Presentation of preparation and optimization of butl ester production

DSSMSG

1. Department Of Mechanical Engineering University Institute of Engineering & Technology Kurukshetra University Kurukshetra A Dissertation Presentation On Preparation & Process Optimization of Butyl Ester (Biodiesel) From Waste Cooking Oil Using Taguchi Statistical Approach Presented By Vishal Kashyap Insan Roll No. 2513674 Under the Supervision of Mr. Upender Dhull Assistant Professor U.I.E.T, Kurukshetra University Kurukshetra

2. What Is Biodiesel ? Biodiesel is an Eco-friendly, Domestically produced Alternative diesel fuel derived from renewable feedstock such as vegetable oils and animal fats by the use of chemical process called Transesterification . “A mixture of long-chain mono alkyl esters of fatty acids obtained from renewable resources, to be used in diesel engines . ” Definition of Biodiesel - American Society For Testing and Materials The name “ Biodiesel” was introduced in the United States during 1992 by the National Soy Diesel Development Board (presently National Biodiesel Board ) which has pioneered the commercialization of Biodiesel in the United States . Biodiesel can be used in diesel engines, alone or blended with diesel oil & has been reported as possible substitute for conventional diesel fuel.

3. History Of Biodiesel Dr. Rudolph Diesel (Inventor of Diesel Engine) first time tested peanut oil in his prime model of diesel engine on August 10, 1893 in Augsburg , Germany. In memorial of this event, August 10 has been declared “International Biodiesel Day.” In his speech in 1912, Rudolf Diesel said that "the use of vegetable oils for engine fuels may seem insignificant today but such oils may become, in the course of time, as important as petroleum and the coal-tar products of the present time.”

4. How Is Biodiesel labeled? Biodiesel is designated by the letter B and a number representing the percent of the fuel that is biodiesel. B100 Indicates pure biodiesel. Blends with diesel fuel are indicated as ‘‘ Bx ’’, where ‘‘x’’ is the percentage of biodiesel in the blend. For instance, “B20” indicates a blend with 20% biodiesel and 80% diesel fuel which is preferred by various vehicular use. In India , B5 is mostly used for railway, aircraft , agriculture usage.

5. Why Biodiesel Use As Alternative Fuel? Biodiesel is a clean burning renewable fuel. Blended with petroleum diesel fuel in any proportion. Require no modifications to a diesel engine to be used. Reduced exhaust emissions up to 95%. Biodiesel has lower toxicity. Biodiesel is easier to use and safer to handle. Biodiesel is biodegradable i.e. Eco-friendly . Reduced the dependence on petroleum imports & create the employment potential. Higher cetane rating which improves engine efficiency & operating life cycle.

6. The four well-established methods for biodiesel production are: Pyrolysis Micro emulsification Dilution Transesterification Out of All above mentioned methods “Transesterification method” is most popular and usually preferred. Methods of Biodiesel Production

7. The conversion of vegetable oil or fat into its corresponding ester and glycerol by reacting oil with appropriate alcohol in the presence of a suitable catalyst is called transesterification. The general transesterification reaction involves triglycerides converted to mono alkyl esters. Transesterification Process Reaction Figure: The General Transesterification Reaction. R1, R2, R3 is a mixture of various fatty acid chains. The alcohol used for producing biodiesel is usually methanol (R′ = CH 3 ) ethanol (R′ = C 2 H 5 ), butanol (R′ = C 4 H 9 ).

8. Process Variables in Transesterification Process Type of Raw Material (oil). Oil Temperature Reaction Temperature Type of alcohol Molar Ratio of Alcohol to Oil Type & Concentration of Catalysts Stirring Speed Purity of Reactants. Reaction Time

9. Institute Working On Biodiesel In India National Oil seeds and Vegetable Oil Board, Gurgaon PCRA - Petroleum Conservation Research Association (MOP&NG) IOC (R&D) Centre, Faridabad Delhi College of Engineering New Delhi Indian Institute of Technology, Delhi Indian Institute of Petroleum, Dehradun (Uttaranchal) Alternate Hydro Energy Centre, Indian Institute of Technology, Roorkee Indian Institute of Chemical Technology, Hyderabad Council of Scientific & Industrial Research (CSIR), India Ministry of New and Renewable Energy Central Pollution Control Board Bureau of Indian Standards Indian Renewable Energy Development Agency Harcourt Butler Technological Institute, Kanpur Eastern Biodiesel Technologies Pvt. Ltd, Kolkata Sardar Swaran Singh National Institute Of Renewable Energy, Kapurthala

10. Literature Review

11. Literature Review

12. After a brief study of the existing literature review a number of gaps have been pointed out : Most of work have been done for the production of biodiesel with the utilization of methanol, ethanol as alcohol, but least work has been reported on the utilization of butanol as alcohol. No rarer work has been done with the alkali metals as catalyst such as metal sodium etc. Limited research work associated with in the field of optimization of process of biodiesel production with butanol has been reported. Gap In Literature

