ULTRAFILTRATION MEMBRANE PRE-TREATMENT

TOWARDS STABLE QUALITY OF REFINED PALM OIL

Noor Hidayu Othman
Sime Darby Research Sdn Bhd
PIPOC 2017
Table of Content
Introduction
Methodology
Results & Discussion
Conclusion
Acknowledgement

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 Sime Darby Plantation

 Our Business Operation

• Encompass more than 250 • 11 Refineries (Asia Pacific, Main Research Centre Core business in
estates and 70 mills Europe and Africa) • SDR Carey Island • Bio-chemicals
• Located in Malaysia, • 4 Kernel Crushing Plants • SDR Banting • Nutraceuticals &
Indonesia, Liberia, Papua (Malaysia & Indonesia) • SDTC, MTDC-UPM Wellness
New Guinea & Solomon • 1 Biodiesel plant • Bio-energy Space.
Island (Malaysia)

 Product Offerings
SD offers a broad portfolio of best quality vegetable oil based ingredients for application in
food and non-food.

3
Introduction
Palm Oil Industry – Current Issue

 Recently, palm oil industry has been hit with the presence of food contaminants
specifically known as 3-monochloropropanediol (3-MCPD) esters and glycidyl
fatty acid esters (GE).

O 3-MCPD Esters
GE esters
CH2 O R  Nephrotoxic
O  Probably carcinogenic
(EFSA Report 2016) to humans
 Non-genotoxic
CH O R  Genotoxic carcinogen O
carcinogen
CH2 Cl
RO CH2 CH CH2

 Palm oil industry actively been involved in investigating how these compounds
form during processing and how to decrease their content in a variety of food
products including vegetable fats and oils as well as infant formula
 Chloride or other chlorine-containing compound act as chlorine donor for the
formation of 3-MCPD esters.
 The phosphoric acid also had a greater effect on the development of chloroesters
and 3-MCPD formation due to its acidity.
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Introduction
Membrane Technology in Vegetable Oil Processing

 Membrane technology is a mature industry and has been successfully applied in various food
industries for separation of undesirable fractions from valuable components.
 In vegetable oil processing, the developing membrane application includes solvent recovery,
degumming, deacidification, pigment removal, wax removal and extraction of minor
components (tocopherols and carotenoids).
 Considerable amount of work has been conducted by previous researchers in the area of
membrane-based degumming and other process steps.

aPI= Polyimide, PVDF = Polyvinylidene fluoride, PES=Polyethersulfone; PSU=Polysulfone

bMF=Microfiltration,
UF=Ultrafitration, NF=Nanofiltration 5
cPho = Phosphorus, FFA = Free fatty acid
Objectives

(2) To compare the quality and

(1) To investigate the efficiency of in-
stability performance of membrane
house made PVDF ultrafiltration
refine bleached deodorized palm oil
membrane in removing impurities
(MRBDPO) with conventional refined
especially PLs without adding chemical
bleached deodorized palm oil
for degumming of CPO
(RBDPO).

The application of UF membrane by elimination of phosphoric acid in degumming

process is one of the potential approach in producing low 3-MCPD palm oil.

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Methodology
Preparation of PVDF Hollow Fiber Membrane

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Methodology
UF Membrane Pre-treatment Refining System

Membrane pre-treatment system for CPO Refining

Operating Condition
 Source – CPO with FFA between 3 - 5%
 Lab-scale designed: Cross-flow filtration mode
 Operating pressure : 1 – 2 bar
 Operating temperature : 60 – 70oC

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Methodology
Palm Oil Refining Process

CPO

Integrated-Membrane Conventional Physical

Refining Refining
Membrane Degumming Acid Degumming
 PVDF-UF membrane  Acid dosage : 0.04% H3PO4
 Temperature : 50 - 60⁰C  Temperature : 85⁰C
 Pressure : 1 - 2 bar  Time : 20 min

Bleaching
 Dosage : 1% Bleaching earth
 Temperature : 95 ⁰C
 Time : 30 minutes

Deodorisation
 Temperature : 240⁰C
 Time : 90 min

MRBDPO RBDPO 9
 Results & Discussion
Membrane Characterization

Overview Cross Section Partial Cross Section Outer Surface

(80 x) (250 x) (25,000 x)
FESEM photographs of (a) 14PVDF membrane and (b) 18PVDF membrane

 The changes in membrane structure is due to the slower rate of solvent and non-
solvent exchange during phase inversion process as a result of higher solution
viscosity for 18PVDF dope solution.

