Wayne State University Department of Chemical Engineering and Material Sciences
Strategic Planning of Biodiesel Production in Michigan Process Design, Modification, and Sustainability Assessment
Jonathan Zatkoff, Archana Manoharan, Tadewos Woldemariam 4/26/2010
Table of Contents Executive Executive Summary............................... ................................................ .................................. ................................. ................................. .................................. .................................. ................. 4 Introduct Introduction ion ................................. ................................................. ................................. ................................. ................................. .................................. ................................. ............................ ............ 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 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 Modificati Modifications ons ............................... ................................................ .................................. .................................. ................................. ................................. .................................. ..................... .... 22 Water Heat Exchanger Network ....................................................................................................... 22 Replacing Heat Exchanger Network Network With Heater and Cooler Modification .................. ......... ................... ................... ......... 23 Sustaina Sustainabilit bility y ................................. .................................................. .................................. ................................. ................................. ................................. ................................. ........................ ....... 24 Economic Sustainability ....................................................................................................................... 24 Environmental Sustainability ................................................................................................................ 25 Inherent Safety Analysis ....................................................................................................................... 29 IChemE Sustainability Assessment ....................................................................................................... 31 Overall Overall Sustainabi Sustainability... lity................... ................................. .................................. .................................. ................................. ................................. .................................. ..................... .... 32 Geographical Analysis Analysis of Biodiesel Demand and Production in Michigan................... .......... .................. ................... ................... ......... 35 Upper Peninsul Peninsulaa .................................. .................................................. ................................. ................................. ................................. .................................. ................................ ............... 35 Northern Lower Peninsula .................................................................................................................... 37 Southern Lower Peninsula .................................................................................................................... 37 Conclusion Conclusionss ................................. ................................................. ................................. ................................. ................................. .................................. ................................. .......................... .......... 40 Recommenda Recommendation tionss ............................... ................................................ .................................. ................................. ................................. .................................. .................................. ................... 42 References References ............................... ................................................ .................................. ................................. ................................. .................................. .................................. ............................. ............ 43 Appendix A - Full Stream Data and Large Process Images ...................................................................... 46 Appendix Appendix B - Raw Data ................... .................................... .................................. .................................. ................................. ................................. .................................. ..................... .... 64 Economic Economic ................................. ................................................. ................................. ................................. ................................. .................................. ................................. .......................... .......... 64 Page 2 of 80
Environmen Environmental........... tal............................ .................................. ................................. ................................. ................................. ................................. .................................. ........................ ....... 67 Inherent Inherent Safety Safety ................................. ................................................. ................................. ................................. ................................. .................................. .................................. ................... 67 IChemE IChemE Evaluati Evaluation on ............................... ................................................ ................................. ................................. .................................. ................................. ............................. ............. 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 analysis of the biodiesel biodiesel production process. process. Starting with equipment modifications to improve quantity and quality of biodiesel, the project moves towards evaluating the Michigan biodiesel industry industry in particular. A through sustainability analysis for each process design examining examining net profits, profits, social and environmental 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 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 a nd 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 sustainability metrics were used Net Annual Profit Profit Page 4 of 80
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. advantages are presented along with constraints and possible solutions.
Probable
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 Page 5 of 80
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, alkalicatalyzed 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 Modifications o 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 Modification o Ethanol Recovery Non-catalytic Process Operated at Supercritical Condition of Methanol Modifications o 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 9 8% purity. Page 10 of 80
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
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric acid* Trisodium phosphate*
Unit C kPa kg/h
106 60 395 701.6695 0.037541 0.164611 0.716532 0.07419 0.007125 0 0 0
203 60 120 590.485 0.04461 0.007313 0.851451 0.088159 0.008467 0 0 0
301 60 110 531.9334 0.049456 0.004818 0.945169 0 0 0.000557 0 0
302 60 120 64.09128 0.000537 0.027389 0.000028 0.812228 0.078008 0.081811 0 0
502 263.3066 50 52.54935 0.000033 0 0.000659 0.99069 0.004757 0.000007 0.003854 0
401 196.3723 10 500 0 0.000218 0.999721 0 0 0.000062 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 (MOleate) 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. Page 11 of 80
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
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric acid* Trisodium phosphate*
Unit C kPa kg/h
106 60 395 1292.138 0.040772 0.092718 0.778197 0.080575 0.007739 0 0 0
203 60 120 1180.959 0.044611 0.007304 0.851459 0.08816 0.008467 0 0 0
301 59.21506 110 1063.202 0.049427 0.003856 0.945744 0 0 0.000972 0 0
302 60.00062 120 128.8359 0.001027 0.035124 0.000155 0.808108 0.077612 0.077972 0 0
502 263.3396 50 157.7756 0.000063 0 0.001384 0.989948 0.004753 0.000001 0.003851 0
401 185.1412 10 1000.001 0 0.00024 0.999612 0 0 0.000148 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
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric acid* Trisodium phosphate*
Unit C kPa kg/h
106 60 395 1882.606 0.041976 0.065922 0.80118 0.082954 0.007967 0 0 0
203 60 120 1771.39 0.044612 0.007277 0.851482 0.088162 0.008467 0 0 0
301 59.21492 110 1594.783 0.049428 0.003844 0.945757 0 0 0.000971 0 0
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302 60.00018 120 193.2267 0.001022 0.034985 0.000155 0.808222 0.077623 0.077993 0 0
502 263.3396 50 157.7756 0.000063 0 0.001384 0.989948 0.004753 0.000001 0.003851 0
401 160.9465 10 1499.998 0 0.000432 0.999309 0 0 0.000259 0 0
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
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric acid* Trisodium phosphate*
Unit C kPa kg/h
106 60 395 2473.075 0.042605 0.051922 0.813188 0.084198 0.008087 0 0 0
203 60 120 2361.87 0.044611 0.007283 0.851476 0.088162 0.008467 0 0 0
301 59.21504 110 2126.384 0.049428 0.003847 0.945754 0 0 0.000971 0 0
302 59.99969 120 257.6448 0.001024 0.03502 0.000155 0.808193 0.077621 0.077988 0 0
502 263.3375 50 208.566 0.000063 0 0.001398 0.998499 0.000038 0.000002 0 0
401 134.5357 10 1999.977 0 0.000875 0.998655 0 0 0.00047 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 o f Trisodium Phosphate and Heat Exchanger Network Modifications
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium H2O Phosphoric acid* Trisodium
Unit C kPa kg/h
106 60 395 1292.1 0.0407 0.0927 0.7781 0.0805 0.0077 0 0 0
203 60 200 1180.954 0.044611 0.0073 0.851462 0.08816 0.008467 0 0 0
301 59.21462 110 1063.2 0.049427 0.003855 0.945746 0 0 0.000972 0 0
302 60.00023 120 128.8333 0.001027 0.035104 0.000155 0.808125 0.077614 0.077975 0 0
502 262.409 50 105.2056 0.000063 0 0.00139 0.989742 0.004752 0.000203 0.00385 0
401 185.164 10 999.9995 0 0.00024 0.999612 0 0 0.000148 0 0
306S 25 100 12.97858 0 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 byproduct 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 C holine Chloride - Urea Mixture Modification
Temperature Pressure Mass Flow Triolein M-Oleate Glycerol Methanol Choline Chloride/ Urea* KOCH3*
Unit C kPa kg/h
106 50 100 1311.279 0.008007 0.79638 0.08242 0.095496 0 0.017696
202B 50 200 1177.181 0.00892 0.887099 0.091809 0.012168 0 0.000004
301 302 40 50 110 120 1052.676 127.0049 0.00298 0.016535 0.99702 0 0 0.85096 0 0.112782 0 0.019684 0 0.000038
402 263.403 50 107.9997 0.019444 0 0.980556 0 0 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 [23] formation than the other three and was the worst catalyst in terms of soap formation.”
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 Choline Chloride Urea 2:1 Molar Ratio
Melting Point ( °C) 302 133 12
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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 3,5,5triamino-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
Temperature Pressure Mass Flow Triolein M-Oleate Glycerol Methanol Choline Chloride/ Urea* KOCH3*
Unit C kPa kg/h
106 50 100 1311.186 0.008008 0.796436 0.082426 0.095432 0 0.017698
202B 50 200 1176.981 0.008921 0.88725 0.091825 0.012 0 0.000004
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301 302 40 50 110 120 1052.676 126.805 0.00798 0.016561 0.99202 0 0 0.852301 0 0.111384 0 0.019715 0 0.000038
402 263.3865 50 110.1762 0.01906 0 0.980939 0.000001 0 0
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
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Table 9 - Important Stream Data for Alkali-catalyzed Process Using Ethanol
Temperature Pressure Mass Flow CetylC1cryla Triolein Ethanol NaOH H2O Glycerol
Unit C kPa kg/h
1a 25 101.3 312.9 0 0 1 0 0 0
4 70 101.3 1610.388 0.653212 0.000103 0.27596 0.006148 0 0.064577
14 295.26 101 109 0 0 0 0.090825 0 0.909175
11 30 101 1052.091 0.999842 0.000158 0 0 0 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
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Table 10 - Important Stream Data for Et hanol Recovery Modification
Temperature Pressure Mass Flow CetylC1cryla Triolein Ethanol NaOH H2O Glycerol
Unit C kPa kg/h
1a 25 101.3 156.1708 0 0 1 0 0 0
4 70 101 1610.31833 0.653241 0.000103 0.275929 0.006148 0 0.06458
14 295.25979 101 109 0 0 0 0.090826 0 0.909174
11 30 101 1052.091 0.999842 0.000158 0 0 0 0
13a 78.090801 101 156.69801 0 0 1 0 0 0
13b 276.00524 101 4.900494 0 0 0.001291 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
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Table 11 - Important Stream Data for No n-catalytic Process Operated at Supercritical Condition of Methanol
Unit 202 206 C 250.59369 66.50435 kPa 2000 10 kg/h 3229.8259 3229.8259 m 3 /h 3.847395 3.847395 0.018077 0.018077 0.561929 0.561929 0.380589 0.380589 0.039405 0.039405 0 0
Temperature Pressure Mass Flow Liquid Volume Triolein Methanol M-Oleate Glycerol n-Decane
401 502 603 608 179.52149 176.22760 360 278.6878 1 2 5000 5000 1212.2570 120.40002 7920 7920 1.382485 0.095496 10.8090210.80902 0 0 0 0 0.000084 0 0 0 0.999916 0 0 0 0 1 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 re quires 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
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Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol H2O
Unit 202 C 250.5941 kPa 2000 kg/h 3229.864 0.018078 0.561935 0.380584 0.039404 0
206 66.50517 10 3229.864 0.018078 0.561935 0.380584 0.039404 0
401 187.3731 1 1212.2 0 0.000046 0.999954 0 0
502 176.2276 2 120.4 0 0 0 1 0
603 320 5000 1150 0 0 0 0 1
607 235.4331 5000 1150 0 0 0 0 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 a nd Cooler Modification
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol
Unit C kPa kg/h
202 250.6075 2000 3229.826 0.018079 0.561929 0.380587 0.039404
206 66.50428 10 3229.826 0.018079 0.561929 0.380587 0.039404
401 502 179.498 176.2276 1 2 1212.2 120.4 0 0 0.000084 0 0.999916 0 0 1
This modification replaces the HEN with a heater and cooler, which internally recycles the utilities. The goal of this modification is to reduce the amount of raw materials required for the process, reducing the total manufacturing cost. Again this process creates high quality biodiesel and glycerol. Page 23 of 80
Sustainability Economic Sustainability In order to determine the economic viability of each process a net annual profit after taxes (N APAT) was used to determine the number of years necessary to recoup the total investment. Table XX shows the calculated total production cost, N APAT, break even time, and biodiesel production per year. Table 14 - Economic Analysis of All Processes using N APAT
Process Alkali-catalyzed Methanol 4,000 ton/yr 8,000 ton/yr 12,000 ton/yr 16,000 ton/yr Modifications Sale of Na3PO4 KOCH3 /Choline Cl KOCH3 /Choline Cl Alkali-catalyzed Ethanol Ethanol Recovery Non-catalytic Supercritical Methanol Oil HEN Water HEN Heater/Cooler
Total Production Cost ($)
NAPAT ($)
4,963,683.86 8,001,526.05 11,138,391.44 14,288,388.93
-250,257.93 462,804.98 1,125,972.28 1,785,085.53
Break Even Point (years)
Biodiesel Production (tons/yr)
N/A 17.29 9.89 8.00
4,000 8,000 12,000 16,000
/HEN 8,060,140.20 488,805.90 7,373,539.76 957,230.12 7.70 /HEN 7,332,727.74 977,636.13
16.49
8,000 8,400
7.50
8,400
9,277,575.65
5,212.18
1,779.98
8,400
8,150,174.92
588,512.54
13.85
8,400
37,351,531.85 11,903,355.05 9,944,270.02
-13,301,053.93 -576,965.52 402,576.99
N/A N/A 24.70
9,696 9,696 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.
