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9/12/2011

GROUP A

BIODIESEL PRODUCTION

Annick Guehi (A.G), Hamza Javar Magnier (H.J.M), Gulzhan Khamitova (G.K), Minqing Zhu(M.Z) , Parinitha Rao (P.R), Rogelio Ernesto Zuniqa Montanez (R.E.Z.M)

Table of Content
1. Introduction.... 2. Synthesis routes...... 2.1. Transesterification... a) Lipase catalyzed Route 1: Soybean oil reaction in a packed bed reactor Route 2: Rapeseed oil in a batch reactor Route 3: Waste cooking palm oil in a packed bed reactor Route 4: Algae in a batch reactor

b) Alkali catalyzed Route 5: Soybean oil in a continuous flow reactor Route 6: Soybean oil in a packed bed reactor Route 7: Sunflower oil in CSTR and PFR Route 8: Coconut oil in a batch reactor Route 9: Jatropha oil in a PFR

c) Supercritical method Route 10: Jatropha using supercritical methanol in a PFR

2.2. Pyrolysis... Route 11: Pyrolysis of animal fat in a rotating stirrer

2.3. Microemulsion Route 12: Microemulsion of vegetable oil

3. Gross Profit Analysis...... 3.1 A summary of investigated 3.2 Feedstock comparison....... 3.3 Catalyst Comparison.. 3.4 Yield comparison.. 3.5 Reaction Condition and Duration Comparison .....

3.6 Gross Profit........ 3.7 Conclusion.. 4. Plant Location....

5. Units of Measurement and conventions Units of Measurement and conventions.... 6. Block flow diagram. 7. Overall material balance 8. Overall energy balance... 9. Process flow diagram.. 10. Heuristics. 11. References........... Appendix

1. Introduction
With the declining petroleum resources and continuous increase in demand for fuel in todays world, it is crucial to find an alternative fuel which is sustainable, meets the stringent environmental regulations and is economically viable. The use of biodiesel seems like a promising and potential alternative to energy crisis. Biodiesel is monoalkyl esters of fatty acids, known as a clean and renewable fuel. Several raw materials used to produce biodiesel can be broadly classified into edible oils (Soybean oil, rapeseed oil, coconut oil etc.), non edible oils (eg. Jatropha oil, Algae) and animal fats. There are various methods used to convert these raw materials into useful fuel such as, transesterification, microemulsion, dilution and pyrolysis (1). Research has showed that biodiesel has benefits such as its production from domestic waste cooking oils, the reduction of exhaust emissions; it is less toxic, unlike most fuels, it is renewable, visible smoke, noxious fumes and odors, it is biodegradable and limited by blending it with petroleum, it also has the capacity to improve the quality of the diesel (2). However there are few challenges to consider, the engine incompatibility issues the cost of the fuel in the market may be high, the preservation and management is more difficult, than the one of fossil fuels, due to its oxidation and it is prone to microbial development (3).

The biodiesel market has been increasing in the past years. With an increase of a world acceptance for clean energies, biodiesel has become an important alternative fuel for various types of engines
(4).

The main market of biodiesel is the transportation industry such as aircrafts, trains, heating and
(5)

commercial boilers. Furthermore, biodiesel is one of the best substitutes for diesel engine, knowing that the global consumption of diesel in 2010 is estimated to be 934 million tonnes per year, similarly biodiesel market demand has increased from 2005 particularly in the USA (5). The price of biodiesel is one of the disadvantages that this renewable fuel has. It is more expensive than petro diesel and all other type of fuel (gasoline regular, ethanol, propane and CNG). Even if governments give incentives for biodiesel production, it is not that profitable. Biodiesel can be combined with diesel to different ratios. A mixture of 20% of biodiesel and 80% of diesel is called B20; a mixture of 99% of biodiesel and 1% of diesel is called B20. In America the nationwide average price of diesel is $3.81 compared to $4.02 for biodiesel (B20) and $4.19 for biodiesel (B99100) (6). Besides, biodiesel current cost is 700/tonne on market it is expected to double between 2009 and 2015, but the offer is expected to grow threefold. And in the present there is an overcapacity in the biodiesel industry, the actual utilization rates are below 50%. This means that the offer will always
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be bigger than the demand, and this can cause serious market problems (7). With no competing food uses, the use of less expensive feedstock with fatty acids such as inedible oils, is an alternative way to reduce the biodiesel production costs. Finally, the major biodiesel markets are located in European Union (Germany, France, Italy, Spain, UK, Poland, Austria), in The Americas (USA, Brazil, Colombia, Argentina, Canada) and in Asia/Pacific (Malaysia, Indonesia, Australia, China, India, Philippines, Thailand, Singapore) (8). This means that for making this product the most feasible possible, we should locate our company in or near one of these markets. The following study will investigate several synthesis routes to produce biodiesel. Alternative raw materials, reaction types, catalysts, performances and production scales will be compared. The choice of the selected route will mainly be based on the gross profit analysis.

2. Synthesis routes of production of biodiesel


The production of biodiesel from vegetable and waste cooking oil, animal fats, and algae is accomplished by breaking down triglycerides bonds, hence reducing their viscosity. There are at least three known process that converts various feed into biodiesel: 1. Transesterification 2. Pyrolysis 3. Microemulsion Among these processes, transesterification is the most commonly used, because of the purity of its product compared to the two other processes, and its economical feasibility; hence our focus on this process. A detailed literature review on formation of biodiesel from transesterification show there are many different routes on industrial or lab scale, varying raw materials, catalysts, and type of reactor. We chose to divide our analysis, based on the use of one of the three major types of catalysts: lipase-catalysed reaction (enzymatic), alkali-catalysed reaction, and non-catalytic reaction (supercritical method).

2.1.

