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FFA (0.3-5%)
Acylglycerols (92-95%)
-Mainly Triacylglycerols
-Some Di- and Monoacylglycerols

Phospholipids (<3%)
-Hydratable PL
Minor components (0.3-2%)
-Non-hydratable PL
- Tocopherols, Sterols, Pigments,…
- Contaminants, Impurities,….
 # )

Valuable Minor Components Side Reaction Products

Tocopherols, Sterols,…. Trans FA, polymers,

(3-MCPD esters),…

- Desired in the refined oil

- Formed during refining
- Good nutritional properties
- Bad nutritional properties
- To be retained during refining
- Unwanted
Contaminants
- Present in crude oils
- Carcinogenic/Toxic
Pesticides, PAH, Dioxins,… - To be removed during refining
 & - ) . / /
MCPD ESTERS
OH OR OR’

OR OH OR

Cl Cl Cl

3-MCPD mono-(sn1) ester 3-MCPD mono-(sn2) ester 3-MCPD di-ester

GLYCIDOL ESTERS
H
H
H2C C CH2 H2C C CH2

O O
OH OCOR

Free glycidyl Glycidyl-ester

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* Current advice of Toxicologists : LOWERING RESIDUAL LEVELS IN FOOD

- Current TDI for 3-MCPD should never be exceeded
- MOE for Glycidyl is > 10.000 in all cases

Source : Rietjens, Y. (2011)

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OIL N°Samples Average content Max. content
Rapeseed Oil 31 0.3 mg/kg 1.5 mg/kg
Sunflower Oil 49 1.0 mg/kg 5.7 mg/kg
Corn Oil 15 2.8 mg/kg 7.0 mg/kg
Palm Oil 37 4.5 mg/kg 13 mg/kg

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MCPD ester and related compounds in various vegetable oils (Matthaus et al.,2011)
Oil N° Average content Max. content
Samples (ppm) (ppm) *
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Rapeseed Oil 10 1 1
/$ 87F9
Soybean Oil 11 0.5 0.6
Sunflower Oil 5 2 4
Corn Oil 4 7 9
Coconut Oil 3 7 7.5
Palm Oil 70 6 14

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M C P D es ter c ontent (m g/k g)

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Monoglyceride-content (%) Diglyceride content (%)

Palm Oil, deodorized at 260°C Palm Oil, deodorized at 260°C

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∆ O
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270°C O O
H2C O C R > 240°C
H2 C O C R H2C O C R
DAG Radicalar mechanism Glycidol-esters

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 Crude Palm Oil
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DRY DEGUMMING
-6 8 9
0.05-0.15% H3PO4 (85%) '
70-90°C, 1-15 min

BLEACHING -) *
0.6-1.2% Activated Bleaching Earth + *
90-110°C, 20-40 min, 30-100 mbar

DEODORIZATION
250-270°C, 45-90 min % 1+
2-4 mbar,0.6-1.2% stripping steam

Refined Palm Oil

 44 ! 4 "( <( !
CPO DOBI FFA (%) DAG (%) Activated Bleaching Earth (HCl) Natural Bleaching Earth
MCPD (ppm) GE (ppm) MCPD (ppm) GE (ppm)
Columbian 1.6 3 5.2 2.3 3.0 1.1 3.6
Malaysian 1 1.6 5.1 6.2 9.6 3.8 2.7 4.6
Malaysian 2 3.1 3.8 5.2 9.7 3.5 2.1 4.0

Bleaching with 1.5% activated or natural bleaching earth; Deodorization at 260°C during 1 hr at 3 mbar

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Bleaching pH1 Cl- content MCPD ester 12
earth (mg/100g)2 content (ppm)
10

MCPD content (ppm)

Natural 7.7 0 1.7 8

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Activated 3.65 7.1 2.6
4
Activated 3.10 14.2 3.9
2

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Cl- content BE (m g/100g)
1measured in 10% aqueous suspension; 2measred in aqueous suspension
Palm oil bleached with 1.5% bleaching earth; flash heated to 220°C

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esters esters
3,5 : 1 hr; : 2 hr : 4 hr 50 : 1 hr; : 2 hr : 4 hr
45

G l y c i d o l e s te r s (p p m )
3 40
35
3-MCPD ester (ppm)

2,5
30
2 25
1,5
20
15
1 10
0,5
5
0
0 150 200 250 300
150 200 250 300
Temperature (°C)
Tem perature (°C)

Temperature more important parameter than time

At t > 240°C, mainly glycidyl-esters are formed (exponential increase)
3-MCPD ester formation occurs already at 180°C



 








 








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MC PD + MC PD -FS (ppm)

2,5 230°C
220°C
2

1,5 200°C
1

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0 50 100 150 200 250 300 350
Deodorization Time (min.)

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MCPD+MCPD-FS (ppm)

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Color (R- 5,25")

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6
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1,4 223N
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1 2
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Deodorization time (hr) Deodorization time (hr)

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14 8
MCPD/MCPD+ GE (ppm)

MCPD + GE MCPD + GE
13 7

MCPD/MCPD + GE (ppm)
12
6
11
5
10
4
9 MCPD
MCPD
8 3
210 220 230 240 250 260 270
2
Deodorization temperature (°C)
210 220 230 240 250 260 270
Deodorization temperature (°C)
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