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Since the alkali-catalyzed process-using methanol did not earn profit after taxes at all production rates, it would be advisable to know the minimum flow rate, which this process must operate at to break even. 2.00E+06
) $ ( s e x a T r e t f A t i f o r P t e N
1.50E+06
1.00E+06
5.00E+05
0.00E+00 4,000
6,000
-5.00E+05
8,000
10,000
12,000
14,000
16,000
Biodiesel Production Rate (tons/year)
Figure 13 - Break Even Production Rate
As shown by Figure 13, the minimum production rate is approximately 5,500 tons per year.
Environmental Sustainability Environmental impact of a process design is important aspect that needs be addressed during design proposal. To understand the impact of the processes the Waste Reduction Algorithm (WAR) developed by Environmental Protection Agency (EPA) was used. The Potential Environmental Impact (PEI) of the Alkali-Catalyzed Process using Methanol, Alkali-Catalyzed Process using Ethanol and Non-Catalytic Process Operated at Super Critical Condition of Methanol were calculated. Based on the waste output and energy consumption of each process, the algorithm is used to determine the process with the most Potential Environmental Impact (PEI). Two distinct analyses can be performed using WAR algorithm, product and non-product analysis depending on the product stream of biodiesel. The overall PEI of a given chemical is determined by taking the summation of the specific PEI of that chemical‟s overall possible impact categories. k l k
l
l
Where,
kl
is every impact category of a chemical, l is the weighing factor. Page 25 of 80
(Eq. 1)
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.
Toxicological Impacts
Global Atmospheric Impacts
Global Warming Potential (GWP) Ozone Depletion Potential (ODP) Acidification Potential (AP) Photochemical Oxidation Potential (PCOP)
Human Toxicity Potential by Ingestion (HIPI) Human Toxicity Potential by Exposure (HTPE) Aquatic Toxicity Potential (ATP), and
The total output rate of PEI (PEI/hr) allows one to compare an alternative processes in terms of the potential effects on the environment. In other words, the total output rate of PEI is very necessary in assessing if a given geographical location can accommodate a process plant. It can also be used to determine how a given processes design with variable production rate impacts the environment. For production of biodiesel using alkali catalyzed with methanol, production rate biodiesel is directly proportional to the impact on the environment. The HTPI and HTPE areas of concerns are a little higher than the ones mentioned above. This is due to the corrosive nature of the strong base sodium hydroxide in the feed stream and the distillation tower. Of all categories of environmental concern AP (Acidification Potential) exhibits the highest environmental concern. What this tells us is that geographical locations with frequent rain throughout the year most likely are not encouraged to build biodiesel plants because of the possibility of acid rain. In Figure 14, the AP category of the smallest production rate (500kg/hr) has a total output rate of PEI 1.5 per hour while the AP for the production of biodiesel with the highest production of biodiesel (2000 kg/hr) has a PEI of 5.2 per hour. 6.00E+01 5.00E+01 4.00E+01 I E P
3.00E+01 2.00E+01
1.00E+01 0.00E+00 HTPI 500
1000
HTPE 1500
TTP
ATP
2000
GWP 1000HEN
ODP
AP
1000HEN(DES)
Figure 14 - Total Output rate of PEI (PEI/hr)
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PCOP
Also using the WAR algorithm comparisons of the total output rate of PEI (PEI/hr) for production of 1000kg/hr production of biodiesel in the Alkali catalyzed Method using Methanol was made. Figure 15, shows the unmodified process and suggested HEN modification. These two have similar impact on the indicated categories. This is because the major change in the design is the reduction of energy consumption. However, in the second modification of potassium methoxide catalyst replacing sodium hydroxide, the potential impact is consistent and comparable. 2.00E+00 1.80E+00 1.60E+00 1.40E+00 1.20E+00 I E P
1.00E+00 8.00E-01 6.00E-01 4.00E-01 2.00E-01 0.00E+00
HTPI
HTPE
1000kg/hr(unmodified)
TTP
ATP
GWP
1000(HEN)(modfied)
ODP
PCOP
AP
1000HEN(DES)(modified)
Figure 15 - Total Output rate of PEI for 1000kg/hr Production of Biodiesel
Figure 16 compares the total PEI leaving the system per kg of product. For the unmodified process of alkali catalyzed with methanol, 0.045 PEI per kilogram of product is exhibited for unmodified process is 0.00025 and 0.0078 PEI per kilogram is exhibited for first and second modifications respectively. Alkali-catalyst production using methanol impacts the environment in the acidification potential (AP) category. This is the result of waste products which might produce or decompose themselves into acidic gases generate acid rain.
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2.50E-02
2.00E-02 I E P
1.50E-02 1.00E-02 5.00E-03 0.00E+00 HTPI
HTPE
1000
TTP
ATP
1000HEN
GWP
ODP
PCOP
AP
1000HEN(DES)
Figure 16 - Total PEI per kg o f product
In the following figure 17, the total output rate of PEI for the production of biodiesel at supercritical condition indicates a higher impact in the category of Photochemical Oxidation impact (PCOP) at about 122 PEI/hr. This could be due to the production of biodiesel by product (glycerol) at highest temperature. Similarly, the Aquatic Potential Impact (A) for is significantly higher (190 PEI/hr) than the other areas of categorical impacts. Modification to use water instead of n-decane is responsible for this change. In other words, the inlet of water used to heat the reaction to supercritical condition has to still come out of the process at fairly high temperature. This stream must be cooled to an acceptable aquatic temperature before it is lead to oceans. 1.40E+02 1.20E+02 1.00E+02 I E P
8.00E+01 6.00E+01 4.00E+01 2.00E+01 0.00E+00 HTPI
HTPE
TTP
ATP
GWP
ODP
1000-A(HEN)
1000-AHEN(DES)
1000-C (Eth.Recovery)
1000-F(modified)
PCOP
AP
Figure 17 - Total Output Rate of PEI Comparison
In Figure 18, a similar trend to the previous scenario is shown when comparing the three modified chemical processes according to total output of PEI per kg of product . Refer to Figure 18. Page 28 of 80
1.20E-01 t c u d o r P f o g k / I P E
1.00E-01 8.00E-02 6.00E-02 4.00E-02 2.00E-02 0.00E+00
HTPI
HTPE
TTP
ATP
GWP
ODP
1000-A HEN
1000-A HEN(DES)
1000-C (Eth.Recovery)
1000-F(modified)
PCOP
AP
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].
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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 Alkali-catalyzed Process Using Methanol 4,000 tons/yr Alkali-catalyzed Process Using Methanol 8,000 tons/yr Alkali-catalyzed Process Using Methanol 12,000 tons/yr Alkali-catalyzed Process Using Methanol 16,000 tons/yr Alkali-catalyzed Process Using Methanol With Cooler and HEN Modification Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea and KOCH3 Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea, KOCH3, and HEN Modification Alkali-catalyzed Process Using Ethanol Alkali-catalyzed Process Using Ethanol Recovery Modification Non-catalytic Process Operated at Supercritical Condition of Methanol Non-catalytic Process Operated at Supercritical Condition of Methanol with Water HEN Modification Non-catalytic Process Operated at Supercritical Condition of Methanol with Heater/Cooler Modification
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Total Inherent Safety 12 12 13 13 12 11 11 10 9 15 14 14
The alkali-catalyzed process using ethanol recovery offers the best overall safety, with a score of 9. However, this process is not the most economically viable. The alkali-catalyzed process using methanol with choline chloride/urea, KOCH3, and HEN modification, received a middle score of 11, which is lower than the unmodified process due to lower reactor operating temperatures, 50 °C compared with 60 °C for the unmodified process. The non-catalytic process is least safe due to high operating temperatures (350 °C) and pressures (2000 kPa), as well as requiring more storage for raw materials in two of the processes. In all the processes operating temperature and pressures contributed the most to raising the TIS score. The highest temperatures occur in the bottoms of the distillation columns, these temperatures ranged between 200 °C and 350 °C. The other factor which caused a TIS score to increase was that with increased production there needed to be more storage for raw materials and products. It was assumed that storage would take place on site. The use of choline chloride and urea did not increase the TIS score because it biodegradable and is internal to the process. Additionally, the potassium methoxide had negligible effect on the TIS score because is internal to the process.