13. The various objectives of present research work were: To evaluate the feasibility of production of biodiesel from waste cooking rice bran oil using butanol as alcohol and metal sodium as catalyst. To evaluate the important properties of optimized biodiesel extracted from waste cooking rice bran oil and compare it with the ASTM 6751 standards for biodiesel. To identify the optimum conditions of effective process parameters which optimize the yield of biodiesel extracted from waste cooking rice bran oil using Taguchi statistical approach. To analyze the process parameter which most significantly effect the production of biodiesel from waste cooking rice bran oil using ANOVA analysis. Objective Of Present Work

14. Classification of biofuels

15. Experimental Work The preparation of the biodiesel and the other laboratory tests were conducted in the Bio-Chemistry lab of University Institute of Engineering & Technology, Kurukshetra University, Kurukshetra. Ingredients Used For Production of Biodiesel Waste cooking rice bran oil Butanol (n-butyl alcohol) as alcohol Metal Sodium as base catalyst Sulphuric acid as acid catalyst Magnetic stirrer with hot plate Separating funnels used for settling and separating purpose Thermometer for temperature readings 2-3 Beakers each of 100ml, 500ml and 100ml capacity. 50 ml graduated cylinder

16. Instruments & Raw Material Used For Biodiesel Production Metal Sodium Metal Sodium Dissolved In Butanol as Alcohol Magnetic Stir with Hot Plate Waste Cooking Rice Bran Oil Ostwald Viscometer with Water Bath Assembly in Chemistry Department Weighing Balance Used For Measurement Pyknometer Pensky–Martens Closed-Cup Flash-Point Apparatus

17. Characterization of Waste Cooking Rice B ran Oil Waste cooking rice bran oil was characterized by using the below listed properties in accordance with the use of various standard methods. Waste Cooking Rice Bran Oil Physical Properties of Waste Cooking Rice Bran Oil

18. Titration Crude glycerol Pure Biodiesel Purification using Warm water Crude Biodiesel Phase Separation Transesterification using base catalyst Butanol Metal Sodium Esterification using acid catalyst Free Fatty Acid >2.5% Free Fatty Acid < 2.5% Waste cooking Rice bran Oil Pretreatment oil Process Flow Chart of Production of Butyl Ester (Biodiesel) From Waste Cooking Rice Bran Oil

19. Prepared Butyl Ester (Biodiesel) Samples

20. The spectrum was characterized with asymmetric and symmetric strong stretching vibrations of Carboxyl group at 3300-2500 cm-1, along with the O-H stretching of the hydroxyl bonded with alcohol at 3500-3200 cm-1 (broad) with Alcohols, Phenols groups. Ester group strongly stretched found at 1736.0 cm-1 (1750-1735 cm-1). C-O group combined with carboxylic group Ester group strongly stretched at 1173.0 cm-1 (1320-1000 cm-1). Finally, Alkanes (C-H) groups strongly stretched at 1466-1373 cm-1. The composition of Ester so prepared was determined by using highly reliable FTIR (Fourier transform infrared spectroscopy) test. The Ester peaks obtained by the result were found to be well satisfactory. Biodiesel Confirmation Analysis By FTIR Analyzer The FTIR (Fourier transform infrared spectroscopy) Test Result of one of sample of Butyl Ester (Biodiesel )

21. Selection Of Process Parameters & Their Levels The three most effective parameters selected f or conducting the experiments were the molar ratio, concentration of catalyst and reaction temperature with their levels are as given below: Figure : Selected Effective Process Parameters and their levels

22. Taguchi Method : An Statistical Approach Taguchi method was formulated by Dr. Genichi Taguchi of Japan in 1980 . The Taguchi method is a standardized statistical approach for determining the best combination of inputs parameters to produce a high quality product or service. This method is mostly used in different fields of engineering for optimizing the process parameters . Taguchi method is useful for 'tuning' a given process for 'best' results.

23. L9 Taguchi orthogonal array design is used for optimization work. This is a combination of nine experiments of three effective input parameters with their three levels. L9 Taguchi Orthogonal Array Figure :Generated L9 Taguchi Orthogonal Array for DOE with three effective parameters at three levels

24. Figure : Yield of the butyl ester (biodiesel) & signal to noise ratio for the under nine sets of experimentations Experimental Yield of Butyl Ester Produced The yield of the biodiesel produced can be calculated by using following :

25. SNRs are the log functions of the expected outcome which would be serving as objective of optimization problem, helps in the data analysis & prediction of optimum results . Larger the better signal to ratio analysis was used for the present research work. According to the analysis for the case of the larger the better the mean squared deviations of each of experiment were calculated using the following : Where n is the number of repetitions of each experiment and η i the yield of Butyl ester produced. Then the Signal to Noise ratio was calculated using the equation. S/N ratio = -10 log 10 (MSD) Signal To Noise Ratio (SNR) Analysis

26. The optimum level of each parameter for the maximum yield of butyl ester produced were A (Molar ratio of methanol to oil) at level 2 (5.5:1), B (concentration of catalyst) at level 3 (.21%), and C (temperature of reaction) at level 2 (85 C).

