food safety forum 14 september 2017 current and future...
TRANSCRIPT
Current and future solutions to mitigate 2/3 MCPD & GE in
oil refining and modification while preserving the overall
organoleptic and nutritional quality of the oil
Dr. Ir. Marc Kellens
Innovation for a
sustainable industry
Food Safety Forum
14 September 2017
PO+SBO RSO+SFO1991/92: 34.3 Mio T 17.8 Mio T
2017/18: 123.8 Mio T 43.7 Mio T3.6x in 25Y 2.5x in 25Y
267%
increase
70% on VO basis 25% on VO basis
Oil processing industry dominated by SBO & PO
70% food/feed
30% non-food (Oleo)
3
REFINING
Crude Oil
MODIFICATION
OLEOCHEMICAL PROCESSING
Refined oil Modified oil Oleochemical
Continuous improvement of existing processes and development
of new technologies to meet ever changing quality, safety and
sustainability standards in cost-efficient way
> 600.000 TPD> 200.000 TPD
> 200.000 TPD
Oil Processing
Acylglycerides (92 - 95%)
- mainly triglycerides
- some di- and monoglycerides
Free Fatty Acids
(0.3-5%)
Phospholipids (<3%)
- Hydratable PL
- Non-hydratable PL
Minor components (0.3-2%)
- Tocopherols, Sterols, Pigments,…
- Contaminants, degradation products,
Crude Vegetable Oils : General Composition
Most Crude Oils need to be refined for Human Consumption
Unwanted
Unwanted
Wanted
Wanted
Unwanted
Oil refining: removal of unwanted minorcomponents
while avoiding production of contaminants
Crude Oil Refined OilREFINING
Foreign
Pesticides
PAHC’s
PCB
Dioxines
Aflatoxines
...
Oil related
Gums
FFA
Color bodies
Oxidation products
Metals
...
Process related
TFA
Polymers
Acrolein
Dialkylketones
3-MCPDE/GE
...
With improving analytical detection methods more “unwanted”
componenents are and will be found in the oil (eg. 3-MCPDE/GE)
SBO
PO
MCPDE and GE in food oils: the next challenge
0 500 1000 1500 2000 2500 3000 3500 4000Concentration (µg/kg)
2-MCPD
3-MCPD
GE
Highest levels of 3-MCPDEs and
GE are found in palm oil
Levels of MCPDE and GE in food oils (2012-2015)
Main precursors
3-MCPDE ← “Chlorine”
(organic/ acid)
GE ← “DAG”
(FFA/alcaline)1set by FEDIOL; 2 set by producers of infant foods
* Expressed in FREE MCPD & Glycidol
Industry Targets (ppm) – for all oils
Year 3-MCPDE* GE*
20171
20182
20202
-
< 1
< 0.35
max 1
< 0.5
< 0.3
Limits:
EFSA (EU)
?JECFA
(WHO/FAO)
3MCPDE/GE: a problem mainly for palm oil, less for soft oils
� GE is for PO what TFA is for SBO/RSO: temperature-time related
• High DAG content in PO vs high 18:3 content in SBO/RSO
� 3MCPDE is mainly feedstock quality driven
• High FFA, low DOBI, presence of Chlorine precursor (origin?)
• HCL is also a precursor (eg. HCL activated BE)
• Appears at T > 140°C
OR
OR
Cl
OH
OH
Cl
Free 3-MCPD3MCPD Di-ester
Avg MW : 614.5g MW : 110.5g
H2C
OH
CH
O
CH2
Glycidyl-ester
H2C CH
O
CH2
OCOR
Free Glycidol
Avg MW : 326g MW : 74g
2 ppm free 3-MCPD = 11 ppm 3-MCPD di-ester
1 ppm free Glycidol = 4.4 ppm Glycidyl ester
Limits 2017: 2 ppm free 3-MCPD
1 ppm free Glycidol
DRY DEGUMMING
0.05-0.15% H3PO4 (85%)70-90°C, 1-15 min
BLEACHING
0.6-1.2% Activated Bleaching Earth90-110°C, 20-40 min, 30-100 mbar
DEODORIZATION
250-265°C, 45-90 min2-4 mbar,0.6-1.2% stripping steam
Crude Palm Oil
Refined Palm Oil
Mitigation options
- Wet degumming
- Other degumming acid
- No acid at all > caustic
- Natural bleaching earth
- Silicas/silicates /zeoliths
- Combination of adsorbents
- acid & alcaline conditions
- Lower temp / longer time
- Dual temp stripping/deodo
- Low P (1-2 mbar)
- Postbleaching/deodorising
3-MCPDE
GE
- fresh oil with high DOBI
- Low FFA / low DAG (GE)
- low Chlorine (3MCPDE)
QUALITY
CPO
washing
Dual
bleaching
Dual temp
stripping /
deodorising
Mild
refining
Solutions
How to mitigate 3MCPDE & GE in oil refining? Ex. Palm Oil
CPO
production
Crude Washed Water
PO
Parameter CPO Washed CPO
FFA (C16:0) 3.67 3.53
P (ppm) 22.3 8
Fe (ppm) 20.3 2.68
Ca (ppm) 20.1 8.7
Mg (ppm) 12.3 1.7
K (ppm) 21.6 0.7
Na (ppm) 1.4 1.2
Reduce
impurities
Less
adsorbents
chemlcals
Crude Degummed Gums
SBO
Parameter Crude Soya WDG Soya
FFA (C 18:1) 0.74 0.38
P (ppm) 700 104
Fe (ppm) 2.77 0.8
Ca (ppm) 71.9 50.7
Mg (ppm) 73.5 29.1
K (ppm) 25.9 7.9
Na (ppm) 1 0.9
WaterdegummingPrevent
settling
during
storage
and
transport
“Simple” waterwashing
Palm oil refining: will washing CPO reduce 3-MCPD?
