053 0 0 0.000063 0 0 0.948879
Methanol 0 0.922216 0.032932 0.036378 0 0.239478 0 0.493595 0.00024 0
M-Oleate 0 0 0.001068 0.00118 0 0 0.001391 0.393114 0.999612 0.051121
Glycerol 0 0.000077 0.760054 0.839592 0 0.000189 0.989941 0 0 0
H2O 0 0.077707 0.104557 0.115499 0 0.760333 0 0.113291 0.000148 0
Phosphoric acid* 1 0 0.002957 0.003266 0 0 0.003851 0 0 0
Page 48 of 80
Unit 101 103 101A 101B 102 105B 105A 105 v1 106 201
Temperature C 25 25 25.00067 25.13398 26.31768 60 26.94912 25 60 60 28.19579
Pressure kPa 100 100 100 400 395 400 400 100 395 395 20
Mass Flow kg/h 175.91 14.99892 190.909 190.909 302.1101 1580.496 1580.496 1580.496 0 1882.606 111.2159
Triolein 0 0 0 0 0 1 1 1 0.042313 0.041976 0
Methanol 1 0 0.921434 0.921434 0.950353 0 0 0 0.066452 0.065922 1
M-Oleate 0 0 0 0 0 0 0 0 0.807614 0.80118 0
Glycerol 0 0 0 0 0 0 0 0 0.08362 0.082954 0
H2O 0 0 0 0 0 0 0 0 0 0 0
Phosphoric acid* 0 0 0 0 0 0 0 0 0 0 0
Unit 202 201A 1201 202A 203 water 301 302 301A 301B 303
Temperature C 114.1318 28.37256 28.37256 114.2438 60 25 59.21492 60.00018 60 60 60.00026
Pressure kPa 30 395 395 200 120 110 110 120 110 120 120
Mass Flow kg/h 1771.39 111.2159 111.2011 1771.39 1771.39 16.61893 1594.783 193.2267 1594.783 0 193.2267
Triolein 0.044612 0 0 0.044612 0.044612 0 0.049428 0.001022 0.049428 0 0.001022
Methanol 0.007277 1 1 0.007277 0.007277 0 0.003844 0.034985 0.003844 0 0.034985
M-Oleate 0.851482 0 0 0.851482 0.851482 0 0.945757 0.000155 0.945757 0 0.000155
Glycerol 0.088162 0 0 0.088162 0.088162 0 0 0.808222 0 1 0.808222
H2O 0 0 0 0 0 1 0.000971 0.077993 0.000971 0 0.077993
Phosphoric acid* 0 0 0 0 0 0 0 0 0 0 0
Unit H3PO4 v2 304 305 306 501 502 401A 401 402
Temperature C 60 60 60 60 60 59.59958 263.3396 160.9465 160.9465 336.2895
Pressure kPa 120 110 110 110 109 40 50 10 10 20
Mass Flow kg/h 12.2451 0 205.4711 186.0032 19.46788 28.22757 157.7756 7.82138 1499.998 86.96332
Triolein 0 0 0.000048 0.000053 0 0 0.000063 0 0 0.906443
Methanol 0 0.921934 0.032801 0.036234 0 0.238759 0 0.700943 0.000432 0
M-Oleate 0 0 0.001063 0.001174 0 0 0.001384 0.150814 0.999309 0.093557
Glycerol 0 0.000078 0.760154 0.839715 0 0 0.989948 0 0 0
H2O 0 0.077989 0.10458 0.115526 0 0.761241 0.000001 0.148242 0.000259 0
Phosphoric acid* 1 0 0.002957 0.003267 0 0 0.003851 0 0 0
Page 49 of 80
Unit 101 103 101A 101B 102 105B 105A 105 v1 106 201
Temperature C 25 25 25.00067 25.13398 26.11103 60 26.94912 25 60 60 28.19579
Pressure kPa 100 100 100 400 395 400 400 100 395 395 20
Mass Flow kg/h 234.5467 19.99856 254.5453 254.5453 365.7464 2107.328 2107.328 2107.328 0 2473.075 111.205
Triolein 0 0 0 0 0 1 1 1 0.042953 0.042605 0
Methanol 1 0 0.921434 0.921434 0.945321 0 0 0 0.052346 0.051922 1
M-Oleate 0 0 0 0 0 0 0 0 0.819818 0.813188 0
Glycerol 0 0 0 0 0 0 0 0 0.084884 0.084198 0
H2O 0 0 0 0 0 0 0 0 0 0 0
Phosphoric acid* 0 0 0 0 0 0 0 0 0 0 0
Trisodium 0 0 0 0 0 0 0 0 0 0 0
phosphate*
Unit 202 201A 1201 202A 203 water 301 302 301A 301B 303
Temperature C 114.0666 28.37256 28.37256 114.1787 60 25 59.21504 59.99969 60 60 59.99976
Pressure kPa 30 395 395 200 120 110 110 120 110 120 120
Mass Flow kg/h 2361.87 111.205 111.2011 2361.87 2361.87 22.15857 2126.384 257.6448 2126.384 0 257.6448
Triolein 0.044611 0 0 0.044611 0.044611 0 0.049428 0.001024 0.049428 0 0.001024
Methanol 0.007283 1 1 0.007283 0.007283 0 0.003847 0.03502 0.003847 0 0.03502
M-Oleate 0.851476 0 0 0.851476 0.851476 0 0.945754 0.000155 0.945754 0 0.000155
Glycerol 0.088162 0 0 0.088162 0.088162 0 0 0.808193 0 1 0.808193
H2O 0 0 0 0 0 1 0.000971 0.077988 0.000971 0 0.077988
Phosphoric acid* 0 0 0 0 0 0 0 0 0 0 0
Trisodium 0 0 0 0 0 0 0 0 0 0 0
phosphate*
Unit H3PO4 v2 304 305 306 501 502 401A 401 402
Temperature C 60 60 60 60 60 59.70562 263.3375 134.5358 134.5357 329.2866
Pressure kPa 120 110 110 110 109 40 50 10 10 20
Mass Flow kg/h 16.3268 0 273.9706 246.6582 27.3124 38.0922 208.566 7.821758 1999.977 118.5846
Triolein 0 0 0.000048 0.000053 0 0 0.000063 0 0 0.88631
Methanol 0 0.92138 0.032833 0.036469 0 0.236148 0 0.822044 0.000875 0
M-Oleate 0 0 0.001064 0.001182 0 0 0.001398 0.034097 0.998655 0.11369
Glycerol 0 0.000078 0.760129 0.844297 0 0 0.998499 0 0 0
H2O 0 0.078542 0.106205 0.117966 0 0.763852 0.000002 0.143859 0.00047 0
Phosphoric acid* 1 0 0 0 0 0 0 0 0 0
Trisodium 0 0 0.099691 0 1 0 0 0 0 0
phosphate*
Page 50 of 80
Figure 25 - Alkali-catalyzed Process Using Methanol With Cooler and HEN Modification
Table 23 - Stream Data for Alkali-catalyzed Process Using Methanol With Cooler and HEN Modification
Unit 101 103 101A 101B 102 105B 105A 105 v1 106 201
Temperature C 25 25 25.00067 25.13398 26.6352 60 25 23.05339 60 60 28.19579
Pressure kPa 100 100 100 400 395 400 400 100 395 395 20
Mass Flow kg/h 117.2734 9.999277 127.2726 127.2726 238.4738 1053.664 1053.664 1053.664 0 1292.138 111.1837
Triolein 0 0 0 0 0 1 1 1 0 0.040772 0
Methanol 1 0 0.921434 0.921434 0.95807 0 0 0 0.999984 0.092718 1
M-Oleate 0 0 0 0 0 0 0 0 0.000006 0.778197 0
Glycerol 0 0 0 0 0 0 0 0 0.00001 0.080575 0
H2O 0 0 0 0 0 0 0 0 0 0 0
Phosphoric acid* 0 0 0 0 0 0 0 0 0 0 0
Unit 201A 1201 202A 203 water 301 302 301A 301B 303 H3PO4
Temperature C 28.37256 28.37256 114.1655 60 25 59.21462 60.00023 60 60 60.00031 60
Pressure kPa 395 395 200 200 110 110 120 110 120 120 120
Mass Flow kg/h 111.1837 111.2011 1180.954 1180.954 11.07929 1063.2 128.8333 1063.2 0 128.8333 8.1634
Triolein 0 0 0.044611 0.044611 0 0.049427 0.001027 0.049427 0 0.001027 0
Methanol 1 1 0.0073 0.0073 0 0.003855 0.035104 0.003855 0 0.035104 0
M-Oleate 0 0 0.851462 0.851462 0 0.945746 0.000155 0.945746 0 0.000155 0
Glycerol 0 0 0.08816 0.08816 0 0 0.808125 0 1 0.808125 0
Sodium Hydroxide* 0 0 0.008467 0.008467 0 0 0.077614 0 0 0.077614 0
H2O 0 0 0 0 1 0.000972 0.077975 0.000972 0 0.077975 0
Phosphoric acid* 0 0 0 0 0 0 0 0 0 0 1
Unit 304 305 306 501 502 401A 401 402 306S 202B 202
Temperature C 60 60 60 59.56245 262.409 185.164 185.164 360.6392 25 112.3524 114.0519
Pressure kPa 110 110 109 40 50 10 10 20 100 200 30
Mass Flow kg/h 136.9962 124.0176 12.97858 18.81198 105.2056 7.82002 999.9995 55.38065 12.97858 1180.954 1180.954
Triolein 0.000048 0.000053 0 0 0.000063 0 0 0.948904 0 0.044611 0.044611
Methanol 0.032912 0.036357 0 0.239681 0 0.493335 0.00024 0 0 0.0073 0.0073
M-Oleate 0.001067 0.001179 0 0 0.00139 0.393398 0.999612 0.051096 0 0.851462 0.851462
Glycerol 0.760068 0.83961 0 0 0.989742 0 0 0 0 0.08816 0.08816
Sodium Hydroxide* 0.003649 0.004031 0 0 0.004752 0 0 0 0 0.008467 0.008467
H2O 0.104561 0.115503 0 0.760319 0.000203 0.113267 0.000148 0 0 0 0
Phosphoric acid* 0.002957 0.003266 0 0 0.00385 0 0 0 0 0 0
Trisodium phosphate* 0.094737 0 1 0 0 0 0 0 1 0 0
Page 52 of 80
Figure 26 - Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea and KOCH3 Modification
Table 24 - Stream Data for Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea and KOCH3 Modification
Unit 101 105 101A 105A 105B 102 v1 106 201 202 202A
Temperature C 25 25 25.0559 26.9491 50 22.7302 50 50 20.1724 99.2844 99.3960
Pressure kPa 100 100 100
1 400
2 400 100
5 100 100 20
7 30
6 200
1
Mass Flow kg/h 127.26 1050 127.330 1050 1050 261.278 0 1311.27 134.098 1177.18 1177.18
Triolein 0 1 01 1 1 06 0.00800 0.00800
9 0 0.00892
1 0.00892
1
M-Oleate 0 0 0 0 0 0 0.79638
7 0.79638
7 0 0.88709 0.88709
Glycerol 0 0 0 0 0 0 0.08242 0.08242 0 0.09180
9 0.09180
9
Methanol 1 0 0.99944 0 0 0.91118 0.09549 0.09549 0.82699 0.01216
9 0.01216
9
Choline Chloride/ 0 0 09 0 0 07 06 06 02 08 08
KOCH3*
Urea* 0 0 0.00055 0 0 0.08881 0.01769 0.01769 0.17300 0.00000 0.00000
1 Page 53 of 80 3 6 6 8 4 4
Unit 202B choline chloride / 301 302 303 304 401 402 201A 1201 103
Temperature C 50 50
urea 40 50 50 50 43.6919 263.403 20.2138 20.2279 25
Pressure kPa 200 120 110 120 120 120 40
7 50 100
6 100 100
Mass Flow kg/h 1177.18 2.5 1052.67 127.004 124.504 2.5 16.5051 107.999 134.098 133.948 0.07012
Triolein 0.00892
1 0 0.00298
6 0.01653
9 0.01686
9 0 06 0.01944
7 0 05 0
M-Oleate 0.88709 0 0.99702 05 07 0 0 04 0 0 0
Glycerol 0.09180
9 0 0 0.85096 0.86804 0 0.13186 0.98055 0 0 0
Methanol 0.01216
9 0 0 0.11278 0.11504
7 0 0.86784
1 06 0.82699 0.82728 0
Choline Chloride/ 08 1 0 0.01968
2 07 1 03 0 02 06 0
KOCH3*
Urea* 0.00000 0 0 0.00003
4 0.00003 0 0.00029 0 0.17300 0.17271 1
4 8 9 5 8 4
Figure 27 - Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea, KOCH3, and HEN Modification
Page 54 of 80
Table 25 - Stream Data for Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea, KOCH3, and HEN Modification
Unit 101 105 101A 103 105A 105B 102 106 201 202 1201
Temperature C 100 25 99.97864 25 26.9491 50 62.9021 50 20.1784 99.7053 20.2412
Pressure kPa 100 100 100 100 400
2 400 100 100 20
9 30
6 100
Mass Flow kg/h 126.94 1050 127.0101 0.07012 1050 1050 261.186 1311.18 134.205 1176.98 134.176
Triolein 0 1 0 0 1 1 01 0.00800
6 03 0.00892
1 0
M-Oleate 0 0 0 0 0 0 0 0.79643
8 0 0.88725
1 0
Glycerol 0 0 0 0 0 0 0 0.08242
6 0 0.09182 0
Methanol 1 0 0.999448 0 0 0 0.91115 0.09543
6 0.82712 0.012
5 0.82757
Choline Chloride/ 0 0 0 0 0 0 05 02 09 0 08
KOCH3*
Urea* 0 0 0.000552 1 0 0 0.08884 0.01769 0.17287 0.00000 0.17242
5 8 1 4 2
Unit 202A 202B choline chloride / 301 302 303 304 401 402 202_A1 201A
Temperature C 98.6331 50 50
urea 40 50 50 50 42.5612 263.386 98.5215 20.2198
Pressure kPa 200
6 200 120 110 120 120 120 40 50
5 30
7 100
7
Mass Flow kg/h 1176.98 1176.98 2.5 1052.67 126.805 124.305 2.5 14.1288 110.176 1176.98 134.205
Triolein 0.00892
1 0.00892
1 0 0.00798
6 0.01656 0.01689 0 06 0.01906
2 0.00892
1 03
M-Oleate 0.88725
1 0.88725
1 0 0.99202 01 04 0 0 0 0.88725
1 0
Glycerol 0.09182 0.09182 0 0 0.85230 0.86944 0 0 0.98093 0.09182 0
Methanol 0.012
5 0.012
5 0 0 0.11138
1 0.11362
3 0 0.99965 0.00000
9 0.012
5 0.82712
Choline Chloride/ 0 0 1 0 0.01971
4 05 1 09 01 0 09
KOCH3*
Urea* 0.00000 0.00000 0 0 0.00003
5 0.00003 0 0.00034 0 0.00000 0.17287
4 4 8 9 1 4 1
Page 55 of 80
Figure 28 - Alkali-catalyzed Process Using Ethanol
Table 26 - Stream Data for Alkali-catalyzed Process Using Ethanol
Unit 2 2a 1d 1e 3 vapor 4 1a 1b 1c 5 9
Temperature C 25 25 25 41.78382 40.78808 70 70 25 25 25 78.17196 60.31282
Pressure kPa 101.3 101.3 101.3 101.3 101.3 101.3 101.3 101.3 101.3 101.3 101.325 101.325
Mass Flow kg/h 1000 1000 322.8 610.3696 1610.37 0 1610.388 312.9 9.9 322.8 287.5165 287.5165
CetylC1cryla 0 0 0 0 0 0.000024 0.653212 0 0 0 0 0
Triolein 1 1 0 0 0.620975 0 0.000103 0 0 0 0 0
Ethanol 0 0 0.969331 0.98378 0.372877 0.999968 0.27596 1 0 0.969331 1 1
NaOH 0 0 0.030669 0.01622 0.006148 0 0.006148 0 1 0.030669 0 0
H2O 0 0 0 0 0 0 0 0 0 0 0 0
Glycerol 0 0 0 0 0 0.000008 0.064577 0 0 0 0 0
Page 56 of 80
Unit 10 13 14 6 6a 11 12
Temperature C 60.31616 78.48236 295.26 102.0929 61.7034 30 90.08969
Pressure kPa 101.325 101 101 101.325 101.325 101 101
Mass Flow kg/h 287.5696 161.7798 109 1322.871 1322.871 1052.091 270.7802
CetylC1cryla 0 0 0 0.795183 0.795183 0.999842 0
Triolein 0 0 0 0.000126 0.000126 0.000158 0
Ethanol 1 0.969751 0 0.118595 0.118595 0 0.579385
NaOH 0 0 0.090825 0.007484 0.007484 0 0.036561
H2O 0 0 0 0 0 0 0
Glycerol 0 0.030249 0.909175 0.078612 0.078612 0 0.384054
Figure 29 - Alkali-catalyzed Process Using Ethanol Recovery Modification
Page 57 of 80
Table 27 - Stream Data for Alkali-catalyzed Process Using Ethanol Recovery Modification
Uni 2 2a 1d 1e 3 vapor 4 1a 1b 1c 5 9
Temperature C
t 25 25 25 55.40179 53.63448 70 70 25 25 25 78.090801 60.236408
Pressure kPa 101. 101. 101.3 101
3 101
8 101 101 101.3 101.3 101.3 101 101
Mass Flow kg/ 1000
3 1000
3 166.07083 610.3 1610.3 0 1610.31833 156.17083 9.9 166.07083 287.62857 287.62857
CetylC1cryl h 0 0 03 0 0 0.00002 0.653241
2 03 0 03 05 05
Triolein
a 1 1 0 0 0.621002 04 0.000103 0 0 0 0 0
Ethanol 0 0 0.940387 0.983778 0.37285 0.99996 0.275929 1 0 0.940387 1 1
NaOH 0 0 0.059613 0.016222 0.006148 08 0.006148 0 1 0.059613 0 0
H2O 0 0 0 0 0 0 0 0 0 0 0 0
Glycerol 0 0 0 0 0 0.00000 0.06458 0 0 0 0 0
8
Uni 10 13 14 6a 11 12 13a 13b 6 13a1
Temperature C
t 60.2 78.4 295.25979 61.62917 30 90.0844 78.090801 276.00524 102 78.090801
Pressure kPa 101
3 101
8 101
6 101
2 101 101
3 101 101
7 101 101
Mass Flow kg/ 287. 161. 109 1322.689 1052.091 270.598 156.698016 4.900494 1323 156.70665
CetylC1cryl h 05 06 0 0.795292
8 0.999842
3 04 0 0 0.795 02
Triolein
a 0 0 0 0.000126 0.000158 0 0 0 1E-04 0
Ethanol 1 0.97 0 0.118474 0 0.57910 1 0.001291 0.118 1
NaOH 0 0 0.090826 0.007485 0 0.03658
3 0 0 0.007 0
H2O 0 0 0 0 0 06 0 0 0 0
Glycerol 0 0.03 0.909174 0.078623 0 0.38431 0 0.998709 0.079 0
2
Page 58 of 80
Figure 30 - Non-catalytic Process Operated at Supercritical Condition of Methanol
Table 28 - Stream Data for Non-catalytic Process Operated at Supercritical Condition of Methanol
Unit 102 101 101A 102A 101B 103 201 202 203
Temperature C 24.854068 15.212473 -8.994137 37.98 -8.076586 -6.97251 300 250.593694 183.5
Pressure kPa 10 10 10 2000 2000 2000 2000 2000 2000
Mass Flow kg/h 1282 139 1947.773778 1282 1947.773778 3229.773778 3229.773778 3229.825966 3229.825966
Liquid Volume m3/h 1.399632 0.174685 2.447813 1.399632 2.447813 3.847445 3.847445 3.847395 3.847395
Triolein
Flow 1 0 0 1 0 0.396932 0.396932 0.018077 0.018077
Methanol 0 1 1 0 1 0.603068 0.603068 0.561929 0.561929
M-Oleate 0 0 0 0 0 0 0 0.380589 0.380589
Glycerol 0 0 0 0 0 0 0 0.039405 0.039405
n-Decane 0 0 0 0 0 0 0 0 0
Page 59 of 80
Unit 204 205 206 301 302 301B 301A 303 304
Temperature C 172.481008 150.752821 66.50435 - 94.346443 -10.868611 -10.868611 98.848423 60
Pressure kPa 1500 800 10 210.872296 3 10 10 10 10
Mass Flow kg/h 3229.82597 3229.82597 3229.825966 1808.8122 1421.01374 1808.773778 1808.812226 1290.071012 130.942727
Liquid Volume m3/h 3.847395 3.847395 3.847395 2.273177 1.574218 2.273129 2.273177 1.468657 0.105561
Triolein
Flow 0.018077 0.018077 0.018077 0 0.041088 0 0 0.045258 0
Methanol 0.561929 0.561929 0.561929 1 0.004308 1 1 0.001898 0.028049
M-Oleate 0.380589 0.380589 0.380589 0 0.865042 0 0 0.952844 0
Glycerol 0.039405 0.039405 0.039405 0 0.089563 0 0 0 0.971951
n-Decane 0 0 0 0 0 0 0 0 0
Unit 401A 401 402 501 502 601 602 603 604
Temperature C 179.521496 179.521496 435.646591 - 176.227602 25 28.39215 360 360
Pressure kPa 1 1 2 111.135984 2 1000 5000 5000 5000
Mass Flow kg/h 19.42799 1212.25703 58.38599 10.542701 120.400027 7920 7920 7920 2500
Liquid Volume m3/h 0.022429 1.382485 0.063743 0.010065 0.095496 10.809025 10.809025 10.809025 3.41194
Triolein
Flow 0 0 0.999999 0 0 0 0 0 0
Methanol 0.120774 0.000084 0 0.348379 0 0 0 0 0
M-Oleate 0.879226 0.999916 0.000001 0 0 0 0 0 0
Glycerol 0 0 0 0.651621 1 0 0 0 0
n-Decane 0 0 0 0 0 1 1 1 1
Unit 605 606 607 608

