1. Free Fatty Acid
Reduction in Edible Oils
ROHIT BANGERA
Advanced Enzyme
Technologies Ltd., India
Ghent, 22 September 2016

2.  About Us
 Introduction
 Industrial Deacidification methods
 Reesterification (FFA reduction)
- Chemical
- Enzymatic
 Laboratory studies
 Application in existing refinery plants
 Advantages and way forward
Contents

3. 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

4. 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

5. INTRODUCTION

6.  Lipids – Oils & Fats
- Triglycerides, Di glycerides & Mono glycerides
- Sterols
- Phospholipids
 Triglycerides contain 3 fatty acids connected to glycerol backbone
Chemistry of Oils & Fats

7.  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

8.  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
O
C 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

9. INDUSTRIAL DEACIDIFICATION METHODS

10. Industrial De-acidification Methods
Chemical Physical

11.  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)

12.  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

13. RE-ESTERIFICATION

14.  Condensation of fatty acid on glycerol
 Acyl Acceptors
Re-esterification / Glycerolysis
Mono-Glyceride Di-Glyceride Glycerol

15. Condensation of FA on Glycerol

16.  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

17. Chemical Re-Esterification
Alfa Laval – Advanced Glycerol Treatment

18.  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

19.  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

20. 0
2
4
6
8
10
12
0 1 2 3 4 5 6
FFA%
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

21.  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

22. Physical Refining
RICE BRAN OIL
(Enzymatic) Degumming
Bleaching
Dewaxing
Deodorization
Enzymatic
Deacidification
PALM OIL
Dry Pre-treatment
Bleaching
Deodorization
Enzymatic
Deacidification

23. Chemical Refining
SOFT OILS
Deodorization
Bleaching
Neutralization
Degumming
Enzymatic
Deacidification

24.  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

25.  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!

26.  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..

27.  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..

28. 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
Contact us

29. THANK YOU!