Cl (ppm) 4 < 2 *
* detection limit
1
1.5
2
2.5
3
3.5
0 1 2 3 4 5
2.54
3-M
CP
D in
re
fin
ed
pa
lm o
il (p
pm
)
C/R
Optimized Physical Refining
Effect of water washing on 3-MCPD ester formation
No Caustic Water AcidWashing
2.29
2.64
3.01
1.86
- Positive effect of water washing (bad quality, stored CPO)
- Most effect of ‘caustic washing’, but less than chemical refining
- More pronounced effect expected when washing is applied on fresh CPO
- not all Cl is a precursor for 3MCPDE (eg. NaCl)
25%
40%
Efficient,
Flexible,
Low effluent
wet CPO
pretreatment
LP
Nano
Allowing
washing
under various
conditions
and even full
chemical
neutralisation
CPO DOBI FFA (%) DAG (%) Activated Bleaching
Earth (HCl)
Natural Bleaching
Earth
MCPD (ppm) MCPD (ppm)
Columbian 1.6 3 5.2 2.3 1.1
S.-E. Asian 1 2.7 4.2 6.1 8.1 1.7
South-American 2.3 4.6 7.2 7.5 1.6
S.-E. Asian 2 1.6 5.1 6.2 9.6 2.7
S.-E. Asian 3 3.1 3.8 5.2 9.7 2.1
Physical Refining : Bleaching with 1.5% activated or natural bleaching earth; Deodorization at 260°C during 1 hr at 3 mbar
- Crude palm oil quality
* more important in physical refining (‘less forgiving’)
* no good quality parameter(s) yet to ‘predict’ 3-MCPDE forming potential
* geographical/regional differences (S.E.Asia vs L-America)
- Type of bleaching earth / adsorbent
* HCL activated BE to be avoided (but what with H2SO4 activated BE?)
* Natural bleaching earth gives lowest 3-MCPDE but less good bleaching
- Specific adsorbents (silicates /zeolithes) can reduce 3-MCPDE but at what cost?
Palm oil refining: how reducing 3-MCPDE in bleaching?
Dual
Bleaching
dry CPO
pretreatmentCombined
use of BE &
specific
adsorbents
under acid &
alkaline
conditions
Minimize GE Formation : Effect of time and temperature
0
2
4
6
8
10
12
14
16
18
20
0 1 2 3 4 5 6
Time (hr)
Gly
cid
yl este
rs (
ppm
) 260°C
240°C230°C
220°C
- Almost no net formation of Glycidyl esters at T < 230°C
- Very fast formation at T > 240°C
- GE measured is the sum of what is formed vs what is stripped
Palm oil refining: can dual temp stripping/deodorisation reduce GE?
“Similar” to TFA in
SBO & RSO
GE can be stripped
(TFA not when in TAG)
3 mbar
1% SS
Can GE be Stripped During Deodorization ?
