industrial studies of contaminants removal by oil · pdf fileindustrial studies of...

Industrial Studies of Contaminants Removal by

Oil Refining Xavier Pages

ITERG, French Institute for Fats and Oils, Pessac, FRANCE

1

106 th AOCS Congress, Orlando 2015 May 3-6

106 th AOCS Congress, Orlando, 3-6 May 2015

- ITERG‘s presentation

- Origins of undesirable compounds

- Industrial studies concerning the influence of the

refining process on contaminants residues removal

- Conclusion

Content

2


ITERG is the French Technical Research Centre for producers & transformers of fats and oils (located

at Pessac near Bordeaux)

turn over 2015 : 6 M €

staff : 80 employees

ISO 9001 / ISO 17025 and other quality labels

www.prestations.iterg.com - www.iterg.com

ITERG’s PRESENTATION

3


ITERG’s TECHNOLOGY UNIT

Main facilities : pilot scale equipments

Reactors of (10, 20 & 30 L)

for degumming and

neutralization

bleacher + filter press

deodorizers (2L, 18L, 50

L)

batch hydrogenation,

inter and esterification,....

Lipochemistry reactors

5

http://images.google.fr/imgres?imgurl=http://fond-gouv.qc.ca/110/images/logo_ecocert.jpg&imgrefurl=http://fond-gouv.qc.ca/103/index.htm&h=1772&w=1772&sz=325&hl=fr&start=3&tbnid=JHuY1V041QQ3kM:&tbnh=150&tbnw=150&prev=/images?q=ecocert&svnum=10&hl=fr


Physical and Chemical Refining

( 350 kg - 1 tonne)

ITERG’s TECHNOLOGY UNIT

Main facilities : semi industrial refining unit

6


Use for: processing different fats and oils, research and development

and training

DEODORIZATION UNIT

1Ton capacity

7


Use for research and development in the field of “green chemistry”

New unit (CEDOP 9M€)

8


- Origins of undesirable compounds

- Influence of the refining process on

contaminants residues removal (HAP, phtalates

and pesticides)

- Conclusion

9


Origins of undesirable compounds

10

Environmental contamination metals, dioxins & PCBs, PAHs,

mineral oil

Crop protection pesticide residues, mineral oil

Production process PAHs, mineral oil, phthalates,

3-MCPD esters & glycidol esters Transport & storage phthalates, mineral oil


- Influence of the refining process on

pesticides residues removal : iterg ‘s

studies

- Conclusion

11


•Pesticides tested

Organophosphorus compounds

Dichlorvos, Fenitrothion, Malathion,

Pirimiphos -methyl, ,

Pyrethroids family : Deltamethrin and Cypermethrin

Oils spiked at 2 levels : 0.2 ppm and 2/5 ppm

(obtained by addition of pesticides in crude oils)

Tested Pesticides

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Dichlorvos

Cl

Cl O P

O

O

O CH3CH3

H

Malathion

CH3

O2N O

PS

OO

CH3CH3

Fenitrothion Pyrimiphos-methyl

O

N

NNCH3

CH3

P

SO

O

CH3

CH3

CH3

Tested pesticides : Organophosphorus

compounds

13


Br

Br

CH3

O

O

CN

O

CH3

Deltamethrin

Cypermethrin

Tested pesticides : Pyrethroid

compounds

14


Pesticides

octanol/water

partition factor

(log P)

water

solubility

(mg/L)

molecular

weight

(g/mol)

Vapour

pressure

(mPa)

Dichlorvos 1,47 8800 221 1600

Fenitrothion 3,38 14 277 18

Malathion 2,89 145 330 5,3

Pirimiphos methyl 4,2 5 305 2

Cypermethrin 6,3 0,01 416 3.10-9mm

Deltamethrin 4,6 0,002 505 0,012

•Other important charateristics: Thermal stability

and chemical stability

Main characteristics of studied

pesticides

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Acid conditioning : 0,1% phosphoric acid, 80°C, 45 mn

Neutralization : caustic soda 3N, 70°C, 30 mn,

Centrifugation, Washings and drying

Bleaching : 0.5- 1% of Tonsil optimum 210 FF, 90°C, 40 mbar, 40 mn,

Filtration

Deodorization : 180 - 220°C, O.5- 1 %/h of steam, 3-4 mbar 1-4H ( depending of trial)

Chemical refining : Operating

conditions on 1ton capacity unit

16


Acid conditionning : 0,1% phosphoric acid, 80°C, 45 mn

Bleaching:

0.5-1 % Tonsil optimum 210 FF, 90°C, 40 mbar, 45

mn

Filtration

Deacidification :

240/260 °C, 0.5-1 %/h of steam, 3 mbar

2h30 - 4H

Physical refining

Operating conditions

17


313,5 320,9 313,2

221,6

0 0 0 0 0

0

50

100

150

200

250

300

350

Crude

Dop

ed

Dem

ucila

gine

d

Con

ditio

nned

Neutra

lized

Was

hed

Neutra

lized

Was

hed

2 tim

es

Bleac

hed

0,8%

180°

C, 2h3

0, 0

,5%

vap

220°

C, 3h,

0,5

% v

ap

Dic

hlo

rvo

s c

on

ten

t (µ

g/K

g)

Content of DICHLORVOS content during

chemical refining (1 ton)