Transesterification reaction

The general form of transesterification is the reaction of triglyceride with alcohol, in the presence of catalyst, to produce glycerine and fatty acid methyl-ester. And it follows this mechanism:

Figure 1.Overall mechanism of transesterification

The main transesterification reactions are:

Figure 2.Transesterification reaction

Transesterification reaction can be enzyme catalyzed, alkali-catalyzed, non-catalyzed (supercritical method), and acid catalyzed. We will show different process for the first three types, then we are going to identify the most suitable one.

a) Enzyme catalyzed reactions

Although enzymatic reactions gives a high yield, one major limitation is the cost of the catalyst. In most of the cases, enzymatic reactions are done only on lab scale because the cost of the enzyme is

too high, hence making the process economically unfeasible on industrial scale. But it is always interesting to take a look at the high specificity of the enzyme, and the substrate-enzyme interactions.

Route 1: Soybean oil in a packed bed reactor The enzyme Novozyme 435 is used as the immobilized enzyme packed in a packed bed reactor. The soybean oil (0.05 M), tertiary butyl alcohol (32.5% by weight of soybean oil) along with methanol in ratio 4:1 (alcohol: substrate) are mixed well in a mixer and sent into the packed bed reactor at a flow rate of 0.1 mL/min with a reaction temperature of 52.1C. The maximum conversion obtained at optimum conditions was 81%. It was observed that with the increase in flow rate there was a decrease in conversion. By using this process the conversion achieved was 95.898.9%, without deactivation of the catalyst for 550 hours (9).

Route 2: Rapeseed oil in batch reactor Rapeseed oil, methanol and tertiary butanol (methanol/ oil ratio = 4, oil/ ter- butanol ratio= 1) were mixed in a rotary batch reactor at 130 rpm maintained at 35C. This is followed by the addition of Lipozyme TL IM and Novoenzym 435 (3% and 1% by weight of oil respectively). The reaction time was 12 hours and the conversion obtained was 95%. The lipase activity was intact until 200 cycles repeatedly and this process showed good results even when experimented on waste oils (11).

Route 3: Waste cooking palm oil in a continuous a packed bed reactor. Waste cooking oil disposal has had a great impact in environmental control problems. As it is a product disposed mainly from restaurants and houses, the cost of producing biodiesel from this material is really low. Two of the most important benefits of lipase-catalyzed transesterification against chemical transesterification are that it makes the glycol recovery easier, and reduces the amount of alkaline wastewater from the catalyst. A mixture of waste cooking oil and methanol, with a 1:4 molar ratio, is introduced to the continuous packed bed reactor. The solvent used is tertbutanol, in a volume ratio of 1:1 with the waste cooking oil. The reaction is held at 40C. In a packed bed reactor with height of 10.53 cm and 0.57 ml/min substrate mixture (waste palm oil and methanol) flow rate, the experimental yield is 79% after 3 hours. When scaling it up to industrial scale, it is profitable. One example of this is The Louisville Biodiesel Cooperative, Louisville/Jefferson County Metropolitan Sewer District and The Green Triangle in the Ninth District. (13)

Route 4: Algae in batch reactor. Oil extracted from the algae is mixed with alcohol and an acid or a base to produce the fatty acid methyl esters (biodiesel). Methanol is used in excess to favor the right side of the equation. The excess methanol is then reused for further reaction. Lipases is used as a biocatalyst, (The solvent and temperature choice of the enzymes is important in order to have an efficient process.) in a batch reactor. The use of a solvent enhances the lipase-catalyzed methanolysis of triacylglycerols to produce biodiesel. Algae oil and methanol are used as reagents in the presence of a catalyst NaOH. The alcohol: oil theoretical molar ratio is 3:1; the molar ratio of 6:1 gives a more accurate, completed reaction. The ratio of feedstock mass input: biodiesel mass output is about 1:1, therefore theoretically, 1 kg of oil results to approximately 1 kg of biodiesel. The results were obtained at industrial scale. The industrial scale ups is feasible, as it is shown by Oilgae, a company that supports the algae fuels industry (14). b) Alkali catalyzed Most industries use alkali-catalyzed reactions. Although the base catalysts are not very expensive, alkali-catalyzed reactions have many disadvantages. - Saponification side reaction: free fatty acids react with the catalyst to give water and soap - Need of a pretreatment step to get rid of the free fatty acids which increase the capital cost significantly - The use of a pretreatment step with cause the yield to decrease, making the process less efficient

Route 5:Waste canola oil in a two phase continuous flow reactor separator. Waste canola oil is pre-treated to 65C with methanol and HCl( catalyst) to remove traces of free fatty acids. The pre-treated oil and Methanol along with KOH (catalyst 1.3% by wt of oil) is sent into the reactor at are sent to the reaction vessel through a y-joint and the static mixing unit to the reaction vessel with a flow rate 0.95lt/min and 0.22lt/min respectively. Biodiesel formed is removed from the top of the reactor and the glycerol is removed from the bottom of the reactor. The reaction time was 6 hours and the conversion obtained was 99 % 99.3%. This reactor offers simultaneous production of biodiesel and its separation from glycerol, with a separation efficiency of over 99%. Studies also demonstrate that a good approximation for scaling up to an industrial level, the following conditions should be followed: 1:6 molar ratio of oil and

alcohol, temperatures around 55C, atmospheric pressure and a reaction time of 3 hours to achieve a 97% conversion(10).

Route 6: Soybean oil in Batch reactor. In a conventional process, biodiesel is produced via transesterification of triglyceride vegetable oils using methanol and a homogenous base (KOH or NaOH) as a catalyst. This would require a large amount of water in order to separate the catalyst. Hence the use of heterogeneous catalyst would decrease the cost of the reaction and it would be more environment friendly with the use of minimum amount of water. At optimized conditions, the reaction of transesterification of soybean oil to biodiesel was performed in a 100ml batch reactor, using 50 ml of soybean oil, 18.3 ml of methanol (molar ratio of Methanol to VO is 9:1), 10 ml of n-hexane ( co-solvent, 5:1 ratio of VO to co-solvent), and 1 g of catalyst (Na/NaOH/Al 2 O 3 /NaOH). The temperature of the reaction was set at 60 oC, run for 2h at a stirring speed of 300rpm. Within 1 hour, the maximum biodiesel production yield of 94% was reached, almost the same as the conventional base catalyst. The use of a batch reactor is mainly for small-scale process, if a scaling up is desired, the type of reactor should be modified (12).