Temperature C 360 165.113945 238.13535 278.68784
Pressure kPa 5000 5000 5000 5000
Mass Flow kg/h 5420 5420 5420 7920
Liquid Volume m3/h 7.397086 7.397086 7.397086 10.809025
Triolein
Flow 0 0 0 0
Methanol 0 0 0 0
M-Oleate 0 0 0 0
Glycerol 0 0 0 0
n-Decane 1 1 1 1
Page 60 of 80
Figure 31 - Non-catalytic Process Operated at Supercritical Condition of Methanol with Water HEN Modification
Table 29 - Stream Data for Non-catalytic Process Operated at Supercritical Condition of Methanol with Water HEN Modification
Unit 102 101 101A 102A 101B 103 201 202 203 204 205 206
Temperature C 24.85407 15.21247 -8.99417 37.98 -8.07662 -6.97257 300 250.5941 183.5 172.481 150.7529 66.50517
Pressure kPa 10 10 10 2000 2000 2000 2000 2000 2000 1500 800 10
Mass Flow kg/h 1282 139 1947.812 1282 1947.812 3229.812 3229.812 3229.864 3229.864 3229.864 3229.864 3229.864
Triolein 1 0 0 1 0 0.396927 0.396927 0.018078 0.018078 0.018078 0.018078 0.018078
Methanol 0 1 1 0 1 0.603073 0.603073 0.561935 0.561935 0.561935 0.561935 0.561935
M-Oleate 0 0 0 0 0 0 0 0.380584 0.380584 0.380584 0.380584 0.380584
Glycerol 0 0 0 0 0 0 0 0.039404 0.039404 0.039404 0.039404 0.039404
H2O 0 0 0 0 0 0 0 0 0 0 0 0
Page 61 of 80
Unit 301 302 301B 301A 303 304 401A 401 501 502 601 602
Temperature C -10.8723 94.16359 -10.8686 -10.8686 98.64366 60 187.3731 187.3731 -11.1837 176.2276 25 25.37684
Pressure kPa 2 3 10 10 10 10 1 1 1 2 1000 5000
Mass Flow kg/h 1808.814 1421.05 1808.812 1808.814 1290.086 130.9646 42.54897 1189.147 10.56457 120.4 1150 1150
Triolein 0 0.041089 0 0 0.04526 0 0 0 0 0 0 0
Methanol 1 0.004334 1 1 0.001909 0.028214 0.056615 0.000046 0.349761 0 0 0
M-Oleate 0 0.865017 0 0 0.952831 0 0.943385 0.999954 0 0 0 0
Glycerol 0 0.08956 0 0 0 0.971786 0 0 0.650239 1 0 0
H2O 0 0 0 0 0 0 0 0 0 0 1 1
Unit 603 604 607 402