IChemE Sustainability Assessment The IChemE Sustainable Development Progress Metrics[6] was used to assess sustainability for all the processes listed in Table 17. To provide a fair and well rounded comparison both modified and unmodified processes were evaluated. This allows for an unbiased comparison between different modifications and the effect of these modifications on sustainability. The IChemE metrics uses 49 detailed factors that are helpful in evaluating a company‟s progress towards a more sustainable operation[5]. Eleven broad areas were considered in the metrics, these are listed below: Energy Aquatic Impacts Material (Fuel and water excluded) Impacts to Land Water Profit, Value and Tax Land Investments Atmospheric Impacts Workplace 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 imp act on the atmosphere, land and water resources. In general terms, energy evaluations deal with the processes‟ energy use per the value of product produced, material analysis dealt with raw material usage and hazard waste production. Water and land analysis evaluated the amount of these resources used by the processes. Social impacts were also studied such as profit sharing, investment and workplace dynamics. Analyses for all processes examined are presented in Appendix B. In all categories, the suggested modified processes fared better than the unmodified processes. As mentioned earlier Page 31 of 80
several factors were considered in this analysis but, three specific factors are presented below as an example. The above table shows the results for three best suggested modifications. Table 17 - Notable IChemE Criteria
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
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
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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 Alkali-catalyzed Methanol 4,000 tons/yr Alkali-catalyzed Methanol 8,000 tons/yr Alkali-catalyzed Methanol 12,000 tons/yr Alkali-catalyzed Methanol 16,000 tons/yr Alkali-catalyzed Cooler and HEN Alkali-catalyzed Choline Chloride/Urea Alkali-catalyzed Choline Chloride/Urea, HEN Alkali-catalyzed Process Ethanol Alkali-catalyzed Process Ethanol Recovery Non-catalytic Process Methanol Non-catalytic Water HEN Non-catalytic Heater/Cooler
Index
1 2 3 4 5 6 7 8 9 10 11 12
Economic Sustainability 0 5 6 7 4 8 10 1 5 0 0 3
Inherent Safety 6 6 5 5 7 8 9 8 9 3 4 4
Figure 19 - Three Dimensional Sustainability Analyses
Score 0 5 10
Meaning Not Viable Average Excellent
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Environmental Sustainability 8 6 5 4 10 9 9 9 10 1 1 2
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.
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Geographical Analysis of Biodiesel Demand and Production in Michigan Based on the process analysis and sustainability assessment conducted an effective solution to the biodiesel deficit in Michigan is suggested. The total demand of biodiesel in Michigan is assumed to be 50,000 tons/year. Michigan is divided into three geographical areas, Upper Peninsula, Northwestern Michigan, and Southeastern Michigan. Figure 20 shows nine biodiesel plants of varying capacities and geographical locations are recommended to fulfill the demand. Population density, raw material production, and transportation are the factors evaluated to determine the plant locations. Each plant has a functioning radius within which the raw materials would be produced and product biodiesel distributed. It is important to mention that this is a preliminary analysis and locations and capacities of the plants could change based on various factors.
Figure 20 - Proposed Locations of Biodiesel Plants
Upper Peninsula The Upper Peninsula (UP) is allotted two plants one in Marquette and the other in Sault Ste. Marie. The population distribution in the UP is the lowest in the entire state averaging out to be less than one per square mile according to the US census Figure 23. Based on studies conducted [9] area surrounding the Sault Ste. Marie plant by Michigan‟s Biomass Energy Program (MBEP) is most suitable for the production of energy crops. Thus it is recommended that this plant be an alkali-catalyst ethanol plant. The idea here is to utilize the resources available locally, by building an ethanol plant around a farm land which is able to produce high volumes of ethanol, Page 35 of 80
sustainability is ensured. The effective radius of this plant covers all the high tourist spots guaranteeing supply of biodiesel at high demand periods. It is estimated that the potential biodiesel demand for this plant would be 3000 tons/year.
Depending on availability of raw materials the Marquette plant could either be an ethanol or methanol plant. This choice can be made based on the socio-economic impact, for example if incentives are provided for energy crops, an ethanol plant would be built. Due to the lower population density and geographical isolation this plant is only expected to have a low biodiesel demand of 2000 tons/year. For the same reasons this plant is expected to have high transportation costs also. The Northwestern Michigan portion of the state is allocated four varied capacity plants. Northern portion of the state is covered by two Figure 22 – Energy Crops
plants, one in Traverse City and another in Alpena. Both these plants most likely will have to use methanol as a raw material since MBEP studies indicate no surrounding cropland highly conducive for ethanol production. Traverse City is a high tourist location (travel ref) and is estimated to have a demand of 3500 tons/ year. Effective radius of this plant is larger in comparison and intersects with the coverage of both the Alpena and Sault Ste. Marie plants. This is intentional and is aimed to provide better coverage. By creating a grid of plants that are interconnected adequate support can be provided during high peak tourist months. Also the grid Figure 21 - Pasture Land
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ensures redundancy in case one plant faces production delays or fails to function. The plant in Alpena is expected to have a demand of 1500 tons/yr of biodiesel. Combined the Northwestern Michigan region would have a total biodiesel demand of 5000 tons/yr.
Northern Lower Peninsula Western and Mid Michigan are included in the Northwestern Michigan region, plants in Grand Rapids and Mt. Pleasant are recommended for these regions respectively. Both these plants would excel at biodiesel production from ethanol. According to the MBEP study the radii covered by these plants have the highest production of energy crops, thus ensuring low transportation costs and ample raw material supply. Each of these plants is predicted to have a total demand of 5000 ton of biodiesel per year. Due to the advantage of their location in farm and rural area their production would possibly be higher than the demand. The plant in Mt. Pleasant would possibly be able to support the Southern Michigan biodiesel demands. The concept of redundancy and plant gird is again implemented in this region. This ensures supply is kept up with possible changes in demand over the region.
Figure 23 - Population Density
Southern Lower Peninsula The Southeastern Michigan region of state is the densest of all the regions both in population density and transportation. Biodiesel is expected to be directly proportional to population Page 37 of 80
density. Therefore, this region is predicted to have the highest demand in the state a total of 30,000 tons/yr. The transportation costs for this region are estimated to be lowest for the entire state, as it is highly connected. Three plants are recommended for this region, they would be centrally located in Detroit, Ann Arbor and Flint. These plants are expected to produce enough biodiesel to support the entire Southeastern Michigan region. Detroit and Flint plant would be methanol plants and Ann Arbor possibly an ethanol plant. A highly connected grid is created by these three plants; they are estimated to produce 10,000 tons/yr of biodiesel. To effectively compete with gasoline in this area an active offensive approach would be required. By overlapping the effective radius these plants redundant failsafe system is created. As these plants are closer to each other more recharging stations can be supported at low transportation costs while simultaneously increasing profits. Of the nine plants recommended three plants would be alkali-catalyzed ethanol plants and six would be run as alkali-catalyzed methanol plants. Based on the Total Inherent Safety conducted, these plants offer tangible safety improvements. Additionally it is important to note that, the choline chloride/urea extraction can be used for either methanol or ethanol transesterification. All the above analysis is conducted on the assumption that there is a certain demand for biodiesel. The truth however is that there is very low demand for biodiesel in Michigan today. Hence the industry is facing severe crisis that threatens its very existence. Superior process engineering is only one aspect of the solution; the plan is to propose a solution to completely revive Michigan‟s biodiesel industry. This can only be achieved when a combined multi-aspect solution is created. One big problem faced by the biodiesel industry is that biodiesel is a new product that requires customers to acclimate. Decades of using gasoline provide a certain level of convincing and predictability. To overcome this barrier, incentives need to put in place either by the biodiesel industry or the Michigan government. One suggestion is to make available either for a minimal fee or free of charge engine convertors. Vehicle engines running on gasoline can be converted to use biodiesel by simply installing these converters. By increasing the ease in switching to biodiesel from gasoline the biodiesel industry will greatly benefit. Convertors are sold by the local biodiesel producer Arbor Biofuels, located in Milan, Michigan this company has managed to sustain and thrive by keeping their production process up to standards with new developments in biodiesel production.
Advantages: The suggested proposal offers many advantages for Michigan. The most vital benefit would be job creation and the resulting economic activity. Technicians, engineers and general labor force will be required for each plant. As a result biodiesel plants would help produce both direct and indirect employment. The proposal also would benefit indirectly the rural farmers growing energy crops for all the ethanol plants thus increasing rural economic development. A study Page 38 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.
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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 Modifications o 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 Modifications o Water Heat Exchanger Network Heat and Cooler Substituted for Heat Exchanger Network
Of the modified processes, the process using potassium methoxide and methanol is found to be the most profitable and requiring the least amount of time to break even. Process using ethanol with potassium methoxide as the catalyst was found to be the most safe and environmentally friendly. Michigan is divided into three geographical regions: Upper Peninsula, Northwestern Michigan and Southeastern Michigan. The Upper Peninsula is expected to have the highest transportation costs and a biodiesel production of 5,000 tons/yr. A total of nine plants with varying capacities and geographical locations are recommended. Marquette and Sault Ste. Marie are the two suggested plant locations for this region. The Northwestern Michigan region is assigned a total of four plants and includes both Mid Michigan and Western Michigan. The plants would be located at Traverse City, Alpena, Mt. Pleasant, and Grand Rapids. A total biodiesel demand of Page 40 of 80
15,000 tons/yr is estimated for this region. These plants are expected to be ethanol based and have lower transportation costs than UP plants. The densest region in terms of population and demand for biodiesel is the Southeastern Michigan. The plants are suggested at Flint, Ann Arbor, and Detroit. This region is expected to have the highest demand of 30,000 tons/yr and the lowest transportation costs. Advantages of the proposal include local job creation and economic activity. Rural economic development is expected with all the energy crops created for ethanol production is another advantage of the proposal. Dependence on fossil fuel is expected to decrease thus creating a more sustaining and self reliant Michigan economy. Some of the possible constraints could be the performance of biodiesel in cold weather. Additives to final biodiesel product to reduce gel temperature of biodiesel would solve this problem. Low biodiesel demand resulting from lack of consumer awareness is a possibility. Incentives to provide awareness of biodiesel usage and benefits could help transition consumers towards biodiesel and away from gasoline.
Page 41 of 80
Recommendations Equipment recommendations: For alkali-catalyzed processes replacing the catalyst with potassium methoxide is recommended and extremely beneficial. Also a simple heat exchanger system replacing a heater and cooler will help with the optimization of the process. Instead of using a distillation column to purify biodiesel using a DES system of choline chloride and urea is suggested. For the process using ethanol, ethanol recovery is suggested and for the non-catalytic process using methanol at super critical conditions using heated water is more beneficial over the use of heated oil.
