3rd draft- last version

8/2/2019 3rd Draft- Last Version

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9/12/2011

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)

GROUP A BIODIESEL PRODUCTION


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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 .....


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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


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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

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

(1).

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

(2).

(3).

The biodiesel market has been increasing in the past years. With an increase of a world acceptancefor 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

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, (5)

similarly biodiesel market demand has increased from 2005 particularly in the USA

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 (B99-

100)

(5).

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

(6).


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be bigger than the demand, and this can cause serious market problems (7).

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)

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.

This means that for making this product the most feasible possible, we should locate our company

in or near one of these markets.

(8).

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).


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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 aregoing 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. Inmost of the cases, enzymatic reactions are done only on lab scale because the cost of the enzyme is


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alcohol, temperatures around 55 C, atmospheric pressure and a reaction time of 3 hours to achieve a

97% conversion (10)

.

Route 6

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.

: Soybean oil in Batch reactor.

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 2O3 /NaOH). The temperature of the reaction was set at 60 o

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

C, 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.

(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.


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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 theabsence of air, reactants are taken to high temperature ranging from 450 oC - 800 o

C, 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 fluidmicrostructuresThese are formed spontaneously from two normally immiscible liquids and one ormore ionic or non-ionic amphophiles. A microemulsion works by reducing the viscosity of oilswith 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 non-

ionic. 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 economicallysuitable route, so a price summary table is provided.

Raw material Cost(/ton)

Soybean oil 720Waste canola oil 260

Rapeseed oil 780

Jatropha 188

Waste palm cooking oil 914

Algae n/a

sunflower oil 1005

Coconut oil 774

Animal fat 29

Methanol 254

Ethanol 1230 Table 2.Summary table of raw material price


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Catalyst Cost (/ton)

Novozyme 435 640082

HCl 25

KOH 1735

Lipozyme TL IM n/a

NaOH 967

Activated charcoal supported palladium 79364840

H2SO4 1555.6

Al2O3 25160

KNO3 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 thescale 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; whichis 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).

- Jatropha cannot be used for nutritional purposes without detoxification (inedible oil)

The use of Jatropha as

oil as a raw material in route 10 is very advantageous:

- 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, allcomponents 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).

- Lack of use of catalyst

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:

- 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 YesReaction time Seconds-Minutes Minutes-hoursTemperature (C) 200-300 50-80Pressure (bar) 100-200 1Free fatty acids sensitive No YesWater sensitive No YesPre-treatment No YesCatalyst removal No YesSoap 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.

Route Gross Profit1-soybean -97,373,1285- Wast canola oil 35,067,0026- Algae -68,236,5419- Jatropha (alkali-catalyzed) 37,919,44510- Jatropha (supercritical methanol) 43,873,186

Table 5.Gross profit analysis

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)

Factor WeightRaw material availability 4Minimum labour cost 1Land price 2Electricity 2Global location 1TOTAL 10

. We decided to choose India, China and Ghana as possible plant locations. Aweighted comparison study was held to choose the final location. The factors analysed for this study

are:

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 GhanaRaw material availability (grad 10.00 (23) 10.00 (27) 6.00 (31)

Minimum labour cost (/h) 1.28 (24) 0.98 (28) 0.18 (32)

Land price (/m2) 14.26 (25) 8.00 (29) 7.92 (33)

Electricity (/kW/h) 0.10 (26) 0.05 (30) 0.04 (34) 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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IndiaFactor Grade Weighted gradeRaw material availability 10 4Minimum labour cost 5 0.5Land price 10 2Electricity 9 1.8Global location 9 0.9TOTAL 9.2

Table 8.Indias economical weight

ChinaFactor Grade Weighted gradeRaw material availability 10 4Minimum labour cost 2 0.2Land price 7 1.4Electricity 6 1.2Global location 9 0.9TOTAL 7.7

Table 9.China's economical weight

GhanaFactor Grade Weighted grade

Raw material availability 6 2.4Minimum labour cost 10 1Land price 10 2Electricity 10 2Global location 5 0.5TOTAL 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 becultivated 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 conversionas 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 morethan 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 supercriticalmethanol 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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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) 857.14Methanol 32Glycerol 92Biodiesel 857.14+4.032 = 861.172 Table 11.Molecular weight of the reactant and products

Calculation of Feed Rate of Jatropha Oil from Production Basi

Process 1 Process

Process 3

Methanol

Jatrophaoil

Methanol

Glycerin

Biodiesel

Bottoms

Residue

PROCESS 1 PROCESS 2

PROCESS 4

Products

PROCESS 3

Figure 6.Block flow diagram

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


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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) = 1,141Production 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


