Dear Sumit,

The attached publications cover the answer to your question.

1-Transesterification, Modeling and Simulation of Batch Kinetics of Non- Edible Vegetable Oils for Biodiesel Production

Pankaj Tiwari, Rajeev Kumar and Sanjeev Garg

Department of Chemical Engineering, IIT Kanpur, 208 016, India

Abstract

Biodiesel derived from renewable plant sources is monoalkyl esters of long chain fatty acids which fall in the carbon range C12-C22. It has similar properties as mineral diesel. Various processes exist to convert vegetable oils (mainly triglycerides) into biodiesel. Transesterification of vegetable oils using alcohol in a catalytic environment is most commonly used method for producing biodiesel. The equilibrium conversions of Triglycerides (TG) is affected by various factors, namely, type of alcohol used, molar ratio of alcohol to TG, type of catalyst, amount of catalyst, reaction temperature, reaction time and feedstock quality (like free fatty acid content, water content etc.). The present work reports the characterization of non-edible feedstock oils of Indian origin, production, separation, characterization of biodiesel and byproduct. This study also reports the optimal operating parameters for different oils in batch reactor. The main thrust of the present work was to study the kinetics, modeling and simulation of alkali-catalyzed

transesterification of Linseed and Jatropha curcas oils. Experiments were carried out in a 2.0 l batch reactor to generate kinetic data and a reversible kinetic model was developed. The effects of temperature, catalyst concentrations, and molar ratios of methanol to TGs and stirring rates were investigated. A few fuel properties were also measured for biodiesel to observe its competitiveness with conventional diesel fuel. The equilibrium conversions of TG were observed to be in the range of 88-96 %. (Linseed) and 50-83% (Jatropha). The equilibrium conversions were achieved in less than 45 minutes for both oils. It was also observed that increasing the temperature and molar ratio increased the equilibrium conversions; while increase in catalyst concentration had no significant effect on reaction time. Characterization of the feedstock oils and biodiesel produced were carried

out. It was observed that the biodiesel produced had similar properties to mineral diesel. Model parameters (order and rate constants) for the reversible model were calculated. Gear’s technique was used to solve the initial value problem and genetic algorithm was used with the mathematical model to minimize the error between experimental and model predicted conversions. Activation energies for forward and backward reactions were estimated. Model fitness values were observed to be more than 0.9. Various simulations were also carried out at

different conditions and showed that beyond a critical molar ratio there is no significant effect on transesterification kinetics.

2-Biodiesel production by using heterogeneous catalyst

MSc. thesis

Samir Najem Aldeen Khurshid

Division of Chemical Technology

Department of Chemical Engineering and Technology

Royal Institute of Technology (KTH)

Stockholm, Sweden

March 2014

ABSTRACT

Industrial development is associated with an increasing in pollution levels and rising fuel prices. Research on clean energy contributes in decreasing global warming impacts (significant environmental benefits), reducing emissions gases. The developing of renewable energies increases the energy independence and

impacts on agriculture in a positive way. Transesterification reaction of triglycerides to produce fatty acid methyl ester (FAME) was investigated by using virgin rapeseed oil and doped lithium calcium oxide Li-CaO as a heterogeneous solid basic catalyst. The influence of different parameters conditions such as the catalyst weight % base oil weight, mass ratio of methanol to oil, operation time, reaction temperature and mixing intensity on the yield and properties of the produced biodiesel were studied The used catalyst and the produced biodiesel were characterized by using techniques of gas chromatography (GC), X-ray diffraction (XRD), BET surface area measurement (BET) and viscometer. The results indicate the influence of the various reaction conditions such as molar ratio of methanol to oil, mass ratio of catalyst to oil and reaction temperature on the on the yield and properties of the obtained biodiesel yield. Increasing the temperature under a range lower than methanol boiling point will increase the yield. An increase of the amount of catalyst from 2.5 wt% to 5 wt% does not increase the amount produced

biodiesel. The yield of produced biodiesel increases with the alcohol to oil ratio.

