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

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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.

Production Rate of Biodiesel - 8,000 tons/yr

Table 2 - Important Stream Data for Alkali-catalyzed Process Using Methanol at 8,000 tons/yr

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

Sodium Hydroxide*

0.007739 0.008467 0 0.077612 0.004753 0

H2O

0 0 0.000972 0.077972 0.000001 0.000148

Phosphoric acid*

0 0 0 0 0.003851 0

Trisodium phosphate*

0 0 0 0 0 0

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.

Production Rate of Biodiesel - 12,000 tons/yr

Table 3 - Important Stream Data for Alkali-catalyzed Process Using Methanol at 12,000 tons/yr

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

Sodium Hydroxide*

0.007967 0.008467 0 0.077623 0.004753 0

H2O

0 0 0.000971 0.077993 0.000001 0.000259

Phosphoric acid*

0 0 0 0 0.003851 0

Trisodium phosphate*

0 0 0 0 0 0

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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.

Production Rate of Biodiesel - 16,000 tons/yr

Table 4 - Important Stream Data for Alkali-catalyzed Process Using Methanol at 16,000 tons/yr

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

Sodium Hydroxide*

0.008087 0.008467 0 0.077621 0.000038 0

H2O

0 0 0.000971 0.077988 0.000002 0.00047

Phosphoric acid*

0 0 0 0 0 0

Trisodium phosphate*

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.

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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

Hydroxide*

0.0077 0.008467 0 0.077614 0.004752 0 0

H2O 0 0 0.000972 0.077975 0.000203 0.000148 0

Phosphoric acid* 0 0 0 0 0.00385 0 0

Trisodium

phosphate*

0 0 0 0 0 0 1

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

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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.

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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

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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 18 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

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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 20 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

Production Rate of Biodiesel - 8,400 tons/yr

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 21 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 22 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

4

66.50435 179.52149

6

176.22760

2

360 278.6878

4 Pressure kPa 2000 10 1 2 5000 5000 Mass Flow kg/h 3229.8259

66

3229.8259

66

1212.2570

3

120.40002

7

7920 7920 Liquid Volume

Flow

m3/h 3.847395 3.847395 1.382485 0.095496 10.80902

5

10.80902

5 Triolein

0.018077 0.018077 0 0 0 0 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

Production Rate of Biodiesel - 9,696 tons/yr

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 23 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 24 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

Process

Total

Production

Cost ($) NAPAT ($)

Break Even

Point (years)

Biodiesel Production

(tons/yr)

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

Ethanol 9,277,575.65 5,212.18 1,779.98 8,400

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 25 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.

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.

l

klk l (Eq. 1)

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

-5.00E+05

0.00E+00

5.00E+05

1.00E+06

1.50E+06

2.00E+06

4,000 6,000 8,000 10,000 12,000 14,000 16,000

Ne

t P

rofi

t A

fter

Tax

es

($)

Biodiesel Production Rate (tons/year)

Page 26 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

Global Warming Potential (GWP)

Ozone Depletion Potential (ODP)

Acidification Potential (AP)

Photochemical Oxidation Potential (PCOP)

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.

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

0.00E+00

1.00E+01

2.00E+01

3.00E+01

4.00E+01

5.00E+01

6.00E+01

HTPI HTPE TTP ATP GWP ODP PCOP AP

PEI

500 1000 1500 2000 1000HEN 1000HEN(DES)

Toxicological Impacts

Human Toxicity Potential by Ingestion (HIPI)

Human Toxicity Potential by Exposure

(HTPE)

Aquatic Toxicity Potential (ATP), and

Terrestrial Toxicity Potential (TTP)

Page 27 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.

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.

0.00E+00

2.00E-01

4.00E-01

6.00E-01

8.00E-01

1.00E+00

1.20E+00

1.40E+00

1.60E+00

1.80E+00

2.00E+00

HTPI HTPE TTP ATP GWP ODP PCOP AP

PEI

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

Page 28 of 80

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.

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.

0.00E+00

5.00E-03

1.00E-02

1.50E-02

2.00E-02

2.50E-02

HTPI HTPE TTP ATP GWP ODP PCOP AP

PEI

1000 1000HEN 1000HEN(DES)

0.00E+00

2.00E+01

4.00E+01

6.00E+01

8.00E+01

1.00E+02

1.20E+02

1.40E+02

HTPI HTPE TTP ATP GWP ODP PCOP AP

PEI

1000-A(HEN) 1000-AHEN(DES)

1000-C (Eth.Recovery) 1000-F(modified)

Page 29 of 80

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]

.

