KAUTILYA INSTITUTE OF TECHNOLOGY & ENGINEERING JAIPUR

Session 2013-2014 A Synopsis

On EXTRATION OF BIODIESEL FROM SOYBEAN OIL AND INVESTIGATE EMISSIONS PARAMETER ON A SINGLE CYLINDER DIESEL ENGINE

Submitted to: Mr. Rakesh Mahavar Mechanical engg. Dept.

Submitted by:Sonu Pareekh Shashank Pathak Ram Naresh Suthar Pooran Mal Yadav

Mechanical Engineering Department Kautilya Institute of technology & Engineering

ACKNOWLEDGEMENT

It is really matter of great pleasure for me to present this creative and practical work. Project which is important part of learning and every engineering student prepares it in final year of his B.tech. In preparation of this report I have received encouragement and support from various persons. I would like to express my helpful thanks and gratitude to all of them. I am thankful TO Mr. Rakesh mahavar (Asst. prof. ME department) for guiding me for preparation of this report.

Thank you

ABSTRACT
Due to limited resource of fossil fuel and high rise in the demand of them the need for alternative fuels is all time high. Where countries are trying to find the best alternative fuel and to encourage the domestic production of fuels for self efficiency. The article gives a condensed overview of biodiesel extraction from cotton seed oil with caliberation in their catalyst content and alcohol content, viscocity, density, flash point, fire point, calorifc value and abopve all cost efficiency are measured and determined. The process of conversion of vegetable oil into biodiesel employed is transesterification. And the production method employed is base catalyzed. Alcohol used for this process is methanol and a base catalyst catalyst is used for the prcess i.e. potassium hydroxide (KOH). The paper tries to throw some light on the best and most biodiesel obtaioned with varitions in the amount of catalyst and alocohol with the help in iteration process of finding out the best combination for maximum biodiesel and less amount of residual substitute.

INTRODUCTION
In todays world where the population is increasing marginally and the demand to have automobiles is also at all time high and further only going to increase. With tthis scenario the demand of fossil fuel and its consumption is increasing exponentialy and is a matter of concern for developing countries who are not self sufficient. Vegetable oil is the most desired alternative fuel available at the present scenario and in near coming future. Also the pollution caused by the combustion of these fossil fuels is a major concern for the enviroment and the search of alternative fuel has gained much importance. Biodiesel is also named as Methyl Esters. Methyl esters are clean burning fuel with no sulfur emission. Although its heat of combustion is slightly lower than that of the petrodiesel, there is no engine adjustment necessary and there is no loss in efficiency . Methyl esters are non-corrosive and are produced at low pressure and low temperature conditions. Direct use of vegetable oils or animal fats as fuel can cause numerous engine problems like poor fuel atomization, incomplete combustion and carbon deposition formation, engine fouling and lubrication oil contamination, which is due to higher viscocity. Through this paper we try to make the idea of biodiesel more feasible by running some iterations in the production process of biodiesel from cotton seed oil. The process used for the production is transestrification metchod. The production process involved is base catalyzed and the alcohol used in the production is methanol as it is cheap and provides better and has easy recovery. The catalyst being used in this process is potassium hudroxide (KOH).

EXPERIMENTAL SETUP
The experimental setup is shown in figure 1. A 2000 ml three-necked round-bottomed flask was used as a reactor. The flask was placed in a water bath, whose temperature could be controlled within + 2 oC. One of the two side necks was equipped with a condenser and the other was used as a thermowell. A thermometer was placed in the thermowell containing little glycerol for temperature measurement inside the reactor. A blade stirrer was passed through the central neck, which was connected to a motor alongwith speed regulator for adjusting and controlling the stirrer speed. Esterification: A known amount of Cottonseed oil was taken in the above-mentioned setup. Required amount of sulphuric acid and methanol were added to the oil and stirred continuously maintaining a steady temperature of 640C. Intermittently samples were collected at regular intervals (30min) and acid value was determined. After the confirmation of complete reduction of acid valve to less than 1.0, the heating was stopped and the products were cooled. The unreacted methanol was separated by separating funnel. The remaining product was analyzed for acid value and it was found that the acid value varied from 1.0 to 0.5. This oil sample was for transesterified to obtain methyl esters. Transesterification: In the same setup, known amount of esterified Cottonseed oil was charged. Required amount of catalyst NaOH was desolved in methanol and the rest amount of methanol alongwith the catalyst solution was added to the oil sample. After proper closing of the flask it was put on the water bath.The system was maintained airtight to prevent the loss of alcohol. The reaction mix was maitained at temperature just above the boiling point of the alcohol i.e. around 70C to speed up the reaction rate. Excess alcohol was used to ensure total conversion of the oil to its esters. The formation of methyl ester was monitered by using thin layer chromatography (TLC) technique. Coated silicagel glass plates were spotted with Cottonseed oil and the sample of ester. The spotted samples were developed in solvent system in glass chamber using solvent ratio of 80:20 hexane/ether by volume. This confirms the formation of methyl esters. This procedure was followed for all the samples collected at regular interval of time to check the formation of methyl ester. After the confirmation of completion of methyl ester formation, the heating

