A PROJECT REPORT ON

Designing OF a HIGH performance BIODIESEL PROCESSOR

AND EXTRACTION OF BIODIESEL

Submitted in partial fulfillment of the requirements For the award of the degree BACHELOR OF ENGINEERING IN ____________________________________ ENGINEERING

SUBMITTED BY -------------------- (--------------) --------------------- (---------------) --------------------- (---------------)

DEPARTMENT OF _______________________ ENGINEERING __________COLLEGE OF ENGINEERING AFFILIATED TO ___________ UNIVERSITY

CERTIFICATE

This is to certify that the dissertation work entitled Designing of a high performance biodiesel processor and extraction of biodiesel is the work done by _______________________________________________ submitted in partial fulfillment for the award of BACHELOR OF ENGINEERING (B.E) in Mechanical Engineering from_______ College of Engineering affiliated to _________ University , Bhubaneswar .

________________ (Head of the department, ECE)

____________ (Assistant Professor)

EXTERNAL EXAMINER

ACKNOWLEDGEMENT

I wish to express my sincere gratitude to my project guide

Dr ----------------

---------------------------- Professor (Mechanical Engineering) for providing me the opportunity to accomplish to my major project on Designing

of a high performance

biodiesel processor and extraction of biodiesel.

It was their invaluable guidance

that the project was completed successfully. Their friendly, co-operative and helping nature along with sympathetic and encouraging attitude has been a constant source of inspiration to me during this endeavor.

I am immensely thankful to, Dean(Academic), for his guidance and moral support.

I wish to express my deep sense of regards to my family members and friends for their moral support.

Your name

DECLARATION

We, the undersigned, declare that the project entitled Designing of a high performance biodiesel processor and extraction of biodiesel from cooking oil, being submitted in partial fulfillment for the award of Bachelor of Engineering Degree in Mechanical Engineering, affiliated to _________ University, is the work carried out by us.

__________ __________

_________ _________

_________ _________

ABSTRACT

Fuel crisis because of dramatic increase in vehicular population and environmental concerns have renewed interest of scientific community to look for alternative fuels of bio origin. Diesel engines are very common. In spite of proving a great boon to the transportation and industry, they also are a major contributor to pollution in India as well as the rest of the world. Biodiesel is very effective alternative fuel as it can be used in any existing diesel engine with negligible or no modifications. But the problem is that biodiesel is not widely available in India. In this project biodiesel has been produced through a process which is very much cost effective and the performance is very high. For this project biodiesel sample has been prepared, and comparison has been made between different oils. The performances of this biodiesels have been checked by the performance parameters. This report will outline the processes involved in extracting oil from plant which acts as raw material for fabrication of biodiesel, also it will show detailed process followed in making a biodiesel processor. It will justify every decision made using analytical data, calculations and professional opinions.

CONTENTS OF THE REPORT:

Certificate Acknowledgements Abstract

i ii iii

Chapters

Title

Page No

Chapter No. 1 : Introduction. 1.1 General 1.2 Indian Scenario in Biodiesel 1.3 Resources of Biodiesel 1.4 Storage, Handling and Distribution 1.4.1 Additives for Oxidative Stability of Biodiesel 1.4.2 Material Compatibility 1.5 Chemistry of Biodiesel 1.6 Properties of Biodiesel 1.7 Motivation 1.8 Organization of the Report 2.LITERATURE REVIEW 2.1 Biodiesel Production Techniques

1-9

Chapters

Title

Page No

2.2 Performance Studies 2.3 Conclusions Chapter No. 3 : Vegetable Oils 3.1Introduction 3.2Advantages of Vegetable Oils as Engine Fuels, Challenges and Technical difficulties 3.3Vegetable Oils vs. Diesel Fuel 3.4Problems associated with the usage of Vegetable Oils in Diesel Engines 23-43

Chapter No. 4 : The Alternative Fuel-Biodiesel

44-53

4.1Bio-diesel as an option. 4.2ASTM D-6751 standards for biodiesel 4.3Properties of Biodiesel.

Chapters

Title

Page No

CHAPTER NO.5 BIODIESEL PRODUCTION METHODOLOGY 5.1Introduction 5.2Various Techniques For Fuel Modification 5.3Methods of Transesterification 5.4ProcessVariables in trans-esterification. 5.5Raw material and its quality for the production of biodiesel 5.6Blending of Esters & Diesel Chapter No. 6 : Operation of Biodiesel Reactor 6.1 Chemicals and materials required 6.2 Steps involved in production

INTRODUCTION
GENERAL:-

Today the world is facing two major challenges which include the energy (fuel) crisis and environment degradation. The costs of crude oil products depend on international markets and petroleum reserves are limited to nearly 40 years with current consumption rate. Many countries all over the world have been developing new crops since the mid-1970s in order to increase the biomass resource base for production of bio energy. Indias economy has often been unsettled by its need to import about 70% of its petroleum demand from the highly unstable and volatile world oil market. India is projected to become the third largest consumer of transportation fuel in 2020, after the USA and China, with consumption growing at an annual rate of 6.8% [1]. In India 90% of imported oil is consumed for the transportation and energy generation and its economy are highly depending on the import of crude oil. Therefore role of bio fuel as a transportation fuel will play a very vital role. The idea of using vegetable oil as a substitute for diesel fuel was demonstrated by the inventor of the diesel engine, Rudolph Diesel, around the year 1900, when vegetable oil was proposed as fuel for engines. The oil use as diesel fuel was limited due to its high viscosity (near 10 times of the gas oil). In order to adapt the fuel to the existing engines the properties of vegetable oil had to be modified. Various products derived from vegetable oils have been proposed as an alternative fuel for diesel engines [2]. ASTM International defines biodiesel as the mono alkyl esters of long chain fatty acids derived from renewable lipid feedstock, such as vegetable oils and animal fats, for use in compression ignition engines. In the 1980s and 1990s significant R&D was conducted to evaluate a variety of biodiesel blending stocks, develop emissions data, assess engine/vehicle performance, and develop cost-effective manufacturing processes. The main commodity sources of biodiesel in India are non edible oils obtained from plant species such as Jatropha, Pongamia pinnata etc [3]. Biodiesel can be blended at any level with petroleum diesel to create a biodiesel
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blend or can be used in its pure form. Just like petroleum diesel, biodiesel operates in compression ignition engine; which essentially require very little or no engine modifications because biodiesel has properties similar to petroleum diesel fuels. It can be stored just like petroleum diesel fuel and hence does not require separate infrastructure. The use of biodiesel in conventional diesel engines results insubstantial reduction of un-burnt hydrocarbons (HC), carbon monoxide (CO) and particulate matters [4]. But uses of biodiesel slightly increase nitrogen oxide (NOx) which can be reduced by incorporating EGR system. Biodiesel is considered as a clean fuel since it has almost no sulphur, no aromatics and has about 10% built in oxygen, which helps it to burn fully. Its higher cetane number improves the ignition quality even when blended in the petroleum diesel. Due to the fact that vegetable oils are produced from plants, their burning leads to a complete recyclable CO2 (green house gas).There are also some drawbacks in the bio diesel fuel as compared to petroleum fuels which includes high cost of biodiesel which is around 1.5 times to that of petroleum diesel, unavailability at large scale, and requirement of large area of land. Now a days various techniques have been developed for producing biodiesel. Some of them are mechanical stirring, ultrasonic cavitation, hydrodynamic cavitation and supercritical methanol. Advantages of the bio-diesel over petroleum based diesel fuel are given below: 1. Biodiesel is a good lubricant about 66% better than petro diesel 2. Biodiesel produce less smoke and particulate maters as it is free of sulphur and aromatics. 3. Biodiesel has higher cetane number having well anti knocking property. 4. Produce lower carbon monoxide and hydrocarbon emissions. 5. Bio-diesel is renewable, biodegradable and non-toxic. In comparison with petroleum-based diesel fuel, biodiesel is characterized by: Lower heating value (by about 10-12%) Higher cetane value (typically 45-60)
10

 About 11% oxygen content (petroleum-based diesel contains no oxygen) No aromatics contents (and no PAHs) No sulphur or extremely low sulphur content Better lubricant Higher viscosity Higher freezing temperature (higher cloud point and pour point) Higher flash point No toxicity or low toxicity Biodegradability Different corrosive properties Some of the above properties, such as the high cetane value or good lubricity, are obvious advantages of biodiesel while others, including the lower heating value, high freezing point (and inferior flow properties at low temperature), or corrosion properties are its drawbacks. Biodiesel changes the character and can increase the intensity of the odour of diesel exhaust [5]. 1.2 Indian scenario in biodiesel The country's energy demand is expected to grow at an annual rate of 6.8 per cent over the next couple of decades. Most of the energy requirements are currently satisfied by fossil fuels coal, petroleum based products and natural gas. Past and projected increased demand is shown in Table 1.1. Domestic production of crude oil can only fulfil 25-30 per cent of national consumption rest we are importing from other countries. In these circumstances bio fuels are going to play an important role in meeting Indias growing energy needs. Bio fuels offer an attractive alternative to fossil fuels, but a consistent scientific framework is needed to ensure policies that maximize the positive and minimize the negative aspects of bio fuels. SOURCE UNITS 199411

2001-

2006-

2011-

95 Electricity Billion units Coal Natural gas Oil products Million tonnes 290 76.67

02

07

12

480.08 712.67 1067.88 108.9 15730 99.64 134.6 18291 173.5 20853

Million cubic 9880 meters Million tonnes 63.55

139.85 196.47

The government of India has formulated an ambitious National Biodiesel Mission to meet 20 per cent of the countrys diesel requirements by 20162017.Requirement of bio fuel for blending under different scenario are given in Table 1.2. A commercialization period during 2007-2012 will continue Jatropha cultivation and install more transesterification plants which will position India to meet 20 per cent of its diesel needs through biodiesel. Table 1.2 Demand for diesel and biodiesel requirement YEA R DIESEL DEMAND( MT) BLENDING@ BLENDING@ BLENDING@ 5% 5% 5% 2.62 3.35 4.18 5.23 6.69 8.36 10.46 13.38 16.72

200 52.32 6-07 201 66.91 1-12 201 83.58 6-17

The main problem in getting the biodiesel programme rolling has been the difficulty in initiating the large-scale cultivation of Jatropha because
12

farmers do not consider Jatropha cultivation rewarding enough. Therefore government needs to sponsor confidence-building measures such as establishing a minimum support price for Jatropha oilseeds and assuring farmers of timely payments.The plantations under this mission will be established by NGOs, public and private sectors. The Ministry of Forests and Environment (MoEF) and the National Oilseed and Vegetable Oil Development (NOVOD) Board will serve as responsible agencies for the cultivation in the forest and non-forest areas, respectively by providing the necessary information and financial assistance. In India, there are about 100 varieties of oil seeds but only 10-12 varieties have been tapped so far, amongst which Jatropha and Pongamia are the key wild plant species identified as the potential feedstock for biodiesel production. Their cultivability in wasteland and relatively adverse climatic conditions are the key attribute for their promotion as a feedstock material. According to the Economic Survey of Government of India, out of the total cultivated land area, about 175 million hectares of land is classified as waste and degraded land. It is perceived at various levels of government that encouraging sustainable cultivation of Pongamia and Jatropha trees on these lands can meet part of the countrys energy requirements. With this background, the Planning Commission of India, along with the Ministries of Petroleum, Rural Development, Poverty Alleviation and Environment, has conceptualized a national mission that recommends a major multidimensional program to commercialize the biodiesel industry in India. One prime objective is the progressive replacement of petro-diesel by blending in 5%, 10%, and, eventually, 20% of biodiesel. There are many key challenges and market barriers for biodiesel promotion in India. Information regarding the agro economic practices are limited, which often discourages the risk-averse small and marginal farmers from growing nonedible oil seeds. Still there is uncertainty about the potential yields and reliability of seeds. Further cultivation of such crops having relatively longer gestation period such as Jatropha (3 years) & Pongamia (5 Years). At present the country is relying on imported technology, which is extremely expensive and is also proven for edible oil as feedstock. There are risks associated with the technology for its costs and compatibility. Though indigenous technologies are available at low costs and in smaller plant sizes with lower levels of performance regarding conversion of oil to diesel.
13

Finance of biodiesel projects are a major constraint but few venture capital firms and banking institutions are coming forward to finance biodieselmanufacturing plants. The production costs of bio-diesel are currently higher than conventional fuels, so it will be very difficult to gain market share without Government intervention in terms of favourable duty and taxation levels. At present wide and uncertain price band ranging from Rs 17-45 per litre of biodiesel discourage the seller & distributor to set up separate distribution channels. Lack of mandate to blend biodiesel at certain % of fossil diesel does not encourage oil-marketing firms to get sufficiently encouraged for involving in its promotion. Furthermore, lack of adequate consumer awareness regarding its reliability and performance also discourages the end users to use it in their vehicles voluntarily.