0
1
2
3
4
5
6
7
225 230 235 240 245 250 255 260 265
Temperature (°C)
GE
(p
pm
)
3 mbar
2 mbar
1 mbar
Glycidyl esters can be stripped from the oil, but……
- Stripping will only be significant at higher temperature/lower pressure
- Under ‘normal’ deodorizing conditions: formation > stripping
- Best strategy is therefore to limit formation (temp. < 240°C)
- Best compromise: strip at high T (250-260°C) , deodorise at low T (230-240°C)
The lower the Pressure,
the higher the NO losses
(MAG, DAG, Toco)
60 min, 1% SS
Effect packed column stripping on GE
Temperature
(°C)
GE
(ppm)
Color
(R – 5,25”)
FFA
(% C16:0)
220 0.10 20 0.12
230 0.14 19 0,09
240 0.17 14 0,07
260 0.20 12 0,04
Dual temp high temp fast stripping / low temp mild deodorisation
Short residence time at high(er) temperature gives:
- Almost no formation of glycidyl esters, even at T > 240°C
- Very efficient FFA stripping but only limited heat bleaching
≠ GE
0.1 ppm≠ FFA
0.0.8%
10 min, 0.5% SS
Dual temp
Dual pressureRBPO
final
treatment
Intermediate
cooling
Optional low P
prestripping
and
poststripping
Low P
Safe
Efficient
Reliable
RBPO final
treatment
P 0.75 - 1.5 mbar
Becoming a std
for new refineries
Safety, a key
concern = now
solved
ParameterCrude
Palm Oil
Standard
PHYSICAL
refining
Standard
PHYSICAL
refining
CHEMICAL
refining
Optimized
PHYSICAL
refining
Activated BE
1%
Natural BE
1%
Natural BE
1%
Natural BE
1%
FFA (% C16:0) 5.83 0.02 0.017 0.013 0.02
Color (Lovibond 5 ¼ “) N.A. 1.8R/23Y 2.0R/24Y 2.3R/19Y 2.5R/32Y
Total chlorine (ppm)
3-MCPD (ppm)
Glycidyl esters (ppm)
5.0
-
N.A.
4.21
3.12
N.A.
1.25
2.94
N.A.
0.48
0.48
N.A.
1.18
0.55
Optimized Physical Refining
3-MCPD esters : standard PR with ABE > standard PR with NBE = optimized PR > Chemical refining
Glycidyl esters : standard PR with ABE = standard PR with NBE > optimized PR = Chemical refining
Standard physical refining : 60 min/260°C/3mbar Chemical refining : 120 min/225°C/3mbar
Optimized physical refining : 15 min/245°C followed by 45 min/230°C
>70%
>80%
0
1
2
3
4
5
6
0 1 2 3 4
Sample number
3-M
CP
D +
GE
(p
pm
)
RBD PO
Post-bleached
Redeodorized
at 260°C
Redeodorized
at 230°C
GE may again be formed during post-deodorization
low deodorization temperature required
4.3
0.1
2.8
0.3
Elimination of GE from Refined Palm Oil
Gly
cid
yl e
ste
rs (p
pm
)
Post-bleaching : 0.5% Activated BE, 110°C, 30 min. Post-deodo : 0.5% stripping steam, 3 mbar, 60 min.
Mild post-refining of RBDPO
MCPDE are more difficult to remove during postrefining
Shift from Chemical to Physical now back to Chemical Refining?
98
99
100
101
102
103
104
105
106
107
108
0 1 2 3 4
% FFA
4%
1.5%
rape
Chemical
Physical
Palm
Re
lative
op
era
tin
g c
ost
Ongoing trend towards more Physical
Refining of Soft Oils
- Cost is main driver
- Applied by refiners with own crushing
- Consistent good refined oil quality is a challenge
Trend to more Chemical Refining for Palm Oil
- Food safety main driver (very low 3-MCPDE/GE)
- Especially for infant food most preferred
A Matter of Cost versus Quality
Chemical Refining: mainly for 3-MCPDE mitigation:
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
0 2 4 6 8 10
0,5
3-M
CP
D (
pp
m)
3-MCPD Esters in Chemical Refined Palm Oil
Industrial +
lab refined samples
- 3-MCPDE formation cannot be completely avoided by Chemical Refining
- Most chemical refined PO : 0.8-1.2 ppm 3-MCPD (= close to 2018 target)
- Still important effect of CPO quality; 3-MCPD < 0.5 ppm remains a challenge
Nano Neutralization in a CPO refinery:
what to expect
Feedstock
Water-degummed soybean oil
(120-170 ppm P; 0.45-0.55% FFA)
Nano Neutralization Classical caustic refining
Process parameters
- Phosphoric acid (ppm)
- NaOH (% 16.6 °Be)
- Pressure (bar)
- Temperature (°C)
0-100
0.7
65
50-60
850-900
1.2
low
70 to 90
Refined Oil Quality
- P-content (ppm)
- Ca & Mg (ppm)
- FFA (%)
- Soaps (ppm)
1-3
< 1
< 0.03
< 100
6-8
< 3
< 0.05
200-300
Ex. 500 TPD Nano Neutralisation of soybean oil
Industrial data
NANO-neutralising/washing
Less
effluent
Less
adsorbentsLess
chemicals
Infant food
food
personal care
oleochemicals
biodiesel
palm oil
Objective parameters
DOBI > 2.5?