27. Analysis of variance (ANOVA) is a statistical analysis which is capable of identifying which effective parameter has influenced the output significantly and how much each effective parameter contributes to the output. Analysis Of Variance (ANOVA)

28. Prediction Of Maximum Yield Of Butyl Ester Using Minitab Statistical Software And Its Validation By using the Minitab 17 statistical software, The predicted maximum yield of Butyl ester under the optimum conditions was received to be 86.4578%. The experimental value of yield of Butyl ester under the optimum conditions was obtained to be 86.1086%. this closely matches with that of predicted value. The important fuel properties of optimized Butyl ester (biodiesel) were also determined as per the standard methods. These were in the acceptable ranges according to the American Society for Testing and Materials ASTM 6751 biodiesel standards too. Therefore, the result obtained from the research work is considered to be reliable and satisfactory.

29. Butyl Ester (Biodiesel) produced from the waste cooking oil under the Optimum Conditions Obtained . Physical Properties of Optimized Sample of Butyl Ester

30. On the basis of results of the Experimental work, the following conclusions were evoked : A two stage transesterification process was required for the feasible production of butyl ester from waste cooking rice bran oil having higher free fatty acid. The experimentally analyzed optimum levels for the production of Butyl ester from waste cooking rice bran oil were: 5.5:1 molar ratio of butanol to oil, .21wt% concentration of catalyst, 85 o C reaction temperature of reaction. From the ANOVA table for signal to ratios, It was observed that concentration of catalyst was the most significant parameter for production of butyl ester from waste cooking rice bran oil with contribution 88.31% subsequently followed by molar ratio of alcohol to oil with contribution 5.83% and the reaction temperature has the least influencing parameter with contribution 3.00% on the yield of Butyl ester. Conclusions

31. Further research work can be done on the following fields : Efforts for making the appropriate use of the waste or used cooking oil from processing units for the production of biodiesel using man made artificial heterogeneous catalyst can be undertaken by future researchers. Waste products from industries and thermal power plants like ‘fly ash’ had been found a good alternate as heterogeneous catalyst in ethanol based biodiesel production. It can also be used in future research for preparing butanol based biodiesel production Further studies can be carried out for making proper use of the by-products from prepared biodiesel. Further experimental investigation such as optimization with different techniques other than taguchi for the production of esters from different alcohols with the use of different catalysts can also be carried out. Optimization work covers with performing the engine test runs from biodiesel blends of various proportions should be carried out. Performance & emission testing of butanol based biodiesel can be done on IC engines to find out the performance and emission characteristics of butanol based biodiesel characteristics. Scope For Future Work

32. Specification for Pure Biodiesel (B100) as per the ASTM D6751 Biodiesel Standards by American Society for Testing and Materials

33. [1] Ma F, Hanna M.A, 1999, “Biodiesel production: a review.” Bioresource Technology, Vol.70 No.1, pp.1–15. [2 ] Gerhard Knothe, Jon Van Gerpen, Jürgen Krahl, 2005, “ The Biodiesel Handbook ” AOCS Press Champaign, Illinois, Chap. 1 [ 3] P. K. Gupta, R. Kumar, B. S. Panesar , and V. K.Thapar , 2007“Parametric Studies on Bio-diesel prepared from Rice Bran Oil. ” Agricultural Engineering International: the CIGR Ejournal . Manuscript EE06 007, Vol. IX, April 2007. [4] S. P. Singh, D. Singh, 2009, “ Biodiesel production through the use of different sources and characterization of oils and their esters as substitute of diesel: A review ” Renewable and Sustainable Energy Reviews, 14, pp. 200-216. [ 5] Charoenchaitrakool M, Thienmethangkoon. J, 2011, “ Statistical optimization for biodiesel production from waste frying oil through two-step catalyzed process. ” Fuel processing Technology. Vol. 92. pp.112–118. [6] Dingra S., Kashyap K. D., & Bhushan G., 2013 “ Enhancement in Jatropha-based biodiesel yield by process optimization using design of experiment approach ” International Journal of Sustainable Energy , vol. 33 No. 4, pp. 842-853. [7] Kumar R. S, Kumar K. S, Velraj R, 2014, “ Optimization of biodiesel production from Manilkara zapota (L.) seed oil using Taguchi method .” Fuel 140,pp. 90-96. References

34. List Of Publications Serial Number Title 1 T. Gupta, V. Kashyap , U. Dhull , N. Gehlot , “ Comprehensive Study on Biodiesel Production: A Review ,” Proc. 2th National Conference On Converging Technologies Beyond-2020 (2CTB-2020) , Kurukshetra University, Kurukshetra, November 28-29, 2014. pp. 339-348.

35. Thank You