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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 Hf (kJ/mol)

Methanol 238.57Jatropha oil 4178Biodiesel 1445Glycerin 659.76

Figure 7.Heat of formation of different product

Material Cp (J/mol K) at 298.15 KMethanol 79.5Jatropha oil 2000Biodiesel 1900Glycerin 220.23

Figure 8.Heat capacity of different compounds

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

Material going in Mass flow rate (kg/h) Molar flow rate (mol/h)Methanol 1191 37218.75

Jatropha oil 10634 12406.37 Figure 9.Molar flow rates in and out


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Material going out Mass flow rate (kg/h) Molar flow rate (mol/h)Glycerin 1141 12402.17Biodiesel in destillate 10577.16 12282.28Jatropha oil in distillate 21.2 24.73

Jatropha oil in residue 421.8 492.1Biodiesel in residue 106.84 124.06Glycerin in residue 3.42 37.17 Figure 10.Mass flow rate in and out

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 aninput of energy). This is intuitively expected since our reaction takes place at high temperature, highpressure.


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11. References

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characterization of oils and their esters as the substitute of diesel: A Review," Renewable and

Sustainable Energy Reviews, vol. 14, pp. 200-216, 2010.

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advantages-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.
http://www.mcdonalds.co.uk/ourworld/environment/waste.shtml/http://www.mcdonalds.co.uk/ourworld/environment/waste.shtml/http://www.mcdonalds.co.uk/ourworld/environment/waste.shtml/http://www.mcdonalds.co.uk/ourworld/environment/waste.shtml/


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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.

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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 OilUsing Mg-Al Layered Double Hydroxide Catalysts" Chemical Engineering Department,Uni Versity of La Laguna, 2009.

21. (2011) Indian Programs Available at: http://www.bloomberg.com/markets/stocks/world-

indexes/ Last assessed: 23/11/2011

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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:

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

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25. World Indexes Available at: http://www.bloomberg.com/markets/stocks/world-indexes/ (2011)

Last assessed: 23/11/2011
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Appendix

Synthesis route 1

Material Price (pound/ton) Amount used (t/year) Cost (pound/year)

Soybean oil 724 98,315.80 71,180,638

methanol 171 11,006.71 1,882,148

tert-butanol 2,600 31,952.63 83,076,850

biodiesel 700 80,000.00 56,000,000

glycerol 256 10,802.45 2,766,508GP (Gross Profit) -97,373,128

Appendix A. Calculation of synthesis route 1

Synthesis route 5Material Price (pound/ton) Amount used (t/year) Cost (pound/year)waste Canol oil 260 80808 21,010,101

methanol 171 12194 2,085,173KOH 1,736 105 182,326biodiesel 700 80000 56,000,000glycerol 256 9155 2,344,601GP 35,067,002 Appendix B. Calculation of synthesis route 2

Synthesis route 6

Material Price (pound/ton) Amount used (t/year) Cost (pound/year)Soybean oil 724 85106 61,617,021methanol 171 28024 4,792,105Na/NaOH/-Al 2O 3 25,160 1891 47,583,924n-hexane 743 17021 12,638,298biodiesel 700 80000 56,000,000glycerol 256 9351 2,394,808GP -68,236,541

Appendix C. Calculation of synthesis route 6


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Synthesis route 9Material Price (pound/ton) Amount used (t/year) Cost (pound/year)Jatropha 188 83,333 15,676,667methanol 171 27,989 4,786,090NaOH 130 67 8,667biodiesel 700 80,000 56,000,000glycerol 256 9,339 2,390,868GP 37,919,445 Appendix D. Calculation of synthesis route 9

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

Appendix E. Calculation of synthesis route 10

Sample Calculations:


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Feed MW (g/mol)Jatropha oil 857.4methanol 32biodiesel 861.4triglyceride (ton/cycle) 2.7triglyceride (mol/cycle) 3244.6total methanol (mol/cycle) 136274methanol used (mol/cycle) 9733methanol recovered (mol/cycle) 125275

Molecular weight calculations

The average molecular weight M of vegetable oil is given by the formulaM = f i /((f i /M i

Where

)) 3 + 38.049

f i M

is the mass of fatty acid in the oil

i

Average molecular weight of biodiesel M

is the molecular weight of the fatty acid

b

= 4.032+ M

Oil Average Molecular Weight (M) Average Molecular weight of biodiesel (M b)Soybean oil 874.63 878.662Jatropha Oil 857.485 861.517Canola oil 848.24 852.272Sunflower oil 870.814 874.846Rapeseed oil 957.8 961.832

3rd draft- last version

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