FFA < 3.5?
?
CPO quality key determining factor in mitigation of 3-MCPDE & GE
Industry to adopt new best practices to ensure highest CPO quality for food
Clear need for segregation of good & excellent Q for food vs rest for non-food
PO Industry today can produce good-excellent quality food oil (70% FFA < 3.5%,
DOBI >2.5) which equals the amount of PO used in food, so where is the problem?
- Washing of fresh CPO: at 90°C, addition of 5% water followed by mechanical
agitation (5 min) & centrifugation
- Bleaching: CPO mixed with 0.15% citric acid (30% solution) at 85°C for 10 min,
followed by bleaching with BE (Oil- Dri Pure Flo B-80), at 105 °C, 50 mbar, 30
min, & then filtered (1% for good-excellent; 1.5% average-poor quality)
- Neutralization: CPO high shear mixed at 85°C with NaOH solution (14%; 10%
molar excess). 3% water added, maturation 10 min & centrifugation
- Deodorization: dual temperature deodorization at 240°C for 10 min followed by
220°C for 120 min; steam 2% (0.8+1.2%); 3 mbar vacuum.
Effect CPO origin on 3-MCPDE/GE formation: Quality does matter !
3 types of CPO tested: FFA % DOBI
Excellent 1.3 3.4
Good 3.4 2.6
Poor 6.0 1.7
Feedstock RBD PO
Good quality
RBD PO
Good quality
RBD PO
Excellent Q
RBD PO
Excellent Q
Treatment Unwashed
physical refining
Washed
physical refining
Unwashed
physical refining
Unwashed
Chemical refining
FFA % (16:0) 0.04 0.04 0.03 0.02
Color Lovibond
51/4 cell
2.0R/51Y 2.2R/57Y 1.2R/28Y 0.7R/16Y
3-MCPD (ppm)1
2-MCPD (ppm)
GE (ppm)
1.21
0.66
0.40
0.34
0.21
0.42
0.46
0.25
0.27
0.08
0.05
0.24
Effect CPO origin:
Quality does matter !
CPO: 3.4% FFA / DOBI 2.6 CPO: 1.3% FFA / DOBI 3.4
Feedstock RBD PO
Good quality
RBD PO
Good quality
RBD PO
Poor quality
RBD PO
Poor quality
Treatment Unwashed
physical refining
Washed
physical refining
Unwashed
physical refining
Unwashed
Chemical refining
FFA % (16:0) 0.04 0.04 0.06 0.02
Color Lovibond
51/4 cell
2.0R/51Y 2.2R/57Y 6.0R/70Y 2.4R/39Y
3-MCPD (ppm)1
2-MCPD (ppm)
GE (ppm)
1.21
0.66
0.40
0.34
0.21
0.42
2.78
1.31
0.59
1.76
0.79
0.52
Effect CPO origin:
Quality does matter !
CPO: 3.4% FFA / DOBI 2.6 CPO: 6.0% FFA / DOBI 1.7
1. AVOID FORMATION
• Lower Cl precursors in CPO (eg. washing)
• Lower DAG content in CPO (eg. FFA < 3%)
3. REMOVE from refined oil (postrefining)
• Strong alcali to degrade 3-MCPDE
• Strong acid to degrade GE (postbleaching)
• Strip GE (post-stripping at very low P)
2. MINIMIZE FORMATION
• Avoid ABE (HCL) & too strong acids
• Time/temp/pressure control during deodorisation
TARGET
Refined
palm oil with
Low 3-MCPDE &
GE content
Ways to minimize 3MCPDE / GE in RBD Palm Oil
INTERESTERIFICATIONchemical or enzymatic
No change of fatty acid profile
Redistribution of FA in glycerides
HYDROGENATION
Chemical process
Saturation/isomerisation of FA
DRY FRACTIONATIONPhysical Process
Fully Reversible
Some effect on FA composition and TAG distribution
Oil Modification & 3MCPDE/GE: Solution or Problem ?