1.3 Resources of Biodiesel Many developed countries have active biodiesel programs. Currently biodiesel is produced mainly from field crop oil like rapeseed, sunflower etc. in Europe and soybean in US. Malaysia utilizes palm oil for biodiesel production while in Nicaragua it is jatropha oil. The productions of vegetable oil globally and in India are given in Table 1.3. There are many countries which have large amount of bio-diesel potential. And if this potential is used for the production of biodiesel than the crisis of petroleum based diesel and fossil fuel can be solved. The global warming problem can also be solved because biodiesel is bio- fuel and it has no harmful emission in diesel engine. In Table 1.4 top 10 countries biodiesel potential (Liter) and there production cost ($/Liter) is given.

14

Table 1.3 Global productions of the major vegetable oils [6] OIL SOYAB EAN RAPES EED COTTO NSEED SUNFL OWER PEANU T PRODUCTION (MT) 27.8 OIL PRODUCTION (MT) OIL PRODUCTIO N(MT)

PALM 2.9 KERN EL OLIV E COR N 2.7 2.0

SESA 0.26 ME CAST 0.25 OR NIGE 0.03 R COC OCN UT RICE BRA N 0.55

13.7 4.0 8.2

CAST 0.5 OR GRO UND NUT 1.4

5.1

0.55

Table 1.4: Top 10 countries in terms of biodiesel potential [7] RANK COUNTRY VOLUME POTENTIAL 14540,000,000 7595,000,000 5255,000,000 3212,000,000 2567,000,000 2496 2024
15

PRODUCTION COST(PER LITRE) $ 0.53 $ 0.49 $ 0.62 $ 0.70 $ 0.62 $ 0.75 $ 0.79

1 2 3 4 5 6 7

Malaysia Indonesia Argentina USA Brazil Netherlands Germany

8 9 10

Philippines Belgium Spain

1234 1213 1073

$ 0.53 $ 0.78 $ 1.71

1.4 Storage, Handling and Distribution Biodiesel is significantly safer than diesel. The storage and handling procedures for petroleum diesel can also be used for biodiesel. The fuel is best stored in a dark, dry and clean environment, in storage tanks, preferably steel, aluminium, Teflon, fluorinated polyethylene or polypropylene. Materials which should be avoided include lead, copper, brass, tin and zinc. Biodiesel has a flash point higher than diesel. Many diesel fuel suppliers recommend storing diesel for no more than three to six months unless using a stabilizing additive. The current industry recommendation is that biodiesel or biodiesel blends also be used within six months. A longer safe life is possible and storage enhancing additives can provide additional benefits. Acid numbers in biodiesel and biodiesel blends will become elevated if the fuel ages, or if it was not properly manufactured. Raised acid numbers have been associated with fuel system deposits and reduce the life of fuel pumps and filters. Pure biodiesel and biodiesel blends should be stored at temperatures higher than the pour point of the fuel. Biodiesel blends will not separate in the presence of water however it is recommended that good housekeeping be maintained. This is in respect to tank and fuel maintenance, to ensure water in storage systems is monitored and minimised [8]. 1.4.1 Additives for oxidative stability of biodiesel Oxidative stability is a major industry issue for diesel and biodiesel fuels. Some biodiesels are more stable than others and some unstable biodiesel contain stability additives that perform very well. The tendency of a fuel to be unstable can be predicted by the Iodine number (ASTM D 1510) but the
16

test method may not pick up the presence of stability additives. Iodine number actually measures the presence of C=C bonds that are prone to oxidation. The general rule of thumb is that instability increases by a factor of 1 for every C=C bond on the fatty acid chain; thus, 18:3 are three times more reactive than C18:0. Stability can be predicted from knowledge of the feedstock only if you know the proportion of C18:2 and C18:3 fatty acids present in the fuel and know whether or not the fuel has been treated for stability. High fractions of those two types of fatty acids can adversely affect fuel stability if additives are not used. Poor stability can lead to increasingly high acid numbers, increasing viscosity, and the formation of gums and sediments that can clog filters. Comparing the fuels acid number and viscosity over time can provide some idea about whether or not the fuel is oxidizing, but you need to take a sample at the beginning when the fuel is fresh and then sample on a regular basis after that. Long-term storage in the presence of diesel fuel, diesel additives, water, sediments, heat, and air has not been adequately documented in the field. Biodiesel and blends of biodiesel and diesel fuel should not be stored for longer than 6 months in either storage tanks or vehicles until better field data is available. If it becomes necessary to store biodiesel longer than 6 months, or the storage conditions are poor, use antioxidants. The common antioxidants that work with biodiesel are TBHQ (t-butyl hydroquinone), Tenox 21, and tocopherol (Vitamin E). Most of these are sold by food additive firms. Powdered antioxidants are difficult to mix into biodiesel. A trick used is to heat a small amount of biodiesel (1 gal or so) up to 37.7 C or until all the powdered antioxidant is dissolved. Then mixed the treated biodiesel into the bulk biodiesel fuel [9]. 1.4.2 Material compatibility Brass, bronze, copper, lead, tin, and zinc will oxidize diesel and biodiesel fuels and create sediments. Lead solders and zinc linings should be avoided, as should copper pipes, brass regulators, and copper fittings. The fuel or the fittings will tend to change color and sediments may form, resulting in plugged fuel filters. Affected equipment should be replaced with stainless steel or aluminum. Acceptable storage tank materials include aluminum, steel, fluorinated polyethylene, fluorinated polypropylene, and Teflon. The effect of B20 on vulnerable materials is diluted compared to
17

higher blends. Some slow oxidation can occur, although it may take longer to materialize. Biodiesel can also affect some seals, gaskets, and adhesives, particularly those made before 1993 made from natural or nitride rubber. It is primarily for these reasons that vehicle and storage equipment are modified. Most engines made after 1994 have been constructed with gaskets and seals that are generally biodiesel resistant. Earlier engine models or rebuilds may use older gasket and seal materials and present a risk of swelling, leaking, or failure. Fuel pumps may contain rubber valves that may fail. The typical approach is to create a maintenance schedule that checks for potential failures. Users can also contact engine manufacturers for more information [9]. 1.5 Chemistry of Biodiesel Biodiesel is made using the process of transesterification. In the transesterification of different type of oils, triglycerides react with an alcohol, generally methanol or ethanol, to produce esters and glycerin. To make it possible, a catalyst is added to the reaction.

Where, term R represents to different alkyl groups. The overall process is normally a sequence of three consecutive steps, which are reversible reactions. In the first step from triglycerides, diglyceride is obtained. From diglyceride, monoglyceride is produced and in the last step from monoglycerides, glycerin is obtained. In all these reactions esters are produced. The stochiometric relation between alcohol and the oil is 3:1. However, an excess of alcohol is usually more appropriate to improve the reaction towards the desired product.
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Triglycerides (TG) + ROH Diglycerides (DG) + RCOOR1

Diglycerides (DG) + ROH Monoglycerides (MG) + RCOOR2

Monoglycerides (MG) + ROH Glycerin (GL) + RCOOR3

The catalyst used for the reaction is mainly of three types which is given below.

Alkali Catalyst

This catalyst can be used with methanol or ethanol as well as any kind of oils, refine, crude or frying. The main alkali catalysts are sodium hydroxide (NaOH) and potassium hydroxide (KOH).

Acidic Catalyst

Acid transesterification is a great way to make biodiesel if the sample has relatively high free fatty acid content. The main acidic catalysts are Sulfuric acid (H2SO4) and Sulfonic acid.

Enzymes-catalyzed

Enzymes-catalyzed procedures, using lipase as catalyst, but the lipases are very expensive for industrial scale production and there are three-step process was required to achieve a 95% conversion. Due to this three step process the reaction time is too large.
19

1.6 Properties of Biodiesel A general understanding of the various properties of biodiesel is essential to study their implications in engine use, storage, handling and safety [10]. Density/ Specific gravity Biodiesel is slightly heavier than conventional diesel fuel (specific gravity 0.88 compared to 0.84 for diesel fuel). This allows use of splash blending by adding biodiesel on top of diesel fuel for making biodiesel blends.

Cetane Number Biodiesels has higher cetane number than conventional diesel fuel. This result in higher combustion efficiency and smoother combustion.

Viscosity

In addition to lubrication of fuel injection system components, fuel viscosity controls the characteristics of the injection from the diesel injector (droplet size, spray characteristics etc.). The viscosity of methyl esters can go to very high levels and hence, it is important to control it within an acceptable level to avoid negative impact on fuel injection system performance. Therefore, the viscosity specifications proposed are same as that of the diesel fuel.

Flash point

Flash point of a fuel is defined as the temperature at which it will ignite when exposed to a flame or spark. The flash point of biodiesel is higher than the petroleum based diesel fuel. Flash point of biodiesel blends is dependent on the flash point of the base diesel fuel used, and increase
20

with percentage of biodiesel in the blend. Thus in storage, biodiesel and its blends are safer than conventional diesel. The flash point of biodiesel is around 160 0C.

Cold filter plugging point (CFPP)

At low operating temperature fuel may thicken and not flow properly affecting the performance of fuel lines, fuel pump and injectors. Cold filter plugging point of biodiesel reflects its cold weather performance. It defines the fuels limit of filterability. Biodiesel thicken at low temperatures so need cold flow improver additives to have acceptable CFPP.

Cloud point

Cloud point is the temperature at which a cloud or haze of crystals appear in the fuel under test conditions and thus becomes important for low temperature operations. Biodiesel generally has higher cloud point than diesel fuels.

Aromatics

Biodiesel does not contain any aromatics so aromatic limit not specified.

Stability

Biodiesel age more quickly than fossil diesel fuel due to the chemical structure of fatty acids and methyl esters present in biodiesel. Typically
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there are up to 14 types of fatty acid methyl esters in the biodiesel. The individual proportion of presence of these esters in the fuel affects the final properties of biodiesel. Saturated fatty acid methyl esters (C14:0, C16:0, C16:0) increase cloud point, cetane number and improve stability whereas more polyunsaturates (C18:2, C18:3) reduce cloud point, cetane number and stability.There are three types of stability criteria namely Oxidation stability, Storage stability and Thermal stability.

Iodine number

Iodine number refers to the amount of iodine required to convert unsaturated oil into saturated oil. It refers to the amount of unsaturated fatty acid in the fuel. One value of iodine number can be obtained by using several grades of unsaturated acids. Therefore an additional parameter, linolenic acid (C18: 3) content is specified and limited to 15% in Austrian Standard ON C 1191.

Acid number/ Neutralization number

Acid number reflects the presence of free fatty acids or acid used in manufacture of biodiesel. It also reflects the degradation of biodiesel due to thermal effect. The resultant high acid number can cause damage to injector and also result in deposit in fuel system and affect life of pumps and filters.

1.7 Motivation The decrease of world petroleum reserves and high energy demand in the power industries and transport sector has necessitated the need for an alternative source of energy. Due to harmful emission and green house gas from fossil fuel, environment is continuously degrading .Therefore there is
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an also need of alternative fuel which improve the environmental condition. Biodiesel obtained from vegetable oil can be alternative source of energy because its property is similar to petroleum derived diesel oil and produces favourable effects on the environment, such as a decrease in acid rain and greenhouse effect. Due to these factors, the use of biodiesel is considered an advantage to that of fossil fuels. Government of India has also setup national biodiesel mission to meet the aim of 20% blend of biodiesel with diesel by 2011-2012. This work hoped a positive way towards security of energy in future. The aim of this project to search for optimum condition for biodiesel production and effective method of biodiesel production, then cheque performance in C.I Engine.

