Process report onProduction of Biodiesel from Vegetable Oils

In Partial Fulfillment of the requirement for the degreeOfBachelor of Science (Chemical Engineering)Session 2011-2015

Submitted by:M. Arslan(E11-15CE37)Azhar Abbas (E11-15CE38)Kazim Hussain(E11-15CE39)Sadain Zafar (E11-15CE40)Supervised by:Dr. Rashid Usman

Institute Of Chemical Engineering And Technology,University Of The Punjab, Lahore.

Dedications

We dedicate our work and utmost efforts to ALLAH almighty the creator of this universe and most merciful and bounteous, you have always been by my side guiding me all the way to this destiny & Holy Prophet (PBUH) the cause of the creation of this universe. Our parents, who taught us how to be persevere and be patient in the midst of trials. Our most respected Teachers who built our knowledge foundations, Our Friends who encouraged and strengthened us, and our siblings who are our supporters and well-wishers.

AcknowledgementAll praises to Almighty ALLAH who gave us light in the darkness and gave us ability and strength to complete our research project and all respects are for His Prophet Muhammad (PBUH, on whom be ALLAHS blessings and salutations) We take immense pleasure in thanking our worthy teachers for their valuable help regarding our process report. We all owe special thanks to our supervisor Dr. Rashid Usman, who helped us throughout our research work. His motivation, guidance and kind words always encouraged us to work with commitment. Whenever we found ourselves in any sort of trouble, we always found him available to cater the issue. This sort of generosity and favors are highly commendable. We also thank our beloved director Dr. Amir Ijaz to provide us a learning environment.

ContentsChapter 171.1What is Biodiesel81.2History of Biodiesel91.3Biodiesel Blends101.3.1 Low-Level Blends101.3.2 B20101.3.3 B100 and High Level Blends101.4Advantages of Biodiesel111.5 Disadvantages of Biodiesel121.6 Raw Materials for Biodiesel Production121.7 Properties of Biodiesel13Chapter 2142.1 Biofuel Sources152.1.1 Algae152.1.2 Carbohydrate rich biomaterial152.1.3 Oil rich biomaterial162.1.4Agriculture wastes (organic and inorganic sources)162.2 Biodiesel as a fuel162.3 Fuel properties172.4 Different methods of biodiesel production182.4.1 Supercritical process182.4.2 Ultra- and high-shear in-line and batch reactors182.4.3 Ultrasonic reactor method182.4.4 Lipase-catalyzed method182.4.5 Volatile Fatty Acids from Anaerobic Digestion of Waste Streams192.5 Biodiesel Production192.5.1 Production Process212.6 Environmental Effects of Biodiesel Fuel232.7 Energy security252.8 Economic benefits25Chapter 3263.1 Procedure of Manufacturing the Biodiesel273.1.1 Filtration273.1.2 Water Removing273.1.3 Calculation for Cottonseed oil, methanol and catalyst283.1.4 Calculation for Mustard oil, methanol and catalyst293.1.3 Calculation for Sunflower oil, methanol and catalyst293.1.4 Preparation of Sodium Methoxide303.1.5 Heating and Mixing313.1.5 Settling323.1.6 Separation333.1.6 Washing333.1.6 Heating343.1.7 Glycerin35Chapter 4364.1 Flash Point374.2 Aniline point384.3 Cloud Point394.4 Pour Point414.5 Calorific Value424.5 Specific Gravity44References45

List of FiguresFigure 1: Trans-esterification Reaction20Figure 2: Flow chart of Biodiesel Production21Figure 3: Removal of Water from Vegetable oil28Figure 4: Preparation of Sodium methoxide31Figure 5: Transesterification Reaction Figure 6: Preparation of Biodiesel32Figure 7: Prepared Biodiesel Figure 8: Separation of Biodiesel32Figure 9: Removal of Glycerin Figure 10: Separated Biodiesel33Figure 11: Washing of Biodiesel33Figure 12: Biodiesel from Sunflower oil Figure 13: Biodiesel from Cottonseed Oil34Figure 14: Different samples of biodiesel34Figure 15: Flash Point Tester37Figure 16: Graph of Flash points38Figure 17: Aniline point Apparatus39Figure 18: Graph of Aniline point39Figure 19: Graph of Cloud Points40Figure 20: Graph of Pour points42Figure 21: Bomb Calorimeter43Figure 22: Graph of GCV43Figure 23 : Graph of specific gravity44

Chapter 1

Introduction

1.1 What is Biodiesel

Biodiesel is a clean burning alternative fuel produced from domestic, renewable resources. The fuel is a mixture of fatty acid alkyl esters made from vegetable oils, animal fats or recycled greases. Where available, biodiesel can be used in compression-ignition (diesel) engines in its pure form with little or no modifications. Biodiesel is a liquid biofuel obtained by chemical processes from vegetable oils or animal fats and an alcohol that can be used in diesel engines, alone or blended with diesel oil. ASTM International (originally known as the American Society for Testing and Materials) defines biodiesel as a mixture of long-chain mono-alkylic esters from fatty acids obtained from renewable resources, to be used in diesel engines. Blends with diesel fuel are indicated as Bx, where x is the percentage of biodiesel in the blend. For instance, B5 indicates a blend with 5% biodiesel and 95% diesel fuel; in consequence, B100 indicates pure biodiesel.Biodiesel is not the same as straight vegetable oil or animal fat. A normal diesel engine will eventually be damaged through the use of straight vegetable oil or straight animal fat fuel. Vegetable oils or animal fats must be converted into biodiesel by reacting the oil or fat with an alcohol and a catalyst. This process is referred to as "trans-esterification."1.2 History of BiodieselDeveloped in the 1890s by inventor Rudolph Diesel, the diesel engine has become the engine of choice for power, reliability, and high fuel economy, worldwide. Early experimenters on vegetable oil fuels included the French government and Dr. Diesel himself, who envisioned that pure vegetable oils could power early diesel engines for agriculture in remote areas of the world, where petroleum was not available at the time. Modern biodiesel fuel, which is made by converting vegetable oils into compounds called fatty acid methyl esters, has its roots in research conducted in the 1930s in Belgium, but todays biodiesel industry was not established in Europe until the late 1980s.The diesel engine was developed out of a desire to improve upon inefficient, cumbersome and sometimes dangerous steam engines of the late 1800s. The diesel engine works on the principal of compression ignition, in which fuel is injected into the engines cylinder after air has been compressed to a high pressure and temperature. As the fuel enters the cylinder it self-ignites and burns rapidly, forcing the piston back down and converting the chemical energy in the fuel into mechanical energy. Dr. Rudolph Diesel, for which the engine is named, holds the first patent for the compression ignition engine, issued in 1893. Diesel became known worldwide for his innovative engine which could use a variety of fuels.The Future of Biodiesel FuelDue to its clean emissions profile, ease of use, and many other benefits, biodiesel are quickly becoming one of the fastest growing alternative fuels in the world. With minimal subsidy biodiesel is cost competitive with petroleum diesel, and millions of users have found and enjoyed the benefits of the fuel. The future of biodiesel lies in the worlds ability to produce renewable feedstocks such as vegetable oils and fats to keep the cost of biodiesel competitive with petroleum, without supplanting land necessary for food production, or destroying natural ecosystems in the process. Creating biodiesel in asustainablemanner will allow this clean, renewable, and cost effective fuel to help ease the world through increasing shortages of petroleum, while providing economic and environmental benefits well into the 21st century.