was stopped and the products were cooled and transferred to a separating funnel. Where the ester layer containing mainly methyl ester and methanol and glycerol layer containing mainly glycerol and methanol were separated. The pH level of both layers were measured and neutralised seperately. For neutralisation a known amount of sulfuric acid in methanol was added to both the layers seperately to neutralize the sodium methoxide present in them. The traces of methanol present in ester layer was recovered in a distillation column under control vacuum. Distilled methanol was weighed and stored in sample bottle. Similar procedure was adopted to recover the traces of methanol present in glycerol layer. The methyl ester was washed and dried under vacuum to remove traces of moisture. A sample of esters were analyzed for acid value by using standard AOCS procedures for standardization. The sample of glycerol layer was analyzed for glycerol content by using AOCS procedure. The glycerol content was found from 80 to 85 %.

TRANSESTERIFICATION PROCESS
The most common way of producing biodiesel is the transesterification of vegetable oils and animal fats . Oil or fat reacts with alcohol (methanol ). This reaction is called transesterification. The reaction requires heat and a strong catalyst (alkalis, acids, or enzymes) to achieve complete conversion of the vegetable oil into the separated esters and glycerin. The reaction is shown below:

A major problem in carrying out the alcoholysis of oil is to limit the presence of water and free fatty acids (FFA) in the oils. The excess presence of FFA may lead to formation of soap in presence of certain catalyst, hence decreasing the yield, as shown by the following reaction.

CATALYST
Transesterification reaction can be catalyzed byboth homogeneous (alkalies and acids) and heterogeneous catalysts. The used alkali catalysts are NaOH, CH3ONa, and KOH for producing biodiesel13,14. The alkali-catalyzed transesterification of vegetable oils proceeds faster than the acid-catalyzed. But the use of base catalyzed transesterification is only limited to oil having low water and FFA content. This reaction is the most widely used process for production of biodiesel worldwide. To keep check on the water and FFA content of the oil, they are first pretreated with an acid catalysed transesterification process, which converts the FFA to esters.

MATERIALS AND METHODS

1. COTTON SEED OIL

India is fifth largest cotton producing country in the word, the first-four being the U.S, China, Russia, and Brazil. Our country produces about 8-9% of the world cotton . Cottonseed oil has a redbrown color because of the presence of pigments, the most important being gossypol. Gossypol is known to have antioxidant properties that may potentially increase the shelf life of the oil and biodiesel . CSO a rich vegetable oil obtained from the seeds of the cotton plant (Gossypium) by pressing or extraction. The specific component of CSO is the pigment gossypol. The gossypol content determines the color and quality of the oil. The darker the color and the more stable is the biodiesel . Unrefined cottonseed oil is a reddish brown liquid, sometimes almost black in color, with a unique odor and bitter taste.

2. ALCOHOL
In transesterification reaction, an alcohol in the presence of catalyst lyses oil into methyl esters and glycerol. The commonly used alcohols for the transesterification include methanol, ethanol, propanol, butanol, and amyl alcohol. Ethanol and methanol is commonly used for transesterification. Methanol is widely used for producing biodiesel compared to other alcohols, as it is not expensive, Prevent soap formation, its reactivity is high even methanol recovery is comparatively easier.