1.8 Organization of the report

First chapter is introduction which deals with the energy demand over world and need of renewable energy to secure the future demand of energy. This chapter comprises of various subheadings like general which is about biodiesel and its advantage over fossil fuel, Indian energy scenario which show the position of India on consumption of energy and contribution towards renewable energy source, resources of biodiesel which show existence of energy crops over the world, storage, handling and distribution of biodiesel and last one is biodiesel properties according to BIS standards. Second chapter is literature review in which literatures available on biodiesel production and its performance testing are summarized. Third chapter is all about vegetable oils . Fourth chapter is describing the alternative fuel biodiesel .Fifth chapter is biodiesel production methodology which deals with various techniques of biodiesel production and its feasibility. Sixth chapter describes the types of biodiesel reactor.

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2. LITERATURE REVIEW

Chapter 2 deals with the biodiesel production techniques and performance studies available in the literature these are described below:

2.1 Biodiesel production techniques

In this topic literature belonging to biodiesel production is collected to review various techniques of biodiesel production. The literature contains biodiesel production through mechanical steering, supercritical methanol, hydrodynamic cavitation and ultrasonic cavitation. With these literatures it can be easily analyzed that which method is most suitable for the biodiesel production at optimum condition.

Demirbas [11], investigated the changes in yield percentage of methyl esters with supercritical methanol method with a molar ratio of 41. The critical temperature and the critical pressure of methanol were 512.4 K and 8.0 MPa, respectively. In that study, it was concluded that increasing reaction temperature, especially supercritical temperatures had a favourable influence on ester conversion.

The study by Balat [12], investigated study the yields of ethyl esters from vegetable oils via transesterification in supercritical ethanol. The critical temperature and the critical pressure of ethanol were 516.2 K and 6.4 MPa, respectively.

Saka and Kusdiana [13], have developed a catalyst-free method for biodiesel production by employing supercritical methanol. The supercritical treatment at 350 0C, 43 MPa and 240 s with a molar ratio of 42 in methanol is the optimum condition for transesterification of rapeseed oil to bio-diesel fuel and it is found
24

that more yielding from methyl ester at this optimum condition and the reaction time much less than any other process of bio-diesel production. The 5 ml reaction vessel made of inconel-625 was used in this system in which pressure and temperature were monitored in real time covering up to 200 MPa and 5500C respectively. The reaction vessel is charged with given amount of rapeseed oil and liquid methanol with a molar ratio of 1: 42 the reaction vessel was then quickly immersed into the tin bath preheated at 350 0C and 400 0C, and kept for a set time interval for supercritical treatment of methanol, from 10 to 250 s and then moved to water bath to stop reaction. Treated oil was allowed to settle down for 30 min than three phases were visible. Top phase consisting of methanol was removed. And for remaining phase upper and lower evaporated at 90 0C for 20 min to remove remaining methanol. Result of this study is shown in the Table 2.1 Table 2.1 Comparison of yield in alkaline catalyzed, acid catalyzed and supercritical methanol[13]
Raw material Rapeseed Free fatty acid(wt%) 2.0 Water content(wt%) 0.002 Yield of methyl esters(wt%) Alkaline catalyst 97 Acid catalyst 98.4 Supercritical methanol 98.5

Palm frying

5.3 5.6

2.1 0.2

94.4 94.1

97.8 97.8

98.9 96.9

Madras et al. [14], investigated the transesterification of sunflower oil in supercritical methanol and supercritical ethanol at various temperatures (2004000C) at 200 bar. For reaction in supercritical methanol and ethanol, no catalyst is required and nearly complete conversion can achieve in very short time (2-4 min). This is because supercritical methanol and oil is in single phase. Synthesis of bio-diesel in supercritical methanol and ethanol were conducted in an 8 ml stainless steel reactor and the molar ratio is taken as 40:1.Initialy maintatained the desired reaction temperature (200-4000C) and pressure (200 bar).the reactor was put into furnace after predetermined reaction time reactor was quenched. Than the methanol or ethanol removed from reactor. The result of this investigation was in methanol, the conversion increased from 78% to 96% with
25

increase in temperature. A similar trend was observed for conversion in ethanol but the conversion were higher, because the solubility parameter of ethanol is lower than that of methanol and closer to oil, the conversion are higher in ethanol compared to conversion obtained in methanol.

Han [15], in this study a co-solvent was added to reaction mixture in order to decrease the operating temperature, pressure and molar ratio of alcohol to oil. Supercritical CO2 is good solvent for small and moderate organic molecule and it is low cost and facile material. Therefore CO2 is used as a co-solvent for study. The experiment was performed in 250 ml cylindrical autoclave at maximum pressure and temperature was 100 MPa and 4500C respectively. It was observed in the study that with optimum reaction temperature 280 0C, molar ratio 24 and CO2 to methanol ratio of 0.1, a 98% yield of methyl ester (biodiesel) was observed in 10 min at reaction pressure of 14.3 MPa, which make the supercritical method viable for the industrial purpose. it is observed that supercritical methanol with cosolvent process is superior to the conventional supercritical methanol method. CO2 is both add and remove from the mixture when reaction is completed. Compared to the conventional processes less energy is required for process and reaction pressure is reduced which make process safer and less costly. Ji et al. [6], performed experiments on Power Ultrasonic (PU) (19.7 kHz), Hydrodynamic Cavitation (HC), and Mechanical Stirring (MS). They use soybean oil as vegetable oil mixed with KOH for production of biodiesel. In Power Ultrasonic (PU) method the reactions were carried out in an ultrasonic reactor. The temperature of the reaction mixture was controlled by a water bath. Vegetable oil (100 g) was poured into the reactor at the beginning. The reaction started when a quantitative amount of methanol liquor dissolved in KOH was poured into the heated reactor.

Orthogonality experiments were designed with 4 factors and 3 levels, which are listed in Table 2.2.

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Table 2.2 Orthogonality experiments design [6] Factor A,power(w) B,molar ratio C,pulse frequency 3:1 4.5:1 6:1 0.4 0.7 1.0 D,temperature(oc)

I II III

100 150 200

25 35 45

2.2 Performance studies

In this topic literature of performance study of biodiesel derived from various vegetable in diesel engine has been reviewed. In this literatures performance and emission of biodiesel is compared with diesel at various blend of biodiesel.

Hebbal et al. [19], have presented the investigation on deccan hemp, a nonedible vegetable oil in a diesel engine for its suitability as an alternate fuel. The performance and emission characteristics of blends are evaluated at variable loads of 0.37, 0.92, 1.48, 2.03, 2.58, 3.13 and 3.68 kW at a constant rated speed of 1500 rpm and results are compared with diesel. The thermal efficiency, brake specific fuel consumption (BSFC), and brake specific energy consumption (BSEC) are well comparable with diesel but the emissions were little higher for 25% and 50% blends. At rated load, smoke, carbon monoxide (CO), and unburnt hydrocarbon (HC) emissions of 50% blend are higher compared with diesel by 51.74%, 71.42% and 33.3%, respectively.

Agarwal and Agarwal [20], conducted experiments were conducted using various blends of Jatropha oil with mineral diesel to study the effect of reduced blend viscosity on emissions and performance of diesel engine. The acquired data were analyzed for various parameters such as thermal efficiency, brake specific fuel consumption (BSFC), smoke opacity, CO2, CO and HC emissions. While
27

operating the engine on Jatropha oil (preheated and blends), performance and emission parameters were found to be very close to mineral diesel for lower blend concentrations. However, for higher blend concentrations, performance and emissions were observed to be marginally inferior.

Purushothaman and agarajan [21], presented work the performance, emission and combustion characteristics of a single cylinder, constant speed, direct injection diesel engine using orange oil as an alternate fuel were studied and the results are compared with the standard diesel fuel operation. Results indicated that the brake thermal efficiency was higher compared to diesel throughout the load spectra. Carbon monoxide (CO) and hydrocarbon (HC) emissions were lower and oxides of nitrogen (NOx) were higher compared to diesel operation. Peak pressure and heat release rate were found to be higher for orange oil compared to diesel fuel operation.

Labeckas and Slavinskas [22],This article presents the comparative bench testing results of a four stroke Diesel engine when operating on neat rapeseed oil methyl ester and its 5%, 10%, 20% and 35% blends with Diesel fuel. The purpose of this research is to examine the effects of rapeseed oil inclusion in Diesel fuel on the brake specific fuel consumption (bsfc) of a high speed Diesel engine, its brake thermal efficiency, emission composition changes and smoke opacity of the exhausts. The brake specific fuel consumption at maximum torque and rated power is higher for rapseed oil by 18.7% and 23.2% relative to Diesel fuel. The maximum brake thermal efficiency is higher for rapseed oil at higher load. The maximum NOx emissions increase proportionally with the mass percent of oxygen in the bio fuel and engine speed. The carbon monoxide, CO, emissions and visible smoke emerging from the biodiesel over all load and speed ranges are lower by up to 51.6% and 13.5% to 60.3%, respectively. The carbon dioxide (CO2) is slightly higher in case of biodiesel. The emissions of unburned hydrocarbons, HC, for all biofuels are low.

In the study of Altuna et al. [23], a blend of 50% sesame oil and 50% diesel fuel was used as an alternative fuel in a direct injection diesel engine. Engine
28

performance and exhaust emissions were investigated and compared with the ordinary diesel fuel in a diesel engine. The experimental results show that the engine power and torque of the mixture of sesame oil diesel fuel are close to the values obtained from diesel fuel and the amounts of exhaust emissions are lower than those of diesel fuel. Hence, it is seen that blend of sesame oil and diesel fuel can be used as an alternative fuel successfully in a diesel engine without any modification and also it is an environmental friendly fuel in terms of emission parameters. Sureshkumar et al. [24], presented the results of performance and emission analyses carried out in an unmodified diesel engine fuelled with Pongamia pinnata methyl ester (PPME) and its blends with diesel. Engine tests have been conducted to get the comparative measures of brake specific fuel consumption (BSFC), brake specific energy consumption (BSEC) and emissions such as CO, CO2, HC, NOx to evaluate the behaviour of PPME and diesel in varying proportions. BSFC and BSEC for all the fuel blends and diesel tested decrease with increase in load. This is due to higher percentage increase in brake power with load as compared to increase in the fuel Consumption. For the blends B20 and B40, the BSFC is lower than and equal to that of diesel, respectively, and the BSEC is less than that of diesel at all loads. This could be due to the presence of dissolved oxygen in the PPME that enables complete combustion engine emits more CO for diesel as compared to PPME blends under all loading conditions The CO2 emission increased with increase in load for all blends. The lower percentage of PPME blends emits less amount of CO2 in comparison with diesel. Blends B40 and B60 emit very low emissions. This is due to the fact that biodiesel in general is a low carbon fuel and has a lower elemental carbon to hydrogen ratio than diesel fuel. HC emission decreases with increase in load for diesel and it is almost nil for all PPME blends except for B20 where some traces are seen at no load and full load. The NOx emission for all the fuels tested followed an increasing trend with respect to load. The reason could be the higher average gas temperature, residence time at higher load conditions. Lapuerta et al. [25], analyzed diesel engine emissions when using biodiesel fuels as opposed to conventional diesel fuels. The basis for comparison is engine power, fuel consumption and thermal efficiency. The engine emissions from biodiesel and diesel fuels are compared, paying special attention to the most
29

concerning emissions: nitric oxides and particulate matter .according to this study: At partial load operation, no differences in power output, since an increase in fuel consumption in the case of biodiesel would compensate its reduced heating value. At full-load conditions, a certain decrease in power has been found with biodiesel. An increase in bsfc has been found when using biodiesel. Such an increase is generally in proportion to the reduction in heating value (9% in volume basis, 14% in mass basis). Consequently, the thermal efficiency of diesel engines is not appreciably affected when substituting diesel by biodiesel fuel either pure or blended. There is slightly increase of NOX with biodiesel because of more oxygen content of biodiesel and at higher temperature it leads to increase NOx. There is a sharp reduction in particulate emissions with biodiesel as compared to diesel fuel. This reduction is mainly caused by reduced soot formation and enhanced soot oxidation. The oxygen content and the absence of aromatic content in biodiesel have been pointed out as the main reasons. CO is usually found to significantly decrease with biodiesel. A more complete combustion caused by the increased oxygen content in the flame coming from the biodiesel molecules has been pointed out as the main reason.

