Organisation/Agency. Malaysian Palm Oil Board. Academic/Professional Qualifications: ⢠Sarjana, DraâInstitute of Technology Bandung, Bandung,. Indonesia.
Session 2 Refining Technology and Quality
Session 2: Chairperson Designation Senior Research Fellow Organisation/Agency Malaysian Palm Oil Board
Academic/Professional Qualifications: Sarjana, Dra–Institute of Technology Bandung, Bandung, Indonesia PhD – State University of Ghent, Belgium
DR AINIE KUNTOM
Working background/ Area of Expertise / Interest: Lecturer at School of Chemical Sciences, Univesity of Sciences Malaysia. Principal Research Officer at Malaysian Palm Oil Board. Senior Research Fellow at Malaysian Palm Oil Board Area of Expertise / Interest Food Safety – palm oil. Quality of palm oil Research in Flavour Chemistry. Pesticide Residue – method development. Soap technology. Standards development. Sustainability – Malaysian Sustainable Palm Oil Codes of practice for oil palm along the whole supply chain
Session 2: Paper 5 Designation Research Officer Organisation/Agency Malaysian Palm Oil Board
DR NUZUL AMRI IBRAHIM
Qualifications: Ph. D (Food Biotechnology) M. Sc. (Environmental Engineering) B. Sc. (Applied Chemistry) Diploma (Rubber & Plastic Technology) Working background/ Area of Expertise / Interest: •Fat and oil modification by enzymatic interesterification •Project leader for mitigation of MCPD esters •Quality parameters of palm oil
POMREQ 2016 @
3-MCPD esters: A New Challenge for Palm Oil Industry Nuzul Amri Ibrahim Muhamad Roddy Ramli Raznim Arni Abdul Razak Ainie Kuntom Malaysian Palm Oil Board
Outline • Introduction – 3-MCPD and 3-MCPD ester – Mechanism hypothesis – Physical refining
• Studies in MPOB – Adoption of BfR 8 – Mitigation studies – Survey
• Conclusions/ Recommendations • Challenges
3-MCPD & 3-MCPD ester Food processed contaminants Compound Effect to health 3-monochloropropanediol (3-MCPD) 3-monochloropropanediol ester (3-MCPDE)
1 Classification
Possibly carcinogenic to humans1 Nephrotoxic (EFSA Report 2016) Nephrotoxic (EFSA Report 2016)
by International Agency for Research on Cancer
Chemical structure R O
O
OR1 Cl 3-MCPD ester
OH OH Cl 3-MCPD
3-MCPD esters • Family of chloropropanols • Categorized as food-processed contaminant • Mainly in refined oils – Due to heat and presence of chloride
Studies on 3-MCPD & 3-MCPDE Year 1978-1980 1983 2004
2006
Presence of free 3-MCPD/ 3-MCPD ester in food Hydrolysed vegetable protein, e.g soy sauce (free) Spanish rapeseed oil (ester) Processed food: toasted bread, cheese, cooked meat, salami, infant formula, coffee and creamer (ester) Vegetable oils (ester)
Formation Mechanism Hypothesis R O
R
OH
O
R
H+ -H2O
OR1 Acylglycerol R = alkyl R1 = H or COR
O O +
ClOR1
Cyclic acyl oxonium ion
Cl
O
R O
OR1
O + OR1 Cl
2- & 3- MCPD ester
2-MCPD
3-MCPD
ILSI Report 2009, Brussels
O
A quick look at physical refining process
Physical refining process Crude palm oil
Phosphoric acid is added
Degumming Bleaching clay is added
Phosphoric acid and gums
Bleaching Gums/Clays and phosphoric acid are removed
Filter Press
Deodorisation
Refined palm oil
Source of H+ and ClFrom oil, water and clays
From acid and acid activated clays
R O
R
R
OH H+
O
O
O +
Cl-
Cl
O O
-H2O OR1 Acylglycerol
R
OR1 Cyclic acyl oxonium ion
OR1
O
O
+ OR1
Cl
2- & 3- MCPD esters
R = alkyl R1 = H or COR 2-MCPD
3-MCPD
Studies in MPOB 1. Adoption of method of analyses • BfR 8 2010 to 2014 • AOCS cd 29a-13 Since 2015 2. Mitigation measures
BfR Method 8 100 mg of oil/fat sample Internal standard (d5-3-MCPD) Acidic transesterification with H2SO4 (hydrolysis for 18h at 40°C) Neutralization with NaHCO3
Derivatization with PBA
GC-MS Analysis
Repeatability of results Concentration (mg/kg),
% Recovery (± SD)
RSD (%)
0.25
97.6 (± 0.022)
0.02
1.0
103.8 (± 0.03)
0.03
4.0
107.7 (± 0.128)
0.12
6.0
107.9 (± 0.115)
0.11
n=6
Calibration curve Area ratio of 3-MCPD and deuterated 3-MCPD
0.9 0.8 0.7
0.6 0.5
y = 0.1361x + 0.0102 R² = 0.9995
0.4 0.3 0.2 0.1 0 0
1
2
3
4
Spiking level of 3-MCPD (mg/kg)
5
6
7
Participation in BfR ring test Values
3-MCPD ester results (mg/kg)
BfR actual values (range)
0.16 – 3.92
Reported values (mean
0.26 – 3.51
range from six laboratories)
MPOB values (range)
< 0.25 – 3.25
Mitigation measures Objectives • To evaluate the possible factors responsible for formation of 3-MCPD esters during refining of CPO. • To suggest possible solutions/alternatives to minimise the formation.