Temperature C 320 -2.19869 235.4331 435.4639
Pressure kPa 5000 5000 5000 2
Mass Flow kg/h 1150 1150 1150 58.38986
Triolein 0 0 0 0.999989
Methanol 0 0 0 0
M-Oleate 0 0 0 0.000011
Glycerol 0 0 0 0
H2O 1 1 1 0
Figure 32 - Non-catalytic Process Operated at Supercritical Condition of Methanol with Heater/Cooler Modification
Page 62 of 80
Table 30 - Stream Data for Non-catalytic Process Operated at Supercritical Condition of Methanol with Heater/Cooler Modification
Unit 102 101 101A 102A 101B 103 201 202 203 204 205 206
Temperature C 24.85407 15.21247 -8.99414 37.98 -8.07659 -6.97251 300 250.6075 183.5 172.481 150.7528 66.50428
Pressure kPa 10 10 10 2000 2000 2000 2000 2000 2000 1500 800 10
Mass Flow kg/h 1282 139 1947.774 1282 1947.774 3229.774 3229.774 3229.826 3229.826 3229.826 3229.826 3229.826
Triolein 1 0 0 1 0 0.396932 0.396932 0.018079 0.018079 0.018079 0.018079 0.018079
Methanol 0 1 1 0 1 0.603068 0.603068 0.561929 0.561929 0.561929 0.561929 0.561929
M-Oleate 0 0 0 0 0 0 0 0.380587 0.380587 0.380587 0.380587 0.380587
Glycerol 0 0 0 0 0 0 0 0.039404 0.039404 0.039404 0.039404 0.039404
Unit 301 302 301B 301A 303 304 401A 401 402 501 502
Temperature C -10.8723 94.19785 -10.8686 -10.8686 98.68203 60 179.498 179.498 435.5754 -11.1769 176.2276
Pressure kPa 2 3 10 10 10 10 1 1 2 1 2
Mass Flow kg/h 1808.783 1421.043 1808.774 1808.783 1290.083 130.9602 19.49095 1212.2 58.39207 10.56016 120.4
Triolein 0 0.041091 0 0 0.045262 0 0 0 0.999995 0 0
Methanol 1 0.004329 1 1 0.001907 0.028183 0.120994 0.000084 0 0.349511 0
M-Oleate 0 0.86502 0 0 0.952831 0 0.879006 0.999916 0.000005 0 0
Glycerol 0 0.08956 0 0 0 0.971817 0 0 0 0.650489 1
Page 63 of 80
Appendix B - Raw Data
Economic
NAPAT
Process A - 500
Item Value ($)