30

2.3 Conclusions

1. Ultrasonic cavitation and Hydrodynamic cavitation technique are much better than conventional techniques of biodiesel production. They take less time and consume very less power than mechanical stirring technique. 2. Supercritical methanol is less time consuming process then other methods but due to its high temperature and pressure it is difficult for commercial production 3. Transesterification with alkali catalyst (KOH & NaOH) is more economical then acid catalyst and enzyme catalyst. 4. Supercritical methanol process using CO2 as a co-solvent is more convenient for industrial purpose then conventional supercritical methanol process. 5. Biodiesel blends has shows less power than diesel at low load condition but at higher load shows slightly more power due to better combustion with excess air. Thermal efficiency is higher for biodiesel blends. Specific fuel consumption (SFC) is higher for biodiesel because of lower heating value. 6. Main advantage analyzed biodiesel over diesel is lower emission. Carbon monoxide and unburned hydrocarbon has lower value in case of biodiesel due to complete combustion. Carbon dioxide from biodiesel can recycle.NOX slightly increases for biodiesel.

31

CHAPTER-3 VEGETABLE OILS

3.1 Introduction

The use of vegetable oils in diesel engines is nearly as old as the diesel engine itself. The inventor of the diesel engine, Rudolf Diesel, reportedly used groundnut (peanut) oil as a fuel for demonstration purposes in 1900. Some other work was carried out on the use of vegetable oils in diesel engines in the 1930's and 1940's. The fuel and energy crises of the late 1970's and early 1980's as well as accompanying concerns about the depletion of the world's nonrenewable resources provided the incentives to seek alternatives to

conventional, petroleum-based fuels. In this context, vegetable oils as fuel for diesel engines were remembered. They now occupy a prominent position in the development of alternative fuels. Hundreds of scientific articles and various other reports from around the world dealing with vegetable oil-based alternative diesel fuels have appeared in print. They have advanced from being purely experimental fuels to initial stages of commercialization. Nevertheless, various technical and economic aspects require further improvement of these fuels. Numerous different vegetable oils have been tested as biodiesel. Often the vegetable oils investigated for their suitability as fuel are those, which occur abundantly in the country of testing. For example, Soya bean oil in the United States, rapeseed and sunflower oils in Europe, palm oil in Southeast Asia (mainly Malaysia and Indonesia), and coconut oil in The Philippines are being considered as substitutes for diesel fuels. This indicates that the use of vegetable oils as the source of diesel fuels in India requires additional steps to increase the production of oilseeds. It is also necessary to develop new and more productive plant sources whose seeds have high oil content [14].

3.1.2

Global Vegetable Oil Production Vegetable oil as alternative diesel engine fuels have received modest interests

for several decades, however economic factors have favoured the use of petroleum based fuels. At present the uncertainties concerning adequate, stable supplies of petroleum fuel have renewed the interests in vegetable oils as diesel engine fuels [15]. Many developed countries have taken initiatives in producing various vegetable oils, depending upon the climatic conditions prevailing. Countries like U.S.A, Brazil etc to an

32

extent have focused their attention on the production and utilization of edible oils as is clear from the following table, which presents the global scenario in vegetable oil production.

Global Production of Major Vegetable Oils (2001) [9] Oil Soybean Rapeseed Cottonseed Sunflower Peanut Coconut Linseed Palm Palm kernel Olive Corn Castor Seasame Total Production (million tonnes) 27.8 13.7 4.0 8.2 5.1 3.5 0.6 23.4 2.9 2.7 2.0 0.5 0.8 95.2

3.1.3

Overview of Indian Vegetable Oil Economy: Indian vegetable oil economy is worlds fourth largest after USA, China and

Brazil. Oilseed cultivation is undertaken across the country in two seasons, in about 26 million hectares; mainly marginal lands, dependent on monsoon rains (unirrigated) and with low levels of input usage. Yields are rather low at less than one ton per hectare.

33

Three oilseeds - Groundnut, Soybean and Rapeseed/ Mustard - together account for over 80 per cent of aggregate cultivated oilseeds output. Cottonseed, Copra and other oil-bearing material too contribute to domestic vegetable oil pool. Currently, India accounts for 7.4% of world oilseeds output; 6.1% of world oil meal production; 5.3% of world oil meal export; 5.5% of world vegetable oil production; 13.9% of world vegetable oil import; and 10.3% of the world edible oil consumption. Indian vegetable oil industry comprises over 15,000 oil mills, 600 solvent extraction units, 400 refining units and 230 Vanaspati (hydrogenated oil) units, employing directly and indirectly over one million people across the country. Indian oilseed based sector accounts for domestic turnover of Rs.60, 000 crores (US$ 12.5 billion) while export-import trade is worth Rs.11, 500 crores (US$ 2.5 billion) per annum. With steady growth in population and personal income, Indian per Capita consumption of edible oil has been growing steadily. However, oilseeds output and in turn vegetable oil production have been trailing consumption growth, necessitating imports to meet supply shortfall [16]. Vegetable oil production in India (2001) [9] Oil Groundnut Soya Rape / Mustard Sunflower Sesame Castor Niger Safflower Linseed Cottonseed Coconut Production (million tonnes) 1.40 0.82 1.55 0.30 0.26 0.25 0.03 0.09 0.10 0.44 0.55

34

Oil Rice Bran Oils from expelled cakes Minor oilseeds Total

Production (million tonnes) 0.55 0.28 0.05 6.67

3.1.4

Composition of Vegetable Oils The basic constituent of vegetable oils is triglyceride. Figure given below shows

a typical triglyceride molecule. Vegetable oils comprise 90 to 98% triglycerides and small amounts of mono- and diglycerides. A triglyceride is a compound, in which one molecule glycerin- a trivalent alcohol is estered with three fatty acid molecules[17].

Structure Of Triglyceride Molecule [18] These contain substantial amounts of oxygen in its structure. Fatty acids vary in their carbon chain length and in the number of double bonds. The variations in these properties make them wide separate from Diesel fuel. The heat capacity of triglycerides increase with increasing the molecular weight. Heat capacity of such compounds also increases slightly with increasing temperature [19]. Combination of number of fatty acids constitutes a vegetable oil molecule. The table given below describes the Structure and Chemical formula of various fatty acids. Chemical structure. of Common Fatty Acids [18] Fatty acids Systematic name. Structure Formula

35

Fatty acids Lauric Myristic Palmitic Stearic Arachidic Behenic Lignoceric Oleic Linoleic Linolenic Erucic

Systematic name.

Structure 12:0 14:0 16:0 18:0 20:0 22:0 24:0 18:0 18:0

Formula C12H24OH C14H28OH C16H32OH C18H36OH C20H40OH C22H44OH C24H48OH C18H34OH C18H32OH C18H30OH C22H42OH

Dodecanoic
Tetradecanoic Hexadecanoic Octadecanoic Eicosanoic Docosanoic Tetracosanoic cis-9-Octadecenoic cis-9,cis-12- Octadecadienoic

cis-9,cis-12,cis-15- Octadecatrienoic 18:0 cis-13-Docosenoir 22:0

The fatty acids, which are commonly found in vegetable oils, are stearic, palmitic, oleic, linoleic and linolenic. Vegetable oils contain free fatty acids (generally 1 to 5%), phospholipids, phosphatides, carotenes, tocopherols, sulphur compounds and traces of water [18]. The fatty acid composition of some vegetable oils is given below.

Chemical composition of vegetable oils [18]

Vegetable oil

Fatty acid composition wt%

18:0 Cottenseed Crambe Linseed Peanut Rapeseed 0 0 0 0 0 16:0 28 2 5 11 3 18:0 1 1 2 2 1 20:0 0 2 0 1 0 22:0 0 1 0 2 0 24:0 0 1 0 1 0 18:1 13 19 20 48 64 22:1 0 59 0 0 0 18:2 58 9 18 32 22 18:3 0 7 55 1 8

36

Vegetable oil

Fatty acid composition wt%

18:0 Safflower Sesame Soya bean Sunflower 0 0 0 0 16:0 9 13 12 6 18:0 2 4 3 3 20:0 0 0 0 0 22:0 0 0 0 0 24:0 0 0 0 0 18:1 12 53 23 17 22:1 0 0 0 0 18:2 78 30 55 74 18:3 0 0 6 0

Chemical Composition Of Vegetable Oils [18] Vegetable oil

Fatty acid composition, wt%

18:0 20:0 0.4-0.6 6.3-12.2 0.0-3.3 0.8-3.4 24:0 0.4-0.9 1.1-3.5 18:1 39.2-43.2 34.2-44.8 41.0-51.0 49.1-61.9 44.5-71.3 18:2 26.4-35.1 2.7 8.9-13.7 2.3-15.8 10.8-18.3

Rice-bran Sal Mahua Neem Karanja

1.7-2.5 34.2-44.8 20.0-25.1 14.4-24.1 2.4-8.9

3.1.5

Properties, which make Vegetable Oils as Viable Alternative Fuels

Fuel properties for the combustion analysis of vegetable oils can be grouped conveniently into physical, chemical, and thermal properties. Physical properties include viscosity, density, cloud point, pour point, boiling range, freezing point and refractive index. Chemical properties comprise chemical structure, acid value, saponification value, iodine value, peroxide value, hydroxyl value, acetyl value, overall heating value, ash and sulphur contents, sulphur and copper corrosions, water and sediment residium, oxidation resistance, ignitability and thermal degradation products. Thermal properties are distillation

temperature, thermal degradation point, carbon residue, specific heating content,

37

thermal conductivity, etc [2]. The table below presents the fuel related properties of fats and oils.
Properties of Various Vegetable Oils [22]. Vegetable Oil Iodine Value Cetane Number Calorific Value (KJ/Kg) Babassu Castor Coconut Corn Cottonseed Linseed Palm Peanut Rapeseed Sesame Soybean Sunflower 10-18 82-88 6-12 103-140 90-119 168-204 35-61 80-106 94-120 104-120 117-143 110-143 38 37.6 41.8 34.6 42 41.8 37.6 40.2 37.9 37.1 39500 39500 39486 39307 39782 39709 39349 39623 39575 Viscosity Cloud (mm2/s) (38oC) Point (oC) -1.1 1.7 1.7 12.8 -3.9 -3.9 -3.9 7.2 Pour Point (oC) -31.7 -40.0 -15.0 -15.0 -6.7 -31.7 -12.2 -12.2 -15.0 Flash Point (oC) 260 277 234 241 271 246 260 254 274

297 34.5 33.5 27.2 39.6 37.0 35.5 32.6 37.1

If the fuel shall be used in the existing engines, some requirements to the fuel properties such as kinematic viscosity, the self ignition temperature, the net heating value, the gross heating value, density etc are to be made so that when subjected to long term endurances, these oils must not yield, hence causing the engine damage [17]. Also materials and metals should be compatible with the type of the oil being used in the engine. The fuel system designer incorporates material into the system based on the historical data. Thus changes in the fuel composition and the introduction of alternative fuels often create many unforeseen problems in seals, gaskets, O-rings and metallic components in the fuel system [21].