Route 7: Sunflower oil by transesterification in CSTR and PFR. Transesterification is the gold standard in the conversion of vegetable oils into biodiesel. It takes 1 hour at 60C. The reaction of sunflower oil with methanol glycerol as by-product using lipase as a catalyst (15) . The yield obtain was 90.7% biodiesel with the use of sodium methoxide as a catalyst. In small scale a batch reactor is efficient on the however large plants tend to use continuous flow process in CSTR and PFR. Within 90 minutes, and using a molar rate of 6:1 alcohol to sunflower oil, the common rate for industrial scale, a conversion of 90-98% can be achieved.

Route 8: Coconut oil by transesterification in batch reactor.

Coconut oil with high free acid is available at a low price and does not have major applications. This oil has high potential as the cheap feedstock can reduce the biodiesel production cost. 100g coconut oil, 20.0% ethanol (wt% coconut oil), 0.8% potassium hydroxide (KOH) as a catalyst at 65C lasting 120 minutes.(16) The yield obtained was 10.4% biodiesel. The very low yield so this type of biodiesel us usually mixed (B10). The yield of glycerol by product were 67.4 %. (17) The use of a batch reactor is mainly for small-scale process, if a scaling up is desired, the type of reactor should be modified.

Route 9: Jatropha oil in PFR (20). Jatropha oil is mixed with methanol in the ratio 1:24 and sent to a batch reactor to give glycerol and methyl ester of fatty acids (biodiesel). The reaction time was 30 minutes and the yield was 96%. The transesterification reaction was carried out in the presence of NaOH base catalyst (0.18% of weight of oil). This reaction is most applicable in industrial companies in India, in a PFR and CSTR, but mainly PFR. The application of this process in a pilot plant showed that at a molar ratio of 8:1 (alcohol to oil) and after 5 hours, a conversion of 90-92% was achieved. The capacity of the pilot plant is 30 gal/day. c) Non-catalyzed supercritical process

Route 10: Jatropha oil by supercritical methanol (21). Jatropha oil is mixed with methanol in the ratio 1:42 and sent to a tubular reactor where transesterification reaction takes place to give biodiesel and glycerol. The reaction temperature ranges from 270-350C and the reaction pressure is 15-20MPa. The biodiesel yield is 96% without using a catalyst having a reaction time of 13-15 minutes. This process describes a potential method to produce high grade biodiesel with methanol recovery using a flash vaporization technique where nearly 86% of methanol is recovered, followed by distillation where 99% of methanol is recovered. Glycerol recovery in this process is also up to 99.6% and the biodiesel produced was neat biodiesel (B100). Though this process has a high capital cost, it has proved to be economically viable due to low operating costs and high recovery. As there are no expenses in catalysts in this process, it is the

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most feasible for producing biodiesel at industrial scale. By utilizing a ratio 1:42 oil to methanol, and by having a reaction time around 20 minutes, a yield of 96% is achieved.

2.2.

Pyrolysis reaction

Pyrolysis is the conversion of one substance into another by means of applying heat. In the absence of air, reactants are taken to high temperature ranging from 450 oC - 800 oC, which leads to the formation of smaller molecules through cleavage of the chemical bonds.

Route 11: Synthesis of biodiesel from waste animal fats by pyrolysis method (18). Waste animal fats can be used to produce biodiesel. Using the most common process, transesterification, for its production results in a fuel with poor low-temperature properties. A solution for this is the utilization of a pyrolysis process. The reaction is held in an electromagnetic induction rotating stirrer type autoclave of 100 ml capacity. The feed consists of 30g of beef tallow and 3 g of activated charcoal supported palladium as a catalyst. Nitrogen gas is used to fill the inside atmosphere. An 85% yield is achieved after 30 minutes of reaction at 420C. Carbon dioxide is obtained as a by product (10%). Pyrolysis is a process with a lower yield than transeterification, and when scaling up the process, the yield reduces. Pyrolysis is not as feasible as transesterification at industrial scale.

2.3.

Microemulsion reaction

Microemulsion is defined as a colloidal equilibrium dispersions of optically isotropic fluid microstructuresThese are formed spontaneously from two normally immiscible liquids and one or more ionic or non-ionic amphophiles. A microemulsion works by reducing the viscosity of oils with solvent, which solve the problem of vegetable oil high viscosity.

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Route 12: Synthesis of biodiesel from Vegetable Oil by microemulsification.

This method is the process of reducing high viscosity of the pure vegetable oil. Microemulsions stability is a crucial aspect for the routine analysis. Therefore, they are categorized as non-ionic or ionic, depending on the surface active compound present. Microemulsions containing, for example, a basic nitrogen compound are termed ionic while those containing, for instance, only of a vegetable oil, aqueous ethanol, and another alcohol, such as methanol or 1-butanol, are termed nonionic. Non-ionic microemulsions are often alluded to as detergent with less microemulsions, indicating the absence of a surfactant (19). As microemulsion has a lower yield than transesterification, there are less attempts of scaling up the laboratory data.

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Table 1.Summary table for different synthesis route


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3. Comparison of process synthesis route

3.1.

Design assumptions

Plant capacity 80000 tones of biodiesel per year (justification of choice in plant location) 7488 working hours per year was used The feed was assumed to be 100% liquid ( free of solid particles) Constant input of year throughout the whole production year

3.2.

A summary of investigated synthesis routes

A summary table of the investigated process synthesis routes is available in table 1. In this section, the prices of raw material and catalyst have a large effect on the choice of most economically suitable route, so a price summary table is provided.
Raw material Soybean oil Waste canola oil Rapeseed oil Jatropha Waste palm cooking oil Algae sunflower oil Coconut oil Animal fat Methanol Ethanol Cost(/ton) 720 260 780 188 914 n/a 1005 774 29 254 1230

Table 2.Summary table of raw material price

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Catalyst Novozyme 435 HCl KOH Lipozyme TL IM NaOH Activated charcoal supported palladium H2SO4 Al2O3 KNO3

Cost (/ton) 640082 25 1735 n/a 967 79364840 1555.6 25160 3960

Tert-butanol 268000 n-hexane 742-755 HF n/a CaO 9310 Nitrogen 420 Table 3.Summary table of reagent and catalyst cost

3.3.