1.3 Biodiesel BlendsBiodiesel can be blended and used in many different concentrations. The most common are: B100 (pure biodiesel), B20 (20% biodiesel, 80% petroleum diesel), B5 (5% biodiesel, 95% petroleum diesel) and B2 (2% biodiesel, 98% petroleum diesel).1.3.1 Low-level BlendsASTM International is developing specifications for a wide variety of products, including conventional diesel fuel (ASTM D975). This specification allows for biodiesel concentrations of up to 5% (B5) to be called diesel fuel, with no separate labeling required at the pump. Low-level biodiesel blends, such as B5 are ASTM approved for safe operation in any compression-ignition engine designed to be operated on petroleum diesel. This can includelight-dutyandheavy-dutydiesel cars and trucks, tractors, boats, and electrical generators.1.3.2 B20B20 (20% biodiesel, 80% petroleum diesel) is the most common biodiesel blend in the United States. B20 is popular because it represents a good balance of cost, emissions, cold-weather performance, materials compatibility, and ability to act as a solvent.B20 and lower-level blends generally do not require engine modifications. Engines operating on B20 have similar fuel consumption, horsepower, and torque to engines running on petroleum diesel. Pure biodiesel (B100) contains about 8% less energy per gallon than petroleum diesel. For B20, this translates to a 1% to 2% difference, but most B20 users report no noticeable difference in performance or fuel economy. Biodiesel has some emissions benefits, especially for engines manufactured before 2010. For engines equipped with selective catalytic reduction (SCR) systems, the air quality benefits are the same whether running on biodiesel or petroleum diesel. However, biodiesel still offers better greenhouse gas (GHG) benefits compared to conventional diesel fuel. The emissions benefit is roughly commensurate with the blend level; that is, B20 would have 20% of the GHG reduction benefit of B100.1.3.3 B100 and High Level BlendsB100 and other high-level biodiesel blends are less common than B20 and lower blends due to a lack of regulatory incentives and pricing. B100 can be used in some engines built since 1994 with biodiesel-compatible material for certain parts, such as hoses and gaskets. B100 has a solvent effect, and it can clean a vehicle's fuel system and release deposits accumulated from petroleum diesel use. The release of these deposits may initially clog filters and require frequent filter replacement in the first few tanks of high-level blends.When using high-level blends, a number of issues should be considered. The higher the percentage of biodiesel above 20%, the lower the energy content per gallon. High-level biodiesel blends can also impact engine warranties, gel in cold temperatures, and may present unique storage issues. B100 use could also increase nitrogen oxides emissions, although it greatly reduces other toxic emissions. B100 requires special handling and may require equipment modifications.