3. CATALYST
Based on the use of catalyst the transesterification can be divided in to three types, they are acid catalyzed, base catalyzed and enzyme catalyzed method. In the case of base catalyst potassium hydroxide (KOH) or sodium hydroxide (NaOH) are used, because it is less expensive, easy to handle in storage and transport. Transesterification reaction can be catalyzed byboth homogeneous (alkalies and acids) and heterogeneous catalysts. The used alkali catalysts are NaOH,

CH3ONa, and KOH for producing biodiesel. The alkali-catalyzed transesterification of vegetable oils proceeds faster than the acid-catalyzed. But the use of base catalyzed transesterification is only limited to oil having low water and FFA content. This reaction is the most widely used process for production of biodiesel worldwide. To keep check on the water and FFA content of the oil, they are first pretreated with an acid catalysed transesterification process, which converts the FFA to esters.

CALCULATION OF CATALYST AND ALCOHOL

Amount of catalyst and alcohol to be added depends on the FFA value. Methanol: For 1 liter of vegetable oil 200 ml of methanol is added. NaOH is added based on FFA as given in below table 1.

To calculate FFA% from a titration value the formula is: FFA%=28.20.1N NaOHBurette readingW Where, Burette Reading: Volume in ml of titration solution. N is the normality of the titration solution (0.1 gram/liter). W is the weight of the sample of oil in grams (10 grams). 28.2 is the molecular weight of oleic acid divided by ten. Table 1: Calculation of NaOH based on FFA

FFA 0 1 2 3 4

AMOUNT OF NAOH IN GMS.

PREPARATION 1. WASHING OF PRODUCTS

After transesterification the upper ester layer may contain traces of NaOH, methanol and glycerol. Since the remaining unreacted methanol in the biodiesel has safety risks and can corrode engine components, the residual catalyst (NaOH) can damage engine components, and glycerol in the biodiesel can reduce fuel lubricity and cause injector coking and other deposits. [2].These being water soluble is removed by washing (4-6 times) the biodiesel with water maintained at 40-50C as shown in fig 2. Washing is carried out by spraying hot water over the biodiesel; precautions were taken to avoid soap formation.

2. HEATING PRODUCTS
After the completion of washing process the biodiesel may contain some traces of water. Biodiesel is heated to 1100C to remove the trapped traces of water.

3. YIELD OF BIODIESEL BY TRANSESTERIFICATION

The main objective is biodiesel production from vegetable oil. In the present study the vegetable oil was successfully converted into biodiesel by transesterification process using base catalyst. We could obtain around 70% biodiesel yield from both cotton seeds and mahua seeds and 80% from neem seeds respectively by base catalyzed method. The biodiesel yield for different batches was presented in table 2, table 3 and table 4. The main factors affecting the transesterification are FFA, reaction time, temperature, amount of alcohol and catalyst, catalyst concentration, and rate of mixing. It was observed, FFA increases if the precaution is not taken to store the vegetable oil. Since higher amount of FFA can directly react with the base catalyst to form soaps, and prevents separation of the biodiesel from the glycerol and decrease the yield, it is better to select reactant oils with low FFA content, or reduce FFA by some means. Experiment was conducted at the FFA range of 3 to 4.6 for cotton, 1.5 to 3 for mahua and 2 to 3.5 for neem seeds. It was found during experiment that separating glycerol from cotton seed biodiesel was bit difficult because both are dark in color.

Table 2. Yield of Biodiesel by transesterification (CSOME)

BATCH FFA CSO(ml.) Glycerol(ml.) Biodiesel Biodiesel Biodiesel from after after washing(ml.) washing(ml.) heating (ml.) I II III IV V VI VII VIII

Conclusion

I am thankful to the Mr. rakesh mahavar to provide me to provide me chance for producing own bio diesel and enhance my knowledge in I.C. engine field. As fossil fuels are limited, and biodiesel will play very important role in future industry, understanding this fact I decided to work on biodiesel so that after getting sufficient base from college level I can continue my research in this field. Thanking you Sonu Parekh Shashank Pathak Ram Naresh Suthar Pooran Mal Yadav

References: Braz. J. Chem. Eng. vol.27 no.4 So Paulo Oct./Dec. 2010 Journal of the Brazilian Chemical Society Transesterification of Vegetable Oils: a Review Ulf Schuchardta, Ricardo Serchelia, and Rogrio Matheus Vargas*b Instituto de Qumica, Universidade Estadual de Campinas, C.P. 6154, 13083-970 Campinas - SP, Brazil Instituto de Qumica, Universidade Federal da Bahia, Campus de Ondina, May 9, 199 K.V.Radha, G.Manikandan, Novel Production of Biofuels from Soybean Oil. Received: