Professional Documents
Culture Documents
MCPD GE Mitigation AOCS 2012 (DGW) Final
MCPD GE Mitigation AOCS 2012 (DGW) Final
"
# $ ! % !
! !( ) *+,*
1
# )
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,….
# )
OR OH OR
Cl Cl Cl
GLYCIDOL ESTERS
H
H
H2C C CH2 H2C C CH2
O O
OH OCOR
2007
2008 ! "
#
!
2009 $% $ &
"' (
) (
2010-2011 *
$ +
0 /
* ( " $
, ./ 0 (1 23 *
,4 ( & ! " *
#
, 1 823779 0 :3 (
, (
& % 8 %739
! 0 21; µ +& * 1
0 7<1= µ +& * 1
8 > 12< µ 9
, 8 9 (
, 4 $ * 8 9
0 / / /
, ( " $
, )"
, & * ( 8 ' 9
' ? %73+ $
, 2 ,+3+++ 4 " 4 !( !
' 0 13;3 @ 721333
' 0 A 71333
0 / / /
, & 8 9
&
" B
4" 4
C * -
C -
$4$ "4$' )
4 "4 E $ *
C' * D
+
4 ' 0 •$ -
A2 8 9 C. * D
A7 8 9
/ /
* 8 0! $' %B 233:9
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
* * ! $$$ 7F 8 "9
,$ 8 9
,
,. # *
/ /
MCPD ester and related compounds in various vegetable oils (Matthaus et al.,2011)
Oil N° Average content Max. content
Samples (ppm) (ppm) *
# !
Rapeseed Oil 10 1 1
/$ 87F9
Soybean Oil 11 0.5 0.6
Sunflower Oil 5 2 4
Corn Oil 4 7 9
Coconut Oil 3 7 7.5
Palm Oil 70 6 14
*/ * ' + '
,. ' -
, 8 9-
/ /
," * % 4' !
, *
, *
, *
,
'
"
/ / /
- -. -
) *
8 9 -
% B*
' 8 !9
- -$ > -
> + >
> -
) 8 9 -
) -
- ) ' !5 # 8,9:
! $$$ 87F9 86 1 @ 233F9
"& *
' "0
' 0
. # 8 B * BG19
" * H
8 9
-
* " 8. B 23779
% 4' > 8 ( > + 9
) * I
-
4 .
" E% %E '%
) * " + "
4"
0) 1 823779B B7 :
) -
K !!"
" (
4
K.
K !!"
0 1 823729B B2: 879B2: <
/ / ) 1
18
8
16
7 " A =L
14
6
12
5
10
4
8
3
2 6
1 4
0 2
0
0 0,2 0,4 0,6 0,8 1 1,2
0 2 4 6 8 10
Monoglyceride-content (%) Diglyceride content (%)
,) * "
,% " +
, " 0 (1 =L 8 M ;L 9
H2C OH
Cl
O H2 C Cl
OH H2C
∆ O
CH O C CH3
O CH O CH
270°C O O
H2C O C R > 240°C
H2 C O C R H2C O C R
DAG Radicalar mechanism Glycidol-esters
,! " > 84 M 2 3N 9
, *
"* 23L B*
,'( * "
;O
0 1 823729B B7 7B7 :7 7 :F
CH B
4" 4 •
C
+
8 9
% C -
+ C8 9 #
C
" + #
0A 2 •
$ 0A 7 • >
' 4 5 " ! (% ! 84 " ! ":
6 *
6 ' 0 )
6 ' + 87+79 0 23 3L
6 !! 0 :;L
J
'
*
# !!
. ' > D
( ! 4 "! " 84 " ! ":
' "
!
8 * 9
$
' * 8 9 +
# "
# 8 9 !!" "
' *P 0 " A =L 8 9 4"
! *
' ! 4 ! " 4" ' 4
"
.K
" #
"
)
* 8 9 8 # 9
" > * D
$
-
1 /
"
0
879 % + 8A 2 9
829 ( + >
8 9 . * 8 9 !$) $)
'
8=9 % *
' ) $4$' )
/ ;1 /
Crude Palm Oil
" '
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
Bleaching with 1.5% activated or natural bleaching earth; Deodorization at 260°C during 1 hr at 3 mbar
, >
!" # $ % & '
!( ( %" # ) & *
!* # + % ) $ & ( %" +
, >
44 ! 4 % 5 $ "!5
* Q
Bleaching pH1 Cl- content MCPD ester 12
earth (mg/100g)2 content (ppm)
10
6
Activated 3.65 7.1 2.6
4
Activated 3.10 14.2 3.9
2
0
Activated 3.26 67.5 9.7 0 10 20 30 40 50 60 70
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
.
8 ' 8 9 9
44 ! 4 8 "= ! : ! ' 6 " !("
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)
6! ,) 5 ' " 4 $ 46 '
3
MC PD + MC PD -FS (ppm)
2,5 230°C
220°C
2
1,5 200°C
1
0,5
0
0 50 100 150 200 250 300 350
Deodorization Time (min.)
' + A2 * * 0
* 8 9
% 4 ( 0 233 2 3N 8 9
6! ,) 5 ' " 4 $ 46 '
% * # ) ' 233 223N 82 * 712; & + 9
2,4 10
2,2 9
8 233N
MCPD+MCPD-FS (ppm)
2
7
Σ8 K 9A2 % *
0
. ' %
8 # 9 8 &9
6! *) 5 4 $ 4 '
! &0 8L !!"B 317 L " B O12L " 9
0 71;L * + 3 +73;N
# 0 O3 + * +7L
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)
> (' !" 66 $ 4 5 '
4 K !!"
8N 9 8 9 8 9 8 @ ;B2;R9 8L 7O039
273 21F 21: 2= 317:
223 21F 13 23 3B72
2 3 13 13 7: 3B3:
2=3 12 12 7= 3B3<
8 9
) B
- Very efficient FFA stripping but only limited heat bleaching
" D
"( ' 8 39? ) 3,:
8 +* 9
4 7 4 2 4
,- ' $
!!" #
4 7 4 2 4
2 3° 223° 223°
4 ,
8 @ ;B2; S9 21F 12 21F
!!" 8L 7O039 3132 3132 3132
K 8 9 ,3@ ,3A ,3@
5 4 $ 4 '
Crude Palm Oil
8 +* 9
High amount of natural bleaching earth
!!" 8 9
Packed column or equivalent
#
Longer time at T < 230°C
1
' + &
/ # # ( 1 " 1 $ 4 #+ 5 . 3
/ # ' + ' $
(
A2 + * B
' > 8 " B 9
) * 8 9
# 4 A 2 3N 8 9
0
8 * &0 & 9
8 9 8 0 !!"B 9
$ B # * 8 9
5 >/ ( " / (" !! !
Q BT