1.4 Advantages of BiodieselSome of the advantages of using biodiesel as a replacement for diesel fuel are:1. Renewable fuel, obtained from vegetable oils or animal fats.2. Low toxicity, in comparison with diesel fuel.3. Degrades more rapidly than diesel fuel, minimizing the environmental consequences of biofuel spills.4. Lower emissions of contaminants: carbon monoxide, particulate matter, polycyclic aromatic hydrocarbons, aldehydes.5. Lower health risk, due to reduced emissions of carcinogenic substances.6. No sulfur dioxide (SO2) emissions.7. Higher ash point (100C minimum).8. May be blended with diesel fuel at any proportion; both fuels may be mixed during the fuel supply to vehicles.9. Excellent properties as a lubricant.10. It is the only alternative fuel that can be used in a conventional diesel engine, without modications. 11. Used cooking oils and fat residues from meat processing may be used as raw materials.1.5 Disadvantages of BiodieselThere are certain disadvantages of using biodiesel as a replacement for diesel fuel that must be taken into consideration: 1. Slightly higher fuel consumption due to the lower caloric value of biodiesel. 2. Slightly higher nitrous oxide (NOx) emissions than diesel fuel. 3. Higher freezing point than diesel fuel. This may be inconvenient in cold climates. 4. It is less stable than diesel fuel, and therefore long-term storage (more than six months) of biodiesel is not recommended. 5. May degrade plastic and natural rubber gaskets and hoses when used in pure form, in which case replacement with Teon components is recommended. 6. It dissolves the deposits of sediments and other contaminants from diesel fuel in storage tanks and fuel lines, which then are ushed away by the biofuel into the engine, where they can cause problems in the valves and injection systems. In consequence, the cleaning of tanks prior to lling with biodiesel is recommended. It must be noted that these disadvantages are signicantly reduced when biodiesel is used in blends with diesel fuel.1.6Raw Materials for Biodiesel ProductionThe raw materials for biodiesel production are vegetable oils, animal fats and short chain alcohols. The oils most used for worldwide biodiesel production are replaced (mainly in the European Union countries), soybean (Argentina and the United States of America), palm (Asian and Central American countries) and sunower, although other oils are also used, including peanut, linseed, safower, used vegetable oils, and also animal fats. Methanol is the most frequently used alcohol, although ethanol can also be used. Since cost is the main concern in biodiesel production and trading (mainly due to oil prices), the use of non-edible vegetable oils has been studied for several years with good results.Besides its lower cost, another undeniable advantage of non-edible oils for biodiesel production lies in the fact that no foodstuffs are spent to produce fuel. These and other reasons have led to medium- and large-scale biodiesel production trials in several countries, using non-edible oils such as castor oil, Tung, cotton, jojoba and jatropha. Animal fats are also an interesting option, especially in countries with plenty of livestock resources, although it is necessary to carry out preliminary treatment since they are solid; furthermore, highly acidic grease from cattle, pork, poultry, and sh can be used. Microalgae appear to be a very important alternative for future biodiesel production due to their very high oil yield; however, it must be taken into account that only some species are useful for biofuel production. Although the properties of oils and fats used as raw materials may differ, the properties of biodiesel must be the same, complying with the requirements set by international standards.1.7 Properties of BiodieselWhat makes a fuel different from others are its cetane number and heat of combustion. The viscosity of a fuel is important because it influences the atomization of the fuel being inserted into the engine combustion chamber. For complete combustion to happen, a small fuel drop is required. The biodiesel fuel property of having the viscosity much closer to diesel fuel than vegetable oil helps create a much lower drop, which burns cleaner.The other main property of biodiesel fuel that we will discuss is its lubricating properties. It has much better lubricating and a higher cetane ratings than today's lower sulfur diesel fuels. Adding Biodiesel also helps in reducing fuel system wear. The fuel injection equipment depends on the fuel for its lubrication. The biodiesel fuel properties increase the life of the fuel injection equipment. Giving better lubricity and a more complete combustion increases the engine energy output, thus partially balancing for the higher energy density of petro diesel. Older diesel Mercedes is well known for running on biodiesel.Observing the physical properties of biodiesel fuel, it is a liquid which can be different in color, from golden and dark brown, all depending on the production feedstock. It is immiscible with water, has a high boiling point and low vapor pressure. The flash point of biodiesel is considerably higher than that of petroleum diesel. Biodiesel fuel has a density of ~ 0.88 g/cm, which is less than that of water.Studying the chemical properties of biodiesel fuel, its calorific value is about 37.27 MJ/L, which is 9% lower than regular petrol diesel. It has practically no sulfur content, and is frequently used as an additive to Ultra-Low Sulfur Diesel (ULSD) fuel. Biodiesel fuel has an effect on copper-based materials and as well as zinc, tin, lead, and cast iron. However, the stainless steels and aluminum are not affected by biofuel.

Chapter 2

Literature Review

2.1 Biofuel SourcesHere are 4 biofuel sources, with some of their applications in developmental stages, some actuallyImplemented:2.1.1 AlgaeAlgae come from stagnant ponds in the natural world, and more recently from algae farms, which produce the plant for the specific purpose of creating biofuel. Advantage of algae focused on the followings: No CO2 back into the air, self-generating biomass, Algae can produce up to 300 times more oil per acre than conventional crops. Among other uses, algae have been used experimentally as a new form of green jet fuel designed for commercial travel. At the moment, the upfront costs of producing biofuel from algae on a mass scale are in process, but are not yet commercially viable.2.1.2 Carbohydrate rich biomaterialIt comes from the fermentation of starches derived from agricultural products like corn, sugar cane, wheat, beets, and other existing food crops, or from inedible cellulose from the same. Produced from existing crops, can be used in an existing gasoline engine, making it a logical transition from petroleum. It used in the Auto industry, heating buildings (flue less fireplaces).At present, the transportation costs required to transport grains from harvesting to processing, and then out to vendors results in a very small net gain in the sustainability stakes.2.1.3 Oil rich biomaterialIt comes from existing food crops like rapeseed (aka Canola), sunflower, corn, and others, afterit has been used for other purposes, i.e. food preparation (waste vegetable oil, or WVO), or even in the first usage form (straight vegetable oil, or SVO). Not susceptible to microbial degradation, high availability, re-used material. It is used in the creation of biodiesel fuel for automobiles, home heating, and experimentally as a pure fuel itself. At present, WVO or SVO is not recognized as a mainstream fuel for automobiles. Also, WVO and SVO are susceptible to low temperatures, making them unusable in colder climates.

2.1.4 Agriculture wastes (organic and inorganic sources)It comes from agricultural waste which is concentrated into charcoal-like biomass by heating it. Very little processing required, low-tech, naturally, holds CO2 rather than releasing it into the air. Primarily, bio char has been used as a means to enrich soil by keeping CO2 in it, and not into the air. As fuel, the off-gasses have been used in home heating. There is controversy surrounding the amount of acreage it would take to make fuel production based on bio char viable on a meaningful scale. Furthermore, use of agriculture wastes which rich with inorganic elements (NPK----) as compost (fertilizer) in agriculture.2.2 Biodiesel as a fuelBiodiesel (B100) is defined as a fuel comprised of mono-alkyl esters of long-chain fatty acids derived from vegetable oils or animal fats. Biodiesel Fuel can be produced from a variety of natural crops, including rapeseed, soybean, mustard, flax, sunflower, canola, palm oil, hemp, jatropha and waste vegetable oils. In addition, it must meet all of the parameters as defined within the ASTM specification D6751,Standard Specification for Biodiesel Fuel Blend Stock (B100) for Middle Distillate Fuels. Biodiesel has been registered with the U.S. EPA as a fuel and a fuel additive under Section 211(b) of the Clean Air Act. Biodiesel is a fuel designed as a blendstock for use in blending with petroleum diesel fuel. It is not intended for use with gasoline. Biodiesel has been proven to reduce the emissions of hydrocarbons, carbon monoxide and particulates when used alone or with blends that include petroleum diesel. Biodiesel has excellent lubricity properties and is typically low in sulfur content, thus meeting the needs of the EPA and new generation fuels.This fuel source is said to reduce engine wear and produce less harmful emissions. Biodiesel is used as an alternative fuel source, but requires engine modifications. Biodiesel's physical properties are similar to those of petroleum diesel, but it is a cleaner-burning alternative. Using biodiesel in place of petroleum diesel, especially in older vehicles, can reduceemissions.