Feedstock comparison

In the process of choosing the best synthesis route, the choice of the feedstock is one of the most important factor, that affects the profitability, the plant location (availability of material), and the scale of production. Synthesis route 1 and 6 uses soybean oil, and synthesis route 2 uses rapeseed oil. These types of vegetable oil are one of the most expensive vegetable oil (table 2). And since we are working on a scale of production of 80000 ton/year, the price of the feedstock has the major effect on our net profit. Within synthesis route 4, the use of algae as a feedstock has promising expectations in term of yield, price and availability. This route also needs to consider the hole algae life cycle from its growth to its processing. This will have a high production cost, decreasing the profitability. Also, to work on industrial scale, a large amount of algae need to be processed; which is not easy to get. Synthesis routes 3 and 7 use respectively palm oil and sunflower oil. The price of the previous feedstock is higher than the selling price of biodiesel, so the routes were discarded intuitively. Within synthesis route 11, the use of waste animal fat gives a biodiesel with a 100 ppm of sulphuric content, which is 10 times higher than the accepted content (4). The use of Jatropha as oil as a raw material in route 10 is very advantageous: Jatropha cannot be used for nutritional purposes without detoxification (inedible oil) Jatropha is the less expensive feedstock Jatropha is widely available in some countries of interest
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All these characteristics turns our attention to the use of Jatropha oil as our raw material.

3.4.

Catalyst Comparison

When analyzing catalyst, different routes make use of very expensive catalysts, such as Novozyme 435, Activated charcoal supported palladium, tert-butanol, and CaO, hence reducing the profit to a minimum (table 2). Synthesis route 1 and 2 are enzyme catalyzed reaction. With the high price of the enzyme (640082 /ton), these routes are economically unfeasible. Route 10 uses methanol in 42:1 ratio (Appendix 1). But since after each cycle 99% of it is recycled, this will not affect the feasibility of the route.

3.5.

Yield comparison

A yield comparison was carried out with the remaining synthesis routes: 5, 8, 9, 10, 11, and 12. Route 12 was discarded from the process since no data was available. Also, in this route the process was microemulsion. There are some disadvantages of this process. The preparation of microemulsion needs to take surfactant, co-surfactant and water into biodiesel. Hence, all components have to be in demanded proportions. Synthesis route 8 uses coconut oil with a yield of 10% (table 2). This is a very low yield and the process is anticipated to be economically unfeasible since the cost of the coconut oil is also very high (table 2). Further to this route, routes 5, 9, 10 and 11 showed excellent yield.

3.6.

Reaction Condition and Duration Comparison

A final comparison of reaction conditions and duration was established to finalize on the most suitable synthesis route. Alkali-catalyzed transesterification, although is the most applicable in industries, has many disadvantages. The presence of water causes ester saponification and reduces the catalyst efficiency. The reaction of saponification that occurs in transesterification reaction follows the following mechanism:

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Figure 3.Saponification from free fatty acids

Although Pyrolysis of fats is a very successful reaction, it is noted that the equipments of Pyrolysis are very expensive. Also, although Pyrolysis products are chemically similar to conventional biodiesel, operating in an oxygen free medium will decrease the oxygen content in the product and decrease its environmental benefits of being an oxygenated fuel. Another disadvantage is that pyrolysis process causes the elimination of unsaturated bonds in the product; this results in the cold filter plugging point not being in a practical range for cold climate regions. This means that at low temperatures a certain volume of a fuel will not pass through the filtration system in the specified amount of time (20). Hence route 11 is discarded. Route 12 uses microemulsion. This process is not very applicable because in longer term testing, incomplete combustion, carbon deposits and increasing viscosity of lubricating oils where reported. The use of supercritical method in route 10 shows many advantages and the economical analysis. Although intuitively it seems that the use of a large number of methanol (42:1 ratio), and the cost of enery needed to operate at high pressure and temperature will make the process unprofitable, but after investigating further more in the process, many advantages are noted: Lack of use of catalyst No sensitivity to free fatty acids and water No side reaction No need for pre-treatment Free fatty acids in the oil are esterified simultaneously

A comparison between the conventional and the supercritical method is summarized in table. 4:
Properties Supercritical Conventional Catalyst need No Yes Reaction time Seconds-Minutes Minutes-hours Temperature (C) 200-300 50-80 Pressure (bar) 100-200 1 Free fatty acids sensitive No Yes Water sensitive No Yes Pre-treatment No Yes Catalyst removal No Yes Soap removal No Yes
Table 4.Properties of conventional and supercritical method

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3.7.

Gross Profit analysis

In order to finalize our decision a gross profit analysis should be taken into consideration. Although through elimination, only routes 5, 9 and 10 remains, the GP analysis will be done for routes 1 and 6 also. Soybean oil has a similar price to rapeseed oil, coconut oil, and waste canola oil, So by doing a gross profit analysis for one, we will have a rough idea about all others (since they have almost similar routes). Also, the calculation for route 6 is done to see the economical potentials that lie in the use of algae as raw material. For detailed calculations, check Appendix 2.

Gros s Profit 1-soybean -97,373,128 5- Wast canola oil 35,067,002 6- Algae -68,236,541 9- Jatropha (alkali-catalyzed) 37,919,445 10- Jatropha (supercritical methanol) 43,873,186
Table 5.Gross profit analysis

Route

3.8.

Conclusion

From the comparison of raw material, catalysts, yield reaction time and conditions, and gross profit analysis, route 10 is the most economically and industrially profitable.