Economic Recommendations: To minimize the raw material costs, plants located in the regions of energy crop production should use ethanol for biodiesel production. Lower number of equipment is always recommended in a process as long same or better results are obtained. This reduces the equipment, instillation, operating and maintenance costs.
Inherent Safety Recommendation: Non-catalytic process with methanol at super critical is the most unsafe of all the processes and is not recommended for this reason. The operating temperatures and pressures of this process require high safety review. The best recommendation for inherent safety is the modified process using ethanol.
Michigan's Biodiesel Industry: To compete effectively with gasoline the Michigan biodiesel industry would need to be spread into three geographical regions, Upper Peninsula, Northwestern Michigan and Southeastern Michigan. A total of nine plants is recommended to support the demand of the entire state. Three of the plants would run on ethanol and 6 on methanol. To overcome possible failures and hindrances in supply of biodiesel plants in high density regions are created to form a supply grid. Plants should invest in biodiesel additives to improve performance in cold weather. Also to improve customer awareness of biodiesel incentives such a cheap engine convertors and tax breaks are recommended.
Page 42 of 80
References HYSYS Simulations [1] The problems in design and detailed analyses of energy consumption for biodiesel synthesis at supercritical conditions (Process F), Glisic and Skala, 20 09 [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 Soybe an 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 8Hour 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 43 of 80
[11] United States, Department of Agriculture, 1997 National Re sources Inventory, (1999), p. 20. [12] Environmental Considerations in Energy Crop Production, J. W. Ranne y 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 E mma 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 44 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
Page 45 of 80
Appendix A - Full Stream Data and Large Process Images
Figure 24 - Alkali-catalyzed Process Using Methanol
Table 19 - Stream Data for Alkali-catalyzed Process Using Methanol Prod ucing 500 kg/hr
Temperature
Unit
101
103
101A
101B
102
105B
105A
105
v1
106
201
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
Temperature
Unit C
202 113.9852
201A 28.37256
1201 28.37256
202A 114.0976
203 60
water 25
301 50
302 60
301A 60
301B 60
303 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
C
60
60
60
60
60
61.66437
263.3066
196.3723
196.3723
522.936
Temperature 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 0.000011
M-Oleate
0
0
0.000508
0.000561
0
0
0.000659
0.516618
0.999721
Glycerol
0
0.000096
0.76365
0.843988
0
0
0.99069
0
0
0
Sodium Hydroxide*
0
0
0.003667
0.004053
0
0
0.004757
0
0
0
H2O
0
0.098168
0.108293
0.119686
0
0.80821
0.000007
0.047192
0.000062
0
Phosphoric acid*
1
0
0.002971
0.003283
0
0
0.003854
0
0
0
Trisodium phosphate*
0
0
0.095189
0
1
0
0
0
0
0
Page 47 of 80
Table 20 - Stream Data for Alkali-catalyzed Process Using Methanol Producing 1000 kg/hr
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric acid* Trisodium phosphate*
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric acid* Trisodium phosphate*
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric acid* Trisodium phosphate*
Unit C kPa kg/h
101 103 25 25 100 100 117.2734 9.999277 0 0 1 0 0 0 0 0 0 1 0 0 0 0 0 0
101A 101B 102 25.00067 25.13398 26.6352 100 400 395 127.2726 127.2726 238.4738 0 0 0 0.921434 0.921434 0.95807 0 0 0 0 0 0 0.078566 0.078566 0.04193 0 0 0 0 0 0 0 0 0
Unit C kPa kg/h
202 201A 114.0296 28.37256 30 395 1180.959 111.1789 0.044611 0 0.007304 1 0.851459 0 0.08816 0 0.008467 0 0 0 0 0 0 0
1201 28.37256 395 111.2011 0 1 0 0 0 0 0 0
Unit C kPa kg/h
H3PO4 60 120 8.1634 0 0 0 0 0 0 1 0
304 305 60 60 110 110 136.9988 124.0203 0.000048 0.000053 0.032932 0.036378 0.001068 0.00118 0.760054 0.839592 0.003649 0.004031 0.104557 0.115499 0.002957 0.003266 0.094735 0
v2 60 110 0 0 0.922216 0 0.000077 0 0.077707 0 0
105B 60 400 1053.664 1 0 0 0 0 0 0 0
202A 203 water 114.1424 60 25 200 120 110 1180.959 1180.959 11.07929 0.044611 0.044611 0 0.007304 0.007304 0 0.851459 0.851459 0 0.08816 0.08816 0 0.008467 0.008467 0 0 0 1 0 0 0 0 0 0 306 60 109 12.97858 0 0 0 0 0 0 0 1
Page 48 of 80
501 59.56967 40 18.83937 0 0.239478 0 0.000189 0 0.760333 0 0
105A 105 26.94912 25 400 100 1053.664 1053.664 1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0
v1 60 395 0 0 0.999984 0.000006 0.00001 0 0 0 0
106 60 395 1292.138 0.040772 0.092718 0.778197 0.080575 0.007739 0 0 0
201 28.19579 20 111.1789 0 1 0 0 0 0 0 0
301 59.21506 110 1063.202 0.049427 0.003856 0.945744 0 0 0.000972 0 0
302 60.00062 120 128.8359 0.001027 0.035124 0.000155 0.808108 0.077612 0.077972 0 0
301A 60 110 1063.202 0.049427 0.003856 0.945744 0 0 0.000972 0 0
301B 60 120 0 0 0 0 1 0 0 0 0
303 60.00069 120 128.8359 0.001027 0.035124 0.000155 0.808108 0.077612 0.077972 0 0
502 263.3458 50 105.1809 0.000063 0 0.001391 0.989941 0.004753 0 0.003851 0
401A 401 402 185.1412 185.1412 360.6182 10 10 20 7.819739 1000.001 55.38204 0 0 0.948879 0.493595 0.00024 0 0.393114 0.999612 0.051121 0 0 0 0 0 0 0.113291 0.000148 0 0 0 0 0 0 0
Table 21 - Stream Data for Alkali-catalyzed Process Using Methanol Producing 1500 kg/hr
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric acid* Trisodium phosphate*
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric acid* Trisodium phosphate*
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric acid* Trisodium phosphate*
Unit C kPa kg/h
101 25 100 175.91 0 1 0 0 0 0 0 0
103 25 100 14.99892 0 0 0 0 1 0 0 0
Unit C kPa kg/h
202 201A 114.1318 28.37256 30 395 1771.39 111.2159 0.044612 0 0.007277 1 0.851482 0 0.088162 0 0.008467 0 0 0 0 0 0 0
1201 28.37256 395 111.2011 0 1 0 0 0 0 0 0
Unit C kPa kg/h
H3PO4 60 120 12.2451 0 0 0 0 0 0 1 0
304 305 60 60 110 110 205.4711 186.0032 0.000048 0.000053 0.032801 0.036234 0.001063 0.001174 0.760154 0.839715 0.00365 0.004032 0.10458 0.115526 0.002957 0.003267 0.094748 0
v2 60 110 0 0 0.921934 0 0.000078 0 0.077989 0 0
101A 101B 25.00067 25.13398 100 400 190.909 190.909 0 0 0.921434 0.921434 0 0 0 0 0.078566 0.078566 0 0 0 0 0 0
102 105B 26.31768 60 395 400 302.1101 1580.496 0 1 0.950353 0 0 0 0 0 0.049647 0 0 0 0 0 0 0
202A 203 water 114.2438 60 25 200 120 110 1771.39 1771.39 16.61893 0.044612 0.044612 0 0.007277 0.007277 0 0.851482 0.851482 0 0.088162 0.088162 0 0.008467 0.008467 0 0 0 1 0 0 0 0 0 0 306 60 109 19.46788 0 0 0 0 0 0 0 1
Page 49 of 80
501 59.59958 40 28.22757 0 0.238759 0 0 0 0.761241 0 0
105A 105 26.94912 25 400 100 1580.496 1580.496 1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0
v1 60 395 0 0.042313 0.066452 0.807614 0.08362 0 0 0 0
106 60 395 1882.606 0.041976 0.065922 0.80118 0.082954 0.007967 0 0 0
201 28.19579 20 111.2159 0 1 0 0 0 0 0 0
301 59.21492 110 1594.783 0.049428 0.003844 0.945757 0 0 0.000971 0 0
302 60.00018 120 193.2267 0.001022 0.034985 0.000155 0.808222 0.077623 0.077993 0 0
301A 60 110 1594.783 0.049428 0.003844 0.945757 0 0 0.000971 0 0
301B 60 120 0 0 0 0 1 0 0 0 0
303 60.00026 120 193.2267 0.001022 0.034985 0.000155 0.808222 0.077623 0.077993 0 0
502 263.3396 50 157.7756 0.000063 0 0.001384 0.989948 0.004753 0.000001 0.003851 0
401A 401 402 160.9465 160.9465 336.2895 10 10 20 7.82138 1499.998 86.96332 0 0 0.906443 0.700943 0.000432 0 0.150814 0.999309 0.093557 0 0 0 0 0 0 0.148242 0.000259 0 0 0 0 0 0 0
Table 22 - Stream Data for Alkali-catalyzed Process Using Methanol Producing 2000 kg/hr
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric acid* Trisodium
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric acid* Trisodium
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric acid* Trisodium
Unit C kPa kg/h
101 25 100 234.5467 0 1 0 0 0 0 0 0
