Bio-diesel Production using Heterogeneous Catalyst

A K GUPTA INDIAN INSTITUTE OF PETROLEUM DEHRADUN, INDIA

XIII Refinery Technology Meet (RTM)

November 14-16, 2005, Hyderabad

Commercial Biodiesel Technologies

Currently used technologies for producing biodiesel can be classified into three categories: 1) Base catalyzed transesterification with refined oils 2) Base catalyzed transesterification with low fatty acid greases and fats 3) Acid esterification followed by transesterification of lower or high free fatty acid fats and oils.

Other processes under development include biocatalyzed transesterification, pyrolysis of vegetable oil/ seeds and transesterification in supercritical methanol.

The goal of all technologies is to produce fuel grade esters meeting standard specifications (e.g. ASTM/ European/BIS).

The key quality control issues involve :

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complete (or nearly complete) removal of alcohol, catalyst, water, soaps, glycerine and unreacted or partially reacted triglycerides and free fatty acids (FFA).

Failure to remove these contaminants causes the biodiesel to fail one or more fuel standards.

Problems of Biodiesel Production

Both base and acid catalyzed processes are associated with several inherent problems:

Free fatty acids interfere with transesterification deactivate the base catalysts loss of catalyst and biodiesel yield. Water deactivates both basic and acidic catalysts. Drying of oil may be required. Soaps formed with base catalyst, form emulsion and foam and difficult to remove. When processing feed stocks with high free fatty acids additional steps must be taken. After basic transesterification, the purification and adequate testing during processing is required to produce fuel grade esters.

Appropriate Technology
The selection of appropriate technology for production of bio-diesel requires careful selection of processing steps, catalyst and downstream process integration. The quality of feed vegetable oil particularly FFA content plays and important role in identifying the suitable technology.

The important factors to be considered include:

Must be able to process variety of vegetable oils without or minimum modifications. Must be able to process high free fatty containing oils/ feed stocks. Must be able to process raw both expelled and refined oil. Process should be environment friendly almost zero effluents. Able to produce marketable by products glycerin, fatty acids, soap if any. Must be able to produce fuel grade esters; Biodiesel produced should meet the standard specifications. The process should be adaptable over a large range of production capacities.

Feedstocks in Indian Context

For India non-edible oils obtained from plants which can be grown on waste/ semi arid lands are more suitable. Species can be selected based on the regional climatic conditions Most of the non-edible oils available in India contains high FFA (2-12%)

IIP Heterogeneous Process for Bio-diesel Production

Reference Patents: US 2007282118 EP 1711588

Fresh Vegetable Oil Fresh Methanol Recycle Methanol

Esterification & Transesterfication Methanol Recovery

Phase Separation Glycerine Phase

Glycerine Refining

Biodiesel Purification

BIODIESEL

Glycerine IIP Heterogeneous Process for Biodiesel

The reaction is performed at higher temperature and pressure than in homogenous catalyzed processes. Excess alcohol is recovered by flash vaporization. Glycerin is separated in a settler and biodiesel is purified by distillation.

Chemistry
In the production of biodiesel (methyl or ethyl ester of fatty acids), the triglycerides of vegetable oils react with alcohol to form ester and glycerin. Fatty acids react with alcohol to form esters and water. The over all reactions are as follows: 1. Transesterification
O R R R C O C O C O O O CH 2 CH CH 2 + + + CH 3 OH CH 3 OH CH 3 OH Methanol Catalyst, Energy R R R O C O C O C O O O CH 3 CH 3 CH 3 OH + OH OH CH2 CH CH2

Triglyceride

Methyester

Glycerin

2. Esterification
R-C-O-H Fatty acid + CH OH 3 Methanol Catalyst

R - C - O - CH + H2O 3 Methyl ester

Both reactions are equilibrium controlled reactions.

Feedstocks
Vegetable oils/ feedstocks having wide range of FFA or 100% FFA. Methanol purity is normally at least 99.85 wt% However lower purity methanol can be processed.

Catalyst
The IIP process uses a unique heterogeneous catalyst which catalyses transesterification and esterification simultaneously Provides improved selectivity and unit flexibility and suppresses corrosion and by product formation. No pretreatment of vegetable oil is necessary to remove FFA. The catalyst also convert FFA into biodiesel. Catalyst is not deactivated either by water or FFA.

Product & byproduct yields

Conversion of triglycerides and FFA is greater than 99%. Yields of ester of over 98% based on Triglycerides and FFA present in the oil are obtained. Unconverted MeOH is recycled. Glycerin purity is 99%.

Main Features of IIP Process

Flexibility for processing variety of vegetable oils separately or mixed.

Tolerance of higher levels of free fatty acids. Requires no pretreatment or removal of FFA.
Conversion of free fatty acids present in feed oils to biodiesel. Tolerance of water in alcohol and oil The process can produce both methyl and ethyl esters
Continued...

IIP Process

No emulsion or soap formation Biodiesel produced meets the standard specification (ASTM, European or proposed BIS). Glycerine produced is ~ 99% pure.

Process can be adapted to wide range of production capacities.

The process is ecofriendly with almost zero effluents.

Comparison of Biodiesel (IIP Processes) With National & International Specifications

Characteristics ASTM D6751 BIS (India) Draft EU Jatropha Curcas Oil Karanja Oil Mahua Oil

Density, 15C Viscosity @ 40C Flash Point, C Sulfated Ash content max., % max

1.9-6.0 130 0.05

0.86-0.90 2.5-6.0 120 0.02

0.86-0.90 3.5-5.0 >100 0.01

0.8887 4.55 135 0.008

0.8944 5.07 174 0.002

0.8808 5.13 120 0.002

Sulphur max. % mass

Cu corrosion 3 hr/50C, max Neutral No. mgKOH/g Carbon residue % max Cetane Number

0.05
No. 4 0.8 0.5 --

0.05
1 0.5 0.05
51

0.01
1 --

<1 ppm
1 0.5 0.13 56.6

4.5 ppm
1 0.6 0.45 --

4.3 ppm
1 0.58 0.14 --

Technological and economic benefits

Use of heterogeneous catalyst has direct impact on the economics of biodiesel production. Several neutralisation and washing steps needed for processes using homogeneous catalysts such as NaOH, KOH, MeONa etc. are eliminated. Associated waste streams are eliminated.

Economics of Biodiesel production: Effect of Technology improvements Process Relative Operating cost 0.93 0.60 0.71 1.0 Remarks

IIP Process I IIP Process II IIP Process III Conventional Process

-Base catalyst, withPretreatment step -Heterogeneous catalyst -Base catalyst, solvent added to make single phase -Base catalyst

Present Status

Developed and tested solid catalyst for Biodiesel production batch. Testing of catalyst in continuous fixed-bed pilot reactor is being carried out to collect scale up data.

The pilot plant is operating for last 4 months on the same catalyst charge. No deterioration of conversion or yield has been observed.