0.00E+00

2.00E-02

4.00E-02

6.00E-02

8.00E-02

1.00E-01

1.20E-01

HTPI HTPE TTP ATP GWP ODP PCOP AP

EPI/

kg o

f P

rod

uct

1000-A HEN 1000-A HEN(DES)

1000-C (Eth.Recovery) 1000-F(modified)

Page 30 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 8,000 tons/yr 12

Alkali-catalyzed Process Using Methanol 12,000 tons/yr 13

Alkali-catalyzed Process Using Methanol 16,000 tons/yr 13

Alkali-catalyzed Process Using Methanol With Cooler and HEN Modification 12

Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea and KOCH3

Modification

11

Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea, KOCH3, and

HEN Modification 11

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

HEN Modification 14

Non-catalytic Process Operated at Supercritical Condition of Methanol with

Heater/Cooler Modification 14

Page 31 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

Material (Fuel and water excluded)

Water

Land

Atmospheric Impacts

Society

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

Aquatic Impacts

Impacts to Land

Profit, Value and Tax

Investments

Workplace

Page 32 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

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

Energy Usage (GJ)

Ozone Depletion per

Value Added (tons/$)

Indirect

Community

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

Page 33 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

Process Index Economic Sustainability

Inherent Safety

Environmental Sustainability

Alkali-catalyzed Methanol 4,000 tons/yr 1 0 6 8 Alkali-catalyzed Methanol 8,000 tons/yr 2 5 6 6 Alkali-catalyzed Methanol 12,000 tons/yr 3 6 5 5 Alkali-catalyzed Methanol 16,000 tons/yr 4 7 5 4 Alkali-catalyzed Cooler and HEN 5 4 7 10 Alkali-catalyzed Choline Chloride/Urea 6 8 8 9 Alkali-catalyzed Choline Chloride/Urea, HEN

Modification

7 10 9 9 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 34 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 35 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.

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,

Figure 20 - Proposed Locations of Biodiesel Plants

Page 36 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

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 22 – Energy Crops

Figure 21 - Pasture Land

Page 37 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.

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

Figure 23 - Population Density

Page 38 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

Page 39 of 80

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 40 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 41 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 42 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 43 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).

Page 44 of 80

[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

Page 45 of 80

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

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

Page 47 of 80

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

Trisodium phosphate*

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 48 of 80

Table 20 - Stream Data for Alkali-catalyzed Process Using Methanol Producing 1000 kg/hr

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

Sodium Hydroxide*

0 1 0.078566 0.078566 0.04193 0 0 0 0 0.007739 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 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

Sodium Hydroxide*

0.008467 0 0 0.008467 0.008467 0 0 0.077612 0 0 0.077612

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

Trisodium phosphate*

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

Sodium Hydroxide*

0 0 0.003649 0.004031 0 0 0.004753 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 Trisodium phosphate*

0 0 0.094735 0 1 0 0 0 0 0

Page 49 of 80

Table 21 - Stream Data for Alkali-catalyzed Process Using Methanol Producing 1500 kg/hr

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

Sodium Hydroxide*

0 1 0.078566 0.078566 0.049647 0 0 0 0 0.007967 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 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

Sodium Hydroxide*

0.008467 0 0 0.008467 0.008467 0 0 0.077623 0 0 0.077623

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

Trisodium phosphate*

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

Sodium Hydroxide*

0 0 0.00365 0.004032 0 0 0.004753 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 Trisodium phosphate*

0 0 0.094748 0 1 0 0 0 0 0

Page 50 of 80

Table 22 - Stream Data for Alkali-catalyzed Process Using Methanol Producing 2000 kg/hr

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

Sodium Hydroxide*

0 1 0.078566 0.078566 0.054679 0 0 0 0 0.008087 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 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

Sodium Hydroxide*

0.008467 0 0 0.008467 0.008467 0 0 0.077621 0 0 0.077621

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

phosphate* 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 59.70562 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

Sodium Hydroxide*

0 0 0.000029 0.000032 0 0 0.000038 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

phosphate* 0 0 0.099691 0 1 0 0 0 0 0

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

Sodium Hydroxide*

0 1 0.078566 0.078566 0.04193 0 0 0 0 0.007739 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 201A 1201 202A 203 water 301 302 301A 301B 303 H3PO4