38

3.2

Advantages of Vegetable Oils as Engine Fuels [23]

Vegetable oils do have the potential to over tap diesel as the major energy source. Following are some of the advantages of using vegetable oil as I.C. engine in India:
(i) Vegetable oil is produced domestically which helps to reduce costly petroleum imports; (ii) Development of the bio-diesel industry would strengthen the domestic, and particularly the rural, agricultural economy of agricultural based countries like India; (iii) (iv) It is biodegradable and non-toxic; It is a renewable fuel that can be made from agricultural crops and or other feedstocks that are considered as waste; (v) (vi) (vii) It has 80% heating value compared to that of diesel; It contains low aromatics; It has a reasonable cetane number and hence possesses less knocking tendency; (viii) (ix) (x) (xi) Low sulphur content and hence environment friendly; Enhanced lubricity, thereby no major modification is required in the engine; Personal safety is improved (flash point is 100 vC higher than that of diesel); It is usable within the existing petroleum diesel infrastructure (with minor or no modification in the engine). Challenges [23] The major challenges that face the use of vegetable oil as I.C. engine fuels are listed below: (i) (ii) The price of vegetable oil is dependent on the feed stock price; Feed stock homogeneity, consistency and reliability are questionable;

39

(iii)

Homogeneity of the product depends on the supplier, feed stocks and production methods;

(iv) (v) (vi) (vii) (viii) (ix)

Storage and handling is difficult (particularly stability in long term storage); Flash point in blends is unreliable; Compatibility with I.C. engine material needs to be studied further; Cold weather operation of the engine is not easy with vegetable oils; Acceptance by engine manufacturers is another major difficulty; Continuous availability of the vegetable oils needs to be assured before embarking on the major use of it in I.C. engines.

(x)

Efforts to be focused on responding to fuel system performance, material compatibility, petroleum additive compatibility and low fuel stability under long term storage;

(xi)

Continued engine performance, emissions and durability testing in a variety of engine types and sizes need to be developed to increase consumer and manufacturer confidence;

(xiii)

Environmental benefits offered by vegetable oil over diesel fuel needs to be popularized;

(xiv)

Studies are needed to reduce the production cost, develop low cost feed stocks and identify potential markets in order to balance cost and availability;

3.3

Vegetable Oils vs. Diesel Fuel Petroleum based diesel fuels have different chemical structure and

physical properties from vegetable oils. The former contain only carbon and hydrogen atoms, which are arranged in normal or branched chain structures, as well as aromatic configurations. The normal structures are preferred for better ignition quality [24]. The structure of petroleum oil molecule and vegetable oil molecule is being shown below [25] and the difference in the composition of various atoms can be easily viewed.

40

Diesel Oil

Vegetable Oil Molecule Diesel fuel can contain both saturated and unsaturated hydrocarbons, but the latter are not present in large amounts to make the fuel oxidation a problem. The aromatics present are generally oxidation-resistant. On the other hand, in the case of vegetable oils, oxidation resistant is markedly affected by the fatty acid composition. The large size of vegetable oil molecules (typically three or more times larger than hydrocarbon fuel molecules) and the presence of oxygen in the molecules suggest that some fuel properties of vegetable oils would differ markedly from those of hydrocarbon fuel [26]. The general difference between the properties of the vegetable oils and diesel are shown in the figure [27] given below. The difference in the properties is presented in terms of percentage increase or decrease w.r.t Vegetable Oil.

% Difference w.r.t Veg Oil

20 10 0 -10 -20 -30 -40
Sp. Gravit y 0.1 O2 Conte nt 10

Viscos ity 14

Carbo n Res 16

Heatin g Val -15

Cetan e No. -35

Suphu r Con -0.45

% Difference

41

A Comparison of Different Properties of Vegetable Oils & Diesel

The following points explain the major differences between vegetable oils and diesel fuel: 1) Viscosities of the vegetable oils are significantly higher and densities are slightly higher. 2) 3) Heating values of vegetable oils are about 10% lower (on mass basis). The presence of molecular oxygen in vegetable oils raises the stochiometric fuel/air ratio. 4) Vegetable oils could experience thermal cracking by the fuel spray in naturally aspirated engines [28]. 5) The cetane number of vegetable oils is 32-40% lower than diesel, while the sulphur content is negligible in vegetable oils compared to 0.45% in diesel [27]

3.4

Problems Associated with the Usage of Vegetable Oils in Diesel Engines

The problems encountered during engine tests can be classified into two groups:

1.

Operational Problems - relate to starting ability, ignition, combustion and performance.

2.

Durability Problems - relate to deposit formation, carbonization of ring sticking and lube oil dilution or degradation.

injector tip,

3.4.1 1)

Operational Problems Fuel Filter Plugging: Crude vegetable oil when used for long hours chokes the fuel filter because of high viscosity of crude oil. To avoid this, the oil must be

filtered and then re-filtered. Within 3-12 hours the filter usually gets choked. 2) Cold Starting: Starting ability of engine gets impaired due to high viscosity and low cetane number in certain cases [29]. 3). Injector Coking: In long run tests carbon deposits build up in and around the

nozzle between 70-150 hours. Carbon build up interferes with the fuel flow and

42

can ultimately stop it. Post-injection dribble increases and leads to less power, more black smoke and reduced efficiency. Vinyard et al reported an extensive coking problem while using degummed sunflower oil. The oil produced unacceptable coking levels after only 50 hours of operation under part load even when diluted with up to 30% diesel fuel [30]. Other methods of reducing coking have been reported by Peterson et al. and Mora and Peterson where coking was reduced by proper choice of fatty acid and transesterification[31]. 4) Carbon Deposition in Combustion Chamber: - Very hard carbon deposits of 3-4 mm thickness have been found in the vicinity of exhaust area. The proper choice of vegetable oil can reduce engine deposit problem engine life [32]. 5) Piston Ring Sticking: - Top or fine ring sticks to the groove due to gum formation and this makes the other ring to suffer more. Injector coking and consequent poor atomization leads to the sticking of piston rings, heavy deposits in the engine and polymerization of lubricating oil [32]. 6). Lubricating Oil Contamination: Lubricating oil has been found contaminated with reasonably high percentage of iron, zinc etc., along with nominal increase in viscosity after 100-200 hrs. Basically, the sticking rings are not able to seal enough and the vegetable oil fuel passes through the clearance into the crankcase and contaminates the lubrication oil [17]. This makes the oil galleries choked and the friction of crank bearing and camshaft increases. Loss in piston cooling and much wear occurs. So it has to be regularly changed. This may result in piston seizure and thus engine breakdown beyond repair. 7). Effect on Performance Parameters: Fuel consumption increases sharply, power developed reduces, thermal efficiency reduces, blow-by losses reduce and exhaust temperature rises sharply. Thus the performance reduces to the level of an old engine. and somewhat extend use of propane fumigation and

3.4.2 1.

Durability Problems The high viscosity of the vegetable oils results in degraded fuel atomization, which in turn results in the observed durability problems.

43

2.

The durability problems associated with the use of vegetable oils as fuels result directly from the chemical structure of the oils and the affect of these structures on the combustion chemistry.

3.

The durability problems are a result of incomplete combustion of the fuels (either spray or chemically induced) and the subsequent reaction of the fuels and/or partial combustion products on the metal surface and in the lube oil.

4.

Fuel filter pressure drop can increase ten times faster than on Diesel fuel due to starch particles in the vegetable oil. Crude degummed oils are typically filtered to 12 level.

5.

The fuel supply should not have fuel exposed to surface temperature greater than 90C. Local oxidation will generate gums that will plug lines & filters [33].

3.4.3 Remedial Measures

At least three major proposals have been made to alleviate the problems associated with the use of vegetable oils as fuels. 1. Heating the fuel to temperatures sufficient to bring the viscosity to specification range. At 145 C, the viscosity of vegetable oil is about 4.0 Cst. 2. Conversion of the vegetable oils to the simple esters of Methyl, Ethyl or Butyl type. Results till date indicate that the esters are superior fuels for D.I. engine 3. Dilution of vegetable oils with other materials to bring the viscosity to near specification e.g. mixture (50/50) of these oils with diesel fuel have viscosities in the range of 4-8 times that of diesel fuel.
o

near

Any of these procedures of modifying vegetable oils result in an improvement in engine performance when these modified oils are used instead of base vegetable oils alone. This improvement is attributed to the characteristics of the modified fuels, which permit full degree of atomization in the injector nozzles.

These characteristics are believed to be a direct result of the viscosity reduction with the modified procedures. The vegetable oils can be successfully utilized as fuels in C. I. Engines by modifying the fuel properties as well as by engine modifications [24].

44

Engine Modifications: 1 2 3 Dual Fueling Injection System Modification Heated Fuel Lines

Fuel Modifications: 1 2 3 4 Blending Micro Emulsion Transesterification Pyrolysis

45

Chapter 4

THE ALTERNATIVE FUEL

4.1

Biodiesel as an option
Bio-diesel is a fatty acid of ethyl or methyl ester made from virgin or used

vegetable oils (both edible and non-edible) and animal fats. Chemically, it is defined as the mono-alkyl esters of long chain fatty acids derived from renewable lipid sources. Biodiesel is typically produced through the reaction of a vegetable oil or animal fat with methanol or ethanol in the presence of a catalyst to yield glycerin and biodiesel. Biodiesel has been accepted as clean alternative fuel all over the world. Biodiesel can be used in neat form or blended with petroleum diesel for use in diesel engines. The physical and chemical properties of biodiesel, as they relate to the operation of diesel engines are similar to petroleum-based diesel fuel. It is simple to use, biodegradable, nontoxic, and essentially free of sulfur and aromatic compounds [40]. Though biodiesel could be produced from soya bean, rapeseed, sunflower, the source of edible oil, existing shortage of edible oil in the country and its price, would not make these crops viable for use as feed stock for production of biodiesel. The main commodity sources for biodiesel in India can be non-edible oils obtained from plant species such as Jatropha Curcas (Ratanjyot), Pongamia Pinnata (Karanj), Calophyllum inophyllum (Nagchampa), Hevca brasiliensis (Rubber) etc. The potential of total nonedible oils in India is around 100,000 tons / annum (Source: Report on Role of NGOs, and Inform, vol. 13, 151-157, Feb. 2002).

Considering the petroleum crises, rapidly increasing prices, uncertainties concerning petroleum fuels availability and environment and type of land required for the growth of Biodiesel plants available with India, fuel from renewable products like edible/non-edible oil cannot be ignored. Their incorporation within a larger domain seems to be inevitable at some immediate point in future.

46

4.2

ASTM D-6751 standards for biodiesel [58]

130C min. (150C average) 0.050% by vol., max. 1.9-6.0 mm2/s 0.10 0.020% by mass, max. 0.05% by mass, max. No. 3 max 47 min. 0.050% by mass, max. 0.80 max. 0.020 % mass

Flash point (closed cup) Water and sediment Kinematic viscosity at 40C Ramsbottom carbon residue, % mass Sulfated ash Sulfur Copper strip corrosion Cetane Carbon residue Acid number -- mg KOH/g Free glycerin Total glycerine (free glycerine and unconverted glycerides combined) Phosphorus content Distillation

0.240% by mass, max.

0.001 max. % mass 90% @ 360C

Comparison of the set standards for biodiesel and diesel[43]

Fuel Property Fuel Standard Fuel Composition Lower Heating Value, Btu/gal Kin. Viscosity, @40 C Specific Gravity, kg/l @ 60 F Petrodiesel ASTM D975 C10-C21 HC 131,295 1.3-4.1 0.85 Biodiesel ASTM D6751 C12-C22 FAME 117,093 1.9-6.0 0.88

47

Fuel Property Density, lb/gal @ 15 C Water, ppm by wt. Carbon, wt% Hydrogen, wt% Oxygen by dif. Wt% Sulphur, wt% Boiling Point, Degrees C Flash Point, Degrees C Cloud Point, Degrees C Pour Point, Degrees C Cetane Number Stoichometric Air/Fuel Ratio BOCLE Scuff, gm HFRR, microns

Petrodiesel 7.079 161 87 13 0 0.05 max. 188-343 60-80 -15 to 5 -35 to -15 40-55 15 3,600 685

Biodiesel 7.328 0.05% max. 77 12 11 0.00-0.0024 182-338 100-170 -3 to 12 -15 to 10 48-65 13.8 >7,000 314

48

4.3

Properties of Bio-Diesel [9]: A general understanding of the various properties of bio-diesel is essential to study their

implications in engine use, storage, handling and safety. 4.3.1 Density/ Specific Gravity: Bio-diesel is slightly heavier than conventional diesel fuel (specific gravity 0.88 compared to 0.84 for diesel fuel). This allows use of splash blending by adding bio-diesel on top of diesel fuel for making bio-diesel blends. Bio-diesel should always be blended at top of diesel fuel. If bio-diesel is first put at the bottom and then diesel fuel is added, it will not mix. 4.3.2 Cetane Number: Cetane number of a diesel engine fuel is indicative of its ignition characteristics. Higher the cetane number, better it is in its ignition properties. Cetane number affects a number of engine performance parameters like combustion, stability, drivability, white smoke, noise and emissions of CO and HC. Bio-diesel has higher cetane number than conventional diesel fuel. This results in higher combustion efficiency and smoother combustion. 4.3.3 Viscosity: In addition of lubrication of fuel injection system components, Fuel viscosity controls the characteristics of the injection from the diesel injector (droplet size, spray characteristics etc.) . The viscosity of methyl esters can go to very high levels and hence, it is important to control it within an acceptable level to avoid negative impact on fuel injection system performance. 4.3.4 Distillation characteristics: The distillation characteristics of bio-diesel are quite different from that of diesel fuel. Biodiesel does not contain any highly volatile components; the fuel evaporates only at higher temperature. This is the reason that sometimes sump lubrication oil dilution observed in many tests. The methyl esters present in bio-diesel generally have molecular chains of 16- 18 carbons, which have very close boiling points. In other words, rather than showing distillation characteristics, bio-diesel exhibits a boiling point. Boiling point of bio-diesel generally ranges between 330 to 357C.

