the study of degradation and stabilization of epoxidized palm oil ms. thitimaporn duangmanee...
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THE STUDY OF DEGRADATION AND STABILIZATION OF EPOXIDIZED
PALM OIL
Ms. Thitimaporn Duangmanee
National Metal and Materials Technology Center
What is epoxidized palm oil (EPO)?
Why is EPO interesting?
How to produce and test the EPO?
How about the study?
What is the conclusion from the study?
Introduction
Objectives
Experiments
Results & Discussion
Conclusions
Contents
2
3
Epoxidized Vegetable Oil
Epoxidation is the epoxide functional group consists of a three-member ring with two carbon atoms and one oxygen atom.
Epoxides are most commonly synthesized from reacting alkenes with peracids.
4
Applications of Epoxides
Raw materials for variety of chemicals such as alcohols and glycols Stabilizers for PVC to improve stability Improve properties of polymers towards heat and UV radiation Improve elasticity of plastics Replace materials derived from petroleum
Readily Available
Biodegradable
Environmental
Friendly
Renewable
Low Cost
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Mechanism of Epoxidation
Main reaction
Side- reaction
RCOOH + H2O2 +R CO
O
OHH2O 1
R CO
O
OH+ C C RCOOH C
OC+ 2
CO
C + H2OH+
C C
OH OH
3
CO
C + RCOOHH+
OH
C C
OCOR
4
The reaction steps were suggested by Gan et al. in 1992, using carboxylic peracid in an acidic environment, with hydrogen peroxide as showed in main reaction.
The side-reaction show oxirane ring cleavage to glycol that are degradation reactions of the oxirane ring on the yield of the epoxidation process.
The plantation area and product of palm trend to increase every year from year 2006-2011.
Palm oil in Thailand
Crude palm production in Thailand, year 2006-2011
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Objectives
Stabilized EPO using
an antioxidant
Epoxidized Palm Oil (EPO)
using Epoxidation
Refined Palm Oil
Side reactions of epoxidation process lead to decrease of % oxirane oxygen and formation of glycol.
Minimization of side reactions effect need to be done to maintain high % oxirane oxygen(epoxides).
Proposed solution: Addition of antioxidants in EPO
• Antioxidant is normally being used in food for longer storage period and prevent oxidation of oil or fats in food.
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Raw Material & Chemicals Palm oil was manufactured by Siam Oil & Fat. Co., Ltd. (Samut sakhon,
Thailand). Antioxidants
Butylatedhydroxyanisole (BHA) Tert-butylhydroquinone (TBHQ) Propyl Gallate Gallussäure-propylester (PG)
For synthesis Glacial acetic acid (AA), 30 wt% aqueous hydrogen peroxide, 32wt% solution Hydrogen bromide in acetic acid Sulfuric acid were obtained from Merck.
For %Oxirane oxygen using the titration method (AOCS Cd 9-57) HBr in acetic acid was diluted with glacial acetic acid to prepare 0.1 N HBr. Crytal violet solution was used as an indicator.
For Glycol using the titration method (May, “Epoxy resins: chemistry and Technology”, 1973) Chloroform Benzyltrimethylammonium periodate used as Oxidation Reagent Sodium thiosulfate solution Potassium iodide Starch solution
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Properties of Palm Oil
Palm oil feedstock was determined fatty acid composition that refined palm oil was selected as raw material for this study.
Fatty acidComposition (% wt)
Refined Non-refinedLauric acid methyl ester C12:0Myristic acid methyl ester C14:0Palmitic acid methyl ester C16:0Stearic acid methyl ester C18:0Arachidic acid methyl ester C20:0
Saturated
0.2430.798
39.3893.9150.200
44.545
0.2550.920
42.6114.0760.264
48.126
Palmitoleic acid methyl ester C16:1Oleic acid methyl ester C18:1Linoleic acid methyl ester C18:2Linolenic acid methyl ester C18:3Eicosenoic acid methyl ester C20:1
Unsaturated
0.06143.82911.3210.1680.076
55.455
0.09040.62110.855
0.2140.095
51.875
Total Fatty Acid 100.0 100.0
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Synthesis of EPO
200 g of palm oil is poured into round-bottom flask, heated up to 65oC and
stirred at 1400 rpm
Calculated amount of acetic acid and sulfuric acid are added and the mixture
is stirred for 30 minutes
30% aqueous solution H2O2 is added slowly and the reaction is continued for
30 minutes
Mixture is washed until the pH reaches 7
Remaining water is separated by using Oil Test Centrifuge and is removed with
sodium sulphate anhydrous crystals
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Stabilization of EPO
Test for 12 weeks
Text in hereText
in here
EPO+
TBHQ
EPO+
TBHQ
EPO+
PG
EPO+
PG
EPO+
BHA
EPO+
BHA
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Changes of %Oxirane Oxygen
All EPO had decreased. EPO without antioxidant has the highest percentage oxirane oxygen.
Antioxidants had lead to a more rapid opening of oxirane ring and faster degradation of EPO.
0 1 2 3 4 5 6 7 8 9 10 11 121
1.2
1.4
1.6
1.8
2
2.2
EPO BHA
TBHQ PG
Week
% O
xira
ne
Oxy
gen
Changes of glycol
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0 1 2 3 4 5 6 7 8 9 10 11 120.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
EPO
BHA
TBHQ
PG
Week
Gly
colA
mou
nt
(mol
es/1
00g)
Degradation of EPO synthesized leads to the production of glycol.
The testing of glycol amount for 12 weeks, the glycol amounts for EPO was rather not very consistent.
Glycol amount decreased at the first half of the 12 weeks and increased at Week 7.
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Hygroscopic Characteristics of Glycol
Glycol has a strong affinity towards water molecules due to the formation of weak electrostatic absorbing power known as H-bond by the electronegativity of the atoms.
In addition, glycol can react with acetic acid form ethylene glycol monoaceate and water.
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Conclusions
It was possible to produce epoxidized oil from palm oil
Three types of antioxidants into the EPO synthesized has no significant effect on the glycolamount
Antioxidants will result in greater opening of oxirane rings and thus reduce the %Oxirane oxygen.
Antioxidants cannot be used to prevent the degradation of the epoxidized palm oil.
Acknowledgment
National Metal and Materials Technology Center (MTEC) a member of National Science and Technology Development Agency (NSTDA)
Many thanks to Mr. Tan Seng Yee from Universiti Teknologi PETRONAS, Malaysia and Mr. Athip Achalanant from Thammasat University, Thailand for experiment and testing.