Page 52 of 80

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

Trisodium phosphate*

0 0 0 0 0 0 0 0 0 0 0

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 53 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

1

26.9491

2

50 22.7302

5

50 50 20.1724

7

99.2844

6

99.3960

1 Pressure kPa 100 100 100 400 400 100 100 100 20 30 200

Mass Flow kg/h 127.26 1050 127.330

1

1050 1050 261.278

6

0 1311.27

9

134.098 1177.18

1

1177.18

1 Triolein

0 1 0 1 1 0 0.00800

7

0.00800

7

0 0.00892 0.00892

M-Oleate

0 0 0 0 0 0 0.79638 0.79638 0 0.88709

9

0.88709

9 Glycerol

0 0 0 0 0 0 0.08242 0.08242 0 0.09180

9

0.09180

9 Methanol

1 0 0.99944

9

0 0 0.91118

7

0.09549

6

0.09549

6

0.82699

2

0.01216

8

0.01216

8 Choline Chloride/

Urea* 0 0 0 0 0 0 0 0 0 0 0

KOCH3*

0 0 0.00055

1

0 0 0.08881

3

0.01769

6

0.01769

6

0.17300

8

0.00000

4

0.00000

4

Page 54 of 80

Unit 202B choline chloride /

urea

301 302 303 304 401 402 201A 1201 103

Temperature C 50 50 40 50 50 50 43.6919

7

263.403 20.2138

6

20.2279 25

Pressure kPa 200 120 110 120 120 120 40 50 100 100 100

Mass Flow kg/h 1177.18

1

2.5 1052.67

6

127.004

9

124.504

9

2.5 16.5051

6

107.999

7

134.098 133.948

5

0.07012

Triolein

0.00892 0 0.00298 0.01653

5

0.01686

7

0 0 0.01944

4

0 0 0

M-Oleate

0.88709

9

0 0.99702 0 0 0 0 0 0 0 0

Glycerol

0.09180

9

0 0 0.85096 0.86804

7

0 0.13186

1

0.98055

6

0 0 0

Methanol

0.01216

8

0 0 0.11278

2

0.11504

7

0 0.86784

3

0 0.82699

2

0.82728

6

0

Choline Chloride/

Urea* 0 1 0 0.01968

4

0 1 0 0 0 0 0

KOCH3*

0.00000

4

0 0 0.00003

8

0.00003

9

0 0.00029

5

0 0.17300

8

0.17271

4

1

Figure 27 - Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea, KOCH3, and HEN Modification

Page 55 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

2

50 62.9021 50 20.1784

9

99.7053

6

20.2412

Pressure kPa 100 100 100 100 400 400 100 100 20 30 100

Mass Flow kg/h 126.94 1050 127.0101 0.07012 1050 1050 261.186

1

1311.18

6

134.205

3

1176.98

1

134.176

Triolein

0 1 0 0 1 1 0 0.00800

8

0 0.00892

1

0

M-Oleate

0 0 0 0 0 0 0 0.79643

6

0 0.88725 0

Glycerol

0 0 0 0 0 0 0 0.08242

6

0 0.09182

5

0

Methanol

1 0 0.999448 0 0 0 0.91115

5

0.09543

2

0.82712

9

0.012 0.82757

8 Choline Chloride/

Urea* 0 0 0 0 0 0 0 0 0 0 0

KOCH3*

0 0 0.000552 1 0 0 0.08884

5

0.01769

8

0.17287

1

0.00000

4

0.17242

2

Unit 202A 202B choline chloride /

urea

301 302 303 304 401 402 202_A1 201A

Temperature C 98.6331

6

50 50 40 50 50 50 42.5612 263.386

5

98.5215

7

20.2198

7 Pressure kPa 200 200 120 110 120 120 120 40 50 30 100

Mass Flow kg/h 1176.98

1

1176.98

1

2.5 1052.67

6

126.805 124.305 2.5 14.1288

6

110.176

2

1176.98

1

134.205

3 Triolein

0.00892

1

0.00892

1

0 0.00798 0.01656

1

0.01689

4

0 0 0.01906 0.00892

1

0

M-Oleate

0.88725 0.88725 0 0.99202 0 0 0 0 0 0.88725 0

Glycerol

0.09182

5

0.09182

5

0 0 0.85230

1

0.86944

3

0 0 0.98093

9

0.09182

5

0

Methanol

0.012 0.012 0 0 0.11138

4

0.11362

5

0 0.99965

9

0.00000

1

0.012 0.82712

9 Choline Chloride/

Urea*

0 0 1 0 0.01971

5

0 1 0 0 0 0

KOCH3*

0.00000

4

0.00000

4

0 0 0.00003

8

0.00003

9

0 0.00034

1

0 0.00000

4

0.17287

1

Page 56 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 57 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 58 of 80