49

4.3.5

Flash point: Flash point of a fuel is defined as the temperature at which it will ignite when exposed to

a flame or spark. The flashpoint of bio-diesel is higher than the petroleum based diesel fuel. Flashpoint of bio-diesel blends is dependent on the flashpoint of the base diesel fuel used, and increase with percentage of bio-diesel in the blend. Thus in storage, biodiesel and its blends are safer than conventional diesel.

The flashpoint of bio-diesel is around 160 C, but it can reduce drastically if the alcohol used in manufacture of bio-diesel is not removed properly. Residual alcohol in the bio-diesel reduces its flashpoint drastically and is harmful to fuel pump, seals, elastomers etc. It also reduces the combustion quality. 4.3.6 Cold Filter Plugging Point (CFPP): At low operating temperature fuel may thicken and not flow properly affecting the performance of fuel lines, fuel pumps and injectors. Cold filter plugging point of biodiesel reflects its cold weather performance. It defines the fuels limit of filterability. Biodiesel thicken at low temperatures so need cold flow improver additives to have acceptable CFPP. 4.3.7 Pour Point: Normally either pour point or CFPP are specified. French and Italian bio-diesel specifications specify pour point whereas others specify CFFP. Since CFFP reflects more accurately the cold weather operation of fuel.

50

4.3.8

Cloud Point: Cloud point is the temperature at which a cloud or haze of crystals appear in the fuel

under test conditions and thus becomes important for low temperature operations. Biodiesel generally has higher cloud point than diesel fuel. 4.3.9 Aromatics: Bio-diesel does not contain any aromatics. 4.3.10 Stability: Bio-diesel age more quickly than fossil diesel fuel due to the chemical structure of fatty acids and methyl esters present in bio-diesel. Typically there are up to 14 types of fatty acid methyl esters in the bio-diesel. The individual proportion of presence of these esters in the fuel affects the final properties of bio-diesel. Saturated fatty acid methyl esters (C14: 0, C16: 0,C16: 0) increase cloud point, cetane number and improve stability whereas more polyunsaturats (C18: 2,C18: 3) reduce cloud point, cetane number and stability. There are three types of stability criteria, which need to be studied: Oxidation Stability More related to engine operation as engine components attain high temperatures during operation. Storage Stability Thermal Stability 4.3.10.1 Oxidation Stability: Poor oxidation stability can cause fuel thickening, formation of gums and sediments, which, in turn, can cause filter clogging and injector fouling. Iodine number indicates the tendency of a fuel to be unstable as it measures the presence of C=C bonds that are prone to oxidation. Generally instability increase by a factor of 1 for every C=C bond on the fatty acid chain. Thus, C18: 3 are three times more unstable than C18: 0 fatty acids. Oxidation stability of bio-diesel varies greatly depending upon the feedstock used. 4.3.10.2 Thermal Stability: Current knowledge and database is still inadequate. More information is needed in this area.

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4.3.10.3 Storage Stability: Very little data is available on the long-term storage stability of biodiesel. Effect of presence of water, sediments, and additives on storage stability need to be investigated more. Based on the data available so far, bio-diesel and its blends should not be stored in a storage tank or vehicle tank for more than 6 months. Depending upon the storage temperature and other conditions use of an appropriate antioxidants (e.g. Tenox 21, t-

butylhydroquinone etc.). The antioxidants must be properly mixed with the fuel for good effectiveness. To avoid growth of algae in fuel, water contamination need to be minimized and if necessary some biocide should be used. 4.3.11 Iodine Number and polyunsaturated methyl ester : In diesel engines, Methyl esters have been known to cause engine oil dilution by the fuel. A high content of unsaturated fatty acids in the ester (indicated by high Iodine number) increases the danger of polymerization in the engine oil. Oil dilution decreases oil viscosity. Sudden increase in oil viscosity, as encountered in several engine tests, is attributed to oxidation and polymerization of unsaturated fuel parts entering into oil through dilution. In saturated fatty acids all the carbon is bound to two hydrogen atoms by double bonds. More the double bonds the lower is the cloud point of oil. The tendency of the fuel to be unstable can be predicted by Iodine number. Different bio-diesel have different stability performance. When iodine is introduced in the oil, the iodine attaches itself over a single bond to form a double bond. Thus iodine number refers to the amount of iodine required to convert unsaturated oil into saturated oil. It does not refer to the amount of iodine in the oil but to the presence of unsaturated fatty acids in the fuel. Iodine number is not well suited to indicate the influence of methyl ester on engine. One value of iodine number can be obtained by using several grades of unsaturated acids. So an additional parameter, linolenic acid (C18: 3) content is specified and limited to 15% in Austrian Standard ON C 1191. 4.3.12 Free and Total glycerol: The degree of conversion completeness of the vegetable oil is indicated by the amount of free and total glycerol present in the bio-diesel. If the actual number is higher than the specified values, engine fouling, filter-clogging etc can occur. Manufacturing process controls are necessary to ensure low free and total glycerin. Free glycerol if present can build up at the bottom of the storage and vehicle fuel tanks. 4.3.13 Mono-, Di-, and Triglycerides:

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Most of the bio-diesel standards, except Austrian and ASTM, specify a max. limit of 0,08 for Mono-glycerides. Draft EU standard calls for same limit. Di-and Triglycerides are also controlled in most of the standards. High levels of these glycerides can cause injector fouling, filter clogging etc. 4.5.14 Ester content: France (96.5%), Italy (98%) and Sweden (98%) specify a minimum eater content whereas Austrian and ASTM Standards do not specify any limit. 4.3.15 Alkaline matter (Na, K): Alkaline matter is controlled mainly to ensure that the catalysts used in the esterification process are properly removed. 4.3.16 Total contamination: Left over impurities at the time of manufacture (such as free proteins) may form solid particles and clog the fuel lines. Filtration and washing treatments at manufacturing level need to be robust. 4.3.17 Sulfur content: Biodiesel generally contain less than 15ppp sulfur. ASTM D 5453 test is a suitable test for such low level of sulfur. 4.3.18 Lubricity: Wear due to excessive friction resulting in shortened life of diesel fuel pumps and injectors, has some times ascribed to lack of lubricity in the fuel. Numerous premature breakdown and in some cases, catastrophic failures, have occurred failures. All diesel fuel injection equipment (fuel pump and injector) of the diesel engine have reliance on diesel fuels for its lubrication, especially the Rotary (Distributor) and Common Rail type systems. The lubrication of the pump is not provided by viscosity alone but also by the lubricity property of the fuel. Even when the viscosity of the fuel is correct, several parts of the pump can wear out due to lack of lubricity. The lubricity of the fuel depends on the crude source, refining process to reduce sulfur content and the type of additives used. BOCLE (Ball on Cylinder Lubricity Evaluator) and HFFR (High Frequency Reciprocating Rig) are commonly used for evaluating the lubricity of the fuel. BOCLE is normally used for finding the lubricity fuel without additive, as

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it does not properly

characterize the lubricity of fuels with lubricity additives. HFFR method

has been adopted by Fuel Injection Manufactures for lubricity evaluation of diesel fuels and they recommend a limit of 460 microns wear scar diameter (WSD). Lower the WSD better is the lubricity of fuel. In case of BOCLE method a higher value is better. Even with 2% biodiesel mixed in diesel fuel, the WSD values comes down to around 325 micron and is sufficient to meet the lubricity requirements of the fuel injection pump (460 micron max.).. B100 performs still better, with a WSD of about 314 micron. With further reduction of sulfur content is diesel for Euro II and Euro IV fuels; the lubricity loss due to sulfur removal can easily be compensated by the addition of appropriate amount of biodiesel in diesel fuel. 2% inclusion into any conventional diesel fuel is sufficient to address the lubricity problem. It also eliminates the inherent variability associated with use of other additives to make fuel fully lubricious. Second the biodiesel is a fuel component itself- any addition of it does cause any adverse consequences. Since pure biodiesel has high lubricity, it is not specified in the specification. When biodiesel is used as lubricity blend (B2) or diesel fuel extender (B20), its lubricity characteristics has to meet the specification for the base fuel 4.3.19 Sulfated Ash: Sulfated ash is controlled to ensure that all the catalysts used in the transesterification process are removed. Presence of ash can cause filter plugging and or injector deposits. Soluble metallic soap, un-removed catalysts and other solids are possible sources of sulfated ash in the fuel. 4.3.20 Acid number/Neutralization number: Acid number/Neutralization number is specified to ensure proper ageing properties of the fuel and/ or a good manufacturing process. Acid number reflects the presence of free fatty acids or acids used in manufacture of biodiesel. It also reflects the degradation of biodiesel due to thermal effects. For example, during the injection process several times more fuel returns from the injector than that injected into the combustion chamber of the engine. The temperature of this return fuel can, sometimes, be as high as 90C and thus accelerate the degradation of biodiesel. The resultant high acid number can cause damage to injector and also result in deposits in fuel system and affect life of pumps and filters. Sodium hydro peroxide and sulfuric acids are highly corrosive and can cause serious, many times permanent, injuries.

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4.3.21 Water Content: Biodiesel and its blends are susceptible to growing microbes when water is present in fuel. The solvency properties of the biodiesel can cause microbial slime to detach and clog fuel filters. 4.3.22 Phosphorous Content: Phosphorous can come as impurity and can affect oxidation catalyst and cause injector fouling. As more and more OEMs are going to use catalytic converters in diesel engines, it is necessary to keep the level of phosphorous in fuel low. Usually biodiesel have less than 1ppm phosphorus. The specification of min. 10-ppm phosphorous content is intended to ensure compatibility with catalytic converters irrespective of the source of biodiesel. 4.3.23 Methanol/Ethanol content: High levels of free alcohol in biodiesel cause accelerated deterioration of natural rubber seals and gaskets. Damage to fuel pumps and injectors, which have natural rubber diaphragms has been very common type of failure Methanol is membrane-permeable and can cause nerve damage. Therefore control of alcohol content is required.

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4.3.24 Conradson Carbon Residue (CCR):

Carbon residue of the fuel is indicative of carbon depositing tendencies of the fuel. Conradson Carbon Residue (CCR) for biodiesel is more important than that in diesel fuel because it show a high correlation with presence of free fatty acids, glycerides, soaps, polymers, higher unsaturated fatty acids, inorganic impurities and even on the additives used for pour point depression.

