Free Fatty Acid Reduction in Edible Oils

ROHIT BANGERA

Advanced Enzyme Technologies Ltd., India

Ghent, 22 September 2016

About Us

Introduction

Industrial Deacidification methods

Reesterification (FFA reduction) - Chemical - Enzymatic

Laboratory studies

Application in existing refinery plants

Advantages and way forward

Contents

Think of Life Think of Enzymes

Think of us!

Pioneered enzyme production in India in 1958

Leading producer of enzymes in South Asia

Exports to 45+ countries across 6 continents

55+ enzymes and 360+ products

Safe, eco-friendly and biodegradable solutions for 25+ industries

State-of-the-art manufacturing facilities that are ISO and WHO cGMP certified

A bit about us

1958: India's first enzyme manufacturing plant (for Papain) is pioneered by Mr. L.C. Rathi

1978: Rathi Papains Pvt. Ltd. was incorporated

1986: Specialty Enzymes & Biotechnologies, United States is set up

1989: Advanced Enzymes is incorporated (Originally under the name of Advanced Biochemicals Pvt. Ltd. )

1994: Commissioning of our 1st fermentation facility at Sinnar, Maharashtra

2008: Commissioning of 2nd fermentation facility at Pithampur, Madhya Pradesh

2016 : Listed in stock exchange (BSE)

History & Milestones

INTRODUCTION

Lipids – Oils & Fats - Triglycerides, Di glycerides & Mono glycerides - Sterols - Phospholipids

Triglycerides contain 3 fatty acids connected to glycerol backbone

Chemistry of Oils & Fats

Enzymes (Lipases) are responsible for removal of fatty acid. Heat and moisture may cause liberation of Free Fatty acid (FFA).

FFA varies depending on oil type, region, season, harvesting methods, storage conditions, etc.

Fatty acids are more susceptible to oxidation leading to rancidity

High FFA content in edible oils leads to lower yields of refined oils

In existing refining techniques, the FFA is either lost as soap or fatty acid distillates (FAD) – loss of neutral oil

Formation of Free Fatty Acids

Effect fractionation

Act as precursor to process impurities.

Partial Glycerides

Formed from diglycerides at high temperature (T > 230°C) Palm oil is particularly sensitive for glycidyl ester formation - High DAG content (6-8%) - High deodorization temperature (260°C)

Ref : Destaillats et al. (2012), food chemistry,131,1391-1398

CH O

H2C

H2C Cl

O C

OC CH3

O

CH

H2C

H2C Cl

O

O C

O

R

CH

H2C

H2C

O

O C

O

R

270° C

R> 240°C

DAG Glycidyl-esters

OH OH

Radicalar mechanism

INDUSTRIAL DEACIDIFICATION METHODS

Industrial De-acidification Methods

Chemical Physical

Uses alkali like NaOH to neutralize FFA

Soap formed is removed by separation (centrifuge or gravity)

Advantages - Versatile & Acceptable Oil Quality - Combined Degumming / De-colorizing - Miscella Refining / Re-refining of Cottonseed Oil

Disadvantages - Excessive loss of neutral oil / nutrients - Effluent generation

Chemical (Neutralization)

Removal of FFA by steam stripping under high temperature & vacuum

Advantages - Lower operating costs & (maybe) capex - Improved FAD quality - Combined with Deodorizing / Heat bleaching effect

Disadvantages - Stringent Pre-treatment - Good process & equipment design

Physical Deacidification

RE-ESTERIFICATION

Condensation of fatty acid on glycerol

Acyl Acceptors

Re-esterification / Glycerolysis

Mono-Glyceride Di-Glyceride Glycerol

Condensation of FA on Glycerol

Heat : Temperature of about 180 – 220oC

Excess Glycerol

Vacuum – to remove water formed

Catalyst : optional - ZnCl2 , SnCl2, p-toluene sulphonic acid

Initial Feed Stock : High FFA oils, rendered animal fats, trap grease, used cooking oil (UCO) and fatty acid distillates

FFA levels : 10 – 100%

Chemical Re-Esterification

Chemical Re-Esterification

Alfa Laval – Advanced Glycerol Treatment

Advantages : - Increased neutral oil yield - Use cheaper oils to produce technical grade oil for biodiesel, oleochemicals etc.

Disadvantages : - Harsh reaction conditions – polymerization / trans fatty acid formation - Excess Glycerol - high mono- & di- glyceride content - Product may not be suitable for edible purpose - In case of biodiesel, distillation may be necessary after transesterification

Chemical Re-Esterification

The fatty acid molecule is re-esterified with mono- & di- glycerides in the oil or with added glycerol.

This enzyme assisted process is proven!

The bio-refined (enzymatically deacidified) oil contained FFA < 2%

No major changes observed in : - MAG/DAG content - TAG composition - Functional components

Enzymatic FFA Remediation

0

2

4

6

8

10

12

0 1 2 3 4 5 6

FF

A%

Time (hours)

R&D Results : Effect of Glycerol

Without external Glycerol addition, After 6 hours FFA = 5.5%, After 24 hours 4.9% With Glycerol addition, FFA < 2% With higher Glycerol addition, reaction is faster and lower FFA is observed

Substrate : Degummed. Bleached & Dewaxed Rice Bran Oil Glycerol Addition X Stoichiometric quantity

No glycerol addition X 1.0 X 1.5 X 2.0 X 2.5

Oil quality – crude / pretreated

Excess Glycerol

Removal of water produced in the reaction

Enzyme type & dosage

Reactor design : packed column / agitated reactor removal of water

Quality of product

Reaction Dynamics

Physical Refining

RICE BRAN OIL

(Enzymatic) Degumming

Bleaching

Dewaxing

Deodorization

Enzymatic Deacidification

PALM OIL

Dry Pre-treatment

Bleaching

Deodorization

Enzymatic Deacidification

Chemical Refining

SOFT OILS

Deodorization

Bleaching

Neutralization

Degumming

Enzymatic Deacidification

Increased oil yield

No trans fatty acid formation / polymerization / other side reactions

In deodorization step - Lower fuel consumption (to distill the FFA) - Lower consumptions in vacuum system

Use low value oils to produce high value refined products

Flexibility in handling different qualities of raw material

Lesser chemicals and reduced operating costs

Reduced environmental impact

Advantages of Enzymstic FFA Remediation

Better retention of nutraceuticals Oryzanol, Phytosterols, Carotenoids, ...

Lower trans fatty acid formation in the deodorization step.

Higher throughput in existing deodorizer.

Stops formation of glycidyl esters in deodorization

Better crystallization in fractionation

More Advantages!

Uses : - FFA reduction in Rice Bran Oil, Fish Oil and Palm Oil industry - DAG reduction in Palm Oil & CBE (e.g. Shea butter) - High Value Products in Cosmetic & drug industry (EPA/DHA concentrates)

Regulations

Commercial viability - Enzyme cost - Value addition / Energy reduction / Eco-friendly - Enzyme Reusability - Reactor Design

Way Forward..

Food grade preparation of specially designed lipase(s)

Immobilized - can be reused several times

Kosher & Halal certified, non-synthetic & bio-degradable

Dosage - feed stock dependent (adequate trials suggested).

Solutions we offer..

Advanced Enzyme Technologies Ltd.

5th Floor, 'A' wing, Sun Magnetica

LIC Service Road, Louiswadi

Thane (W) 400 604, India

Tel: +91 22 4170 3200 / 3213

Fax: +91 22 2583 5159

Email: info@advancedenzymes.com

www.advancedenzymes.com

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