Equipment
E-100 19900
E-201 19900
MIX-100A 0
MIX-100B 0
MIX-101 0
P-101B 3700
P-103 3600
P-201 3800
P-202 3600
R-101 31400
R-201 20900
RCY-1 0
T-100-tower 38000
T-201-tower 25100
T-201-cond 16400
T-201-cond acc 14700
T-201-reflux pump 4000
T-201-overhead split 0
T-201-bottoms split 0
T-201-reb 20600
T-401-tower 115100
T-401-cond 36500
T-401-reb 20600
T-501-tower 25600
T-501-cond 36500
T-501-reb 20700
X-301 0
X-302 0
Σ= Total bare module cost (TBMCC) 518000
Contingency fee (CF = 0.18TBMCC) 93240
Total basic module cost (TBMC = TBMCC+CF) 611240
Auxiliary facility investment (AFI = 0.3 × TBMC) 183372
Fixed capital investment (FCI = TBMC + AFI) 794612
Working capital investment (WCI = 0.15FCI) 119191.8
Total capital investment (TCI = FCI+WCI) 913803.8
Total raw material

Methanol 84441.6
NaOH 8000
Vegetable Oil 2107200
Water 88.64
H3PO4 11103.04
Operating labor 372101.2308
Supervisory and clerical labor (15% of operating labor) 55815.18463
Utilities
High Pressure Steam 360
Low Pressure Steam 87693.216
Cooling Water 6378.144
Waste disposal
Liquid 11096.4
Solid 2021.088
Maintenance and repairs (6% of FCI) 47676.72
Operating supplies (15% of maintenance and repairs) 7151.508
Laboratory charges (15% of operating labors) 55815.18463
Total manufacturing cost (TMC) 3770745.756
Patents and royalties (3% of TMC) 113122.3727
Σ = Total direct manufacturing cost (TDMC) 3883868.129
Overhead, packaging and storage (60% of the sum of operating labor, 285355.8813
supervision, and maintenance)
Local taxes (1.5% of FCI) 11919.18
Insurance (0.5% of FCI) 3973.06
Σ= Total indirect manufacturing cost (TIMC) 301248.1213
Annual depreciation change (ADC = 10% of FCI) 79461.2
General expenses
Page 65 of 80
Administrative costs (25% of overhead) 71338.97032
Distribution and selling cost (10% of total manufacturing cost) 418511.625
Research and development (5% of total manufacturing cost) 209255.8125
Σ= Total general expenses (TGE) 699106.4078
Total production cost (TPC = TDMC + TIMC + ADC + TGE) 4963683.858