An amount of 2.5 wt% catalyst is enough catalyst in order to achieve high yield of biodiesel. At alcohol to oil ratio 6:1 the yield of produced biodiesel increases when the reaction time increases from 1 to 2 hours. At higher alcohol to ratio (9:1 and 12:1), an increase of reaction time from 1 to 2 hours does not increase

the yield of produced biodiesel. At 60 °C, the yield of obtained biodiesel increase when the mixing rate increases from 160 to 320 rpm. 97 % yield of biodiesel has been obtained using Li-CaO catalyst using 12:1 molar ratio of methanol to oil , 60°C, 160 rpm mixing rate, catalyst loading 2,5% (base oil weight) and one hour reaction time.

3- Kinetics of the pre-treatment of used cooking oil using Novozyme 435 for biodiesel production

Kathleen F. Haigh, Goran T. Vladisavljević, James C. Reynolds, Zoltan Nagy, Basudeb Sahacorrespondenceemail

Open Access

DOI: http://dx.doi.org/10.1016/j.cherd.2014.01.006

Highlights

•An ultra performance liquid chromatography–mass spectrometry method has been developed.

•It was possible to separate and monitor the 1,2 and 1,3 diglyceride isomers.

•Mono- and diglycerides are more readily converted than triglycerides.

•A kinetic model to track the key components has been developed.

Abstract

The pre-treatment of used cooking oil (UCO) for the preparation of biodiesel has been investigated using Novozyme 435, Candida antarctica Lipase B immobilised on acrylic resin, as the catalyst. The reactions in UCO were carried out using a jacketed batch reactor with a reflux condenser. The liquid chromatography–mass spectrometry (LC–MS) method was developed to monitor the mono-, di- and triglyceride concentrations and it was found that the method was sensitive enough to separate isomers, including diglyceride isomers. It was found that the 1,3 diglyceride isomer reacted more readily than the 1,2 isomer indicating stereoselectivity of the catalyst. This work showed that Novozyme 435 will catalyse the esterification of free fatty acids (FFAs) and the transesterification of mono- and diglycerides typically found in UCO when Novozyme 435 is used to catalyse the pre-treatment of UCO for the formation of biodiesel. A kinetic model was used to investigate the mechanism and indicated that the reaction progressed with the sequential hydrolysis esterification reactions in parallel with transesterification.

4-CHEMSUSCHEM

DOI: 10.1002/cssc.200800253

Catalytic Applications in the Production of Biodiesel from

Vegetable Oils

Arumugam Sivasamy,[a, b] Kien Yoo Cheah,[c] Pao

The predicted shortage of fossil fuels and related environmental concerns have recently attracted significant attention to scientific and technological issues concerning the conversion of biomass into fuels. First-generation biodiesel, obtained from vegetable oils and animal fats by transesterification, relies on

commercial technology and rich scientific background, though continuous progress in this field offers opportunities for improvement. This Review focuses on new catalytic systems for the transesterification of oils to the corresponding ethyl/

methyl esters of fatty acids. It also addresses some innovative/emerging technologies for the production of biodiesel, such as the catalytic hydrocracking of vegetable oils to hydrocarbons. The special role of the catalyst as a key to efficient technology is outlined, together with the other important factors that affect the yield and quality of the product, including feedstock-related properties and various system conditions

Hoping this will be helpful,

Rafik

Thank you very much sir for your elaborate and informative suggestion. 

Hello Sumit

As a reference you can see my article "Determination of methanolysis rate constants for low and high fatty acid oils using heterogeneous surface reaction kinetic models "https://www.researchgate.net/publication/267569574_Determination_of_methanolysis_rate_constants_for_low_and_high_fatty_acid_oils_using_heterogeneous_surface_reaction_kinetic_models

Article Determination of methanolysis rate constants for low and hig...

It does not depend on type of oil such as edible or non edible. If oil have high FFA value, you have to search both transesterificaiton and esterification kinetics since they occur similtaneously.