Mitigation of 3-MCPD and G Esters

in refined palm oils

103rd AOCS Annual Meeting & Expo

April 29 – May 2, 2012, Long Beach, CA, USA

Frank Pudel, Bertrand Matthäus,

Anne Freudenstein, Tim Rudolph

Outline

1. Problem

2. Public funded German FEI project

3. Influence of raw material quality on 3-MCPD/G

ester formation

4. Mitigation of 3-MCPD/G ester formation by

changing the refining process

5. Conclusions and outlook

3-MCPD, 2-MCPD, G Esters

Sources: Hrncirik, ILSI Europe Workshop, Nov. 9-10, 2011, Brussels; Granvogl, FEI/BLL/OVID, Nov. 21, Berlin;

Galle-Hoffmann, FEI/BLL/OVID, Nov. 21, Berlin

Free 3-MCPD

- IARC: group 2B „Possibly carcinogenic to

humans“

- SCF/JECFA: TDI of 2 µg/kg body weight

3-MCPD esters

- BfR assumes 100% hydrolysis to free MCPD

by human digestion

Free glycidol

- IARC: group 3

„Probably carcino-

genic to humans“

Glycidyl esters

-Not much data

available

- worst case

assumption

German FEI Project

Clarification of the relationship between formation of 3-MCPD esters and related compounds, process conditions and composition of involved components

Recommendations for the definition of processes resulting in mitigation of 3-MCPD esters and related compounds without impairing product quality

Removal of 3-MCPD esters and related compounds from the refined product

Development of a direct method based on SIVA with LC-MS for the quantification of the esters

Investigations on the formation of 3-monochloropropane-1,2-diol fatty acid esters (3-MCPD esters) in vegetable oils and development of minimization strategies

Deutsches Institut für Lebensmitteltechnik e.V.

Bundesforschungsinstitut für Ernährung und Lebensmittel

Deutsche Forschungsanstalt für Lebensmittelchemie

(DFA)

Mitigation Strategies

Refining

(Changing of the process)

Raw material

(Removal of precursors)

Product

(Removal of the esters)

Soil?

Fertilizer?

Genotype?

Technique of harvest?

Time between ripeness and processing?

Influence of degumming, neutralization,

bleaching and deodorization

Introduction of additionals processing steps

Effect of different organic and inorganic

adsorbens materials with simultaneous

maintenance of the product quality

Capability to form 3-MCPD/G esters

0 1

2 3

4 5 6

7 8

9 10

Avocado- oil

Olive oil

Rapeseed oil

Corn oil Soybean oil

Sun-flower oil

Coconut oil

Palm kernel

fat

3-M

CP

D-F

E a

nd

rel

ated

co

mp

ou

nd

s [m

g/k

g]

Palm- oil

Malaysia

0

2

4

6

8

10

12

14

16

Region A

Region B

Region C

Region D

Region E

Columbia Ghana Indonesia

3-M

CP

D-F

E a

nd

rel

ated

co

mp

ound

s [m

g/k

g]

Heat crude

oils for 2 h

at 240 C.

Influence of DAGs and PCs

0.0

1.0

2.0

3.0

4.0

5.0

6.0

R² = 0.9259

R² = 0.9092

0 5 10 15 20

Diacylglycerols or polar compounds [%]

Diacylglycerol Polar compounds from palm oil

3-M

CP

D e

ster

s an

d r

elat

ed c

om

pound

s [m

g/k

g]

Model

experiments

Influence of CPO´s DAGs

0

5

10

15

20

25

0 1 2 3 4 5 6 7 8 9 10

Content of diacylglycerols [%]

3-M

CP

D e

ster

s an

d r

elat

ed

com

pounds

[mg/k

g]

Importance of Raw Material

Palm fruits are

not suitable for storage

metabolic processes begin already on the tree (at full ripeness) or directly after harvest

very sensitive against pressure and injuries

Formation of

Free fatty acids

Diglycerides

How to Get Good CPO

Fruit harvest

Supply to oil mill

1 – 3 days

Inactivation by thermal treatment

(sterilisation)

Oil extraction

Fruit harvest

Supply to oil mill

3 – 6 hours

Inactivation by thermal treatment

(sterilisation)

Oil extraction

Bunches/loose fruits

intact bunches

Conventional palm oil

Palm oil with low amounts of 3-MCPD esters and related compounds

Influence of Chloride

(TBAC = tetra-n-butyl ammonium chloride)

Added amound of chloride [mg/kg]

R2= 0,9799

0

1

2

3

4

5

6

0 1 2 3 4 5 6 7 8 9 10 11

3-M

CP

D e

ster

s an

d r

elat

ed

com

pounds

[mg/k

g]

Chloride added as NaCl solution

Chloride added as TBAC

R2= 0,9252

Mitigation Strategies

Refining

(Changing of the process)

Raw material

(Removal of precursors)

Product

(Removal of the esters)

Soil?

Fertilizer?

Genotype?

Technique of harvest?

Time between ripeness and processing?