Revenue from biodiesel and byproducts 4463168
Net annual profit (NAP = Revenue - TPC) -500515.8579
Income taxes (IT = 50% of NAP) -250257.9289
Net annual profit after taxes (NAPAT) -250257.9289
Break Even Point -19.8342721 year

s
For complete economic data see: Process A,C,F Economic Comparison.xlsx
Page 66 of 80
Environmental
Individual impact categories

Total output
rate of PEI
Case HTP HTPE (PEI/hr)
TTP ATP GW OD PC AP TOT
500 I
9.44 4.70E-03 9.44E-01 7.68 4.90P P5.1 OP
3.7 1.52 AL
2.59
1000 E-
2.22 1.10E-02 E- E- 6E-
2.22E+00 1.36 8.49 8.9 9.8 2E- E+0
2.63 E+0
5.00
1500 01
E+0
2.03 1.09E-02 2.03E+00 2.0001 1.20
E+0 01 06 4E-
E- 3E-
1.2 01
7.7 1
E+0
3.71 1
E+0
6.13
2000 2.300
E+0 1.38E-02 2.30E+00 2.71 0
E+0 1.7001
E+0 6E-06 01
1.7 0E-
7.1 1
E+0
5.26 1
E+0
8.17
1000H 1.910
E+0 4.81E-03 E+0
1.91E+00 3.38 0 1.08
E+00 9E-
05 7E-
1.1 01
9.5 1
E+0
3.35 1
E+0
2.08
EN
1000H 1.290
E+0 2.01E-03 1.29E-01 4.37 0 3.18
E- 0 4E-
E- 05 6E-
3.3 01
1.1 1
E+0
9.87 1
E+0
1.25
EN(DE 0 otal PEI leaving the system per
E- 01
E- 01 06 7E-
E- 5E- 01 0
E+0 1
E+0
S) 01 mass of products (PEI/kg 01 01 06 04 0 1
product)
Case HTP HTPE TTP ATP GW OD PC AP TOT
500 I
1.69 8.44E-06 1.69E-03 1.38 P
8.79 P9.2 OP
6.6 2.72 AL
4.65
1000 E-
2.01 1.00E-05 E-
2.01E-03 1.23 E-
7.69 5E-
8.0 7E-
8.9 E-
2.38 E-
4.53
1500 03
E-
1.16 6.23E-06 03
E-
1.16E-03 1.14 04
E-
6.84 09
9E-
7.2 04
1E-
4.4 02
E-
2.12 02
E-
3.51
2000 03
E-
9.88 5.94E-06 03
E-
9.88E-04 1.16 04
E-
7.29 09
0E-
7.6 04
0E-
3.0 02
E-
2.26 02
E-
3.50
1000H 03
E-
1.73 4.36E-06 1.73E-03 03
E-
3.06 04
E-
9.79 09
7E-
1.0 04
8E-
8.6 02
E-
3.03 02
E-
1.88
EN
1000H 04
E-
1.10 1.71E-06 03
E-
1.10E-04 3.71 04
E-
2.70 09
3E-
2.8 04
6E-
9.9 02
E-
8.38 02
E-
1.07
EN(DE 03
E- 04
E- 05
E- 09
4E- 04
1E- 03
E- 02
E-
S) 04 04 04 09 08 03 02
Case HTP HTPE TTP ATP GW OD PC AP TOT
1000 I
2.01 1.00E-05 2.01E-03 1.23 P
7.69 P8.0 OP
8.9 2.38 AL
4.53
1000H E-
1.73 4.36E-06 E-
1.73E-03 3.06 E-
9.79 9E-
1.0 1E-
8.6 E-
3.03 E-
1.88
EN
1000H 03
E-
1.10 1.71E-06 03
E-
1.10E-04 3.71 04
E-
2.70 09
3E-
2.8 04
6E-
9.9 02
E-
8.38 02
E-
1.07
EN(DE 03
E- 04
E- 05
E- 09
4E- 04
1E- 03
E- 02
E-
S) 04 04 04 09 08 03 02
For complete data see: ENVIRONMENTAL EMPACT REPORT(2)ii.xlsx
Inherent Safety
Process A - 500
Chemical inherent safety index, ICI Symbol Value Score

Heat of main reaction IRM <200 0
Heat of side reaction, max IRS N/A 0
Chemical interaction IINT Heat of formation 1
Flammability IFL 130C 1
Explosiveness IEX MeOH 7-36% 2
Toxic exposure ITOX MeOH 200 2
Page 67 of 80
Corrosiveness ICOR Stainless 1
Process inherent safety index, IPI
Inventory II 4,000 tons 1
Process temperature IT 529 C 3
Process pressure Ip 400 kPA 0
Equipment safety
Isbl IEQ Tower 1
Osbl N/A 0
Safe process structure IST Preferred 0
Total Inherent Safety 12
For complete data see: Inherent Safety.xlsx
IChemE Evaluation
Table 31 - IChemE Sustainability Process Reference Table
Process IChemE Reference

Number
Alkali-catalyzed Process Using Methanol With Cooler and HEN Modification 5
Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea and 6
KOCH3 Modification
Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea, KOCH3, 7
and HEN Modification
Alkali-catalyzed Process Using Ethanol 8
Alkali-catalyzed Process Using Ethanol Recovery Modification 9
Non-catalytic Process Operated at Supercritical Condition of Methanol 10
Non-catalytic Process Operated at Supercritical Condition of Methanol with Water 11
HEN Modification
Non-catalytic Process Operated at Supercritical Condition of Methanol with 12
Heater/Cooler Modification
Energy
Table 32 - IChemE Energy Comparison
1 2 3 4 5 6 7
Total Net Primary Energy Usage rate = 1.13E 1.90E 2.84E 3.88E 1.90E 5.39E 5.25E GJ
Imports – Exports +01 +01 +01 +01 +01 +00 +00 /y
Percentage Total Net Primary Energy 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E
sourced from renewable +00 +00 +00 +00 +00 +00 +00 %
Total Net Primary Energy Usage per 3.55E 4.21E 4.23E 4.13E 4.21E 1.55E 1.60E kJ/
Page 68 of 80
kg product -04 -04 -04 -04 -04 -03 -03 kg
Total Net Primary Energy Usage per 5.20E 6.79E 1.77E 2.87E 1.43E 1.48E 1.48E kJ/
unit value added +02 +05 +06 +06 +06 +06 +06 $
8 9 10 11 12
Total Net Primary Energy Usage rate = Imports 8.78E+ 1.03E+ 1.10E+ 7.55E+ 7.60E+ GJ/
– Exports 00 01 02 01 01 y
Percentage Total Net Primary Energy sourced 0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+
from renewable 00 00 00 00 00 %
9.57E- 8.13E- 8.79E- 1.28E- 1.27E- kJ/k

Total Net Primary Energy Usage per kg product 04 04 05 04 04 g
Total Net Primary Energy Usage per unit value 1.50E+ 1.51E+ 1.74E+ 1.74E+ 1.74E+
added 06 06 06 06 06 kJ/$
Raw Materials Excluding Fuel and Water
Table 33 - IChemE Raw Material Comparison
1 2 3 4 5 6 7
Total raw materials used per kg 3.36E 1.68E 1.12E 8.41E- 3.36E 1.70E 1.70E kg/
product +00 +00 +00 01 +00 +00 +00 kg
Total raw materials used per unit 2.08E 5.09E 1.33E 2.15E 1.08E 1.11E 1.11E kg/
value added +06 +02 +03 +03 +03 +03 +03 $
Fraction of raw materials recycled 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E kg/
within company +00 +00 +00 +00 +00 +00 +00 kg
Fraction of raw materials recycled 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E kg/
from consumers +00 +00 +00 +00 +00 +00 +00 kg
Hazardous raw material per kg 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E kg/
product +00 +00 +00 +00 +00 +00 +00 kg
8 9 10 11 12
Total raw materials used per kg product