Table 27 - Stream Data for Alkali-catalyzed Process Using Ethanol Recovery Modification

Uni

t

2 2a 1d 1e 3 vapor 4 1a 1b 1c 5 9

Temperature C 25 25 25 55.40179

3

53.63448

8

70 70 25 25 25 78.090801 60.236408

Pressure kPa 101.

3

101.

3

101.3 101 101 101 101 101.3 101.3 101.3 101 101

Mass Flow kg/

h

1000 1000 166.07083

3

610.3 1610.3 0 1610.31833

2

156.17083

3

9.9 166.07083

3

287.62857

5

287.62857

5 CetylC1cryl

a 0 0 0 0 0 0.00002

4

0.653241 0 0 0 0 0

Triolein

1 1 0 0 0.621002 0 0.000103 0 0 0 0 0

Ethanol

0 0 0.940387 0.983778 0.37285 0.99996

8

0.275929 1 0 0.940387 1 1

NaOH

0 0 0.059613 0.016222 0.006148 0 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

8

0.06458 0 0 0 0 0

Uni

t

10 13 14 6a 11 12 13a 13b 6 13a1 Temperature C 60.2

3

78.4

8

295.25979

6

61.62917

2

30 90.0844

3

78.090801 276.00524

7

102 78.090801 Pressure kPa 101 101 101 101 101 101 101 101 101 101 Mass Flow kg/

h

287.

5

161.

6

109 1322.689

8

1052.091

3

270.598

4

156.698016 4.900494 1323 156.70665

2 CetylC1cryl

a 0 0 0 0.795292 0.999842 0 0 0 0.795 0

Triolein

0 0 0 0.000126 0.000158 0 0 0 1E-04 0 Ethanol

1 0.97 0 0.118474 0 0.57910

3

1 0.001291 0.118 1 NaOH

0 0 0.090826 0.007485 0 0.03658

6

0 0 0.007 0

H2O

0 0 0 0 0 0 0 0 0 0 Glycerol

0 0.03 0.909174 0.078623 0 0.38431

2

0 0.998709 0.079 0

Page 59 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

Flow

m3/h 1.399632 0.174685 2.447813 1.399632 2.447813 3.847445 3.847445 3.847395 3.847395 Triolein

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 60 of 80

Unit 204 205 206 301 302 301B 301A 303 304

Temperature C 172.481008 150.752821 66.50435 -

10.872296

94.346443 -10.868611 -10.868611 98.848423 60 Pressure kPa 1500 800 10 2 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

Flow

m3/h 3.847395 3.847395 3.847395 2.273177 1.574218 2.273129 2.273177 1.468657 0.105561 Triolein

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 -

11.135984

176.227602 25 28.39215 360 360 Pressure kPa 1 1 2 1 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

Flow

m3/h 0.022429 1.382485 0.063743 0.010065 0.095496 10.809025 10.809025 10.809025 3.41194 Triolein

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

Flow

m3/h 7.397086 7.397086 7.397086 10.809025 Triolein

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 61 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 62 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 63 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

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-cond acc 14700 T-401-reflux pump 4000 T-401-overhead split 0 T-401-bottoms split 0 T-401-reb 20600 T-501-tower 25600 T-501-cond 36500 T-501-cond acc 14700 T-501-reflux pump 4000 T-501-overhead split 0 T-501-bottoms split 0

Page 65 of 80

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, supervision, and maintenance)

285355.8813 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 66 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 years

For complete economic data see: Process A,C,F Economic Comparison.xlsx

Page 67 of 80

Environmental

Individual impact categories

Total output rate of PEI (PEI/hr)