Unit C kPa kg/h
Unit C kPa kg/h
103 25 100 19.99856 0 0 0 0 1 0 0 0
101A 101B 102 105B 25.00067 25.13398 26.11103 60 100 400 395 400 254.5453 254.5453 365.7464 2107.328 0 0 0 1 0.921434 0.921434 0.945321 0 0 0 0 0 0 0 0 0 0.078566 0.078566 0.054679 0 0 0 0 0 0 0 0 0 0 0 0 0
105A 105 26.94912 25 400 100 2107.328 2107.328 1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0
v1 60 395 0 0.042953 0.052346 0.819818 0.084884 0 0 0 0
106 60 395 2473.075 0.042605 0.051922 0.813188 0.084198 0.008087 0 0 0
201 28.19579 20 111.205 0 1 0 0 0 0 0 0
202 201A 114.0666 28.37256 30 395 2361.87 111.205 0.044611 0 0.007283 1 0.851476 0 0.088162 0 0.008467 0 0 0 0 0 0 0
1201 28.37256 395 111.2011 0 1 0 0 0 0 0 0
202A 203 water 114.1787 60 25 200 120 110 2361.87 2361.87 22.15857 0.044611 0.044611 0 0.007283 0.007283 0 0.851476 0.851476 0 0.088162 0.088162 0 0.008467 0.008467 0 0 0 1 0 0 0 0 0 0
301 59.21504 110 2126.384 0.049428 0.003847 0.945754 0 0 0.000971 0 0
302 59.99969 120 257.6448 0.001024 0.03502 0.000155 0.808193 0.077621 0.077988 0 0
301A 60 110 2126.384 0.049428 0.003847 0.945754 0 0 0.000971 0 0
301B 60 120 0 0 0 0 1 0 0 0 0
303 59.99976 120 257.6448 0.001024 0.03502 0.000155 0.808193 0.077621 0.077988 0 0
H3PO4 60 120 16.3268 0 0 0 0 0 0 1 0
304 60 110 273.9706 0.000048 0.032833 0.001064 0.760129 0.000029 0.106205 0 0.099691
305 60 110 246.6582 0.000053 0.036469 0.001182 0.844297 0.000032 0.117966 0 0
502 263.3375 50 208.566 0.000063 0 0.001398 0.998499 0.000038 0.000002 0 0
401A 401 402 134.5358 134.5357 329.2866 10 10 20 7.821758 1999.977 118.5846 0 0 0.88631 0.822044 0.000875 0 0.034097 0.998655 0.11369 0 0 0 0 0 0 0.143859 0.00047 0 0 0 0 0 0 0
v2 60 110 0 0 0.92138 0 0.000078 0 0.078542 0 0
306 60 109 27.3124 0 0 0 0 0 0 0 1
Page 50 of 80
501 59.70562 40 38.0922 0 0.236148 0 0 0 0.763852 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
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric acid* Trisodium phosphate*
Unit C kPa kg/h
101 25 100 117.2734 0 1 0 0 0 0 0 0
103 25 100 9.999277 0 0 0 0 1 0 0 0
101A 101B 102 25.00067 25.13398 26.6352 100 400 395 127.2726 127.2726 238.4738 0 0 0 0.921434 0.921434 0.95807 0 0 0 0 0 0 0.078566 0.078566 0.04193 0 0 0 0 0 0 0 0 0
105B 60 400 1053.664 1 0 0 0 0 0 0 0
105A 25 400 1053.664 1 0 0 0 0 0 0 0
105 v1 23.05339 60 100 395 1053.664 0 1 0 0 0.999984 0 0.000006 0 0.00001 0 0 0 0 0 0 0 0
106 60 395 1292.138 0.040772 0.092718 0.778197 0.080575 0.007739 0 0 0
201 28.19579 20 111.1837 0 1 0 0 0 0 0 0
Unit
201A
1201
202A
301
302
301A
303
H3PO4
203
water
301B
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric Phosphoric acid* Trisodium Trisodium phosphate* phosphate*
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol Sodium Hydroxide* H2O Phosphoric acid* Trisodium phosphate*
C kPa kg/h
28.37256 28.37256 395 395 111.1837 111.2011 0 0 1 1 0 0 0 0 0 0 0 0 0 0 0 0
114.1655 200 1180.954 0.044611 0.0073 0.851462 0.08816 0.008467 0 0 0
60 25 200 110 1180.954 11.07929 0.044611 0 0.0073 0 0.851462 0 0.08816 0 0.008467 0 0 1 0 0 0 0
Unit C kPa kg/h
304 305 60 60 110 110 136.9962 124.0176 0.000048 0.000053 0.032912 0.036357 0.001067 0.001179 0.760068 0.83961 0.003649 0.004031 0.104561 0.115503 0.002957 0.003266 0.094737 0
306 60 109 12.97858 0 0 0 0 0 0 0 1
501 59.56245 40 18.81198 0 0.239681 0 0 0 0.760319 0 0
59.21462 110 1063.2 0.049427 0.003855 0.945746 0 0 0.000972 0 0
60.00023 120 128.8333 0.001027 0.035104 0.000155 0.808125 0.077614 0.077975 0 0
60 110 1063.2 0.049427 0.003855 0.945746 0 0 0.000972 0 0
60 120 0 0 0 0 1 0 0 0 0
502 401A 401 402 306S 262.409 185.164 185.164 360.6392 25 50 10 10 20 100 105.2056 7.82002 999.9995 55.38065 12.97858 0.000063 0 0 0.948904 0 0 0.493335 0.00024 0 0 0.00139 0.393398 0.999612 0.051096 0 0.989742 0 0 0 0 0.004752 0 0 0 0 0.000203 0.113267 0.000148 0 0 0.00385 0 0 0 0 0 0 0 0 1
Page 52 of 80 of 80
60.00031 60 120 120 128.8333 8.1634 0.001027 0 0.035104 0 0.000155 0 0.808125 0 0.077614 0 0.077975 0 0 1 0 0 202B 202 112.3524 114.0519 200 30 1180.954 1180.954 0.044611 0.044611 0.0073 0.0073 0.851462 0.851462 0.08816 0.08816 0.008467 0.008467 0 0 0 0 0 0
Figure 26 - Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea and KOCH3 Modification
Table 24 - Stream Data for Alkali-catalyzed Process Using Methanol Wit h Choline Chloride/Urea and KOCH3 Modi fication
Temperature Pressure Mass Flow Triolein M-Oleate Glycerol Methanol Choline Chloride/ KOCH3*
Unit C kPa kg/h
101 25 100 127.26 0 0 0 1 0 0
105 25 100 1050 1 0 0 0 0 0
101A 25.0559 100 127.330 0 0 0 0.99944 0 0.00055
105A 26.9491 400 1050 1 0 0 0 0 0
105B 50 400 1050 1 0 0 0 0 0
Page 53 of 80 of 80
102 22.7302 100 261.278 0 0 0 0.91118 0 0.08881
v1 50 100 0 0.00800 0.79638 0.08242 0.09549 0 0.01769
106 50 100 1311.27 0.00800 0.79638 0.08242 0.09549 0 0.01769
201 20.1724 20 134.098 0 0 0 0.82699 0 0.17300
202 99.2844 30 1177.18 0.00892 0.88709 0.09180 0.01216 0 0.00000
202A 99.3960 200 1177.18 0.00892 0.88709 0.09180 0.01216 0 0.00000
Temperature Pressure Mass Flow Triolein M-Oleate Glycerol Methanol Choline Chloride/ KOCH3*
Unit C kPa kg/h
202B 50 200 1177.18 0.00892 0.88709 0.09180 0.01216 0 0.00000
choline chloride / 50 120 2.5 0 0 0 0 1 0
301 40 110 1052.67 0.00298 0.99702 0 0 0 0
302 50 120 127.004 0.01653 0 0.85096 0.11278 0.01968 0.00003
303 50 120 124.504 0.01686 0 0.86804 0.11504 0 0.00003
Figure 27 - Alkali-catalyzed Process Using Methanol With C holine Chloride/Urea, KOCH3, and HEN Modification
Page 54 of 80 of 80
304 50 120 2.5 0 0 0 0 1 0
401 43.6919 40 16.5051 0 0 0.13186 0.86784 0 0.00029
402 263.403 50 107.999 0.01944 0 0.98055 0 0 0
201A 20.2138 100 134.098 0 0 0 0.82699 0 0.17300
1201 20.2279 100 133.948 0 0 0 0.82728 0 0.17271
103 25 100 0.07012 0 0 0 0 0 1
Table 25 - Stream Data for Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea, KOCH3, and HEN Modification
Temperature Pressure Mass Flow Triolein M-Oleate Glycerol Methanol Choline Chloride/ KOCH3*
Temperature Pressure Mass Flow Triolein M-Oleate Glycerol Methanol Choline Chloride/ KOCH3*
Unit C kPa kg/h
101 100 100 126.94 0 0 0 1 0 0
105 25 100 1050 1 0 0 0 0 0
101A 99.97864 100 127.0101 0 0 0 0.999448 0 0.000552
103 25 100 0.07012 0 0 0 0 0 1
105A 26.9491 400 1050 1 0 0 0 0 0
105B 50 400 1050 1 0 0 0 0 0
102 62.9021 100 261.186 0 0 0 0.91115 0 0.08884
106 50 100 1311.18 0.00800 0.79643 0.08242 0.09543 0 0.01769
201 20.1784 20 134.205 0 0 0 0.82712 0 0.17287
202 99.7053 30 1176.98 0.00892 0.88725 0.09182 0.012 0 0.00000
1201 20.2412 100 134.176 0 0 0 0.82757 0 0.17242
Unit C kPa kg/h
202A 98.6331 200 1176.98 0.00892 0.88725 0.09182 0.012 0 0.00000
202B 2 02B 50 200 1176.98 0.00892 0.88725 0.09182 0.012 0 0.00000
choline chloride / 50 120 2.5 0 0 0 0 1 0
301 40 110 1052.67 0.00798 0.99202 0 0 0 0
302 50 120 126.805 0.01656 0 0.85230 0.11138 0.01971 0.00003
303 50 120 124.305 0.01689 0 0.86944 0.11362 0 0.00003
304 50 120 2.5 0 0 0 0 1 0
401 42.5612 40 14.1288 0 0 0 0.99965 0 0.00034
402 263.386 50 110.176 0.01906 0 0.98093 0.00000 0 0
202_A1 98.5215 30 1176.98 0.00892 0.88725 0.09182 0.012 0 0.00000
201A 20.2198 100 134.205 0 0 0 0.82712 0 0.17287
Page 55 of 80 of 80
Figure 28 - Alkali-catalyzed Process Using Ethanol Table 26 - Stream Data for Alkali-catalyzed Process Using Ethanol
Temperature Pressure Mass Flow CetylC1cryla Triolein Ethanol NaOH H2O Glycerol
Unit C kPa kg/h
2 25 101.3 1000 0 1 0 0 0 0
2a 25 101.3 1000 0 1 0 0 0 0
1d 1e 3 25 41.78382 40.78808 101.3 101.3 101.3 322.8 610.3696 1610.37 0 0 0 0 0 0.620975 0.969331 0.98378 0.372877 0.030669 0.01622 0.006148 0 0 0 0 0 0
vapor 70 101.3 0 0.000024 0 0.999968 0 0 0.000008
Page 56 of 80
4 70 101.3 1610.388 0.653212 0.000103 0.27596 0.006148 0 0.064577
1a 25 101.3 312.9 0 0 1 0 0 0
1b 25 101.3 9.9 0 0 0 1 0 0
1c 5 9 25 78.17196 60.31282 101.3 101.325 101.325 322.8 287.5165 287.5165 0 0 0 0 0 0 0.969331 1 1 0.030669 0 0 0 0 0 0 0 0
Temperature Pressure Mass Flow CetylC1cryla Triolein Ethanol NaOH H2O Glycerol