1.46E+ 1.64E+ 2.14E- 1.41E+ 1.41E+ kg/k
Page 69 of 80
00 00 01 00 00 g
Total raw materials used per unit value 1.13E+ 1.13E+ 1.30E+ 1.30E+ 1.31E+
added 03 03 03 03 03 kg/$
Fraction of raw materials recycled within 0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+ kg/k
company 00 00 00 00 00 g
Fraction of raw materials recycled from 0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+ kg/k
consumers 00 00 00 00 00 g
0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+ kg/k

Hazardous raw material per kg product 00 00 00 00 00 g
Water Usage
Table 34 - IChemE Water Comparison
1 2 3 4 5 6 7
Net water consumed per unit 1.27E 2.11E 2.15E 2.27E 2.11E 5.98E 2.11E kg/
mass of product +01 +01 +01 +01 +01 +00 +01 kg
Net water consumed per unit 9.75E 2.48E 1.46E 1.27E 1.17E 3.40E 1.17E kg/
value added +04 +02 +02 +02 +02 +01 +02 $
8 9 10 11 12
Net water consumed per unit mass of 1.01E+0 2.27E+0 6.38E+0 6.38E+0 7.31E+0 kg/k
product 1 2 1 1 1 g
Net water consumed per unit value added 5.64E+0 1.27E+0 3.56E+0 3.56E+0 4.07E+0 kg/$
1 3 2 2 2
Land Usage
Table 35 - IChemE Land Comparison
Plant Area (10000 m^2) 1 2 3 4 5 6 7
Total land occupied + affected for 4.81E 1.96E 7.54E 4.64E 9.29E 9.03E 9.29E m2/(
value added a) -03 +01 +00 +00 +00 +00 +00 $/y)
Rate of land restoration (restored 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E (m2/
per year /total) b) +00 +00 +00 +00 +00 +00 +00 y)/m
2
Plant Area (10000 m^2) 8 9 10 11 12
Total land occupied + affected for value 8.88E+ 8.85E+ 7.67E+ 7.67E+ 7.66E+ m2/($/
added a) 00 00 00 00 00 y)
Page 70 of 80
Rate of land restoration (restored per year 0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+ (m2/
/total) b) 00 00 00 00 00 y)/m2
Atmospheric Impacts
Table 36 - IChemE Atmospheric Impact Comparison
1 2 3 4 5 6 7
Atmospheric acidification burden per 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E
unit value added a) +00 +00 +00 +00 +00 +00 +00 te/
Global warming burden per unit 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E $
value added b) +00 +00 +00 +00 +00 +00 +00 te/
Human Health burden per unit value 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E $
added c) +00 +00 +00 +00 +00 +00 +00 te/
Ozone depletion burden per unit 3.99E 7.97E 1.20E 1.59E 7.97E 3.26E 3.26E $
value added d) -03 -03 -02 -02 -03 -02 -02 te/
Photochemical ozone burden per unit 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E $
value added e) +00 +00 +00 +00 +00 +00 +00 te/
$
8 9 10 11 12
Atmospheric acidification burden per unit 0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+
value added a) 00 00 00 00 00 te/
Global warming burden per unit value added b) 0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+ $
00 00 00 00 00 te/
Human Health burden per unit value added c) 0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+ $
00 00 00 00 00 te/
Ozone depletion burden per unit value added 7.77E- 0.00E+ 5.99E+ 1.37E- 1.37E- $
d) 01 00 01 02 02 te/
Photochemical ozone burden per unit value 0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+ $
added e) 00 00 00 00 00 te/
Aquatic Impacts $
Table 37 - IChemE Aquatic Impact Comparison
1 2 3 4 5 6 7
Aquatic acidification per unit 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E
value added a) +00 +00 +00 +00 +00 +00 +00 te/
Aquatic oxygen demand per unit 2.92E- 5.83E- 8.75E- 1.17E- 5.83E- 2.39E- 2.39E- $
value added b) 02 02 02 01 02 01 01 te/
Ecotoxicity to aquatic life per unit $
value added c)
(i) metals 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E te/
+00 +00 +00 +00 +00 +00 +00 $
Page 71 of 80
(ii) other 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E te/
+00 +00 +00 +00 +00 +00 +00 $
Eutrophication per unit value 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E
added d) +00 +00 +00 +00 +00 +00 +00 te/
$
8 9 10 11 12
Aquatic acidification per unit value added 0.00E+0 0.00E+0 0.00E+0 0.00E+0 0.00E+0
a) 0 0 0 0 0 te/
Aquatic oxygen demand per unit value 0.00E+0 0.00E+0 1.00E- 1.00E- 1.00E- $
added b) 0 0 01 01 01 te/
Ecotoxicity to aquatic life per unit value $
added c)
(i) metals 0.00E+0 0.00E+0 0.00E+0 0.00E+0 0.00E+0 te/
0 0 0 0 0 $
(ii) other 0.00E+0 0.00E+0 0.00E+0 0.00E+0 0.00E+0 te/
0 0 0 0 0 $
Eutrophication per unit value added d) 0.00E+0 0.00E+0 0.00E+0 0.00E+0 0.00E+0
0 0 0 0 0 te/
Impacts to Land $
Table 38 - IChemE Land Impact Comparison
1 2 3 4 5 6 7
Hazardous solid waste per unit 1.30E- 2.60E- 2.60E- 5.20E- 0.00E 0.00E 0.00E te/
value added 02 02 02 02 +00 +00 +00 $
Non-hazardous solid waste per 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E te/
unit value added +00 +00 +00 +00 +00 +00 +00 $
8 9 10 11 12
Hazardous solid waste per unit value added 0.00E+0 0.00E+0 0.00E+0 0.00E+0 0.00E+0 te/
0 0 0 0 0 $
Non-hazardous solid waste per unit value 0.00E+0 0.00E+0 0.00E+0 0.00E+0 0.00E+0 te/
added 0 0 0 0 0 $
Profit, Value and Tax
Table 39 - IChemE Profit, Value, and Tax Comparison
1 2 3 4 5 6 7
Value added a) 2.08E+ 2.04E+ 5.30E+ 8.61E+ 4.30E+ 4.43E+ 4.43E+ $/