2.3 Fuel propertiesThe properties of biodiesel can be grouped by multiple criteria. The most important arethose that influence the processes taking place in the engine (ignition qualities, ease ofstarting, formation and burning of the fuel-air mixture, exhaust gas formation and quality and the heating value, etc.), cold weather properties (cloud point, pour point and cold filter plugging point), transport and depositing (oxidative and hydrolytic stability, flash point, induction period, microbial contamination, filterability limit temperature, etc.), wear of engine parts (lubricity, cleaning effect, viscosity, compatibility with materials used to manufacture the fuel system, etc.).Others properties:Sulfated ash is a measure of ash formed from inorganic metallic compounds. After the burning of biodiesel, in addition to CO2 and H2O a quantity of ash is formed consisting of unburned hydrocarbons and inorganic impurities (e.g. metal impurities). Metallic ash is very abrasive and may cause excessive wear of the cylinder walls and the piston ring.Carbon residue indicates the presence of impurities and deposits in the engine combustion chamber, and is also an indicator of the quantity of glycerides, free fatty acids, soaps andTrans-esterification reaction catalyst residues.Copper-strip corrosion is an indicator of the corrosiveness of biodiesel, of the presence of fattyAcids derived from materials which did not enter into reaction during the production process.Content of metals (Ca, Na, Mg, K and P) can lead to combustion chamber deposits, filter andfuel injection pump clogging, and can harm the catalyst.2.4 Different methods of biodiesel production2.4.1 Supercritical processAn alternative, catalyst-free method for trans-esterification usessupercriticalmethanol at high temperatures and pressures in a continuous process. In the supercritical state, the oil and methanol are in a single phase, and reaction occurs spontaneously and rapidly. The process can tolerate water in the feed-stock, free fatty acids are converted to methyl esters instead of soap, so a wide variety of feed stocks can be used. Also the catalyst removal step is eliminated.High temperatures and pressures are required, but energy costs of production are similar or less than catalytic production routes.2.4.2 Ultra- and high-shear in-line and batch reactorsUltra- and High Shear in-line or batch reactors allow production of biodiesel continuously, semi- continuously, and in batch-mode. This drastically reduces production time and increases production volume.The reaction takes place in the high-energetic shear zone of the Ultra- and High Shear mixer by reducing the droplet size of the immiscible liquids such as oil or fats and methanol. Therefore, the smaller the droplet size the larger the surface area the faster the catalyst can react.2.4.3 Ultrasonic reactor methodIn the ultrasonic reactor method, the ultrasonic waves cause the reaction mixture to produce and collapse bubbles constantly. This cavitation simultaneously provides the mixing and heating required to carry out the trans-esterification process. Thus using an ultrasonic reactor for biodiesel production drastically reduces the reaction time, reaction temperatures, and energy input. Hence the process of trans-esterification can run inline rather than using the time consuming batch processing. Industrial scale ultrasonic devices allow for the industrial scale processing of several thousand barrels per day.2.4.4 Lipase-catalyzed methodLarge amounts of research have focused recently on the use of enzymes as a catalyst for the trans-esterification. Researchers have found that very good yields could be obtained from crude and used oils usinglipases. The use of lipases makes the reaction less sensitive to high free fatty-acid content, which is a problem with the standard biodiesel process. One problem with the lipase reaction is that methanol cannot be used because it inactivates the lipase catalyst after one batch. However, if methyl acetate is used instead of methanol, the lipase is not in-activated and can be used for several batches, making the lipase system much more cost effective.2.4.5 Volatile Fatty Acids from Anaerobic Digestion of Waste StreamsLipids have drawn considerable attention as a substrate for biodiesel production owing to its sustainability, non-toxic and energy efficient properties. However, due to cost reasons, attention must be focused on the non-edible sources of lipids, in particular oleaginous microorganisms. Such microbes have the ability to assimilate the carbon sources from a medium and convert the carbon into lipid storage materials. The lipids accumulated by these oleaginous cells can then be trans-esterified to form biodiesel.2.5 Biodiesel ProductionBiodiesel can be produced from straight vegetable oil, animal oil/fats, tallow and waste oils. There are three basic routes to biodiesel production from oils and fats: Base catalyzed trans-esterification of the oil. Direct acid catalyzed trans-esterification of the oil. Conversion of the oil to its fatty acids and then to biodiesel.Almost all biodiesel is produced using base catalyzed trans-esterification as it is the most economical process requiring only low temperatures and pressures and producing a 98% conversion yield. For this reason only this process will be described in this report.The Trans-esterification process is the reaction of a triglyceride (fat/oil) with an alcohol to form esters and glycerol. A triglyceride has a glycerin molecule as its base with three long chain fatty acids attached. The characteristics of the fat are determined by the nature of the fatty acids attached to the glycerin. The nature of the fatty acids can in turn affect the characteristics of the biodiesel. During the esterification process, the triglyceride is reacted with alcohol in the presence of a catalyst, usually a strong alkaline like sodium hydroxide. The alcohol reacts with the fatty acids to form the mono-alkyl ester, or biodiesel and crude glycerol. In most production methanol or ethanol is the alcohol used (methanol produces methyl esters, ethanol produces ethyl esters) and is base catalyzed by either potassium or sodium hydroxide. Potassium hydroxide has been found to be more suitable for the ethyl ester biodiesel production, either base can be used for the methyl ester. A common product of the trans-esterification process is Rape Methyl Ester (RME) produced from raw rapeseed oil reacted with methanol.The Figure 1 shows the chemical process for methyl ester biodiesel. The reaction between the fat or oil and the alcohol is a reversible reaction and so the alcohol must be added in excess to drive the reaction towards the right and ensure complete conversion.