Unit C kPa kg/h
10 13 14 6 6a 11 12 60.31616 78.48236 295.26 102.0929 61.7034 30 90.08969 101.325 101 101 101.325 101.325 101 101 287.5696 161.7798 109 1322.871 1322.871 1052.091 270.7802 0 0 0 0.795183 0.795183 0.999842 0 0 0 0 0.000126 0.000126 0.000158 0 1 0.969751 0 0.118595 0.118595 0 0.579385 0 0 0.090825 0.007484 0.007484 0 0.036561 0 0 0 0 0 0 0 0 0.030249 0.909175 0.078612 0.078612 0 0.384054
Figure 29 - Alkali-catalyzed Process Using Ethanol Recovery Modification
Page 57 of 80
Table 27 - Stream Data for Alkali-catalyzed Process Using Ethanol Recovery Modification
Temperature Pressure Mass Flow CetylC1cryl Triolein Ethanol NaOH H2O Glycerol
Temperature Pressure Mass Flow CetylC1cryl Triolein Ethanol NaOH H2O Glycerol
Uni C kPa kg/
2 25 101. 1000 0 1 0 0 0 0
2a 25 101. 1000 0 1 0 0 0 0
1d 25 101.3 166.07083 0 0 0.940387 0.059613 0 0
1e 55.40179 101 610.3 0 0 0.983778 0.016222 0 0
3 53.63448 101 1610.3 0 0.621002 0.37285 0.006148 0 0
vapor 70 101 0 0.00002 0 0.99996 0 0 0.00000
4 70 101 1610.31833 0.653241 0.000103 0.275929 0.006148 0 0.06458
1a 25 101.3 156.17083 0 0 1 0 0 0
1b 25 101.3 9.9 0 0 0 1 0 0
1c 25 101.3 166.07083 0 0 0.940387 0.059613 0 0
Uni C kPa kg/
10 60.2 101 287. 0 0 1 0 0 0
13 78.4 101 161. 0 0 0.97 0 0 0.03
14 295.25979 101 109 0 0 0 0.090826 0 0.909174
6a 61.62917 101 1322.689 0.795292 0.000126 0.118474 0.007485 0 0.078623
11 30 101 1052.091 0.999842 0.000158 0 0 0 0
12 90.0844 101 270.598 0 0 0.57910 0.03658 0 0.38431
13a 78.090801 101 156.698016 0 0 1 0 0 0
13b 276.00524 101 4.900494 0 0 0.001291 0 0 0.998709
6 102 101 1323 0.795 1E-04 0.118 0.007 0 0.079
13a1 78.090801 101 156.70665 0 0 1 0 0 0
Page 58 of 80
5 78.090801 101 287.62857 0 0 1 0 0 0
9 60.236408 101 287.62857 0 0 1 0 0 0
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
Temperature Pressure Mass Flow Liquid Volume Triolein Methanol M-Oleate Glycerol n-Decane
Unit C kPa kg/h m3/h
102 24.854068 10 1282 1.399632 1 0 0 0 0
101 15.212473 10 139 0.174685 0 1 0 0 0
101A -8.994137 10 1947.773778 2.447813 0 1 0 0 0
102A 37.98 2000 1282 1.399632 1 0 0 0 0
101B -8.076586 2000 1947.773778 2.447813 0 1 0 0 0
Page 59 of 80
103 -6.97251 2000 3229.773778 3.847445 0.396932 0.603068 0 0 0
201 300 2000 3229.773778 3.847445 0.396932 0.603068 0 0 0
202 250.593694 2000 3229.825966 3.847395 0.018077 0.561929 0.380589 0.039405 0
203 183.5 2000 3229.825966 3.847395 0.018077 0.561929 0.380589 0.039405 0
Temperature Pressure Mass Flow Liquid Volume Triolein Methanol M-Oleate Glycerol n-Decane Tem erature Pressure Mass Flow Liquid Volume Triolein Methanol M-Oleate Glycerol n-Decane Temperature Pressure Mass Flow Liquid Volume Triolein Methanol M-Oleate Glycerol n-Decane
Unit C kPa kg/h m3/h
204 172.481008 1500 3229.82597 3.847395 0.018077 0.561929 0.380589 0.039405 0
301 2 1808.8122 2.273177 0 1 0 0 0
302 94.346443 3 1421.01374 1.574218 0.041088 0.004308 0.865042 0.089563 0
301B -10.868611 10 1808.773778 2.273129 0 1 0 0 0
301A -10.868611 10 1808.812226 2.273177 0 1 0 0 0
303 98.848423 10 1290.071012 1.468657 0.045258 0.001898 0.952844 0 0
304 60 10 130.942727 0.105561 0 0.028049 0 0.971951 0
Unit 401A 401 402 C 179.521496 179.521496 435.646591 kPa 1 1 2 kg/h 19.42799 1212.25703 58.38599 m3/h 0.022429 1.382485 0.063743 0 0 0.999999 0.120774 0.000084 0 0.879226 0.999916 0.000001 0 0 0 0 0 0
501 1 10.542701 0.010065 0 0.348379 0 0.651621 0
502 176.227602 2 120.400027 0.095496 0 0 0 1 0
601 25 1000 7920 10.809025 0 0 0 0 1
602 28.39215 5000 7920 10.809025 0 0 0 0 1
603 360 5000 7920 10.809025 0 0 0 0 1
604 360 5000 2500 3.41194 0 0 0 0 1
Unit C kPa kg/h m3/h
608 278.68784 5000 7920 10.809025 0 0 0 0 1
605 360 5000 5420 7.397086 0 0 0 0 1
205 150.752821 800 3229.82597 3.847395 0.018077 0.561929 0.380589 0.039405 0
206 66.50435 10 3229.825966 3.847395 0.018077 0.561929 0.380589 0.039405 0
606 607 165.113945 238.13535 5000 5000 5420 5420 7.397086 7.397086 0 0 0 0 0 0 0 0 1 1
Page 60 of 80
Figure 31 - Non-catalytic Process Operated at Supercritical Condition of Methanol with Water HEN Modi fication
Table 29 - Stream Data for Non-catalytic Process Operated at Supercritical Condition of Methanol with Water HEN Modification
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol H2O
Unit C kPa kg/h
102 24.85407 10 1282 1 0 0 0 0
101 15.21247 10 139 0 1 0 0 0
101A -8.99417 10 1947.812 0 1 0 0 0
102A 37.98 2000 1282 1 0 0 0 0
101B -8.07662 2000 1947.812 0 1 0 0 0
103 201 202 -6.97257 300 250.5941 2000 2000 2000 3229.812 3229.812 3229.864 0.396927 0.396927 0.018078 0.603073 0.603073 0.561935 0 0 0.380584 0 0 0.039404 0 0 0
Page 61 of 80
203 183.5 2000 3229.864 0.018078 0.561935 0.380584 0.039404 0
204 172.481 1500 3229.864 0.018078 0.561935 0.380584 0.039404 0
205 150.7529 800 3229.864 0.018078 0.561935 0.380584 0.039404 0
206 66.50517 10 3229.864 0.018078 0.561935 0.380584 0.039404 0
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol H2O
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol H2O
Unit C kPa kg/h
301 -10.8723 2 1808.814 0 1 0 0 0
302 94.16359 3 1421.05 0.041089 0.004334 0.865017 0.08956 0
301B -10.8686 10 1808.812 0 1 0 0 0
301A -10.8686 10 1808.814 0 1 0 0 0
Unit C kPa kg/h
603 320 5000 1150 0 0 0 0 1
604 -2.19869 5000 1150 0 0 0 0 1
607 235.4331 5000 1150 0 0 0 0 1
402 435.4639 2 58.38986 0.999989 0 0.000011 0 0
303 304 98.64366 60 10 10 1290.086 130.9646 0.04526 0 0.001909 0.028214 0.952831 0 0 0.971786 0 0
401A 401 501 187.3731 187.3731 -11.1837 1 1 1 42.54897 1189.147 10.56457 0 0 0 0.056615 0.000046 0.349761 0.943385 0.999954 0 0 0 0.650239 0 0 0
Figure 32 - Non-catalytic Process Operated at Supercritical Condition of Methanol with Heater/Cooler Modification
Page 62 of 80
502 601 176.2276 25 2 1000 120.4 1150 0 0 0 0 0 0 1 0 0 1
602 25.37684 5000 1150 0 0 0 0 1
Table 30 - Stream Data for Non-catalytic Process Operated at Supercritical Condition of Methanol with Heater/Cooler Modification
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol
Temperature Pressure Mass Flow Triolein Methanol M-Oleate Glycerol
Unit C kPa kg/h
102 24.85407 10 1282 1 0 0 0
101 15.21247 10 139 0 1 0 0
101A -8.99414 10 1947.774 0 1 0 0
Unit C kPa kg/h
301 -10.8723 2 1808.783 0 1 0 0
302 301B 94.19785 -10.8686 3 10 1421.043 1808.774 0.041091 0 0.004329 1 0.86502 0 0.08956 0
102A 37.98 2000 1282 1 0 0 0
101B -8.07659 2000 1947.774 0 1 0 0
103 201 202 -6.97251 300 250.6075 2000 2000 2000 3229.774 3229.774 3229.826 0.396932 0.396932 0.018079 0.603068 0.603068 0.561929 0 0 0.380587 0 0 0.039404
301A -10.8686 10 1808.783 0 1 0 0
303 304 401A 401 402 501 502 98.68203 60 179.498 179.498 435.5754 -11.1769 176.2276 10 10 1 1 2 1 2 1290.083 130.9602 19.49095 1212.2 58.39207 10.56016 120.4 0.045262 0 0 0 0.999995 0 0 0.001907 0.028183 0.120994 0.000084 0 0.349511 0 0.952831 0 0.879006 0.999916 0.000005 0 0 0 0.971817 0 0 0 0.650489 1
Page 63 of 80
203 183.5 2000 3229.826 0.018079 0.561929 0.380587 0.039404
204 172.481 1500 3229.826 0.018079 0.561929 0.380587 0.039404
205 150.7528 800 3229.826 0.018079 0.561929 0.380587 0.039404
206 66.50428 10 3229.826 0.018079 0.561929 0.380587 0.039404
Appendix B - Raw Data Economic NAPAT Process A - 500 Item Value Equipment
($)
E-100 E-201 MIX-100A
19900 19900 0
MIX-100B MIX-101 P-101B P-103 P-201 P-202 R-101 R-201 RCY-1 T-100-tower T-201-tower T-201-cond T-201-cond acc T-201-reflux pump T-201-overhead split T-201-bottoms split T-201-reb T-401-tower T-401-cond T-401-cond acc T-401-reflux pump T-401-overhead split T-401-bottoms split T-401-reb T-501-tower T-501-cond T-501-cond acc T-501-reflux pump T-501-overhead split T-501-bottoms split
0 0 3700 3600 3800 3600 31400 20900 0 38000 25100 16400 14700 4000 0 0 20600 115100 36500 14700 4000 0 0 20600 25600 36500 14700 4000 0 0
T-501-reb X-301 X-302 Σ= Total bare module cost (TBMCC)
Contingency fee (CF = 0.18TBMCC)
20700 0 0 518000 93240 611240 183372 794612 119191.8 913803.8