Declining
demand
(TFA)
Palm Oil Fractionation – industrial data
PO-1 PO-2
IV
3-MCPD (ppm)
GE (ppm)
52.1
4.02
11.4
53.2
6.99
6.3
Stearin Olein Olein Stearin
Yield (%)
IV
3-MCPD (ppm)
GE (ppm)
3-MCPDolein/feed
GEolein/feed
SFC-slurry (%)1
19.2
31.1
2.03
2.13
80.8
57.1
4.63
13.4
1.15
1.18
13-15
74
59.7
8.16
7.33
1.17
1.16
14
26
35.4
3.8
4.07
1Calculated value, assuming all 3-MCPD are concentrated in olein
3-MCPD & GE Distribution in Palm Oil Fractions
* No formation/degradation of 3-MCPD/GE during dry fractionation (mass balance fits)
* 3-MCPD/GE are concentrated in the olein fraction (ALL 3MCPDE/GE are in the liquid)
Dry Fractionation & 3-MCPDE: even more challenging
• Enrichment of 3-MCPD in palm olein fractions
• Fully refined PO is most used as feedstock for dry fractionation
Source : Hinrichsen (Olenex)- data presented at the DGF symposium (Berlin, April 21st-22nd, 2015
RBD palm oil 3 ppm 3-MCPD
Palm stearin 1.7 ppm 3-MCPD
Palm olein 3.4 ppm 3-MCPD
Palm super olein 4.5 ppm 3-MCPD
Soft PMF 2.1 ppm 3-MCPD
80% 20%
55% 45%
Most RBDPO is fractionated & 3-MCPDE limits will be applied also to
PO fractions.
2 ppm
1.5 ppm
1.3 ppm
0.9 ppm
0.5 ppm
• RBD PO with < 1.3 ppm 3-MCPD is needed to get Palm super olein < 2 ppm 3-MCPD
Effect of Chemical Interesterification on 3-MCPDE/GE
0
10
20
30
40
50
60
70
80
90
0
0.5
1
1.5
2
2.5
0 10 20 30 40 50 60 70
3-MCPD GE
Time (min)
3-M
CP
D (
ppm
)
GE
(ppm
)Industrial scale
1.5kg NaOMe/ton oil,
90°C
Strong Alcaline Conditions
during CIE give :
(1) Fast and nearly complete
degradation of 3-MCPDE
(2) Excessive formation of GE
(also fast)
PO CIE PO
3-MCPD (ppm)
GE (ppm)
9.94
5.53
0.77
87.8
Pilot-scale
1kg NaOMe/ton oil,
90°C, 30 min.
Nucleophilic Substitution
Reaction
Chemical Interesterified palm oil3-MCPD = 0.17 ppm and GE = 87.8 ppm
Effect of Chemical Interesterification on 3-MCPDE/GE
Post-Bleaching with 1% HCl ABE
3-MCPD = 0.51 ppm and GE = 0.09 ppm
Post-Deodorization at 230 oC-3 mbar
3- MCPD = 2.53 ppm and GE = 0.69 ppm
Post-Bleaching with 1% H2SO4 BE
3-MCPD = 0.10 ppm and GE = 0.24 ppm
Post-Deodorization at 230 oC-3 mbar
3- MCPD = 0.71 ppm and GE = 0.39 ppm
Post-bleaching with HCl activated BE will increase 3-MCPD again
Post-bleaching with H2SO4 activated BE and post-deodo at moderate temperature
gives low 3-MCPD (< 1 ppm) and low GE (< 0.5 ppm)
Type of BE criticial for 3MCPDE: challenge for BE suppliers to find right alternatives
Effect of Enzymatic Interesterification on 3-MCPD/GE
pH-correction
Reaction
Catalyst:
Lipase
Brush
Deodorization
Pretreated oil
NB/RB/RBD
Enzymatic Interesterification
0
2
4
6
8
10
12
14
1 2 3
3-MCPD GE
Deodorized
230°C-3 mbar
11.5
4.76
11.4
4.96
9.82
2.33
PO EIE PO0
0.5
1
1.5
2
2.5
3
3.5
1 2 3
3-MCPD GE
2.91
PO EIE PO Deodorized
230°C-3 mbar
Continuous EIE (70°C – Lipozyme TL IM)
• Milder Process
• Limited post-refining
No significant impact of Enzymatic Interesterification on 3-MCPD/GE
3.13
2.83
2.11
3.01
1.45
GE
/3-M
CP
D (
ppm
)
Conclusion
No ”one fits all” 3-MCPDE/GE mitigation solution
Best solution depends on:
(1) Plant configuration : chemical or physical, new or existing plant
(2) Required specs: special vs commodity; individual or formulated fat
(3) Technology development, finding the right balance between efficiency,
quality & sustainability
New technical solutions (preventive and curative) are further explored and
developed taking into account COST factor
final refined food oil must remain affordable