Case HTPI

HTPE TTP ATP GWP

ODP

PCOP

AP TOTAL 500 9.44

E-01

4.70E-03 9.44E-01 7.68E-01

4.90E-01

5.16E-06

3.72E-01

1.52E+0

1

2.59E+0

1 1000 2.22

E+00

1.10E-02 2.22E+00 1.36E+0

0

8.49E-01

8.93E-06

9.84E-01

2.63E+0

1

5.00E+0

1 1500 2.03

E+00

1.09E-02 2.03E+00 2.00E+0

0

1.20E+0

0

1.26E-05

7.70E-01

3.71E+0

1

6.13E+0

1 2000 2.30

E+00

1.38E-02 2.30E+00 2.71E+0

0

1.70E+0

0

1.79E-05

7.17E-01

5.26E+0

1

8.17E+0

1 1000H

EN 1.91E+0

0

4.81E-03 1.91E+00 3.38E-01

1.08E-01

1.14E-06

9.56E-01

3.35E+0

0

2.08E+0

1 1000HEN(DE

S)

1.29E-01

2.01E-03 1.29E-01 4.37E-01

3.18E-01

3.35E-06

1.17E-04

9.87E+0

0

1.25E+0

1

otal PEI leaving the system per mass of products (PEI/kg product)

Case HTPI

HTPE TTP ATP GWP

ODP

PCOP

AP TOTAL 500 1.69

E-03

8.44E-06 1.69E-03 1.38E-03

8.79E-04

9.25E-09

6.67E-04

2.72E-02

4.65E-02

1000 2.01E-03

1.00E-05 2.01E-03 1.23E-03

7.69E-04

8.09E-09

8.91E-04

2.38E-02

4.53E-02

1500 1.16E-03

6.23E-06 1.16E-03 1.14E-03

6.84E-04

7.20E-09

4.40E-04

2.12E-02

3.51E-02

2000 9.88E-04

5.94E-06 9.88E-04 1.16E-03

7.29E-04

7.67E-09

3.08E-04

2.26E-02

3.50E-02

1000HEN

1.73E-03

4.36E-06 1.73E-03 3.06E-04

9.79E-05

1.03E-09

8.66E-04

3.03E-03

1.88E-02

1000HEN(DE

S)

1.10E-04

1.71E-06 1.10E-04 3.71E-04

2.70E-04

2.84E-09

9.91E-08

8.38E-03

1.07E-02

Case HTPI

HTPE TTP ATP GWP

ODP

PCOP

AP TOTAL 1000 2.01

E-03

1.00E-05 2.01E-03 1.23E-03

7.69E-04

8.09E-09

8.91E-04

2.38E-02

4.53E-02

1000HEN

1.73E-03

4.36E-06 1.73E-03 3.06E-04

9.79E-05

1.03E-09

8.66E-04

3.03E-03

1.88E-02

1000HEN(DE

S)

1.10E-04

1.71E-06 1.10E-04 3.71E-04

2.70E-04

2.84E-09

9.91E-08

8.38E-03

1.07E-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 68 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 4,000 tons/yr 1