Total basic module cost (TBMC = TBMCC+CF) Auxiliary facility investment (AFI = 0.3 × TBMC) Fixed capital investment (FCI = TBMC + AFI) Working capital investment (WCI = 0.15FCI) Total capital investment (TCI = FCI+WCI) Total raw material Methanol NaOH Vegetable Oil Water H3PO4 Operating labor Supervisory and clerical labor (15% of operating labor) Utilities
84441.6 8000 2107200 88.64 11103.04 372101.2308 55815.18463
High Pressure Steam
360
Low Pressure Steam
87693.216 6378.144
Cooling Water
Waste disposal Liquid Solid
Maintenance and repairs (6% of FCI) Operating supplies (15% of maintenance and repairs) Laboratory charges (15% of operating labors) Total manufacturing cost (TMC) Patents and royalties (3% of TMC) Σ = Total direct manufacturing cost (TDMC)
Overhead, packaging and storage (60% of the sum of operating labor, Local taxes (1.5% of FCI) Insurance (0.5% of FCI) Σ= Total indirect manufacturing cost (TIMC)
Annual depreciation change (ADC = 10% of FCI) General expenses
Page 65 of 80
11096.4 2021.088 47676.72 7151.508 55815.18463 3770745.756 113122.3727 3883868.129 285355.8813 11919.18 3973.06 301248.1213 79461.2
Administrative costs (25% of overhead) Distribution and selling cost (10% of total manufacturing cost) Research and development (5% of total manufacturing cost) Σ= Total general expenses (TGE)
Total production cost (TPC = TDMC + TIMC + ADC + TGE) Revenue from biodiesel and byproducts Net annual profit (NAP = Revenue - TPC) Income taxes (IT = 50% of NAP) Net annual profit after taxes (NAPAT)
Break Even Point
71338.97032 418511.625 209255.8125 699106.4078 4963683.858 4463168 -500515.8579 -250257.9289 -250257.9289
-19.8342721
For complete economic data see: Process A,C,F Economic Comparison.xlsx
Page 66 of 80
year
Environmental Individual impact categories Total output Case 500 1000 1500 2000 1000H 1000H
HTP 9.44 2.22 2.03 2.30 1.91 1.29
HTPE
Case 500 1000 1500 2000 1000H 1000H
HTP 1.69 2.01 1.16 9.88 1.73 1.10
HTPE
Case 1000 1000H 1000H
HTP 2.01 1.73 1.10
HTPE
9.44E-01 2.22E+00 2.03E+00 2.30E+00 1.91E+00 1.29E-01
ATP 7.68 1.36 2.00 2.71 3.38 4.37
GW 4.90 8.49 1.20 1.70 1.08 3.18
OD 5.1 8.9 1.2 1.7 1.1 3.3
PC 3.7 9.8 7.7 7.1 9.5 1.1
AP 1.52 2.63 3.71 5.26 3.35 9.87
TOT 2.59 5.00 6.13 8.17 2.08 1.25
1.69E-03 2.01E-03 1.16E-03 9.88E-04 1.73E-03 1.10E-04
ATP 1.38 1.23 1.14 1.16 3.06 3.71
GW 8.79 7.69 6.84 7.29 9.79 2.70
OD 9.2 8.0 7.2 7.6 1.0 2.8
PC 6.6 8.9 4.4 3.0 8.6 9.9
AP 2.72 2.38 2.12 2.26 3.03 8.38
TOT 4.65 4.53 3.51 3.50 1.88 1.07
2.01E-03 1.73E-03 1.10E-04
ATP 1.23 3.06 3.71
GW 7.69 9.79 2.70
OD 8.0 1.0 2.8
PC 8.9 8.6 9.9
AP 2.38 3.03 8.38
TOT 4.53 1.88 1.07
TTP
4.70E-03 1.10E-02 1.09E-02 1.38E-02 4.81E-03 2.01E-03 otal PEI leaving the system per
TTP 8.44E-06 1.00E-05 6.23E-06 5.94E-06 4.36E-06 1.71E-06
TTP 1.00E-05 4.36E-06 1.71E-06
For complete data see: ENVIRONMENTAL EMPACT REPORT(2)ii.xlsx
Inherent Safety Process A - 500 Chemical inherent safety index, ICI Heat of main reaction Heat of side reaction, max Chemical interaction Flammability Explosiveness Toxic exposure Page 67 of 80
Symbol IRM IRS IINT IFL IEX ITOX
Value <200 N/A Heat of formation 130C MeOH 7-36% MeOH 200
Score 0 0 1 1 2 2
Corrosiveness
ICOR
Stainless
1
Inventory Process temperature Process pressure Equipment safety Isbl Osbl Safe process structure
II IT Ip
4,000 tons 529 C 400 kPA
1 3 0
IEQ
Tower N/A Preferred
1 0 0 12
Process inherent safety index, IPI
IST
Total Inherent Safety
For complete data see: Inherent Safety.xlsx
IChemE Evaluation Table 31 - IChemE Sustainability Process Reference Table
Process Alkali-catalyzed Process Using Methanol 4,000 tons/yr Alkali-catalyzed Process Using Methanol 8,000 tons/yr Alkali-catalyzed Process Using Methanol 12,000 tons/yr Alkali-catalyzed Process Using Methanol 16,000 tons/yr Alkali-catalyzed Process Using Methanol With Cooler and HEN Modification Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea and KOCH3 Modification Alkali-catalyzed Process Using Methanol With Choline Chloride/Urea, KOCH3, and HEN Modification Alkali-catalyzed Process Using Ethanol Alkali-catalyzed Process Using Ethanol Recovery Modification Non-catalytic Process Operated at Supercritical Condition of Methanol Non-catalytic Process Operated at Supercritical Condition of Methanol with Water HEN Modification Non-catalytic Process Operated at Supercritical Condition of Methanol with Heater/Cooler Modification Energy
IChemE Reference Number 1 2 3 4 5 6 7 8 9 10 11 12
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 GJ +00 /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 68 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
9.57E04
8.13E04
8.79E05
1.28E04
1.27E04
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
8.41E01
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
Total raw materials used per kg product
8
9
10
11
12
1.46E+
1.64E+
2.14E-
1.41E+
1.41E+
Page 69 of 80
kg/k
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
Net water consumed per unit mass of product Net water consumed per unit value added
1
2
3
4
5
6
7
1.27E +01 9.75E +04
2.11E +01 2.48E +02
2.15E +01 1.46E +02
2.27E +01 1.27E +02
2.11E +01 1.17E +02
5.98E +00 3.40E +01
2.11E +01 1.17E +02
kg/ kg kg/ $
kg/k g
Net water consumed per unit mass of product Net water consumed per unit value added
8
9
10
11
12
1.01E+0 1 5.64E+0 1
2.27E+0 2 1.27E+0 3
6.38E+0 1 3.56E+0 2
6.38E+0 1 3.56E+0 2
7.31E+0 1 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) Rate of land restoration (restored per year /total) b)
4.81E -03 0.00E +00
1.96E +01 0.00E +00
7.54E +00 0.00E +00
4.64E +00 0.00E +00
9.29E +00 0.00E +00
9.03E +00 0.00E +00
9.29E +00 0.00E +00
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
Page 70 of 80
m2/( $/y) (m2/ y)/m
m2/($/ y)
Rate of land restoration (restored per year /total) b) Atmospheric Impacts
0.00E+ 00
0.00E+ 00
0.00E+ 00
0.00E+ 00
0.00E+ 00
(m2/ y)/m2
Table 36 - IChemE Atmospheric Impact Comparison
Atmospheric acidification burden per unit value added a) Global warming burden per unit value added b) Human Health burden per unit value added c) Ozone depletion burden per unit value added d) Photochemical ozone burden per unit value added e)
1
2
3
4
5
6
7
0.00E +00 0.00E +00 0.00E +00 3.99E -03 0.00E +00
0.00E +00 0.00E +00 0.00E +00 7.97E -03 0.00E +00
0.00E +00 0.00E +00 0.00E +00 1.20E -02 0.00E +00
0.00E +00 0.00E +00 0.00E +00 1.59E -02 0.00E +00
0.00E +00 0.00E +00 0.00E +00 7.97E -03 0.00E +00
0.00E +00 0.00E +00 0.00E +00 3.26E -02 0.00E +00
0.00E +00 0.00E +00 0.00E +00 3.26E -02 0.00E +00
Atmospheric acidification burden per unit value added a) Global warming burden per unit value added b) Human Health burden per unit value added c) Ozone depletion burden per unit value added d) Photochemical ozone burden per unit value added e) Aquatic Impacts
8
9
10
11
12
0.00E+ 00 0.00E+ 00 0.00E+ 00 7.77E01 0.00E+ 00
0.00E+ 00 0.00E+ 00 0.00E+ 00 0.00E+ 00 0.00E+ 00
0.00E+ 00 0.00E+ 00 0.00E+ 00 5.99E+ 01 0.00E+ 00
0.00E+ 00 0.00E+ 00 0.00E+ 00 1.37E02 0.00E+ 00
0.00E+ 00 0.00E+ 00 0.00E+ 00 1.37E02 0.00E+ 00
te/ te/ te/ te/ te/
te/ te/ te/ te/ te/
Table 37 - IChemE Aquatic Impact Comparison
1
2
3
4
5
6
7
Aquatic acidification per unit value added a) Aquatic oxygen demand per unit value added b) Ecotoxicity to aquatic life per unit value added c)
0.00E +00 2.92E02
0.00E +00 5.83E02
0.00E +00 8.75E02
0.00E +00 1.17E01
0.00E +00 5.83E02
0.00E +00 2.39E01
0.00E +00 2.39E01
(i) metals
0.00E +00
0.00E +00
0.00E +00
0.00E +00
0.00E +00
0.00E +00
0.00E +00
Page 71 of 80
te/ te/
te/ $
0.00E +00 0.00E +00
(ii) other 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 0.00E +00
0.00E +00 0.00E +00
0.00E +00 0.00E +00
8
9
10
11
12
Aquatic acidification per unit value added a) Aquatic oxygen demand per unit value added b) Ecotoxicity to aquatic life 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 1.00E01
0.00E+0 0 1.00E01
0.00E+0 0 1.00E01
(i) metals
0.00E+0 0 0.00E+0 0 0.00E+0 0
0.00E+0 0 0.00E+0 0 0.00E+0 0
0.00E+0 0 0.00E+0 0 0.00E+0 0
0.00E+0 0 0.00E+0 0 0.00E+0 0