06 06 06 06 06 06 06 y
Page 72 of 80
Value added per unit value 5.20E+ 5.09E+ 1.33E+ 2.15E+ 1.08E+ 1.11E+ 1.11E+ $/
of sales 02 02 03 03 03 03 03 $
Value added per direct 6.94E+ 6.79E+ 1.77E+ 2.87E+ 1.43E+ 1.48E+ 1.48E+ $/
employee 05 05 06 06 06 06 06 y
Gross margin b) per direct 1.39E+ 1.36E+ 3.53E+ 5.74E+ 2.87E+ 2.95E+ 2.95E+ $/
employee 06 06 06 06 06 06 06 y
Return on average capital 9.33E- 4.57E- 9.52E- 9.65E- 9.52E- 9.54E- 9.54E- %/
employed 01 01 01 01 01 01 01 y
Taxes paid, as percent of 5.00E- 5.00E- 5.00E- 5.00E- 5.00E- 5.00E- 5.00E- %
NIBT 01 01 01 01 01 01 01
8 9 10 11 12
Value added a) 4.50E+06 4.52E+06 5.22E+06 5.22E+06 5.22E+06 $/y
Value added per unit value of sales 1.13E+03 1.13E+03 1.30E+03 1.30E+03 1.31E+03 $/$
Value added per direct employee 1.50E+06 1.51E+06 1.74E+06 1.74E+06 1.74E+06 $/y
Gross margin b) per direct employee 3.00E+06 3.01E+06 3.48E+06 3.48E+06 3.48E+06 $/y
Return on average capital employed 9.70E-01 9.70E-01 9.70E-01 9.70E-01 9.71E-01 %/y
Taxes paid, as percent of NIBT 5.00E-01 5.00E-01 5.00E-01 5.00E-01 5.00E-01 %
Investments
Table 40 - IChemE Investment Comparison
1 2 3 4 5 6 7
Percentage increase (decrease) in 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E %
capital employed +00 +00 +00 +00 +00 +00 +00 /y
R&D expenditure as % sales 1.25E- 9.48E- 9.69E- 7.18E- 9.36E- 3.38E- 9.11E- %
02 03 03 03 03 02 03
Employees with post-school 1.00E 1.00E 1.00E 1.00E 1.00E 1.00E 1.00E %
qualification a) +00 +00 +00 +00 +00 +00 +00
New appointments/number of 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E %
direct employees +00 +00 +00 +00 +00 +00 +00 /y
Training expense as percentage of 8.99E- 6.82E- 5.35E- 4.50E- 6.82E- 6.82E- 6.82E- %
payroll expense 02 02 02 02 02 02 02
8 9 10 11 12
Page 73 of 80
Percentage increase (decrease) in capital 0.00E+0 0.00E+0 0.00E+0 0.00E+0 0.00E+0 %/
employed 0 0 0 0 0 y
R&D expenditure as % sales 4.29E- 5.98E- 5.19E- 5.19E- 5.19E- %
02 03 03 03 03
Employees with post-school qualification a) 1.00E+0 1.00E+0 1.00E+0 1.00E+0 1.00E+0 %
0 0 0 0 0
New appointments/number of direct 0.00E+0 0.00E+0 0.00E+0 0.00E+0 0.00E+0 %/
employees 0 0 0 0 0 y
Training expense as percentage of payroll 1.03E- 1.03E- 1.03E- 1.03E- 1.03E- %
expense 01 01 01 01 01
Workplace
Table 41 - IChemE Workplace Comparison
1 2 3 4 5 6 7
Benefits as percentage of payroll 2.31E 2.31E 2.31E 2.31E 2.31E 2.31E 2.31E %
expense -01 -01 -01 -01 -01 -01 -01
Employee turnover (resigned + 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E %
redundant/number employed) +00 +00 +00 +00 +00 +00 +00
Promotion rate (number of 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E %
promotions/number employed) +00 +00 +00 +00 +00 +00 +00
Working hours lost as percent of total 7.00E 7.00E 7.00E 7.00E 7.00E 7.00E 7.00E %
hours worked -03 -03 -03 -03 -03 -03 -03
Income + benefit ratio (top 10%/bottom 1.00E 1.00E 1.00E 1.00E 1.00E 1.00E 1.00E
10%) +00 +00 +00 +00 +00 +00 +00
Lost time accident frequency (number 2.00E 2.00E 2.00E 2.00E 2.00E 2.00E 2.00E
per million hours worked) -02 -02 -02 -02 -02 -02 -02
Expenditure on illness and accident 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E 0.00E $/
prevention/payroll expense +00 +00 +00 +00 +00 +00 +00 $
8 9 10 11 12
2.31E- 2.31E- 2.31E- 2.31E- 2.31E- %

Benefits as percentage of payroll expense 01 01 01 01 01
Employee turnover (resigned + redundant/number 0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+ %
employed) 00 00 00 00 00
Promotion rate (number of promotions/number 0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+ %
employed) 00 00 00 00 00
Working hours lost as percent of total hours 7.00E- 7.00E- 7.00E- 7.00E- 7.00E- %
worked 03 03 03 03 03
1.00E+ 1.00E+ 1.00E+ 1.00E+ 1.00E+
Income + benefit ratio (top 10%/bottom 10%) 00 00 00 00 00
Lost time accident frequency (number per million 2.00E- 2.00E- 2.00E- 2.00E- 2.00E-
hours worked) 02 02 02 02 02
Page 74 of 80
Expenditure on illness and accident 0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+ $/
prevention/payroll expense 00 00 00 00 00 $
Society
Table 42 - IChemE Societal Comparison
1 2 3 4 5 6 7
Number of stakeholder a) meetings 7.69E 7.85E- 3.02E- 1.86E- 3.72E- 3.61E- 3.61E- /$
per unit value added -03 03 03 03 03 03 03
Indirect community benefit b) per 5.77E 5.89E+ 2.26E+ 1.39E+ 2.79E+ 2.71E+ 2.71E+ $/
unit value added +03 03 03 03 03 03 03 $
Number of complaints per unit 0.00E 0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+ /$
value added +00 00 00 00 00 00 00
Number of legal actions per unit 0.00E 0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+ 0.00E+ /$
value added c) +00 00 00 00 00 00 00
8 9 10 11 12
Number of stakeholder a) meetings per unit 3.55E- 3.54E- 3.07E- 3.07E- 3.06E- /$
value added 03 03 03 03 03
Indirect community benefit b) per unit value 2.66E+0 2.65E+0 2.30E+0 2.30E+0 2.30E+0 $/$
added 3 3 3 3 3
0.00E+0 0.00E+0 0.00E+0 0.00E+0 0.00E+0 /$
Number of complaints per unit value added 0 0 0 0 0
Number of legal actions per unit value added 0.00E+0 0.00E+0 0.00E+0 0.00E+0 0.00E+0 /$
c) 0 0 0 0 0
For complete data and calculations see: IChemE Evaluation.xlsx
Page 75 of 80
Appendix C – MSDS
Vegetable Oil
Full MSDS: http://sargentwelch.com/pdf/msds/sch94733.pdf
Methanol
Section 1
MSDS Name: Methyl Alcohol, Reagent ACS, 99.8% (GC)

Catalog Numbers: AC423950000, AC423950010, AC423950020, AC423955000, AC9541632, AC423952
Synonyms: Carbinol; Methanol; Methyl hydroxide; Monohydroxymethane; Pyroxylic spirit; Wood alcohol; Wood
naptha; Wood spirit; Monohydroxymethane; Methyl hydrate.
Appearance: clear, colorless. Flash Point: 11 deg C. Poison! Cannot be made non-poisonous. Causes eye and skin
irritation. May be absorbed through intact skin. This substance has caused adverse reproductive and fetal effects in
animals.
Danger! Flammable liquid and vapor. Harmful if inhaled. May be fatal or cause blindness if swallowed. May
cause central nervous system depression. May cause digestive tract irritation with nausea, vomiting, and diarrhea.
Causes respiratory tract irritation. May cause liver, kidney and heart damage.
Target Organs: Kidneys, heart, central nervous system, liver, eyes.
Full MSDS: http://www.biodieselgear.com/documentation/methanol.htm
Glycerol
Common Name: Crude Glycerol/Glycerin

Cas: 56-81-5
RTECS #: MA8050000
Typical Composition:
OSHA PEL ACGH/TLV Percent
15 MG/M3 TDUST 10 MG/M3 (MIST) 9293 99
This product contains no hazardous materials.
SARA Title III, Section 313: Not Listed
Full MSDS: http://www.biodieselgear.com/documentation/MSDS_Glycerol.pdf
Page 76 of 80
Potassium Hydroxide
MSDS Name: Potassium Hydroxide