Alkali-catalyzed Process Using Methanol 8,000 tons/yr 2

Alkali-catalyzed Process Using Methanol 12,000 tons/yr 3

Alkali-catalyzed Process Using Methanol 16,000 tons/yr 4

Alkali-catalyzed Process Using Methanol With Cooler and HEN Modification 5

Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea and

KOCH3 Modification

6

Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea, KOCH3,

and HEN Modification

7

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

HEN Modification

11

Non-catalytic Process Operated at Supercritical Condition of Methanol with

Heater/Cooler Modification

12

Energy

Table 32 - IChemE Energy Comparison

1 2 3 4 5 6 7

Total Net Primary Energy Usage rate =

Imports – Exports

1.13E

+01

1.90E

+01

2.84E

+01

3.88E

+01

1.90E

+01

5.39E

+00

5.25E

+00

GJ

/y

Percentage Total Net Primary Energy

sourced from renewable

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00 %

Total Net Primary Energy Usage per 3.55E 4.21E 4.23E 4.13E 4.21E 1.55E 1.60E kJ/

Page 69 of 80

kg product -04 -04 -04 -04 -04 -03 -03 kg

Total Net Primary Energy Usage per

unit value added

5.20E

+02

6.79E

+05

1.77E

+06

2.87E

+06

1.43E

+06

1.48E

+06

1.48E

+06

kJ/

$

8 9 10 11 12

Total Net Primary Energy Usage rate = Imports

– Exports

8.78E+

00

1.03E+

01

1.10E+

02

7.55E+

01

7.60E+

01

GJ/

y

Percentage Total Net Primary Energy sourced

from renewable

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00 %

Total Net Primary Energy Usage per kg product

9.57E-

04

8.13E-

04

8.79E-

05

1.28E-

04

1.27E-

04

kJ/k

g

Total Net Primary Energy Usage per unit value

added

1.50E+

06

1.51E+

06

1.74E+

06

1.74E+

06

1.74E+

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

product

3.36E

+00

1.68E

+00

1.12E

+00

8.41E-

01

3.36E

+00

1.70E

+00

1.70E

+00

kg/

kg

Total raw materials used per unit

value added

2.08E

+06

5.09E

+02

1.33E

+03

2.15E

+03

1.08E

+03

1.11E

+03

1.11E

+03

kg/

$

Fraction of raw materials recycled

within company

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

kg/

kg

Fraction of raw materials recycled

from consumers

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

kg/

kg

Hazardous raw material per kg

product

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

kg/

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 70 of 80

00 00 01 00 00 g

Total raw materials used per unit value

added

1.13E+

03

1.13E+

03

1.30E+

03

1.30E+

03

1.31E+

03 kg/$

Fraction of raw materials recycled within

company

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

kg/k

g

Fraction of raw materials recycled from

consumers

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

kg/k

g

Hazardous raw material per kg product

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

kg/k

g

Water Usage

Table 34 - IChemE Water Comparison

1 2 3 4 5 6 7

Net water consumed per unit

mass of product

1.27E

+01

2.11E

+01

2.15E

+01

2.27E

+01

2.11E

+01

5.98E

+00

2.11E

+01

kg/

kg

Net water consumed per unit

value added

9.75E

+04

2.48E

+02

1.46E

+02

1.27E

+02

1.17E

+02

3.40E

+01

1.17E

+02

kg/

$

8 9 10 11 12

Net water consumed per unit mass of

product

1.01E+0

1

2.27E+0

2

6.38E+0

1

6.38E+0

1

7.31E+0

1

kg/k

g

Net water consumed per unit value added 5.64E+0

1

1.27E+0

3

3.56E+0

2

3.56E+0

2

4.07E+0

2 kg/$

Land Usage

Table 35 - IChemE Land Comparison

Plant Area (10000 m^2) 1 2 3 4 5 6 7

Total land occupied + affected for

value added a)

4.81E

-03

1.96E

+01

7.54E

+00

4.64E

+00

9.29E

+00

9.03E

+00

9.29E

+00

m2/(

$/y)

Rate of land restoration (restored

per year /total) b)

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

(m2/

y)/m

2

Plant Area (10000 m^2) 8 9 10 11 12

Total land occupied + affected for value

added a)

8.88E+

00

8.85E+

00

7.67E+

00

7.67E+

00

7.66E+

00

m2/($/

y)

Page 71 of 80

Rate of land restoration (restored per year

/total) b)

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

(m2/

y)/m2

Atmospheric Impacts

Table 36 - IChemE Atmospheric Impact Comparison

1 2 3 4 5 6 7

Atmospheric acidification burden per

unit value added a)

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

te/

$ Global warming burden per unit

value added b)

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

te/

$ Human Health burden per unit value

added c)

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

te/

$ Ozone depletion burden per unit

value added d)

3.99E

-03

7.97E

-03

1.20E

-02

1.59E

-02

7.97E

-03

3.26E

-02

3.26E

-02

te/

$ Photochemical ozone burden per unit

value added e)

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

te/

$

8 9 10 11 12

Atmospheric acidification burden per unit

value added a)

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

te/

$ Global warming burden per unit value added b) 0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

te/

$ Human Health burden per unit value added c) 0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

te/

$ Ozone depletion burden per unit value added

d)

7.77E-

01

0.00E+

00

5.99E+

01

1.37E-

02

1.37E-

02

te/

$ Photochemical ozone burden per unit value

added e)

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

te/

$ Aquatic Impacts

Table 37 - IChemE Aquatic Impact Comparison

1 2 3 4 5 6 7

Aquatic acidification per unit

value added a)

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

te/

$ Aquatic oxygen demand per unit

value added b)

2.92E-

02

5.83E-

02

8.75E-

02

1.17E-

01

5.83E-

02

2.39E-

01

2.39E-

01

te/

$ Ecotoxicity to aquatic life per unit

value added c)