Influence of degumming, neutralization,

bleaching and deodorization

Introduction of additionals processing

steps

Effect of different organic and inorganic

adsorbens materials with simultaneous

maintenance of the product quality

Influence of Degumming

3,9 3,4

3,9

5,6

3,3

52,1

27,4

40,5

33,4

11,9

0

1

2

3

4

5

6

7

CPO 20% water 5 % water 5 % water + 0.2% phosphoric acid

5 % water + 0.3% citric acid

3-M

CP

D e

ster

s an

d r

elat

ed

com

po

un

ds

[mg

/kg

]

0

10

20

30

40

50

60

Ph

osp

ho

lipid

s [mg

/10

0g

]

3-MCPD esters and related compounds

Phospholipids

Source: A. Schwaf, Diplomarbeit, 2009

-40%

Influence of Neutralisation

5,6

3,1 3,6

0

1

2

3

4

5

6

7

No treatment Potassium hydroxide

3-M

CP

D e

ster

s an

d r

elat

ed

com

pounds

[mg/k

g]

Sodium hydroxide

Source: A. Schwaf, Diplomarbeit, 2009

-45% -35%

Influence of Bleaching

CPO

CPO 1% Tonsil 4191 FF

-45%

3-M

CP

D e

ster

s an

d r

elat

ed

com

po

un

ds

[mg

/kg

]

Influence of Deodorisation

1 2 4

180

1 2

210

4 1 2

240

4 1 2

270

4

Am

ount

[mg/k

g]

0

5

10

15

20

25

30

35

40

45

50

Glycidyl esters 3-MCPD esters

Time[h]

Temperature [C]

CPO Washing

no

washing

Temperature [C]

Duration [min]

0

1

2

3

4

5

6

7

60

5

80

5

80

20

100

5

100

10

100

20

3-M

CP

D e

ste

rs a

nd

rela

ted

co

mp

ou

nd

s

[m

g/k

g]

Simulation of deodorisation by heating at 240 °C for120 min

- 38 %

Citric Acid during Deodorisation

0

2

4

6

8

10

12

14

16

Palm oil deodorised

250 °C, 90 min

Palm oil deodorised

250 °C, 90 min +

Cristalline citric acid

Palm oil deodorised

250 °C, 90 min +

Citric acid dilution

3-M

CP

D e

ster

s an

d r

elat

ed

com

pounds

[mg/k

g]

- 55 %

- 25 %

Citric acid should open the epoxide structure of glycidyl esters

Diacetin during Deodorisation

Tonsil 215 FF 250°C, 120 min

Diacetin

Tonsil 118 FF 250°C, 120 min

Diacetin

0

1

2

3

4

5

6

7

Tonsil 215 FF 250°C, 120 min

Tonsil 118 FF 250°C, 120 min

3-M

CP

D e

ste

rs a

nd r

ela

ted

com

pou

nds [m

g/k

g]

- 47 %

- 49

%

- 30

%

Diacetin as a competitor to DAG with a low flashpoint

1 and 2 Step Deodorisation

200°C

120 min

270°C

5 min

270°C

5 min

200°C

120 min

250°C

5 min

200 °C

120 min

250°C

10 min

200°C

120 min

200°C

120 min

250°C

5 min

200°C

120 min

250°C

10 min

250 °C

90 min 270°C

90 min

1. step

2. step

Co

nte

nt

[mg

/kg

]

0

2

4

6

8

10

12

14

16

18

20

3-MCPD esters and related compounds

3-MCPD esters

Starting material: Palm oil, bleached with 1,5 % Tonsil Optimum 215

Short Path Distillation C

on

ten

t [m

g/k

g]

Red palm oil after short path distillation Industrial deodorised palm oil 0

1

2

3

4

5

6

7

8

9

10

11

12 3-MCPD esters and related compounds 3-MCPD esters

Conclusions

In General

Deodorization is the most important step

The other refining steps reduce the capability of the oils to form 3-MCPD esters and related compounds during deodorization

Measures of mitigation

Optimization of the pre-processing of palm fruits with short time of storage between ripeness and processing

Choice of raw material with low contents of precursors

Reducing the temperature during deodorization as low as possible

Introduction of a washing step before refining

Addition of diacetin or citric acid during deodorisation

Use of a two-step deodorization

Use of a short path distillation

Removal of glycidyl esters after refining by treatment with adsorbent materials

Conclusions

Still open

Definition of quality parameters for the raw

material

Optimization of the different steps

Realization into industrial facilities

A subsequent project has been

started.

Acknowlegements

Other involved people:

Patrick Benecke, PPM

Jens-Peter Krause, PPM

Peer Fehling, PPM

Chr. Böhme, MRI

Klaus Vosmann, MRI

Petra Weitkamp, MRI

Andrea Schwaf, WWU Münster, MRI

N. Schumacher, FH Münster, MRI

The presented work was supported by the FEI (Research Association of the German Food Industry), the AiF and the Ministry of Economics and Technology.

AiF-Project No.: BG 16004

Thank you for your attention !