200kg/batch refining pilot plant
Pilot-plant scale refining: Condition Parameter
Standard Modified
H3PO4(%)
0.1
0.02-0.2
1
1-2
Deod’n temp(C)
260
220-250
Duration(h)
1.5
3
Acid activated b/clay(%)
Experiments Compare Standard refining process with modified conditions: effects of degumming, acid activated clays, natural clays and deodorization temperature. Checked acidity of clays and chloride contents. Monitor the formation of 3-MCPD ester Results
3.5
8
3
7 6
2.5
5 2 4 1.5 3 1
2
0.5
1
0
0 220
230
240
Deodorization temperature, oC
250
260
Colour, Red
3-MCPDE content, mg/kg
Effect of temperature
3-MCPDE Colour
Effect of deodorization temperature at 230 C Variables: Phos acid and b/clay 3.5
260 C
3-MCPDE, mg/kg
3
Deod’n temp: 230 C*
2.5 2 1.5 1 0.5 0 0.1/1
0.1/2
0.2/1
0.2/2
0.1/1
Phos. acid/B. clay, %
*Residence time: 3 hours
Acidity of clays (pH) Acid activated clays A1 A2 A3
pH 5.8 5.8 5.3
Natural clays N1 N2 N3
6.6 6.6 7.7
Correlation between pH of clays and formation of 3-MCPD esters 3.2
Acid degumming experiments 3-MCPD esters content (ppm)
3.0
2.8 R2 = 0.9759 2.6
2.4
2.2
2.0 5.0
5.5
6.0
6.5 pH
7.0
7.5
8.0
Total chloride contents • • • • •
Clays (n=26) Water(n=7) CPO(n=11) Phosphoric(n=8) Citric acid(n=2)
60-152 ppm 7-38 ppm 8-29 ppm 1-2 ppm 1 ppm
Analysed by a commercial laboratory (March-April 2012)
Effect of Cl in bleaching clay 3-MCPDE content, mg/kg
3 2.8
2
R = 0.9752
2.6 2.4 2.2 2 1.8 0
10
20
30
40
50
60
Level of Cl in bleaching clay, mg/kg
The level of Cl in b/clay shows positive correlation with the formation of the esters
70
Effect of rinsing Deodorization temp: 260 C 6
3-MCPDE content, mg/kg
5
4 Not rinsed 3
Rinsed 1X Rinsed 2X
2
1
0 1
2 CPO samples
Results
Report by other researchers
Deodorisation-time effect (K. Hrncirik, Berlin, 2010)
Formation of 3 –MCPD esters occurs within first 20 mins
Effect of Diacylglycerols Bertrand Matthaus (2010, AOCS Mtg)
Effect of DAG Sample
DAG,% 3-MCPDE, mg/kg
Feed oil
6.1
4.766 ± 0.006
TL IM 3h
13.7
4.023 ± 0.246
TL IM 9h
21.6
3.211 ± 0.171
TL IM 12 h
22.4
2.480 ± 0.019
TL IM 24 h
25.5
2.477 ± 0.057 3-MCPDE
DAG
Effect of FFA and DAG FFA, % DAG, % 3-MCPDE, mg/kg Fresh
0.4
3.5
1.62 ± 0.023
Day 1
0.8
3.1
0.866 ± 0.007
0.6
3.2
1.305 ± 0.031
2.0
3.9
1.252 ± 0.035
1.3
3.8
2.584 ± 0.199
Hydrolysed 56
3.9