(i) metals 0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

te/

$

Page 72 of 80

(ii) other 0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

te/

$

Eutrophication per unit value

added d)

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

te/

$

8 9 10 11 12

Aquatic acidification per unit value added

a)

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

te/

$ Aquatic oxygen demand per unit value

added b)

0.00E+0

0

0.00E+0

0

1.00E-

01

1.00E-

01

1.00E-

01

te/

$ Ecotoxicity to aquatic life per unit value

added c)

(i) metals 0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

te/

$

(ii) other 0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

te/

$

Eutrophication per unit value added d) 0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

te/

$ Impacts to Land

Table 38 - IChemE Land Impact Comparison

1 2 3 4 5 6 7

Hazardous solid waste per unit

value added

1.30E-

02

2.60E-

02

2.60E-

02

5.20E-

02

0.00E

+00

0.00E

+00

0.00E

+00

te/

$

Non-hazardous solid waste per

unit value added

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

te/

$

8 9 10 11 12

Hazardous solid waste per unit value added 0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

te/

$

Non-hazardous solid waste per unit value

added

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

te/

$

Profit, Value and Tax

Table 39 - IChemE Profit, Value, and Tax Comparison

1 2 3 4 5 6 7

Value added a) 2.08E+

06

2.04E+

06

5.30E+

06

8.61E+

06

4.30E+

06

4.43E+

06

4.43E+

06

$/

y

Page 73 of 80

Value added per unit value

of sales

5.20E+

02

5.09E+

02

1.33E+

03

2.15E+

03

1.08E+

03

1.11E+

03

1.11E+

03

$/

$

Value added per direct

employee

6.94E+

05

6.79E+

05

1.77E+

06

2.87E+

06

1.43E+

06

1.48E+

06

1.48E+

06

$/

y

Gross margin b) per direct

employee

1.39E+

06

1.36E+

06

3.53E+

06

5.74E+

06

2.87E+

06

2.95E+

06

2.95E+

06

$/

y

Return on average capital

employed

9.33E-

01

4.57E-

01

9.52E-

01

9.65E-

01

9.52E-

01

9.54E-

01

9.54E-

01

%/

y

Taxes paid, as percent of

NIBT

5.00E-

01

5.00E-

01

5.00E-

01

5.00E-

01

5.00E-

01

5.00E-

01

5.00E-

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

capital employed

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

%

/y

R&D expenditure as % sales 1.25E-

02

9.48E-

03

9.69E-

03

7.18E-

03

9.36E-

03

3.38E-

02

9.11E-

03 %

Employees with post-school

qualification a)

1.00E

+00

1.00E

+00

1.00E

+00

1.00E

+00

1.00E

+00

1.00E

+00

1.00E

+00 %

New appointments/number of

direct employees

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

0.00E

+00

%

/y Training expense as percentage of

payroll expense

8.99E-

02

6.82E-

02

5.35E-

02

4.50E-

02

6.82E-

02

6.82E-

02

6.82E-

02

%

8 9 10 11 12

Page 74 of 80

Percentage increase (decrease) in capital

employed

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

%/

y

R&D expenditure as % sales 4.29E-

02

5.98E-

03

5.19E-

03

5.19E-

03

5.19E-

03 %

Employees with post-school qualification a) 1.00E+0

0

1.00E+0

0

1.00E+0

0

1.00E+0

0

1.00E+0

0 %

New appointments/number of direct

employees

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

%/

y Training expense as percentage of payroll

expense

1.03E-

01

1.03E-

01

1.03E-

01

1.03E-

01

1.03E-

01 %

Workplace

Table 41 - IChemE Workplace Comparison

1 2 3 4 5 6 7

Benefits as percentage of payroll expense

2.31E-01

2.31E-01

2.31E-01

2.31E-01

2.31E-01

2.31E-01

2.31E-01

%

Employee turnover (resigned + redundant/number employed)

0.00E+00

0.00E+00

0.00E+00

0.00E+00

0.00E+00

0.00E+00

0.00E+00

%

Promotion rate (number of promotions/number employed)

0.00E+00

0.00E+00

0.00E+00

0.00E+00

0.00E+00

0.00E+00

0.00E+00

%

Working hours lost as percent of total hours worked

7.00E-03

7.00E-03

7.00E-03

7.00E-03

7.00E-03

7.00E-03

7.00E-03

%

Income + benefit ratio (top 10%/bottom 10%)