Figure 1: Trans-esterification ReactionThe products of the reaction are the biodiesel itself and glycerol.A successful trans-esterification reaction is signified by the separation of the ester and glycerol layers after the reaction time. The heavier, co-product, glycerol settles out and may be sold as it is or it may be purified for use in other industries, e.g. the pharmaceutical, cosmetics etc.Straight vegetable oil (SVO) can be used directly as a fossil diesel substitute however using this fuel can lead to some fairly serious engine problems. Due to its relatively high viscosity SVO leads to poor atomization of the fuel, incomplete combustion, coking of the fuel injectors, ring carbonization, and accumulation of fuel in the lubricating oil. The best method for solving these problems is the trans-esterification of the oil.The engine combustion benefits of the trans-esterification of the oil are: Lowered viscosity Complete removal of the glycerides Lowered boiling point High flash point Lowered pour point

2.5.1 Production Process

An example of a simple production flow chart is proved below with a brief explanation of each step.

Figure 2: Flow chart of Biodiesel ProductionMixing of alcohol and catalystThe catalyst is typically sodium hydroxide (caustic soda) or potassium hydroxide (potash). It is dissolved in the alcohol using a standard agitator or mixer. The alcohol/catalyst mix is then charged into a closed reaction vessel and the oil or fat is added. The system from here on is totally closed to the atmosphere to prevent the loss of alcohol. The reaction mix is kept just above the boiling point of the alcohol (around 160 F) to speed up the reaction and the reaction takes place. Recommended reaction time varies from 1 to 8 hours, and some systems recommend the reaction take place at room temperature. Excess alcohol is normally used to ensure total conversion of the fat or oil to its esters. Care must be taken to monitor the amount of water and free fatty acids in the incoming oil or fat. If the free fatty acid level or water level is too high it may cause problems with soap formation and the separation of the glycerin by-product downstream.

SeparationOnce the reaction is complete, two major products exist: glycerin and biodiesel. Each has a substantial amount of the excess methanol that was used in the reaction. The reacted mixture is sometimes neutralized at this step if needed. The glycerin phase is much denser than biodiesel phase and the two can be gravity separated with glycerin simply drawn off the bottom of the settling vessel. In some cases, a centrifuge is used to separate the two materials faster.Alcohol RemovalOnce the glycerin and biodiesel phases have been separated, the excess alcohol in each phase is removed with a flash evaporation process or by distillation. In others systems, the alcohol is removed and the mixture neutralized before the glycerin and esters have been separated. In either case, the alcohol is recovered using distillation equipment and is re-used. Care must be taken to ensure no water accumulates in the recovered alcohol stream.Glycerin NeutralizationThe glycerin by-product contains unused catalyst and soaps that are neutralized with an acid and sent to storage as crude glycerin. In some cases the salt formed during this phase is recovered for use as fertilizer. In most cases the salt is left in the glycerin. Water and alcohol are removed to produce 80-88% pure glycerin that is ready to be sold as crude glycerin. In more sophisticated operations, the glycerin is distilled to 99% or higher purity and sold into the cosmetic and pharmaceutical markets.Methyl Ester WashOnce separated from the glycerin, the biodiesel is sometimes purified by washing gently with warm water to remove residual catalyst or soaps, dried, and sent to storage. In some processes this step is unnecessary. This is normally the end of the production process resulting in a clear amber-yellow liquid with a viscosity similar to petro-diesel. In some systems the biodiesel is distilled in an additional step to remove small amounts of color bodies to produce a colorless biodiesel.