0.00E+0 0 0.00E+0 0 0.00E+0 0
(ii) other Eutrophication per unit value added d)
te/ $ te/
te/ te/
te/ $ te/ $ te/
Impacts to Land Table 38 - IChemE Land Impact Comparison
Hazardous solid waste per unit value added Non-hazardous solid waste per unit value added
1
2
3
4
5
6
7
1.30E02 0.00E +00
2.60E02 0.00E +00
2.60E02 0.00E +00
5.20E02 0.00E +00
0.00E +00 0.00E +00
0.00E +00 0.00E +00
0.00E +00 0.00E +00
te/ $ te/ $
te/ $ te/ $
Hazardous solid waste per unit value added Non-hazardous solid waste per unit value added Profit, Value and Tax
8
9
10
11
12
0.00E+0 0 0.00E+0 0
0.00E+0 0 0.00E+0 0
0.00E+0 0 0.00E+0 0
0.00E+0 0 0.00E+0 0
0.00E+0 0 0.00E+0 0
Table 39 - IChemE Profit, Value, and Tax Comparison
Value added a)
1
2
3
4
5
6
7
2.08E+ 06
2.04E+ 06
5.30E+ 06
8.61E+ 06
4.30E+ 06
4.43E+ 06
4.43E+ 06
Page 72 of 80
$/ y
Value added per unit value of sales Value added per direct employee Gross margin b) per direct employee Return on average capital employed Taxes paid, as percent of NIBT
5.20E+ 02 6.94E+ 05 1.39E+ 06 9.33E01 5.00E01
5.09E+ 02 6.79E+ 05 1.36E+ 06 4.57E01 5.00E01
1.33E+ 03 1.77E+ 06 3.53E+ 06 9.52E01 5.00E01
2.15E+ 03 2.87E+ 06 5.74E+ 06 9.65E01 5.00E01
1.08E+ 03 1.43E+ 06 2.87E+ 06 9.52E01 5.00E01
1.11E+ 03 1.48E+ 06 2.95E+ 06 9.54E01 5.00E01
1.11E+ 03 1.48E+ 06 2.95E+ 06 9.54E01 5.00E01
$/ $ $/ y $/ y %/ y %
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
Percentage increase (decrease) in capital employed R&D expenditure as % sales Employees with post-school qualification a) New appointments/number of direct employees Training expense as percentage of payroll expense
1
2
3
4
5
6
7
0.00E +00 1.25E02 1.00E +00 0.00E +00 8.99E02
0.00E +00 9.48E03 1.00E +00 0.00E +00 6.82E02
0.00E +00 9.69E03 1.00E +00 0.00E +00 5.35E02
0.00E +00 7.18E03 1.00E +00 0.00E +00 4.50E02
0.00E +00 9.36E03 1.00E +00 0.00E +00 6.82E02
0.00E +00 3.38E02 1.00E +00 0.00E +00 6.82E02
0.00E +00 9.11E03 1.00E +00 0.00E +00 6.82E02
9
10
8
Page 73 of 80
11
12
% /y % % % /y %
Percentage increase (decrease) in capital employed
0.00E+0
0.00E+0
0.00E+0
0.00E+0
0.00E+0
0 4.29E-
0 5.98E-
0 5.19E-
0 5.19E-
0 5.19E-
02 1.00E+0
03 1.00E+0
03 1.00E+0
03 1.00E+0
03 1.00E+0
%
0 0.00E+0
0 0.00E+0
0 0.00E+0
0 0.00E+0
0 0.00E+0
%/
0 1.03E-
0 1.03E-
0 1.03E-
0 1.03E-
0 1.03E-
01
01
01
01
01
R&D expenditure as % sales Employees with post-school qualification a) New appointments/number of direct employees Training expense as percentage of payroll expense Workplace
%/ y %
y %
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
2.31E-
2.31E-
2.31E-
2.31E-
2.31E-
%
01 0.00E+
01 0.00E+
01 0.00E+
01 0.00E+
01 0.00E+
%
00 0.00E+
00 0.00E+
00 0.00E+
00 0.00E+
00 0.00E+
%
00 7.00E-
00 7.00E-
00 7.00E-
00 7.00E-
00 7.00E-
%
03 1.00E+
03 1.00E+
03 1.00E+
03 1.00E+
03 1.00E+
00 2.00E-
00 2.00E-
00 2.00E-
00 2.00E-
00 2.00E-
02
02
02
02
02
Benefits as percentage of payroll expense Employee turnover (resigned + redundant/number employed) Promotion rate (number of promotions/number employed) Working hours lost as percent of total hours worked Income + benefit ratio (top 10%/bottom 10%) Lost time accident frequency (number per million hours worked)
Page 74 of 80
$/ $
Expenditure on illness and accident prevention/payroll expense Society
0.00E+
0.00E+
0.00E+
0.00E+
0.00E+
00
00
00
00
00
$/ $
Table 42 - IChemE Societal Comparison
1
2
3
4
5
6
7
Number of stakeholder a) meetings per unit value added
7.69E -03
7.85E03
3.02E03
1.86E03
3.72E03
3.61E03
3.61E03
/$
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
3.55E-
3.54E-
3.07E-
3.07E-
3.06E-
03 2.66E+0
03 2.65E+0
03 2.30E+0
03 2.30E+0
03 2.30E+0
$/$
3 0.00E+0
3 0.00E+0
3 0.00E+0
3 0.00E+0
3 0.00E+0
/$
0 0.00E+0
0 0.00E+0
0 0.00E+0
0 0.00E+0
0 0.00E+0
/$
0
0
0
0
Number of stakeholder a) meetings per unit value added Indirect community benefit b) per unit value added Number of complaints per unit value added
Number of legal actions per unit value added c) 0 For complete data and calculations see: IChemE Evaluation.xlsx
Page 75 of 80
$
/$
Appendix C – MSDS Vegetable Oil
Full MSDS: http://sargentwelch.com/pdf/msds/sch94733.pdf
Methanol Section 1 MSDS Name: Methyl Alcohol, Reagent ACS, 99.8% (GC) Catalog Numbers: AC423950000, AC423950010, AC423950020, AC423955000, AC9541632, AC423952 Synonyms: Carbinol; Methanol; Methyl hydroxide; Monohydroxymethane; Pyroxylic spirit; Wood alcohol; Wood naptha; Wood spirit; Monohydroxymethane; Methyl hydrate. Appearance: clear, colorless. Flash Point: 11 deg C. Poison! Cannot be made non-poisonous. Causes eye and skin irritation. May be absorbed through intact skin. This substance has caused adverse reproductive and fetal effects in animals.
Danger! Flammable liquid and vapor. Harmful if inhaled. May be fatal or cause blindness if swallowed. May cause central nervous system depression. May cause digestive tract irritation with nausea, vomiting, and diarrhea. Causes respiratory tract irritation. May cause liver, kidney and heart damage. Target Organs: Kidneys, heart, central nervous system, liver, eyes. Full MSDS: http://www.biodieselgear.com/documentation/methanol.htm
Glycerol Common Name: Crude Glycerol/Glycerin Cas: 56-81-5 RTECS #: MA8050000 Typical Composition: OSHA PEL ACGH/TLV Percent 15 MG/M3 TDUST 10 MG/M3 (MIST) 9293 99 This product contains no hazardous materials. SARA Title III, Section 313: Not Listed Full MSDS: http://www.biodieselgear.com/documentation/MSDS_Glycerol.pdf Page 76 of 80
Potassium Hydroxide MSDS Name: Potassium Hydroxide Catalog Numbers: S71978, S71979, S71979-1, S71979-2, P246-3, P250-1, P250-10, P250-3, P250-50,
P250-500, P250-50LC, P251-3, P251-50, P251-500, P251-50KG, P25812, P258212, P25850, P25850LC, PFP25050LC, S71977, S72221D Synonyms: Caustic potash, Lye, Potassium hydrate Appearance: white or yellow.
Danger! Corrosive. Water-Reactive. Harmful if swallowed. Causes severe eye and skin burns. Causes severe digestive and respiratory tract burns. Target Organs: None. Full MSDS: http://www.biodieselgear.com/documentation/KOH.htm
Sodium hydroxide MSDS Name: Sodium hydroxide, solid, pellets or beads Catalog Numbers: S71990, S71990-1, S71991, S71992, S71993, S71993-1, S71993-2, S71993-3,
S71993-4, S78605, BP359-212, BP359-500, BW13580500, BW1358350, BW13583500, S318-1, S31810, 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 r espiratory tract irritation with possible burns. May cause severe digestive tract irritation with possible burns. Target Organs: Eyes, skin, mucous membranes. Full MSDS: http://www.biodieselgear.com/documentation/NaOH.htm
Sodium Methoxide
Full MSDS: http://www.sciencestuff.com/msds/C2658.html
Biodiesel Common Name: Biodiesel Page 77 of 80
Chemical Name: Fatty Acid Methyl Ester Formula: C14-C24 Methyl Esters Chemical Family: CAS No. 67784-80-9 Typical Composition: Alkyl C14-C24 Methyl Esters OSHA PEL ACGH/TLV Percent none none 99 This product contains no hazardous materials. SARA Title III, Section 313: Not Listed Full MSDS: http://www.biodieselgear.com/documentation/MSDS_BD.pdf
Sodium Phosphate Product Name: Sodium phosphate tribasic Catalog Codes: SLS2650, SLS4072 CAS#: 7601-54-9 RTECS: TC9490000 TSCA: TSCA 8(b) inventory: Sodium phosphate tribasic CI#: Not available. Synonym: Trisodium Phosphate Anhydrous; Phosphoric Acid, Trisodium Salt; Trisodium Orthophosphate Chemical Name: Sodium Phosphate Tribasic Chemical Formula: Na3PO4 Full MSDS: http://www.esciencelabs.com/files/safety_sheets/xMSDS-Sodium_phosphate_tribasic9925028.pdf
Page 78 of 80
Appendix D - Workload Partitioning Executive Summary - Archana Manoharan Introduction - Archana Manoharan Alkali-catalyzed Process Using Methanol Unmodified
HYSYS Simulation - Jonathan Zatkoff Write-up - Archana Manoharan
Alkali-catalyzed Process Using Methanol Modification
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 o
Calculations - Jonathan Zatkoff Write-up - Jonathan Zatkoff
Inherent Safety
Calculations - Jonathan Zatkoff Write-up - Jonathan Zatkoff
Page 79 of 80