 Besides changing the cross-sectional structure, low exchange rate of solvent and
non-solvent had resulted in a relatively rougher outer surface 10
Results & Discussion
Membrane Pre-treatment of CPO

a a
Phosphorous FFA (%)
a
Membrane F P R F P R
(ppm) (ppm) (%) (ppm) (ppm) (%)
14PVDF 18.74±0.49 4.39±0.98 76.57 3.88±0.02 3.66±0.11 5.67
18PVDF 25.58±1.10 1.77±0.20 93.08 3.65±0.32 3.21±0.13 12.05
aF = Feed, P = Permeate, R = Rejection

 PLs in nature consisted of both hydrophilic and

hydrophobic functional groups due to its
characteristic as a surfactant. It tends to form
reverse micelles with MW of 20kDa or more in non-
aqueous systems.

 The significant size of PLs mixed micelles provides

synergetic effect during membrane separation
process and make it highly rejected by membrane
from TG

 Membranes play a minor role in minimizing FFA of

CPO, indicating further treatment process is
necessary 11
Results & Discussion
Quality and Stability of Refined Palm Oil : FFA

MRBDPO = Membrane Refined Bleached Deodorised Palm Oil

RBDPO = Refined Bleached Deodorised Palm Oil

 Good stability of MRBDPO produced by integrated-membrane refining process

showed that it is possible for physical refining process to deodorize at lower
temperature of 240°C rather normal at 260°C if certain amount of FFA has been
removed in earlier pre-treatment process.
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Results & Discussion
Quality and Stability of Refined Palm Oil : Colour

MRBDPO = Membrane Refined Bleached Deodorised Palm Oil

RBDPO = Refined Bleached Deodorised Palm Oil

 Low colour after refined at low deodorization temperature of 240C by MRBDPO

was due to about 20% colour reduction recorded after membrane pre-treatment
process.
 Even for normal quality CPO of 5 Max, membrane-integrated refining process was
able to produce a stable colour performance. 13
Results & Discussion
Quality and Stability of Refined Palm Oil : TOTOX Value

MRBDPO = Membrane Refined Bleached Deodorised Palm Oil

RBDPO = Refined Bleached Deodorised Palm Oil

 Total oxidation (TOTOX) value measured both peroxides, hydroperoxides and their
breakdown products (aldehydes and/or ketones), which provides a better
estimation of the progressive oxidative deterioration of fats and oils.

 The rate of total oxidation can be consider low for both MRBDPO and RBDPO since
both had UV TOTOX below 5 after 5 days storage 14
Results & Discussions
The Effect of Membrane Pre-treatment Towards the Removal
of TC, 3-MCPD and GE

 UF membrane can filter any contaminants down to 0.02 microns including

chlorinated compound. These has been proven based on the total chlorine (TC)
analysed after bleaching process.
 A significant TC reduction in MBPO indicates that UF membrane pre-treatment was
able to minimize the decomposition of chlorine-containing compound present in
CPO during deodorisation process. 15
Conclusion

 The membrane-integrated refining process had successfully produced a good

quality and stable refined palm oil although conducted at low deodorisation
temperature of 240°C especially in term of FFA and colour as compared to the
conventional physical refining process.
 The combination of UF membrane pre-treatment system and bleaching process
demonstrated a better removal of 3-MCPD precursor as compared to a
conventional acid degumming and bleaching process with 49% and 33% total
chlorine removal, respectively.
 A significant removal of total chlorine before deodorisation process by UF
membrane pre-treatment had reduced up to 60% 3-MCPD ester formation in
MRBDPO (1.13 ppm) as compared to RBDPO (2.85 ppm).
 Low deodorisation temperature conducted at 240°C had produced a low GE
formation in both MRBDPO and RBDPO of below 1 ppm.

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Acknowledgment

I would like to thank Sime Darby Research Sdn. Bhd. for financial
support and the members of Advanced Membrane Technology Centre
(AMTEC), UTM Skudai, Johor for a technical support in preparing and
producing UF membrane pre-treatment system.

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Thank you
Introduction
Membrane Technology and Its Basic Principles

 Membranes act as selective barrier, allowing the

passage of certain components and retention of
others from predetermined mixture, implying the
concentration of one or more components both
in permeate and retentate.
 The basic membrane systems commercially available include microfiltration (MF),
ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO), each of which
depending on the nature of particle or on the molecular size of the solutes that are
separated.

Membrane MF UF NF RO
Pore Size (Microns) 0.1 – 5 0.1 – 0.01 0.01 – 0.001 0.001 – 0. 0001
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Molecular Weight 200k – 1000k 10k – 300k 15k - 150 Up to 600
Results & Discussion
Quality and Stability of Refined Palm Oil : Oxidative
Stability Index

MRBDPO = Membrane Refined Bleached Deodorised Palm Oil

RBDPO = Refined Bleached Deodorised Palm Oil

 It can be seen that the degree of oxidation by FFA and the degree of
oxidation by OSI had contradict relationship. It may due to various pro-
rancidity factors been applied by rancimat method such as temperature, air
flow and ultraviolet light to speed up the deterioration and shorten the
stability test period. 20