1.00E+00

1.00E+00

1.00E+00

1.00E+00

1.00E+00

1.00E+00

1.00E+00

Lost time accident frequency (number per million hours worked)

2.00E-02

2.00E-02

2.00E-02

2.00E-02

2.00E-02

2.00E-02

2.00E-02

Expenditure on illness and accident prevention/payroll expense

0.00E+00

0.00E+00

0.00E+00

0.00E+00

0.00E+00

0.00E+00

0.00E+00

$/

$

8 9 10 11 12

Benefits as percentage of payroll expense

2.31E-

01

2.31E-

01

2.31E-

01

2.31E-

01

2.31E-

01 %

Employee turnover (resigned + redundant/number employed)

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00 %

Promotion rate (number of promotions/number employed)

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00 %

Working hours lost as percent of total hours worked

7.00E-

03

7.00E-

03

7.00E-

03

7.00E-

03

7.00E-

03 %

Income + benefit ratio (top 10%/bottom 10%)

1.00E+

00

1.00E+

00

1.00E+

00

1.00E+

00

1.00E+

00

Lost time accident frequency (number per million hours worked)

2.00E-

02

2.00E-

02

2.00E-

02

2.00E-

02

2.00E-

02

Page 75 of 80

Expenditure on illness and accident prevention/payroll expense

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

0.00E+

00

$/

$ Society

Table 42 - IChemE Societal Comparison

1 2 3 4 5 6 7

Number of stakeholder a) meetings per unit value added

7.69E-03

7.85E-03

3.02E-03

1.86E-03

3.72E-03

3.61E-03

3.61E-03

/$

Indirect community benefit b) per unit value added

5.77E+03

5.89E+03

2.26E+03

1.39E+03

2.79E+03

2.71E+03

2.71E+03

$/

$

Number of complaints per unit value added

0.00E+00

0.00E+00

0.00E+00

0.00E+00

0.00E+00

0.00E+00

0.00E+00

/$

Number of legal actions per unit value added c)

0.00E+00

0.00E+00

0.00E+00

0.00E+00

0.00E+00

0.00E+00

0.00E+00

/$

8 9 10 11 12

Number of stakeholder a) meetings per unit value added

3.55E-

03

3.54E-

03

3.07E-

03

3.07E-

03

3.06E-

03 /$

Indirect community benefit b) per unit value added

2.66E+0

3

2.65E+0

3

2.30E+0

3

2.30E+0

3

2.30E+0

3 $/$

Number of complaints per unit value added

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0 /$

Number of legal actions per unit value added c)

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0

0.00E+0

0 /$

For complete data and calculations see: IChemE Evaluation.xlsx

Page 76 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 77 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 78 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 79 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

HYSYS Simulation - Jonathan Zatkoff

Write-up - Archana Manoharan

Alkali-catalyzed Process Using Ethanol Unmodified

HYSYS Simulation - Tadewos Woldemariam

Write-up - Tadewos Woldemariam

Alkali-catalyzed Process Using Ethanol Modification

HYSYS Simulation - Tadewos Woldemariam

Write-up - Tadewos Woldemariam

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

Modifications

HYSYS Simulation - Jonathan Zatkoff

Write-up - Jonathan Zatkoff

Economics

NAPAT

o Calculations - Jonathan Zatkoff

o Write-up - Jonathan Zatkoff

Inherent Safety

Calculations - Jonathan Zatkoff

Write-up - Jonathan Zatkoff

Page 80 of 80

Environmental Sustainability

EPA WAR GUI - Tadewos Woldemariam

Write-up - Tadewos Woldemariam

IChemE Sustainability

Calculations - Jonathan Zatkoff

Write-up - Tadewos Woldemariam

Geographical Analysis of Biodiesel Demand and Production in Michigan

Research - Archana Manoharan, Jonathan Zatkoff , and Tadewos Woldemariam

Write-up - Archana Manoharan

Conclusions

Research - Archana Manoharan, Jonathan Zatkoff , and Tadewos Woldemariam

Write-up - Archana Manoharan

Recommendations

Research - Archana Manoharan, Jonathan Zatkoff , and Tadewos Woldemariam

Write-up - Archana Manoharan

References

Write-up - Jonathan Zatkoff