Product QualityPrior to use as a commercial fuel, the finished biodiesel must be analyzed using sophisticated analytical equipment to ensure it meets any required specifications. The most important aspects of biodiesel production to ensure trouble free operation in diesel engines are: Complete Reaction Removal of Glycerin Removal of Catalyst Removal of Alcohol Absence of Free Fatty Acids2.6 Environmental Effects of Biodiesel FuelAlthough biodiesel fuel is fast emerging as the oil of the future, a number of environmental effects of biodiesel fuel are also surfacing associated with its use. These biodiesel fuel environmental effects potentially include decrease in greenhouse gas emissions, deforestation, pollution and the rate of biodegradation. Greenhouse gas emissionsWhether using biodiesel is able to lower greenhouse gas emissions as compared to the fossil fuels may depend on many factors. Carbon dioxide is known to be one of the major greenhouse gases. The plant feedstock used in the making biofuels absorbs carbon dioxide from the atmosphere when it grows and once the biomass is converted into biodiesel and burnt as fuel, the energy released is used to power an engine while the carbon dioxide is released back into the atmosphere. When considering environmental effects of biodiesel fuel due to the total amount of greenhouse gas emissions, it is important to consider the whole production process. Several factors like production methods, type of feedstock play their role. Assuming today's production methods, with no land use change, biodiesel from rapeseed and sunflower oil produce 45%-65% lower greenhouse gas emissions than petro-diesel But calculating the carbon intensity of biodiesel fuels is a complex and inexact process. However, there is continuing research for improving the efficiency of the production process of the biodiesel fuels.DeforestationThere can be grave effects of biodiesel fuel on environment if deforestation and monoculture farming techniques are used to grow biofuel crops. It may damage the ecosystems and biodiversity and increase the emission of climate change gases rather than helping controlling them. To meet the demand for cheap oil from the tropical region, the amount of arable land is being extended in order to increase production at the cost of tropical rainforest. As feedstock oils in Europe and North America are much more expansive than Asia, South America and Africa, imports to these more affluent nations are likely to increase in the future. Tropics forests are being cleared to make room for oil palm plantations. These can lead to serious biodiesel fuel environmental effects as deforestation can be threatening many species of unique plants and animals.PollutionBiodiesel fuel is the only alternative fuel to have effectively completed the Health Effects testing requirements of the Clean Air Act (1990). The particulate emissions as the consequence of production are lowered by around 50 percent compared with fossil-sourced diesel. Having a higher cetane rating than petro-diesel, some positive effects of biodiesel fuel on environment can be seen as it can improve performance and clean up emissions. Biodiesel also consists of fewer aromatic hydrocarbons.BiodegradationAnother of the environmental effects of biodiesel fuels can be sees in its biodegradation rates, which are 5 times faster than petroleum diesel over a period of 28 days. Biodiesel fuel blends can also accelerate the rate of petroleum diesel degradation through co-metabolism. Toxicity studies have revealed no mortalities and any toxic effects of biodiesel fuel on environment.2.7 Energy securityThe US uses roughly 20 million barrels of oil a day. More than half of this number is imported and the number of these barrel imported are slated for a fast rise in the near future. U.S. somehow continues its dependence on foreign sources of oil, which can be dangerous. Its time it looked into ways to lower its dangerous dependence on foreign oil and seek energy security in biodiesel fuel, which is gaining momentum in the U.S. Today, for US, biodiesel is the fastest growing alternative fuel. Let us study energy security due to biodiesel fuel on this page.All across the world, the countries are adopting biodiesel fuel for energy security as it protects the environment, besides boosting the economy. Today, biodiesel is fast turning as the growing alternative fuel not only in America, but other parts of the world as well. Beyond the environmental and health benefits, biodiesel fuel can also help free the countries from the hold of imported oil, thus giving them more energy security due to biodiesel fuel.One of the main reasons behind transition to biodiesel fuel is energy security. As the nation's reliance on foreign oil gets reduced, use of locally available sources is substituted. Thus a country finds energy security in biodiesel fuel without a decrease in greenhouse gas emissions. Although the total energy balance is still a debatable issue, but clearly the energy security due to biodiesel fuel is enhanced.Today, US have made it amply clear using biodiesel fuel for energy security is the main driving force and the main reason behind the US biofuels programme. Clearly changing to biodiesel fuel for energy security is a major reason for promoting biofuel. It has been stressed properly managed biodiesel fuels have the prospective for strengthening the security of supply through branching out of energy sources.2.8 Economic benefits

Multiple economic studies have been performed regarding the economic impact of biodiesel production. One study, commissioned by the National Biodiesel Board, reported the 2011 production of biodiesel supported 39,027 jobs and more than $2.1 billion in household income.The growth in biodiesel also helps significantly increase GDP. In 2011, biodiesel created more than $3 billion in GDP. Judging by the continued growth in the Renewable Fuel Standard and the extension of the biodiesel tax incentive, the number of jobs can increase to 50,725, $2.7 billion in income, and reaching $5 billion in GDP by 2012 and 2013.

Chapter 3

Experimental Work

3.1 Procedure of Manufacturing the Biodiesel

There are some steps which are used to manufacture the Biodiesel, which are given below3.1.1 FiltrationFiltration process is carried out for removing the particles from vegetable oil. This process is carried out by using the double layer of cheesecloth. Cheesecloth helps to remove the solid particles from oil.3.1.2 Water RemovingOil will probably contain water content. After filtration the oil is heated at 100 C because the boiling point of water is 100 C. Water in the oil can slow down the reaction and also causes the soap formation. So for avoiding the specification and slow down the reaction the water is removed from oil by heating.

Figure 3: Removal of Water from Vegetable oil

3.1.3 Calculation for Cottonseed oil, methanol and catalyst

Weight of Cottonseed oil taken, W = 300 gMolecular weight of Cottonseed oil, M = 879 g/gmoleMoles of Cottonseed oil, m = W/M = 0.3412 gmolesFrom literature oil to methanol ratio = 1: 5Moles of Methanol, N= 5* 0.312 = 1.7064 gmoleMethanol required = N*32 = 1.7064*32 = 54.60 gramsTotal no.of moles =0.3412 + 1.7064 = 2.0476 gmoles1% NaOH is taken as Catalyst.Moles of NaOH required for this reaction = 0.01*2.0476 = 0.0204 gmoleNaOH required for this reaction = 0.0204 * 40 = 0.8190 gram3.1.4 Calculation for Mustard oil, methanol and catalyst

Weight of Mustard oil taken, W = 300 gMolecular weight of Mustard oil, M = 308.5489 g/gmoleMoles of Mustard oil, m = W/M = 0.9722 gmolesFrom literature oil to methanol ratio = 1 : 5Moles of Methanol N = 5* 0.9722 = 4.8610 gmoleMethanol required = N*32 = 4.8610 *32 = 154.52 gramsTotal no.of moles =0.9722 + 4.8610 = 5.8332 gmoles1% NaOH is taken as Catalyst.Moles of NaOH required for this reaction = 0.01*5.8332 = 0.0583 gmoleNaOH required for this reaction = 0.0583 * 40 = 2.3332 gram

3.1.3 Calculation for Sunflower oil, methanol and catalyst

Weight of Sunflower oil taken, W = 400 gMolecular weight of Sunflower oil, M = 278.8148 g/moleMoles of Sunflower oil, m = W/M = 1.4346gmolesFrom literature oil to methanol ratio = 1 : 5Moles of Methanol, N = 5* 1.4346 = 7.173gmoleMethanol required = N*32 = 7.173 *32 = 229.53 gramsTotal No.of moles =1. 4346 + 7.173 = 9.1476gmoles1% NaOH is taken as Catalyst.Moles of NaOH required for this reaction = 0.01*9.1476 = 0.0914gmoleNaOH required for this reaction = 0.0583 * 40 = 3.6590 gram

3.1.4 Preparation of Sodium MethoxideCalculated amount of Sodium hydroxide and Methanol are mixed together by heating and stirring. It is stirred and heated at temperature less than that of methanol boiling point till Sodium hydroxide completely dissolved in methanol. Water is removed by heating. The chemical reaction is given below:CH3OH+NaOH CH3ONa + H2O Equation 1