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4. Plant Location
An evaluation of the different factors capable to affect the plant location was performed. Research showed that regions such as South Asia and the sub-Saharan Africa had a very large Jatropha production(22). We decided to choose India, China and Ghana as possible plant locations. A weighted comparison study was held to choose the final location. The factors analysed for this study are:
Factor Weight 4 Raw material availability 1 Minimum labour cost 2 Land price 2 Electricity 1 Global location 10 TOTAL
Table 6.Factors affecting our choice for India

A certain weight was given to each factor, depending on the importance of it in our process. The information gathered was the following:

We consider paying our workers more than the minimum wedge, this minimum wedge was only used as a reference for comparing India with the other countries.
China India (27) (23) Raw material availability (grad 10.00 10.00 (28) Minimum labour cost (/h) 1.28(24) 0.98 (29) Land price (/m2) 14.26(25) 8.00 Electricity (/kW/h) 0.10
(26)

Ghana 6.00(31) 0.18(32) 7.92(33) 0.04(34)

0.05(30)

Table 7..Comparison between China, India and Ghana

By giving a weight to the gathered data we obtained the following tables:

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India Factor Grade 10 Raw material availability 5 Minimum labour cost 10 Land price 9 Electricity 9 Global location TOTAL
Table 8.Indias economical weight

Weighted grade 4 0.5 2 1.8 0.9 9.2

China Factor Grade Weighted grade 10 4 Raw material availability 2 0.2 Minimum labour cost 7 1.4 Land price 6 1.2 Electricity 9 0.9 Global location 7.7 TOTAL
Table 9.China's economical weight

Ghana Factor Raw material availability Minimum labour cost Land price Electricity Global location TOTAL

Grade 6 10 10 10 5

Weighted grade 2.4 1 2 2 0.5 7.9

Table 10.Ghana's economical weight

After analysing the results, India seems to be the best potential location for the plant due to the availability of the raw materials and low costs. It is expected that by 2013, 11 million ha will be cultivated with Jatropha in India (22). It is calculated that 3 MT of oil can be extracted per ha of Jatropha crops (22). This design is expecting to use 83,000 MT (data from Overall Material Balance) of Jatropha oil per year, and cover 0.25% of this crop market.

We consider paying our workers more than the minimum wedge, the minimum wedge of each country was only used as a reference for comparing India with the other countries.

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These low prices will have a great impact in the initial investment, as well as in the variable and fixed costs through the operation lifetime of the plant. The reduction of investments and costs can cause a significant rise of revenues. Considering the global location and world presence of India, this country is within the Asian market, which is one of the most important and active market in the world (35).

5. Units of Measurement and conventions


The System International (SI) will be used throughout this project design to avoid unit conversion as this accepted on an international scale.

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6. Block Flow diagram

Figure 4.Block flow diagram


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7. Process Selection and Heuristics

The quality of biodiesel produced has to be compliant with the European 14214 and American ASTM D 6751 standards to be used as B100 in automobiles. These standards dont permit more than 2400 - 2500 ppm of impurities, which maybe traces of unrecovered glycerol and unreacted triglyceride present along with biodiesel in the final product stream[1]. Separation of catalyst from the product and the recovery of glycerol and triglyceride from the product in the conventional processes is complex; this has resulted in the production of low quality biodiesel which are only used in the form of blends with diesel fuel as B5(5% biodiesel and 95% diesel) B20(20% biodiesel and 80% diesel) instead of B100(100% biodiesel[2]. The selected process of production of biodiesel is a non-catalyticprocess using supercritical methanol and jatropha oil as raw materials.This method has proved to be a promising alternative to the conventional alkali catalysed biodiesel production. The method has several advantages over the conventional process as it does not require any pre-treatment of the triglyceride feed in order to remove traces of water and free fatty acids which can result in side reactions like saponification and decrease the product yield. The selected not only gives a good conversion of triglyceride into biodiesel reducing the amount of triglyceride in the product stream but also does not use catalyst and gives a high recovery of unreacted methanoland glycerol produced upto 99%[3]. Moreover, the residence time of the reaction involving supercritical methanol is much lower than the conventional process. From table 2, it is evident that the solvents and catalysts are the materials which can greatly influence the economic viability of the biodiesel plant. Since the process is non-catalytic the cost of feedstock is reduced considerably form the other processes. Also, from the gross profit analysis it is clear that the cost of raw material can also substantially affect the operating cost of the biodiesel plant. The process of obtaining biodiesel from supercritical methanol though may have higher operating costs due to reaction conditions, definitely has lower feedstock cost (the cost of jatropha oil is almost half the cost of other oils), lower equipment cost and also yields better quality of biodiesel that is complaint with the European and American standards. The entire biodiesel plant is divided for four major units as shown in figure.4. 1. Process 1: Reaction Phase 2. Process 2: Methanol Recovery Unit 3. Process 3: Glycerol Recovery Unit 4. Process 4: Biodiesel Purification Unit
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Process1: Reaction Phase Transesterification reaction is a reversible reaction. From Le Chateliers principle, it is established that, removal of products continuously from the reactor shifts the equilibrium to the right, favouring the forward reaction, leading to better conversion. This is one of the main reasons for choosing a continuous biodiesel production system over a batch system. Apart from that, the continuous production systems ensure better temperature control than batch systems. They deliver better conversion, require lower maintenance andfor large scale productions,reduce capital cost of equipment due to reduction in the reactor size[4]. Considering all these factors we have chosen continuous production of biodiesel over batch production. Studies have further shown that for transesterification reactions using plug flow reactors have shown distinctive benefits over CSTR in terms of volume reduction leading to lower capital cost and also better conversion and better glycerol recovery[5]. In the selected process we use an alcohol to oil ratio of 42:1, this is because the increase in the concentration of methanol in the reaction not only drives the forward reaction yielding a better conversion but also helps reducing the critical temperature of the methanol and oil mixture(2800C) but increasing the critical pressure to7MPa. Studies have shown that reduction of methanol to oil ratio to 22:1 has resulted in the same conversion at the same critical temperature but at a very high critical pressure say around 19MPa[2]. Though this associates extra costs for methanol, having an efficient methanol recovery system can successfully compensate for it. Process 2: Methanol Recovery Unit Since a high methanol to oil molar concentration ratio of 42:1 is used according to the stoichiometry only 3 out of 42 moles are used up in the transesterification reaction. Hence recovery of the unreacted methanol from the process is crucial to make the process economically feasible. Instead of directly sending the product stream into the distillation column, it is first sent to a flash drum operating at a lower pressure at around 0.2 to 0.4 MPa. This method is employed because when the stream coming out of the reactor, already at a high pressure of 6Mpa enters the flash drum maintained at low pressure the methanol flashes and almost 85% of the methanol is recovered in the flash drum itself[6][7]. This makes the distillation process less complicated with less number of stages and reduces the overall capital cost of the unit. On the whole, 99% of methanol is recovered in the methanol recovery unit[3]. The bottoms of the methanol recovery unit consisting of biodiesel, unconverted triglyceride and a small fraction of methanol is sent to a cooler and introduced to a glycerol recovery unit. Process 3: Glycerol Recovery The bottoms stream from the process 2 is introduced into a decanter which is basically a centrifuge. Due to the considerable difference in the density of glycerol, biodiesel and triglyceride, it is easy to
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separate glycerol from unconverted jatropha oil and biodiesel using a centrifuge. Around 99% by weight of the glycerol produced can be recovered in this unit[3]. 1% of unconverted glycerol along with unconverted biodiesel and triglyceride are sent into the biodiesel purification unit. Process 4: Biodiesel Purification Unit The impure biodiesel product stream is sent into the distillation column for further purification of biodiesel to be compliant with the ASTM D- 6751 and European 14214 standards. The distillate contains is 99.8% by weight of biodiesel, with less than 2500 ppm of impurities [3].