Deodorized

Bleached Deodorized

180° 220°

18

neutralized


Pirimiphos-méthyl content . Chemical refining 1 ton

2953.3

3264.83167.3

23.2 0 0

0

500

1000

1500

2000

2500

3000

3500

Brute dopée Neutra centri Neutra lavée 3 fois Décolo 0,7%

terres

220°C, 3h, 3 Kg/h

vap

220°C, 3h, 6 Kg/h

vap

Te

ne

ur

en

Pir

imip

ho

s-m

éth

yl (µ

g/K

g)

:

MRL (oleaginous seeds)

0.05 ppm (FR et UE) level :3 PPM

Content of PIRIMIPHOS-METHYL during chemical refining on pilot

plant (1 ton)

O

N

NNCH3

CH3

P

SO

O

CH3

CH3

CH3

Bleached

19


Why is the bleaching with activated bleaching clay so

efficient to remove the pyrimiphos -methyl from the oil?

min0 5 10 15 20 25 30 35 40

uV

24000

26000

28000

30000

32000

34000

ADC1 B, ADC1 CHANNEL B (04040861\PH000027.D)

27

.90

5

28

.46

9

29

.24

3

35

.56

1 36

.66

7

37

.80

7

Pyrimiphos méthyl

Chlorpyriphos

Fénitrothion

min0 5 10 15 20 25 30 35 40

uV

24000

26000

28000

30000

32000

34000

ADC1 B, ADC1 CHANNEL B (04040861\PH000033.D)

28

.45

6

29

.23

1

35

.54

7 36

.65

3

37

.78

8

O

N

NNCH3

CH3

P

SO

O

CH3

CH3

CH3

- association between positive charges and nitrogen atom

Chomatograms before and after deodorization : no formation of degradation

compounds

Pirimiphos-methyl

20

BleachedVapour *

Vapour ***

180°C

200°C

220°C

240°C

174

84

13

174

27

0

174

00

174

00

0

20

40

60

80

100

120

140

160

180

Teneur

en p

esticid

e (

µg/K

g)

Tdeodorization

temperature, times

2hBleachedDésodo , 1h,

vapour ** Désodo ,

2h30, vapour ** Désodo, 4h,

vapour **

180°C

200°C

220°C

240°C

174

74

37

11

174

26

00

174

00

0

174

00

0

0

20

40

60

80

100

120

140

160

180

Teneur

en p

esticid

e (

µg/K

g)

Deodorization times

Deodorization

temperature

Content of Malathion content during chemical refining (1 ton)


Content of FENITROTHION

during chemical refining (1 ton)

Deodorized

Bleached

22


Deodorized

3901,3

2829,3 2823,7

2577,2

2176,6

987,1

0

500

1000

1500

2000

2500

3000

3500

4000

4500

Brute dopée Neutra centri Neutra lavée 3

fois

Décolo 0,7%

terres

220°C, 3h, 3 Kg/h

vap

220°C, 3h, 6 Kg/h

vap

Te

ne

ur

en

De

lta

mé

thri

ne

(µ

g/K

g)

deltamethrin content during the

chemical refining (1ton)

23


BleachedDésodo ,

1h, vapour

**

Désodo ,

2h30,

vapour **

Désodo,

4h, vapour

**

180°C

200°C

220°C

240°C

6159

47,5

56,3

61

52,5

37 38,2

61

49,446,8

35,6

61

34

21,9

8,10

10

20

30

40

50

60

70

Teneur

en p

esticid

e (

µg/K

g)

Deodorization times

Deodorization

temperature

BleachedVapour *

Vapour ***

180°C

200°C

220°C

240°C

61 62

43,7

61

0

40,8

61

32,632,7

61

26,5

22,4

0

10

20

30

40

50

60

70

Teneur

en p

esticid

e (

µg/K

g)

Deodorization

temperature, times

2h

deltamethrin content during

deodorisation (chemical refining)

Deodorization duration Deodorization temperature, time 2h

24


3147 3145 3108 3066 2951 2957

1063

739

0

500

1000

1500

2000

2500

3000

3500

Huile brutedopée

Huileconditionnée

Huileneutralisée,

lavée etséchée

Huiledécolorée 1%Tonsil 210 FF

Huiledésodorisée

180°C 1h

Huiledésodorisée

180°C 4h

Huiledésodorisée

250°C 1h

Huiledésodorisée

250°C 4h

µg/

kg

Evolution of cypermethrin content

during chemical refining

Deodorization

180°C

250°C

25


Conclusions

• Research of contaminants is part of controls conducted by fat and oil industry to fulfill the EC regulation n°1881/2006.

• Risks are rather limited due to the efficient elimination during oil-refining steps

• Deodorization is the main step for pesticides removal

• Water soluble pesticides are more easy removed by chemical refining

• some contaminants with high molecular weight and low vapor pressure need high temperature of deodorization (pyrethroids)

• For these compounds, analytical controls are advised to manage pesticides removal and in the same time low trans formation and low 3MCPD and glycidol esters formation

28

106 th AOCS Congress, Orlando, 3-6 May 2015 29

Special thanks to….

Florence Lacoste, Marie Gaud,, Jerome Buchoux, Morgan Gouband, Bénédicte Soulet, Cannelle Segalene, Nathalie Trébout

Thank you for your attention !

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