Figure 4: Preparation of Sodium methoxide

3.1.5 Heating and MixingAfter manufacturing the Sodium meth-oxide, it is mixed with required amount of vegetable oil. Now the mixture of Vegetable oil and Sodium meth-oxide is stirred for 1 to 2 hours by magnetic stirrer and heated at 60 C. The temperature should not rise than 77 C otherwise methanol will be evaporating so; the temperature should be maintained below the 77 C. The transesterification process separates the methyl-ester and glycerin. There should be a vortex just on the surface. A vortex can be avoided by the optimum speed of magnetic stirrer. The temperature is maintained at 60 C throughout the process by using ta thermostatFigure 5: Transesterification ReactionFigure 6: Preparation of Biodiesel3.1.5 SettlingAfter a well mixed mixture of Biodiesel and glycerin is put into the separating flask and giving them till glycerin is settled down. Figure 7: Prepared BiodieselFigure 8: Separation of Biodiesel

3.1.6 SeparationAfter completely settling it will show two liquids which is based on density differences. After completely settling the glycerin from the Biodiesel is separated from separating flask. If glycerin is filed in titration flask, then it reheated for easily removing from separating flask.Figure 9: Removal of GlycerinFigure 10: Separated Biodiesel3.1.6 WashingAfter separating the glycerin the biodiesel is washed by water. Water is sprinkled above the surface of biodiesel. Water soluble with methanol so it will dissolve with methanol and finally two liquids will be appeared by density differences. Avoid shaking the mixture while washing otherwise the milky mixture will be appeared and its separation will take several weeks.Figure 11: Washing of Biodiesel3.1.6 HeatingWashing the Biodiesel till waters color appears. Most probably methanol removes with water, but due to better result the biodiesel is heated at 100 C. The heated temperature should not greater than the boiling point of Biodiesel from any vegetable oil. At this temperature methanol and water will be vaporized and finally the Biodiesel is free from all impurities. Figure 12: Biodiesel from Sunflower oilFigure 13: Biodiesel from Cottonseed Oil

Figure 14: Different samples of biodiesel3.1.7 GlycerinThe Glycerin from vegetable oils is brown which turns to a solid below 100 C. After sometime it turns into gelled formed.

Chapter 4

Results

4.1 Flash PointTheflash point is the lowesttemperatureat which oil gives out sufficient vapors to form an ignitable mixture inair and catches fire momentarily when flame is applied. Measuring a flash point requires an ignition source. At the flash point, the vapor may cease to burn when the source of ignition is removed. The value of the flash point is helpful for the storage purpose of the biodiesel.

Figure 15: Flash Point Tester

Procedure Oil cup is cleaned and dried. Sample oil is then passes into the cup up to the level indicated by the filling mark. Place the lid over cup in its position and insert a thermometer in the holder. Apparatus is heated and stirred is rotated at the rate from 1-2 revolution per second. Apply the test flame at temperature intervals of 5 in such a manner that the flame is lowered in one half second, left in its lowered position for one second and quickly raised. The temperature at which a distinct flash is visible in the observation this reading of temperature is recorded as flash point.Flash point of mustard bio-diesel = 61o CFlash point of cotton seed bio-diesel oil = 54o C Flash point of sunflower bio-diesel oil = 67o C.

Figure 16: Graph of Flash points

4.2 Aniline pointTheaniline pointof oil is defined as the minimum temperature at which oil is completely miscible with an equal volume of aniline (C6H5NH2). It is the aromatic content of the oil. Aniline is used in this method because aniline is miscible by most of the aromatics. Higher the aniline point lowers the aromatics and higher the paraffin content with very high cetane number making the oil suitable for use in diesel engine.

Aniline point of mustard bio-diesel = 21o CAniline point of cotton seed bio-diesel oil = 24o C Aniline point of sunflower bio-diesel oil = 26o C.Figure 17: Aniline point Apparatus

Figure 18: Graph of Aniline point

4.3 Cloud PointWhen oil is cooled then the temperature at which it becomes cloudy or hazy is called the cloud point of oil. The haziness is due to the separation of crystals of wax or increase of viscosity at low temperature.In the petroleum industry, cloud point refers to the temperature below whichwaxin diesel or bio wax inbiodieselsform a cloudy appearance. The presence of solidified waxes thickens the oil and clogs fuel filters and injectors in engines. The wax also accumulates on cold surfaces (e.g. pipeline or heat exchangerfouling) and forms anemulsionwith water. Therefore, cloud point indicates the tendency of the oil to plug filters or small orifices at cold operating temperature.Procedure Oil is poured into the test jar. It is important that the inside of jacket shall be clean and dry. The next important factor is the cooling. First the assembly is inserted into a cooling medium. So that only about one inch of the jacket projects above the liquid medium. As the cooling precede the test jar is withdrawn quickly, but without disturbing the oil at every 2 degree celsius fall and examined for cloud. If cloud point doesnt appear, it is cooled again and examined. The first distinct cloudiness or haze in the oil at the bottom of the test jar is regarded as the cloud point

Cloud point of mustard bio-diesel oil = -12.7o C Cloud point of sunflower bio-diesel oil = -1.6o C Cloud point of cotton seed bio-diesel oil =7o C

Figure 19: Graph of Cloud Points

4.4 Pour PointThe temperature at which the oil just ceases to flow (or pure) is called the pour point. It determines the temperature at which oil cannot be used as a lubricant.Incrudeoila high pour point is generally associated with high paraffincontent, typically found in crude deriving from a larger proportion of plant material.Cloud and pour points indicate the suitability of bio-diesel in cold conditions.Procedure Oil is poured into the test jar. It is important that the inside of the jacket shall be clean and dry. The next important factor is the cooling First the assembly is inserted into a cooling medium. As the cooling precede the test jar is withdrawn without disturbing the oil at every 3 fall and examined for pour point. If oil shows any movement under these conditions the test jar is immediately replaced in the jacket and a test for flow repeated at the next temperature 3 lower. As soon as the oil ceases to flow the jar is held in a horizontal position for exactly 5 seconds and then note the temperature.Pour point of mustard bio-diesel oil = -14.7o C Pour point of sunflower bio-diesel oil = -3.6 o C Pour point of cotton seed bio-diesel oil = 5o C