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8. Overall material Balance

Figure 5.Transesterification reaction

Compound Molecular weight (g/mole) Triglyceride (Jatropha oil) 857.14 Methanol 32 Glycerol 92 Biodiesel 857.14+4.032 = 861.172
Table 11.Molecular weight of the reactant and products

Methanol Methanol Process 1 PROCESS1 Products Process 2 PROCESS

Jatropha Calculation of Feed Rate of Jatropha Oil from Production Basi oil Bottoms PROCESS 3 Process 3 PROCESS 4 Biodiesel

Glycerin
Figure 6.Block flow diagram

Residue

Total mass entering the process = Total mass leaving the process + Methanol recylcled

26

Total mass entering the process = Mass flowrate of methanol + Mass flowrate of Jatropha oil Total mass leaving the process = Unreacted Triglyceride + Unrecovered methanol + Glycerol recovered + Biodiesel in the distillate + Residue Biodiesel production basis = 80,000 ton/yr Number of working days in a year assumed = 312 days Production rate of biodiesel (kg/h = 10,684 Production rate of biodiesel (mole/h) = 12,406 Assuming 100% conversion, from mole balance Triglyceride feed (kg/h) = 10,634 The actual conversion of transesterification process of biodiesel production is just 96% Actual triglyceride feed needed (kg/h) = 10,634/ 0.96 = 11,077.08 Actual triglyceride feed (mole/h) = 12,923 In our process we use methanol and triglyceride in molar ratio (42:1) Total methanol feed needed (mole/h) = 542,766 Actual Methanol feed rate (kg/h) = 17,369 Methanol used in the reaction (kg/h) = 1191

Process 1: Reaction Phase Total mass entering process 1 (kg/h) = feed rate of jatropha oil + feed rate of methanol = 11077 + 17369 = 28,446 Rate of methanol leaving process 1 (kg/h) = 17,369 1,191 = 16,178 Triglyceride used in the reaction (kg/h) = 10,634 Rate of triglyceride leaving process 1(kg/h) = 11,077 10,634 = 443 Glycerine production rate in process 1 (kg/h) = 1,141 Production rate of biodiesel in process 1(kg/h) = 10,684 Total mass leaving process 1 = Unreacted triglyceride+ Unreacted methanol + biodiesel formed + glycerol formed = 443 +16,178 + 10684 + 1141 = 28,446.(2)

Process 2: Methanol Recovery unit


27

It is assumed that 99% of unreacted methanol is recovered in process 2 which is recycled Rate of methanol recycled (kg/h) = 16,178 0.99 = 16,016 Rate of methanol leaving process 2 (kg/h) = 16,178 16,016 = 162 Rate of glycerine leaving process2 (kg/h) = 1,141 Rate of biodiesel leaving process 2(kg/h) = 10,684 Rate of triglyceride leaving process 2(kg/h) = 443 Total mass flowrate in the bottoms of process 2(kg/h) = Unrecovered methanol + Unreacted triglyceride + Biodiesel formed + Glycerol formed = 162 + 1141 + 10684 + 443 = 12,430 kg/h Total mass leaving process 2(kg/h) = Mass flow rate in bottoms + Total methanol recovered = 16,016 + 12,430 = 28,446 kg/h Process 3: Glycerol Recovery Unit Data: 99% by weight of total glycerol produced is recovered in Total mass entering process 3 (kg/h) = 12,430 Recovery rate of glycerol in process 3 (kg/h) = 11410.99 = 1,137.58 Glycerol with the impure biodiesel (kg/h) = Total glycerol formed total glycerol recovered = 3.42 Triglyceride with the impure biodiesel fraction (kg/h) = 443 Unrecovered methanol purged (kg/h) = 162 Total mass leaving process 3 = Total mass of glycerine recovered + Unrecovered methanol purged + Unrecovered glycerine + Unreacted triglyceride + biodiesel formed = 1137.58 + 162 + 3.42 + 443 + 10684 = 12,430

Process 4: Biodiesel Purification Unit Data: 99% of biodiesel formed is recovered in the distillate Distillate contains 99.8% by weight biodiesel Assuming that no glycerine is recovered in the distillate Total mass entering process 4 = Unrecovered glycerine + Unreacted triglyceride + Biodiesel formed = 3.42 + 443 + 10684 = 11,130.42 kg/h
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Total biodiesel in the distillate(kg/h) = 10684 0.99 = 10,577.16 Total mass flow rate of distillate(kg/h) = 10577.16100/99.8 = 10,598.36 Total unreacted triglyceride in the distillate (kg/h) = 10,598.36 10,577.16 = 21.2 Triglyceride in the residue (kg/h)= 443 21.2 = 421.8 Glycerine in the residue(kg/h) = 3.42 Biodiesel in the residue(kg/h) = 10684 10577.16 = 106.84 Total mass flow rate of the residue = mass flowrate of (triglyceride + glycerine + biodiesel) = 421.8 + 3.42 + 106.84 = 532.06 kg/h Total mass flow rate leaving process 4 = mass flowrate of residue + mass flow rate of distillate = 532.06 + 10598.36 = 11,130.42 kg/h

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9. Overall energy balance


Material Methanol Jatropha oil Biodiesel Glycerin Hf(kJ/mol) 238.57 4178 1445 659.76

Figure 7.Heat of formation of different product

Material Methanol Jatropha oil Biodiesel Glycerin

Cp (J/mol K) at 298.15 K 79.5 2000 1900 220.23

Figure 8.Heat capacity of different compounds

For the Overall Energy Balance, the following flow rates were used. They were obtained form the Material Balance. The flow rates used are only the ones that reacted; the excess was not taken into consideration for the Energy Balance.