The College is also undertaken a project sponsored by MNES for Development of an efficient biodiesel reactor for rural application and utilization of multi-feedstock derived biodiesel in medium capacity diesel engine

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CHAPTER-5
BIODIESEL PRODUCTION METHODOLOGY
5.1 Introduction The use of vegetable oils as an alternative source of energy, especially for agriculture, most of which is powered by diesel engines is renewed considering the depletion of the worlds petroleum supplies. The vegetable oils fuels must be technically and environmentally acceptable, and economically competitive. Various crude or refined vegetable oils, low grade, non edible or recovered from wastes residues of chemical operations have been tested by numerous researchers for their utilization possibilities either straight or as diesel fuel extenders in Compression Ignition Engines [45]. The neat vegetable oils have been found to be very viscous for prolonged use in Direct Ignition Diesel Engines [46]. Their high viscosities lead to poor atomization and incomplete combustion with an unmodified fuel injection system, can cause fuel system clogging, polymerization during storage and the blow-by causing polymerization of the lubricating oil [33].

To safely negotiate the above undesirable characteristics of vegetable oils to be used as a fuel in C.I engines, some modifications are required.

1. 2.

Adaptation of the engines to the fuel. Adaptation of the fuel to the engines [47].

The former solution doesnt fit, as it requires the changing of the fuel injection system, injector timing, modified combustion chamber, emission treating mechanism etc. The problems with substituting triglycerides for diesel fuels are mostly associated with their high viscosity, low volatility and polyunsaturated character. The problems have been mitigated by developing nonedible oils / edible oils derivatives that approximate the properties and performance and make them compatible with the hydrocarbon-based diesel fuels by changing the chemical

57

characteristics of the fuel through various techniques. The viscosity of the vegetable oils can be overcome in various ways [48]. a) b) c) d) Pyrolysis. Dilution. Micro emulsifying the vegetable oil. Transesterification, which is the conversion of vegetable oils into simple esters.

5.2 5.2.1

Various Techniques For Fuel Modification Pyrolysis Pyrolysis refers to a chemical change caused by the application of thermal energy in the

absence of air or nitrogen. It is the thermal decomposition of vegetable oils to provide a possibility of creating a less viscous fuel with properties more closely related to diesel fuel. Pyrolysis of the vegetable oil implies that its molecular structure and its molecular weight are changed. The process involves the rupturing of long chain hydrocarbon molecules into smaller fragments to produce a liquid with lower molecular weight [28]. The liquid fractions of the thermally decomposed oil are likely to approach diesel fuels. The pyrolyzate had lower viscosity, flash point, and pour point than diesel fuel and equivalent calorific values. The cetane number of the pyrolyzate was lower. The pyrolyzed oils contain acceptable amounts of sulphur, water and sediment and give acceptable copper corrosion values but unacceptable ash, carbon residue and pour point. Pyrolysis processes that maximize yield are of particular interest, since liquid products are easier to handle in subsequent utilization scheme and are of better for retrofitting existing equipment. In addition, Pyrolysis is simple, inexpensive to construct and is probably suitable for small-scale plants located near a raw material source [49].

5.2.2

Blending

Diesel-fuelled engines have the disadvantage of producing soot, particles and nitrogen oxides and are now subjected to increasingly severe legislation following 58

revision of the standards by Auto oil. The required levels are difficult to achieve through engine design alone. Even with high-grade fuels, catalytic systems are being extensively investigated to remove particulates. But, there are still problems in the operation of these. The introduction of oxygenated compounds such as vegetable oils and alcohols into diesel fuel is gaining momentum [50]. Results with this technology have been mixed and engine problems similar to those found with neat vegetable oils as fuels were observed here also. A model on vegetable oil atomization showed that blends of DF2 with vegetable oil should contain from 0 to 34% vegetable oil if proper atomization was to be achieved [14].
5.2.3 Emulsification Emulsion is a colloidal solution, which is formed by mixing the two liquids present in the same phase. The characterization of the emulsions is done by their stability. The stability of an emulsion is the time for which the two mixed liquids doesnt separate [51]. Emulsification can be of two types. 1 Microemulsification: Microemulsions are isotropic, clean or translucent

thermodynamically stable dispersions of oil, water, a surfactant & often a small amphiphilic molecule called Co-surfactant [52].

Factors affecting the formation of the required microemulsion [46]. a. Choice of the Surfactant: - The choice of the surfactant should be made with the

purpose of promoting its maximum solubility in oil phase. b. Choice of the C-surfactant: - The cosurfactant is a non-ionic molecule, that when

associated to the surfactant helps in stabilization of the interfacial layer. c. Choice of the Co-Surfactant & Surfactant ratio: - In order to obtain microemulsions it

is necessary to determine the optimum properties of cosurfactant/surfactant that promotes the maximum solubalisation. 2 Macroemulsions: - These are also called as temporary or non-ionic solutions. NonIonic

emulsions are often referred to as detergentless emulsions, indicating the absence of a surfactant. They are also called macro-emulsions. They do not form thermodynamically colloidal

59

dispersions, and their faces separated, after some time of their forming, hence they are unstable in nature. There are many advantages in using emulsified fuels. They can enhance the transformation efficiency of fuels, and more importantly they can reduce NOx emission and particulates. This is because evaporation of water in the combustion process reduces the oxygen concentration and burning temperature to reduce NOx emission notably and secondary atomization is beneficial to heavy oil to enhance the combustion efficiency. Water vapor reacts with particulates to produce CO and H2 in the region lacking in oxygen, so both the particulate and the equivalence ratio will be reduced. So it can not only reduce the pollutants but also reduce the exhaust loss and enhance the thermal efficiency. When the emulsified oil is used in diesel engines, the efficiency is not notable with a little amount of water. Emulsified oil with a large amount of water can notably improve NOx emission and particulates, but the ignition delay time will increase greatly such that diesel engines cannot start. Thus, it is a difficult problem to solve the normal ignition for diesel engines with a large amount of water in oil [53].

5.2.4

Transesterification : Trans-esterification also called alcoholysis, is the displacement of alcohol from an ester

by another alcohol in a process similar to hydrolysis. This process has been widely used to reduce the viscosity of triglycerides. The trans-esterification reaction is represented by the general equation.

RCOOR + R" = RCOOR" + ROH.

Transesterification is the change of the trivalent glycerin molecule against 3 molecules of monovalent alcohols i.e. Methanol & Ethanol. Each alcohol molecule then form with the fatty acid residue 1 molecule monoester [17]. The transesterification reaction can be represented as:

60

If methanol is used in the above reaction, it is termed methanolysis. The reaction of triglyceride with methanol is represented by the general equation. Triglycerides are readily trans-esterified in the presence of alkaline catalyst at atmospheric pressure and at a temperature of approximately 60 to 70C with an excess of methanol. The mixture at the end of reaction is allowed to settle. The lower glycerol layer is drawn off while the upper methyl ester layer is washed to remove entrained glycerol and is then processed further. The excess methanol is recovered by distillation/evaporation/condensation and sent to a rectifying column for purification and recycled. The trans-esterification works well when the starting oil is of high quality. However, quite often low quality oils are used as raw materials for biodiesel preparation. In cases where the free fatty acid content of the oil is above 1%, difficulties arise due to the formation of soaps which promote emulsification during the water washing stage and at an FFA content above 2% the process becomes unworkable.

5.3 Methods of Transesterification [55] There are two methods of Transesterification 1 2 Using a Catalyst Without the Catalyst

There are two problems associated with the former process 1. The process is relatively time consuming. In this case the mixture requires vigorous stirring for the reaction to proceed.

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2. Purification for the product for catalyst & saponified products are necessary.

Basic Mechanism of Transesterification: Simple alcohols are used for transesterification and this process is usually carried out with a basic catalyst in the complete absence of water. The bonding of alcohol and organic acid with elimination of water produces ester. An excess of alcohol is required to force the reaction to completion. Although other alcohols may be used, methyl or ethyl alcohols are the most common and separation of glycerol, a bi-product occurs readily with it. Soap can be a substantial by-product in the presence of water. This result is a decrease in overall yield of ester, which is not a problem if the presence of water is below 1 percent. In the transesterification process, the alcohols combine with the triglycerides to form glycerol & esters. The glycerol is then removed by density separation. Transesterification has the effect of increasing the volatility and decreasing the viscosity of the oil, hence making it similar to the conventional diesel fuel in these characteristics [24]. The chemistry of transesterification is as shown in the figure [56]. And the figure presents the quantity wise distribution of various ingredients in the process.

Transesterification is the most commonly used process because the molecules triglycerides (a tripod hooked structure), a main constituent of the fat, are changed to the fatty acid esters (slippery structure)[57]. The transesterification reaction differs from the conventional

62

reaction in the way that the oil bearing material contacts acidified alcohol directly instead of reacting with purified oil and alcohol. That is, extraction & transesterification proceed within the same process, the alcohol acting both an extraction solvent & an emulsifying reagent [58]. Various factors affect the yield of an Ester formed during the transesterification process. These factors are listed below [59]: 1 2 3 4 5 Moisture & Free Fatty Acid present in the Oil. Molar Ratio i.e. the ratio of Oil to Alcohol. Overall Reaction Time. Change in the Glyceride Composition During Transesterification. Glycerol Recovery Method.

5.4

Process Variables in trans-esterification. The most important variables that influence trans-esterification reaction time and

conversion are: i. oil temperature ii. reaction temperature iii. ratio of alcohol to oil iv. type of catalyst and concentration v. intensity of mixing vi purity of reactants

5.4.1 Oil Temperature: The temperature to which oil is heated before mixing with catalyst and methanol, affects the reaction. It was observed that increase in oil temperature marginally increases the percentage oil to biodiesel conversion as well as the biodiesel recovery. However, the tests were conducted for 60-70 C as higher temperatures may result in methanol loss in the batch process. 5.4.2 Reaction temperature: The rate of reaction is strongly influenced by the reaction

temperature. Generally, the reaction is conducted close to the boiling point of methanol (60 to

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70C) at atmospheric pressure. The maximum yield of esters occurs at temperatures ranging from 60 to 80C at a molar ratio (alcohol to oil) of 6:1. Further increase in temperature is reported to have a negative effect on the conversion. Studies have indicated that given enough time, trans-esterification can proceed satisfactorily at ambient temperatures in the case of the alkaline catalyst. It was observed that biodiesel recovery was affected at very low temperatures (just like low ambient temperatures in cold weather) but conversion was almost unaffected. 5.4.3 Ratio of alcohol to oil: Another important variable affecting the yield of ester is the molar ratio of alcohol to vegetable oil. A molar ratio of 6:1 is normally used in industrial processes to obtain methyl ester yields higher than 98% by weight. Higher molar ratio of alcohol to oil interferes in the separation of glycerol. It was observed that lower molar ratios required more reaction time. With higher molar ratios, conversion increased but recovery decreased due to poor separation of glycerol. It was found that optimum molar ratios depend upon type & quality of oil. 5.4.4 Catalyst type and concentration: Sodium hydroxides are among the most efficient catalysts used for this purpose, although potassium hydroxide and sodium hydroxide can also be used. Trans methylations occur many folds faster in the presence of an alkaline catalyst than those catalyzed by the same amount of acidic catalyst. Most commercial trans-esterification is conducted with alkaline catalysts. The alkaline catalyst concentration in the range of 0.5 to 1% by weight, yields 94 to 99% conversion of vegetable oil into esters. Further, increase in catalyst concentration does not increase the conversion and it adds to extra costs because it is necessary to remove it from the reaction medium at the end. It was observed that higher amounts of sodium hydroxide catalyst were required for higher FFA oil. Otherwise higher amount of sodium hydroxide resulted in reduced recovery. 5.4.5. Mixing intensity: The mixing effect is most significant during trans-esterification reaction. As the single phase is established, mixing becomes insignificant. The understanding of the mixing effects on the kinetics of the trans-esterification process is a valuable tool in the process scale-up and design. 5.4.6 Purity of reactants: Impurities present in the oil also affect conversion levels. Under the same conditions, 67 to 84% conversion into esters can be obtained, using crude vegetable oils, compared with 94 to 97% when using refined oils. The free fatty acids in the original oils interfere with the catalyst. However, under conditions of high temperature and pressure this problem can be overcome. It was observed that crude oils were equally good compared to

64

refined oils for production of biodiesel. However, the oils should be properly filtered. Oil quality is very important in this regard. The oil settled at the bottom during storage may give lesser biodiesel recovery because of accumulation of impurities like wax etc.

