Biodiesel Feed Stock, Production Technology

BIODIESEL CONCEPT
Diesel (Petroleum derived) Oil When Substituted Partly or Wholly by a Liquid Fuel Derived from Renewable Resource Materials

Rudolf Diesel First Demonstrated in 1900 that Renewable Resource Material like Groundnut (Peanut) oil as a Fuel in Diesel Engine in Place of Petroleum Diesel Without any Problem.

Biodiesel
The present Concept
Conversion of Oils/Fats to Alkyl Esters of Monohydric Alcohols to overcome Problems of High Viscosity, High Boiling Point and Reactivity make
Biodiesel is Now Defined Exclusively as the Monoalkyl Esters of the Long Chain Fatty Acids Derived from the Oils/Fats of Vegetable and Animal Origins that Fulfill almost all the Requirements of Petroleum-Derived Diesels.

BIODIESEL FEEDSTOCK
(A) Oils & Fats of Plant And Animal Origins (B) Refinery byproducts like (1) Fatty Acid Distillates (FADs) (Palm FADs). (2)Acid Oils (Soyabean, Rice bran, Coconut, Mustard). (C) Used Oils Like Frying Oils.

CPO MILLING

TRADITIONAL COCONUT OIL PRODUCTION

TRADITIONAL COCONUT OIL PRODUCTION

separations

Triglyceride

LABORATORY SCALE PRODUCTION

ESTERIFICATION
The reaction fatty acid with an produces ester and water. The Alcohol of+ Acid the alcoholbecause they have low solubility Ester + Water esters can be separated from water in it . Esters can be produced under conditions of low or high temperature and the crude product is distilled, bleached and deodorised as appropriate before a pure ester is produced.

CATALYST Chemical catalyst process Biocatalyst process

Chemical Catalyst Process

One Step Process with a Base Catalyst like Sodium Hydroxide or Potassium Hydroxide or their Alkoxides when the Oils/Fats are Refined (RBD). Two-Step Process on oils Containing FREE FATTY ACIDS
(I) Esterification with Conc. H2SO4, H3PO4 (ii) Transesterification with a base catalyst NaOH, KOH or High Pressure Esterification and Alcoholysis for straight way conversion to Biodiesel.

One-Step Biocatalyst Process for Biodiesel Production

Simultaneous Esterification And Transesterification (Alcoholysis) of Triglyceride Oils. Esterification Lipase R.COOH + MeOH R.COOMe + H2O

TRANSESTERIFICATION
CH2OCOR CH2OH CHOCOR + 3MeOH CH2OCOR CH2OH 3 R.COOMe + CHOH

Lipase

Lipase
Candida Cylindraceae, Candida Rugosa, Candida Antartica & Lipase 3A (1,3-specific lipase)

Chemical Process For Biodiesel Production

A. Single Stage or Direct Transesterification (Alcoholysis) Process.

Refined or Neutral Oil (< 1.5% F.F.A.) + Alcohol (Methanol) 1.6-2 Times

Theoretical Amount Base Catalyst 500C-700C KOH OR NaOH 4-6 Hr. 0.3-1.5% or NaOMe 0.5% or Less ALKYL ESTER PRODUCT Necessary Post-Treatment BIODIESEL (95% yield of 97% purity)

B. TWO-STAGE (COMBINED ESTERIFICATION AND TRANSESTERIFICATION) PROCESS. 1st STAGE ESTERIFICATION PROCESS Acid Catalyst + Alcohol (1.6-2 Times (Conc. H2SO4 the Th. Amount) 0.1-1% on F.F.A 1000-1200C/10-12 hrs. Basis Or 600C/4-5 hrs.Or 350C/2 hrs.1-2 hrs.

Phase

Ester Phase

Glycerol

2nd STAGE TRANSESTERIFICATION PROCESS ESTER PHASE Base Reflux Or at 600C Catalyst For 0.5-6hrs.

Alkyl Ester Phase Purification

Glycerol Phase Acidified

Final Ester Biodiesel Glycerol Phase Acidic Esters Purification

AUTOCATALYTIC ESTERIFICATION PROCESS

Acidic Oils (>5% FFA) Or Acid Oils (>50% FFA) Esterifying Agent 1800C-2200C Like Glycerol 2-6 Torr, (Theoretical Or 6-12 hrs 20-60% Excess Over theoretical Neutral Oil Transesterification Process
Methyl Ester Purification Biodiesel Glycerol (Recycled in the Esterification)

TRANSESTERIFICATION WITH SUPERCRITICAL METHANOL FOR BIODIESEL PRODUCTION Oil + Methanol (1:42 ) 300-5000C 300 Atmospheres Times 3-4 minutes Methyl Esters (98% Conversion)

Biodiesel By Blending of Vegetable Oil With Short Chain Alcohol and an Amphiphilic Compound Vegetable Oil 1-ALKANOL Methanol Or Ethanol

Stable Solution (Liquid) (With Viscosity Sufficiently low for use as Diesel Fuel)

BIODIESEL STANDARDS

Linolenic Acid Methanol Content Monoglycerides Diglycerides Triglycerides Free Glycerol Total Glycerol Alkali Metals Alkali Earth Metals Phosphorus Content

< 12% < 0.02% > 1.0 > 0.25 > 0.25 < 0.02 < 0.38 < 5 ppm < 5 ppm < 10 ppm

FEEDSTOCK
MINYAK NABATI KW 1 (FFA <5%) MINYAKNABATI KW 2 (FFA > 5%, <20%) MINYAK NABATI KW 3 (FFA>20, <70%) PFAD (FFA >70%)

PROSES KIMIA

Esterifikasi
Transesterifikasi

Teknologi proses

FEEDSTOCK

METHANOL

Process conditions
High temperature Medium temperature Low temperature + Catalyst Low temperature + Enzyme
150 oC > 100 130 oC 50 80 oC + Catalyst 30 50 oC + Enzyme

BIODIESEL

GLYCEROL / WATER

Examples (Batch Reaction)

Oil Crude Palm Oil Crude Palm Stearin Rapeseed Sunflower Coconut Palm Kernel Soya bean Corn Tallow

FFA(%) 4.5 3.8 3.2 3.5 1.5 3.2 1.3 9.6 3.9

Yield of Methyl Ester(%) 96 98 95 94 98 98 95 96 93

FUEL CHARACTERISTICS OF METHYL ESTERS OF VARIOUS VEGETABLE OILS CHARACTERISTICS TESTED

METHYL ESTER PALM OIL COCONUT DENSITY

150C
0.872-0.877 0.872

VISCOSITY 400C 4.3-4.5 2.7

CETANE NUMBER 64.3-70 62.7

HEATING VALUE 32.4 MJ/L 30.8 MJ/L

METHYL

DENSITY

VISCOSITY

CETANE

HEATING

ESTER
RAPESEED

150C

400C

NUMBER

VALUE

(LEAR)
SOYABEAN

0.882
0.880 0.830-0.840

4.2
4.0 4.0 2.0-3.5

51.0-59.7
61.2 45.7-56 51.0

32.8MJ/L
32.8MJ/L 32.7MJ/L 35.5MJ/L

SUNFLOWER 0.885

TYPICAL
DIESEL FUEL