Figure 20: Graph of Pour points4.5 Calorific ValueThe calorific value, or heat of combustion or heating value of a sample of fuel is defined as the amount of heat evolved when the unit quantity of fuel is completely burnt and the products of combustion cooled to a standard temperature of 298 degree K. The calorific value is measured by bomb calorimeter.Procedure Take 1-2 gram of sample and place it into the crucible of the calorimeter. A piece of firing wire, copper is stretched across the inner terminus of the bomb and a piece of sewing cotton is attached to it with the other end in contact with the sample. The bomb is charged with oxygen to a pressure of 25 atmospheres through the needle valve without displacing the original air The calorimeter vessel is then with almost 2.5 liters of water to submerge the bomb up till cover completely. Place the bomb in the calorimeter after complete assurance of its tightness. The thermometer is adjusted along with the cover of calorimeter, start the stirrer and allow it to run for 5 minutes before observations to begin. The temperature of water is noted after every 5 minutes. As the temperature rate of change is constant, close the electrical circuit and note the temperature reading.

Figure 21: Bomb CalorimeterGross Calorific value of mustard bio-diesel oil = 44459.03 KJ/kgGross Calorific value of sunflower bio-diesel oil = 34022.18 KJ/kgGross Calorific value of cotton seed bio-diesel oil = 37153.61 KJ/kg

Figure 22: Graph of GCV4.5 Specific GravitySpecific gravityis the ratio of thedensityof a substance to the density (mass of the same unit volume) of a reference substance. Apparentspecific gravity is the ratio of the weight of a volume of the substance to the weight of an equal volume of the reference substance. Take the gravity bottle and measure the weight of bottle by measuring balance. Gravity bottle is filled with vegetable oil up to the mark. Again measure the weight of gravity bottle. Now calculate the difference of weight, which gives us the weight of vegetable oil. For measuring the density of oil we divided measured weight of the oil by volume of oil carrying a gravity bottle. Specific gravity is measured by dividing the calculated density of oil by the density of water.

Specific gravity of Sunflower biodiesel = 0.8469Specific gravity of Mustard biodiesel = 0.8475Specific gravity of Cottonseed biodiesel = 0.8444

Figure 23 : Graph of specific gravity

References

http://www.extension.org/pages/26602/introduction-to-biodiesel#.VdVzqrKqqkohttp://www.make-biodiesel.org/Introductionhttp://energy.about.com/od/renewables/a/Introduction-To-Biodiesel.htmhttps://en.wikipedia.org/wiki/Biodieselhttps://www.dieselnet.com/tech/fuel_biodiesel_std.phphttp://www.sciencedirect.com/science/article/pii/S136403211100390Xhttp://www.berkeleybiodiesel.org/overview-blends-biodiesel.htmlhttp://www.afdc.energy.gov/fuels/biodiesel_blends.htmlhttp://www.sciencedirect.com/science/article/pii/S136403211300141Xhttp://www.sciencedirect.com/science/article/pii/S0196890406002378http://www.sunflowernsa.com/oil/biodiesel/https://www.google.com.pk/url?sa=t&rct=j&q=&esrc=s&source=web&cd=1&ved=0CCAQFjAAahUKEwiz7OrShbfHAhXJXBQKHTk7AGI&url=http%3A%2F%2Fwww.diva-portal.org%2Fsmash%2Fget%2Fdiva2%3A443295%2Ffulltext01.pdf&ei=HnXVVbPlJsm5Ubn2gJAG&usg=AFQjCNFSwocnQHQrv32iZGnNdADDLSHymw&bvm=bv.99804247,d.d24&cad=rjahttps://www.google.com.pk/url?sa=t&rct=j&q=&esrc=s&source=web&cd=3&ved=0CDEQFjACahUKEwiC6NaChrfHAhXDOBQKHcQMAas&url=http%3A%2F%2Fwww.omicsonline.org%2Foptimization-of-biodiesel-production-from-sunflower-oil-using-response-surface-methodology-2157-7048.1000141.pdf&ei=gnXVVYKfO8PxUMSZhNgK&usg=AFQjCNEE4PIYYdNSj-OhkyVCKThXDga3ng&bvm=bv.99804247,d.d24&cad=rjahttp://www.answers-to-your-biodiesel-questions.com/biodiesel-flashpoint.htmlhttps://en.wikipedia.org/wiki/Vegetable_oil_(disambiguation)http://www.scientificpsychic.com/fitness/fattyacids1.htmlhttp://www.extension.org/pages/26611/biodiesel-cloud-point-and-cold-weather-issues#.VdV3CLKqqkohttp://web.cals.uidaho.edu/biodiesel/biodiesel-shortcourse-cold-flow/http://www.make-biodiesel.org/Quality-Testing/cloud-point-and-gel-point-tests.htmlhttp://thepaleodiet.com/vegetable-oil-fatty-acid-composition/https://en.wikipedia.org/wiki/Template:Vegetable_oils,_composition

http://www.fediol.eu/web/chemical+composition/1011306087/list1187970121/f1.htmlhttp://thepaleodiet.com/vegetable-oil-fatty-acid-composition/http://www.sciencedirect.com/science/article/pii/S0308814609006402http://www.sciencedirect.com/science/article/pii/S0003267097005746http://www.scientificpsychic.com/fitness/fattyacids1.htmlhttp://www.biofuelnet.ca/2013/07/31/a-brief-history-of-biofuels-from-ancient-history-to-today/http://www.triplepundit.com/2012/10/history-of-biofuels/http://humantouchofchemistry.com/the-future-of-biofuels.htmhttp://www.mybiodiesel.com/biodiesel-history.php

Book: Introduction to Biofuels by David M. Mousdale

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