5.5 Raw material and its quality for the production of biodiesel

5.5.1 Oil: The oil must be moisture-free because every molecule of water destroys a molecule of the catalyst thus decreasing its concentration. The free fatty acid content should be less than 1%. It was observed that lesser the FFA in oil better is the biodiesel recovery. Higher FFA oil can also be used but the biodiesel recovery will depend upon type of oil and amount of sodium/Potassium hydroxide used. Any sediment would collect at the bottom of the reaction vessel during glycerol settling and at the liquid interface during washing. This would interfere with the separation of the phases and may tend to promote emulsion formation. 5.5.2 Alcohol: Methanol or ethanol can be used. As with the oil, the water affects the extent of conversion enough to prevent the separation of glycerol from the reaction mixture. 5.5.3 Catalyst: Sodium or potassium hydroxide. Best results are obtained, if the catalyst is 85% potassium hydroxide. Best grades of potassium hydroxide have 14-15% water, which can not be removed. It should be low in carbonate, because the carbonate is not an efficient catalyst and may cause cloudiness in the final ester. Sodium hydroxide pellets have given very good results. Because quantity of catalyst used is quite less, good quality catalyst (in-spite of high cost) can be used.

5.6

Blending of Esters & Diesel

Blending conventional Diesel Fuel (DF) with esters (usually methyl esters) of vegetable

oils is presently the most common form of biodiesel. The most common ratio is 80% conventional diesel fuel and 20% vegetable oil ester, also termed "B20," indicating the 20% level of biodiesel. There have been numerous reports that significant emission reductions are achieved with these blends.

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No engine problems were reported in larger-scale tests. Fuel economy was comparable to Diesel fuel. Consumption of biodiesel blend being only 2-5% higher than that of Diesel fuel Another advantage of biodiesel blends is the simplicity of fuel preparation, which only requires mixing of the components. Ester blends have been reported to be stable, for example, a blend of 20% oil with 80% Diesel fuel did not separate at room temperature over a period of 3 months. Several studies have shown that diesel/biodiesel blends reduce smoke opacity, particulate, unburnt hydrocarbons, carbon dioxide and carbon monoxide emissions, but nitrous monoxide emissions are slightly increased. One limitation to the use of biodiesel is its tendency to crystallize at low temperatures below 0C. Such crystals can plug fuel lines and filters, causing problems in fuel pumping and engine operation. Additives can be used for low temperature storage and pumping. Methyl and ethyl esters of vegetable oils will crystallize and separate from diesel at temperatures often experienced in winter time operation. One solution to this problem may be the use of branched-chain esters, such as isopropyl esters. The isopropyl esters of soya bean oil crystallize 7 to 11C lower than the corresponding methyl esters. Another method to improve the cold flow properties of vegetable oil esters is to remove high- melting saturated esters by inducing crystallization with cooling, a process known as winterization.

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CHAPTER-6
OPERATION OF BIODIESEL REACTOR

6.1 Chemicals and materials required:

The alcohol used is methanol, which makes methyl ester .Methanol is highly toxic.it is otherwise called as methyl alcohol.

The lye catalyst used is KOH(potassium hydroxide). As it is easier to use also cheaper. Lye reacts with tin zinc and aluminium, for that we used hdpe (high density polyethylene) container.

Heres what we need per litre of jatropha oil or mahua oil 1.200ml of methanol 2.10gm of potassium hydroxide 3. Blender with a motor having 150 rpm,220v,0.5h , reduction geared motor. 4. Measuring beakers. 5. Thermometer. 6. Control valves. 7. Aluminium container.

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8. Funnels

6.2 Steps involved in production of biodiesel

1. Lye was measured quickly as it rapidly absorbs water from the atmosphere. Per litre of methanol 10 grams of potassium hydroxide was added. All these were done in the closed container. 2.200 ml of methanol was measured and poured into the half litre glass container with the help of funnel. The lye was added carefully to the container. 3.The container was well shaken. The temperature of the container got increased. 4.A blender was used to stir the mixture of oil and chemicals. It was made sure that all the parts of the blender are clean and dry. 5.The oil was preheated to 55oc. then the prepared methoxide was poured into the blender carefully. 6.It was stirred for 1 hour. 7.It was then allowed to settle down keeping the stirring process and heating process off. 8.A thick layer of glycerine was found to be settled at the bottom of the container. 9.Carefully the glycerine was drained through the drain valve.

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10.Again the blender was added with water to wash away the methanol present in it keeping the motor and heater switched on. 11.After 20 min it was allowed to cool down to get biodiesel.

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Reference 1) Annual Report, Mop&NG 2002, Plubished by Ministry of Petroleum and Natural Gas, Government of India. 2) Bersce G.B, Fey J.P, Compatibility of Elastomers and Metals in Bio-Diesel Fuel Blends, SAE Paper No. 971190, 1997, pp. 651-659 3) Aggarwal A.K, Das L.M. Biodiesel Development and Characterization for use as a fuel in Compression Ignition Engine, ASME Journal of Engineering for Gas turbine & Power, Vol.123, April 2001, pp.440-447. 4) Beggs R.E Renewwable Oil Fuels & Diesel Engines as components of sustainable system design 5) Development of Bio Fuels 2003 Publised by Planning Commission , Govt of India, New Delhi. 6) Annual Report, MoP&NG, 2002, Published by Ministry of Petroleum & Natural Gas, Govt. of India. 7) Ann-Marie, Williamsons, Badr O, Assessing The Viability of Using Rape Methyl Ester (RME) as an Alternative to Mineral Diesel Fuel for Powering Road Vehicles in U.K, Applied Energy Vol. 59 No.2-3 1998, pp. 187-214. 8) A report of the committee on the Development of Biofuel, 2003 published by Planning Commission, Govt. of India, New Delhi. 9) Kumar R, Verma R.P, Tuli D.K, Ray S.S, Bhatnagar A.K, Bio-diesel ProductionTransterification of Vegetable Oils, Procedding of third Intl Sym fuels & Lubricants, ISFL-2002, Oct 7-9, 2002, New Delhi. 10) Alternative Transport Fuels: An Overview Parivesh, Central Pollution Control Board, Ministry Of Environment And Forests, April 2003 11) Wang W.G, Lyons D.W, Clarks N.N, Gautam N, Emissions from Nine Heavy Trucks Fueled by Diesel and Bio-Diesel Blend Without Engine Modification, Environment Science & Technology, Vol. 34 No.6 2000, pp. 933-939. 12) 13) www.bpcl.org Knothe.G, Dunn. R.O & Bagby M.O, Biodiesel: The Use of Vegetable Oils & Their Derivatives as Alternate Diesel Fuels, ACS Symposium Series 666, pp 172-208. 14) Humke A.L, Barsia A.J, Performance and Emission Characteristics of a Naturally Aspirated Diesel Engine with Vegetable Oil Fuels, SAE paper 810955, 1981. 15) www.agricoup.nic.in

70

16)

Gerhard, Vellguth, Performance of Vegetable Oils and their Monoesters as Fuels for Diesel Engines, Transactions of the ASAE No. 831358, 1983. Srivastva A & Prasad R, Triglycerides-based Diesel Fuels, Renewable & Sustainable Energy Reviews, Vol. 4 2000, pp 111-133. GoodromeJ.W, Eiteman M.A, Physical Properties of Low Molecular Weight Triglycerides for the Development of Bio-Diesel Fuel Models, Bioresource Technology, Vol. 56, 1996, pp. 55-60 96/6 Niemi S.A, Illikainin P.E, Klaihu V.O, A Tractor Engine Fueled With Mustard Seed Oil Optimization, Emissions And Practical Experiences, SAE Paper No. 972724, 1997, pp. 193-206.

17)

18)

19)

20) 21)

www.svlele.com Goering C.E, Schwab A.W, Daughrly M.J, Pryde E.H, Heakin A.J, Fuel Properties of Eleven Vegetable Oils Transaction of. ASAE Vol-25 No.6 1982, pp 1472-1477 & 1483. Ramadhas A.S, Jayaraj.S, Muraleedharan C, Use of Vegetable Oils as an I.C Engine Fuels A Review, Renewable Energy, 2003. Aggarwal A.K, Vegetable Oil versus Diesel Fuel, TIDE Vol. 8 No. 3 1998, pp. 191205. Nagaraja A.M, PrabhuKumar G.P, Effect of Injection Pressure on the Engine Performance with Rice Bran Oil as Bio Diesel, ISME-2003 XIII National Conference of Indian Society of Mechanical Engineers, December 30-31, 2003, IIT Roorkee, Paper number: TH-065.

22)

23)

24)

25) 26)

www.test biodiesel.net.au Takeuchi R, Ishi Y, Vegetable Oils and their Effect on Farm Engine Performance, Transactions of the ASAE Vol. 30, No. 1, 1987 pp. 2-6. Freedman B, Pryde E.H & Kwolef W.F, Quantitation in the Analysis of Transesterified Soybean Oil by Capillary Gas Chromatography, JAOCS Vol. 63 No. 10 1986, pp. 1370-1374 Ryan T.W, Bagby M.O, Identification of Chemical Change Occurring During the Transient Injection of Selected Vegetable Oils, SAE paper No. 930933, 1993, pp. 201-210. Perkins L.A, Petersons C.L, Auld D.L, Durability Testing of Transesterfied Winter Rape Oil (BRASSICA NAPUS L.) as Fuel in Small Bore, Multi-Cylinder, DI, CI Engine,

27)

28)

29)

71

30)

Peterson C.L, Korus R.A, Mora P.G, Madsen J.P, Fumigation with Propane and Transesterification Effects on Injector Coking with Vegetable Oil Fuels, Transaction of ASAE, Vol.30 No.1, pp.28-35. Baris K, Ozaktas.T, Kara.F, Oskmanoglu, Diesel Engine, Energy source Vol. 19, 1997, pp. 559-556. Geyer S.M, Jacobus M.J, Lestz S.S, Comparison of Diesel Engine Performance and Emissions from Neat and Transesterified Vegetable Oils, Transactions of the ASAE Vol. 27, No. 2, 1984 pp. 375-381.

31)

32)

33) 34) 35) 36) 37) 38)

www.biodiesel.org www.cpcb.nic.in www.alternate .org www.biotech.iitm.ac.in www.teri.res.in A report Biodiesel Fuel & its Integration into Agriculture Economy of the State Background Memorandum, prepared by North Dakota Legislative Committee, August 2001.

39) 40) 41)

www.biodiesel.co.uk www.planningcommission.nic.in Biodiesel News Letter, published by National Biodiesel Board, accessed from www.doe.gov.in Naveen Kumar, Chugh Sachin, Vijay Kumar, Biodiesel- A Bridge for Sustainable Development of India, paper presented at National Conference of Mechanical Engineering, JamiaMiliaIslamia, 23Jan 04. Ozaktas.T, Compression Ignition Engine Fuel Properties of a Used Sunflower Oil Diesel Fuel Blend, Energy Sources Vol. 22 2000, pp. 377-382. Neto A.A.D,Neuma de Castro Dantas, A.C. de Silva, New Micro Emulsion Systems Using Diesel And Vegetable Fuels, Fuel, Vol.80, 2001 Woergetter M, Pilot Project: Biodiesel, Proceedings of 7th European conference on Biomass for Energy and Environment held at Florence from 5-9 October 1992. Kaufman K.R., Ziejewski M, Sunflower Methyl Ester for Direct Injected Diesel Engine, ASAE Vol.27, No.6, 1984, pp 1626-1633. Sensoz.S, Angin.D, Yorgun S, Influence of Particle Size on the Pyrolysis of Rapeseed: Fuel Properties of Bio-Oil, Biomass & Bioenergy, Vol.19, 2000, pp. 271279.

42)

43)

44)

45)

46)

47)

72

48)

De Caro P.S, Z. Mouloungui, G. Vaitilingom, J. Ch. Berge, Interest of Combining an Additive with Diesel-Ethanol Blends for Use in Diesel Engines, Fuel 80 (2001) 565574. Jain P.K, Engineering Chemistry, 1998. Fukuda H, Kondo A, Noda H, Biodiesel Fuel Production by Transesterification of Oils, Journal of Bioscience & Biochemistry, Vol.93, No.5, 2001, pp.405-416.

49) 50)

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