Catalog Numbers: S71978, S71979, S71979-1, S71979-2, P246-3, P250-1, P250-10, P250-3, P250-50,
P250-500, P250-50LC, P251-3, P251-50, P251-500, P251-50KG, P25812, P258212, P25850, P25850LC,
PFP25050LC, S71977, S72221D
Synonyms: Caustic potash, Lye, Potassium hydrate
Appearance: white or yellow.
Danger! Corrosive. Water-Reactive. Harmful if swallowed. Causes severe eye and skin burns. Causes
severe digestive and respiratory tract burns.
Target Organs: None.
Full MSDS: http://www.biodieselgear.com/documentation/KOH.htm
Sodium hydroxide
MSDS Name: Sodium hydroxide, solid, pellets or beads

Catalog Numbers: S71990, S71990-1, S71991, S71992, S71993, S71993-1, S71993-2, S71993-3,
S71993-4, S78605, BP359-212, BP359-500, BW13580500, BW1358350, BW13583500, S318-1, S318-
10, S318-100, S318-3, S318-3LC, S318-5, S318-50, S318-500, S318-50LC, S320-1, S320-10, S320-3,
S320-50, S320-500, S612-3, S612-50, S612-500LB, S613-10, S613-3, S613-50, S613-500LB
Synonyms: Caustic soda; Soda lye; Sodium hydrate; Lye.
Appearance: white.
Danger! Corrosive. Causes eye and skin burns. Hygroscopic. May cause severe respiratory tract irritation
with possible burns. May cause severe digestive tract irritation with possible burns.
Target Organs: Eyes, skin, mucous membranes.
Full MSDS: http://www.biodieselgear.com/documentation/NaOH.htm
Sodium Methoxide
Full MSDS: http://www.sciencestuff.com/msds/C2658.html
Biodiesel
Common Name: Biodiesel
Page 77 of 80
Chemical Name: Fatty Acid Methyl Ester
Formula: C14-C24 Methyl Esters
Chemical Family: CAS No. 67784-80-9
Typical Composition:
Alkyl C14-C24 Methyl Esters OSHA PEL ACGH/TLV Percent
none none 99
This product contains no hazardous materials.
SARA Title III, Section 313: Not Listed
Full MSDS: http://www.biodieselgear.com/documentation/MSDS_BD.pdf
Sodium Phosphate
Product Name: Sodium phosphate tribasic

Catalog Codes: SLS2650, SLS4072
CAS#: 7601-54-9
RTECS: TC9490000
TSCA: TSCA 8(b) inventory: Sodium phosphate tribasic
CI#: Not available.
Synonym: Trisodium Phosphate Anhydrous; Phosphoric
Acid, Trisodium Salt; Trisodium Orthophosphate
Chemical Name: Sodium Phosphate Tribasic
Chemical Formula: Na3PO4
Full MSDS: http://www.esciencelabs.com/files/safety_sheets/xMSDS-Sodium_phosphate_tribasic-

9925028.pdf
Page 78 of 80
Appendix D - Workload Partitioning
Executive Summary - Archana Manoharan
Introduction - Archana Manoharan
Alkali-catalyzed Process Using Methanol Unmodified
 HYSYS Simulation - Jonathan Zatkoff

 Write-up - Archana Manoharan
Alkali-catalyzed Process Using Methanol Modification

Alkali-catalyzed Process Using Ethanol Unmodified
 HYSYS Simulation - Tadewos Woldemariam

 Write-up - Tadewos Woldemariam
Alkali-catalyzed Process Using Ethanol Modification
 HYSYS Simulation - Tadewos Woldemariam

Non-catalytic Process Operated at Supercritical Condition of Methanol Base Case and

Modifications

 Write-up - Jonathan Zatkoff
Economics
 NAPAT
o Calculations - Jonathan Zatkoff
o Write-up - Jonathan Zatkoff
Inherent Safety
 Calculations - Jonathan Zatkoff

Page 79 of 80
Environmental Sustainability
 EPA WAR GUI - Tadewos Woldemariam

IChemE Sustainability
 Calculations - Jonathan Zatkoff

Geographical Analysis of Biodiesel Demand and Production in Michigan
 Research - Archana Manoharan, Jonathan Zatkoff , and Tadewos Woldemariam

Conclusions

Recommendations

References
Page 80 of 80

Bio Plant in Michigan

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Wayne State University

Department of Chemical Engineering and Material Sciences

Jonathan Zatkoff, Archana Manoharan, Tadewos Woldemariam

1. Alkali-catalyzed Biodiesel Production Process Using Methanol

Results of Unmodified Process Design

1. Alkali-catalyzed Process Using Methanol

To provide justification for the proposal on biodiesel manufacturing a through sustainability

Michigan’s Biodiesel Demand Strategic Planning Recommendation

 Job creation and the resulting economic activity.

 Initial establishment of biodiesel plants – guarantee of biodiesel demand.

To successfully recommend process optimizations for biodiesel production a comprehensive

Figure 1 - Transesterification with Methanol

Figure 3 - Catalyst Recovery and Methoxide Catalysts

 Alkali-catalyzed Process Using Methanol

2. Methanol Recovery: Using vacuum distillation methanol is separated from other

Unmodified Analysis of Production Rates

Figure 4 - Alkali-catalyzed Process Using Methanol

Production Rate of Biodiesel - 4,000 tons/yr

Unit 106 203 301 302 502 401

Production Rate of Biodiesel - 8,000 tons/yr

Unit 106 203 301 302 502 401

Production Rate of Biodiesel - 12,000 tons/yr

Unit 106 203 301 302 502 401

Production Rate of Biodiesel - 16,000 tons/yr

Unit 106 203 301 302 502 401

Unit 106 203 301 302 502 401 306S

This process combines two modifications:

Solidification of Na3PO4 and HEN

Heat Exchanger Network (HEN)

Unit 106 202B 301 302 402

Replacing NaOH with KOCH3

The following trend was observed for soap formation:

NaOCH3 > NaOH > KOCH3 >> KOH

KOCH3 > NaOCH3 > KOH >> NaOH

Deep Eutectic Solvents (DES)

Chemical Melting Point (°C)

This modification is expected to be extremely successful in rural areas of Michigan. Choline

Choline Chloride - Urea Mixture and Heat Exchanger Network Modification

Unit 106 202B 301 302 402

Alkali-catalyzed Process Using Ethanol

Figure 8 - Alkali-catalyzed Process Using Ethanol

Production Rate of Biodiesel - 8,400 tons/yr

Ethanol Recovery Modification

Figure 9 - Alkali-catalyzed Process Using Ethanol Recovery Modification

Unit 1a 4 14 11 13a 13b

Non-catalytic Process Operated at Supercritical Condition of Methanol

Figure 10 - Non-catalytic Process Operated at Supercritical Condition of Methanol

Unit 202 206 401 502 603 608

Production Rate of Biodiesel - 9,696 tons/yr

Replacing Heat Exchanger Network With Heater and Cooler Modification

Table 13 - Important Stream Data for Heater and Cooler Modification

Unit 202 206 401 502

Table 14 - Economic Analysis of All Processes using NAPAT

Total Break Even Biodiesel Production

Alkali-catalyzed 9,277,575.65 5,212.18 1,779.98 8,400

Figure 13 - Break Even Production Rate

Where, kl is every impact category of a chemical,  l is the weighing factor.

Global Atmospheric Impacts Toxicological Impacts

 Global Warming Potential (GWP)  Human Toxicity Potential by Ingestion (HIPI)

500 1000 1500 2000 1000HEN 1000HEN(DES)

Figure 14 - Total Output rate of PEI (PEI/hr)

1000kg/hr(unmodified) 1000(HEN)(modfied) 1000HEN(DES)(modified)

Figure 15 - Total Output rate of PEI for 1000kg/hr Production of Biodiesel