Material going in Methanol Jatropha oil


Figure 9.Molar flow rates in and out

Mass flow rate (kg/h) 1191 10634

Molar flow rate (mol/h) 37218.75 12406.37

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Material going out Glycerin Biodiesel in destillate Jatropha oil in distillate Jatropha oil in residue Biodiesel in residue Glycerin in residue
Figure 10.Mass flow rate in and out

Mass flow rate (kg/h) 1141 10577.16 21.2 421.8 106.84 3.42

Molar flow rate (mol/h) 12402.17 12282.28 24.73 492.1 124.06 37.17

Total energy in = Total energy out E = - E reactants + E roducts E supplied = - n in ((Cp T) + H f ) + n out ((Cp T) + H f ) E =- 37218.75 ((79.5298.15/1000) 238.57) - 1240637 ((2000298.15/1000) 4178) + (12282.28+124.06) ((1900298.15/1000) 1445) + (12402.17+37.17) ((220.23289.15/1000) 659.76) + (24.73+492.10) ((2000298.15/1000) 4178) E = +7997083.94+44435895.43-10899155.79-7390192.30-1851130 E= 322.27 kJ/h

Since our feed rate is 80000 ton/y , we can say that our process is slightly endothermic (requires an input of energy). This is intuitively expected since our reaction takes place at high temperature, high pressure.

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10. Process Flow diagram

Figure 11.Process flow diagram


32

Summary table

Stream name Pressure (kPa) Temperature (C) Mole flow (mole/h) Mass flow (kg/h) Component mole fraction methanol Jatropha oil Glycerine Biodiesel

1 2 5 101.3 101.3 226.6(26) 25 25 190(26) 542781 12925 555707 17369 11077 28446

8 200
(26) (26)

9 200
(26) (26)

10 200
(26) (26)

11 101.5
(26) (26)

12

13 106.5
(26) (26)

14
(26)

15
(26)

16

17

170 25 162 68 170 96.5 96.5 535996 101219 434784 65723 500500 35496 12365 28446 13913 13913 2103 16016 12430 1138

170 25 198.6(26) 265(26) 23131 17399 705 11130 10620 532

1 0 0 0

0 1 0 0

0.98 0.02 0 0

0.94 0 0.02 0.03

0.7 0.01 0.12 0.12

1 0 0 0

1 0 0 0

1 0 0 0

0.14 0.01 0.35 0.49

0 0 1 0

0.22 0.02 0 0.76

0 0 0 1

0 0.7 0.05 0.25

Table 12.Stream table for the process flow diagram

33

11. References
1. S.P. Singh, Dipti Singh, "Biodiesel Production through the use of different sources and characterization of oils and their esters as the substitute of diesel: A Review," Renewable and Sustainable Energy Reviews, vol. 14, pp. 200-216, 2010.

2. Biodiesel Advantages and Disadvantages Available: http://www.tcbiodiesel.com/biodieseladvantages-and-disadvantages/. (2011)Last accessed 22/11/11 3. Knothe, Gerhard; Van Gerpen, Jon; Krahl, Jrgen The Biodiesel Handbook , AOCS Press, pp. 172009 4. How do we deal with cooking Oil? Available at:http://www.mcdonalds.co.uk/ourworld/environment/waste.shtml/ Last accessed 22/11/11. (2011)

5. Joon Ching Juan a, Damayani Agung Kartika a, Ta Yeong Wub, Taufiq-Yap Yun Hin c. (2011). Biodiesel production from jatropha oil by catalytic and non-catalytic approaches. Bioresource technology. 102 (1), 452-460.

6.Steve Babcock, U.S Department of energy. Clean cities alternatives Fuel Price report. 1 (1), 3.2010

7. Susanne Retka Schill. Global biodiesel demand to double in 5 years. (2010) Available: http://www.biodieselmagazine.com/articles/3983/global-biodiesel-demand-to-double-in-5-years. Last accessed 23/11/11.

8. World Biodiesel Markets The outlook to 2010. Available: www.agra-net.com/biodieselmarkets. Last accessed 23/11/11. (2010)

9 . Shinji Hama, Sriappareddy Tamalampudi, Ayumi Yoshida, Naoki Tamadani, Nobuyuki Kuratani, Hideo Noda, Hideki Fukuda andAkihiko Kondo, "Process Engineering and Optimization of glycerol Separation in a packed bed reactor for Enzymatic Biodiesel Production," Biosource Technology, vol. 102, pp. 10419-10424, 2011. 10. Matthew B. Boucher, Clifford Weed, Nicholas E. Leadbeater, Benjamin A. Whilhite, James D.

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Stuart and Richard S. Parnas, "Pilot Two Phase Continuous Flow Biodiesel Production Via Novel Laminar Flow Reactor- Separator," Energy & Fuels, vol. 23, pp. 2750-2756, 2009. 11. Linlin Li, Wei Du, Dehua Liu, Li Wang, Zebo Li, "Lipase- Catalysed Transesterification of Rapeseed Oils for Biodiesel production with a novel organic solvent as the reaction medium," Journal of Molecular Catalysis, vol. 43, pp. 58-62, 2006.

12. Continuous biosynthesis of biodiesel from waste cooking palm oil in a packed bed reactor: Optimization using response surface methodology (RSM) and mass transfer studies Halim, S.F.A. ; Kamaruddin, A.H. ; Fernando, W.J.N. Bioresource Technology, 2009, Vol.100(2), p.710-716 [Peer Reviewed Journal]

13. Teresa M. Mataa, 1, Corresponding Author Contact Information, E-mail The Corresponding Author, Antnio A. Martinsa, 2, Nidia. S. Caetano. (2010). Microalgae for biodiesel production and other applications: A review. Renewable and Sustainable Energy Reviews. 14 (1), 217-232. 14. Teresa M. Mataa, 1, Corresponding Author Contact Information, E-mail The Corresponding Author, Antnio A. Martinsa, 2, Nidia. S. Caetano. (2010). Microalgae for biodiesel production and other applications: A review. Renewable and Sustainable Energy Reviews. 14 (1), 217-232. 15. John Ferrell Valerie Sarisky-Reed. (2010). National Algal Biofuels Technology Roadmap. U.S Department of Energy. 1 (1), 56. 16. Piyanuch Nakpong Corresponding Author Contact Information, E-mail The Corresponding Author, Sasiwimol Wootthikanokkhan. (august 2010). High free fatty acid coconut oil as a potential feedstock for biodiesel production in Thailand. renewable evergy. 35 (1), 1682-1687. 17. Pyrolysis of fermented mass containing microbial oil in a fixed-bed reactor for production of biodiesel . Xiaowei Peng, Hongzhang Chen . State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Zhongguancun, Beiertiao 1 Hao, Beijing 100190, PR China . Received 4 September 2009; Accepted 3 February 2010. Available online 10 February 2010.

18. Adam Karl Khan. (2002). Kinectis and catalyst development. Individual inquiry A. 1 (1), 6.

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24. D.H. Qi a,*, H. Chen a, R.D. Matthews b, Y.ZH. Bian. (2010). Fuel. Combustion and emission characteristics of ethanolbiodieselwater. 1 (1), 958-964. 19. J. Das, K.M. Parida, "Heteropoly acid intercalated Zn/Al HTlc as efficient catalyst for esterification of acetic acid using n-butanol"Regional Research Laboratory (CSIR), Bhubaneswar 751 013, Orissa, India,2006 20. A. Brito, M. E. Borges,* M. Garn, and A. Hernandez, "Biodiesel Production from Waste Oil Using Mg-Al Layered Double Hydroxide Catalysts" Chemical Engineering Department, UniVersity of La Laguna, 2009. 21. (2011) Indian Programs Available at: http://www.bloomberg.com/markets/stocks/worldindexes/ Last assessed: 23/11/2011 22. Statistical Data for Labour Available at: http://labourbureau.nic.in/wagetab.htm (2011) Last assessed: 23/11/2011 23. Industrial Land in India Yellow Pages (2011) Available at: http://www.entireindia.com/Classifieds/india.asp?s=industrial%20land Last assessed: 24. (2011) Monthly Report on Shortterm Transactions of Electricity in India Available 23/11/2011 23/11/2011 25. World Indexes Available at: http://www.bloomberg.com/markets/stocks/world-indexes/ (2011) Last assessed: 23/11/2011

at: http://www.cercind.gov.in/2011/MMC/Monthly_Report_June_2011.pdf (2011) Last assessed:

36

Appendix

Synthesis route 1 Material Soybean oil methanol tert-butanol biodiesel glycerol GP (Gross Profit)
Appendix A. Calculation of synthesis route 1

Price (pound/ton) 724 171 2,600 700 256

Amount used (t/year) Cost (pound/year) 98,315.80 11,006.71 31,952.63 80,000.00 10,802.45 71,180,638 1,882,148 83,076,850 56,000,000 2,766,508 -97,373,128

Synthesis route 5 Material Price (pound/ton) Amount used (t/ye ar) Cos t (pound/ye ar) waste Canol oil 260 80808 21,010,101 methanol 171 12194 2,085,173 KOH 1,736 105 182,326 biodiesel 700 80000 56,000,000 glycerol 256 9155 2,344,601 GP 35,067,002
Appendix B. Calculation of synthesis route 2

Synthesis route 6 Material Price (pound/ton) Amount used (t/ye ar) Cos t (pound/ye ar) Soybean oil 724 85106 61,617,021 methanol 171 28024 4,792,105 Na/NaOH/-Al2 O3 25,160 1891 47,583,924 n-hexane 743 17021 12,638,298 biodiesel 700 80000 56,000,000 glycerol 256 9351 2,394,808 GP -68,236,541
Appendix C. Calculation of synthesis route 6

37

Synthesis route 9 Material Jatropha methanol NaOH biodiesel glycerol GP

Price (pound/ton)
188

171 130 700 256

Amount used (t/year) Cost (pound/year) 83,333 15,676,667 27,989 4,786,090 67 8,667 80,000 56,000,000 9,339 2,390,868 37,919,445

Appendix D. Calculation of synthesis route 9

Synthesis route 10 Material Price (pound/ton) Amount used (t/year) Cost (pound/year) 188 83333 15,676,667 Jatropha oil methanol 171 9334 1,596,117 biodiesel 700 80000 56,000,000 glycerol 551 9339 5,145,970 GP 43,873,186
Appendix E. Calculation of synthesis route 10

Sample Calculations:

38

Feed Jatropha oil methanol biodiesel triglyceride (ton/cycle) triglyceride (mol/cycle) total methanol (mol/cycle) methanol used (mol/cycle) methanol recovered (mol/cycle)

MW (g/mol) 857.4 32 861.4 2.7 3244.6 136274 9733 125275

Molecular weight calculations The average molecular weight M of vegetable oil is given by the formula M = f i /((f i /M i )) 3 + 38.049 Where f i is the mass of fatty acid in the oil M i is the molecular weight of the fatty acid Average molecular weight of biodiesel M b = 4.032+ M

Oil Soybean oil Jatropha Oil Canola oil Sunflower oil Rapeseed oil

Average Molecular Weight (M) Average Molecular weight of biodiesel (Mb) 874.63 878.662 857.485 861.517 848.24 852.272 870.814 874.846 957.8 961.832

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