References

Conclusions:

Conclusion and perspectives

Introduction

Objectives

STEARINSTEARINSTEARIN

PALM OILPALM OILPALM OIL

OLEINOLEINOLEIN

SUPERSTEARINSUPERSTEARINSUPERSTEARIN

SOFT STEARINSOFT STEARINSOFT STEARIN

P.M.F.P.M.F.P.M.F.

HARD PMFHARD PMFHARD PMF

RECYCLING

SUPEROLEINSUPEROLEINSUPEROLEIN

TOPOLEINTOPOLEINTOPOLEIN

IV 51-53

IV 70-72

IV 56-59

IV 64-66

IV 32-36

IV 17-21

IV 40-42

IV 32-36

IV 42-48

TREE OF PALMOILTREE OF PALMOILTREE OF PALMOIL

( IV= Iodine Value )( IV= Iodine Value )( IV= Iodine Value )

FIG 2FIG 2FIG 2

Multistep Dry-Fractionation Tree of Palm Oil

Palm Oil is without doubt the most fractionated oil.

Multi-step dry fractionation gives rise to soft fractions (Oleins, Superoleins and Topoleins) that are used as salad, cooking and frying oils, and to harder fractions (Stearins and Palm Mid Fractions) finding applications in frying fats, margarines, sho

and speciality fats.

Palm Oil is principallly made of trisaturated TAG’s (SSS), disaturated TAG’s (SUS), monosaturated TAG’s (SUU) and

triunsaturated TAG’s (UUU).

Limitations due to intersolubility (closely linked to polymorphism) make the separation difficult, as co-crystals are formed at each fractionation step. Only restricted enrichments in TAG’s are possible.

GOAL: Highlight the intersolubility phenomenon involved in the dry fractionation

process of Palm Oil.

Several liquid and solid fractions are selected : « Liquid Route ».

Physico-chemical characteristics are examined in order to establish relationships

between melting/plymorphic properties and chemical composition.

Palm Oils:

• Large range of FAME and IV (GLC) (depending on origin).

• No relationship between IV and CP.

• Large range of TAG’s composition (HPLC).

• DSC :

LMP and HMP.

Total melting H : 72.9 (+/-4.6) J/gr.

-0.8

-0.6

-0.4

-0.2

0.0

0.2

He

at

Flo

w (

W/g

)

-60 -40 -20 0 20 40 60

Temperature (°C)

53.352.454.351.654.651.052.8

Exo Up Universal V3.0G TA Instruments

I.V.

51.0

51.6

52.4

52.8

53.3

54.3

54.6

LMP HMP

sub- , sub- 1, , ’2 , ’1 , ’1 (+ ↓

LMP, zone 5-10 C :

2 endo sub-peaks with variable intensities:

Relationship between CP and

relative intensities:

CP ( C) 20.2 21.5 22.9 23 23.5 24.6 25.3

IV 53.3 51.0 54.6 54.3 52.8 52.4 51.6

LMP

( C)

5.5 VHI 5.9 VHI 5.4 HI 6.3 HI 6.7 LI 6.2 LI 5.3 VLI

7.9 VLI 7.7 VLI 7.7 LI 8.6 LI 8.7 HI 8.3 HI 7.6 VHI

% LMP / % HMP: range 60%/40% :

30

35

40

45

50

55

60

65

20 21 22 23 24 25 26

CP (°C)

%

% LMP

% HMP

Relationship between % LMP / % HMP and

CP with « Break-point » at CP near

23 C.

Palm Stearins:

-1.5

-1.0

-0.5

0.0

0.5

He

at

Flo

w (

W/g

)

-60 -40 -20 0 20 40 60 80

Temperature (°C)

36.234.035.633.8??48.2

Exo Up Universal V3.0G TA Instruments

I.V.

33.8

34.0

35.6

46.8

36.2

See below

• Stearin from Filter-press: IV 33.8-35.6.

• Stearin from Vacuum Filter: IV 46.8.

• TAG’s composition (HPLC):

Differences between Filter-press and Vacuum Filter.

LMP HMP VHMP

SSS: 8-10%; SUS: 44-48%; SUU: 38-42% ; UUU: 6-8%FP: SSS: 30-33%; SUS: 47-49%; SUU: 17-19% ; UUU: 1-2%

VF: SSS: 17%; SUS: 46%; SUU: 32% ; UUU: 5%

• DSC: total melting H FP: 80.0 (+/-7.5) J/gr.

total melting H VF: 79.6 J/gr.

sub- , sub- 1, , ’2 , ’1 , ’1 +

See below

MELTING PROFILE, POLYMORPHIC BEHAVIOUR AND CHEMICAL COMPOSITION OF

SOME SELECTED FRACTIONS

ISSUED FROM THE MULTI-STEP DRY FRACTIONATION OF PALM OIL

S. Danthine 1*, C. Deroanne 1, B. Norberg 3, J. Wouters 3 and V. Gibon 2

1 Food Technology Department, Gembloux Agricultural University (FUSAGx), Gembloux, Belgium. * danthine.s@fsagx.ac.be2 Fractionnement Tirtiaux SA, Fleurus, Belgium. 3 Biological Structural Chemistry Laboratory, University of Namur (FUNDP), Namur, Belgium.

LMP, zone 5-10 C :

2 endo peaks : higher intensity

of the second.

% LMP / % HMP / % VHMP:

• Reduction of LMP contribution

compared to Palm Oil.

• Variations in % HMP / % VHMP

in relation to SSS content,

dropping point, stabilisation in and

total melting H.

Soft Stearin IV 36.2 :

Liquid fraction from Stearin IV 33.8.

DSC : total melting H : 72.6 J/gr.

IV 33.8 36.2

% LMP 26.3 48.4

% HMP 40.2 46.7

% VHMP 33.6 4.9

Methods:• FAME and Iodine Value : AOCS Ce 1e-91 and Cd 1c-85.

0

500

1000

1500

2000

2500

15.00 17.00 19.00 21.00 23.00 25.00 27.00

IV 33.8

IV 35.6

• Cloud and

Dropping point :• TAG’s composition : • DSC : • Powder X-Ray diffraction :

Mettler HPLC

15

16

17

18

19

20

21

22

23

24

25

26

500

1000

1500

2000

2500

3000

Intensity (AU)

2 theta

-35°C

-10°C

-2°C

1°C

6°C

13°C

20°C

32°C

44°C

48°C

Melting, Cooling 25 C/min., Heating 5 C/min.

-1.0

-0.5

0.0

0.5

1.0

He

at

Flo

w (

W/g

)

-60 -40 -20 0 20 40 60

Temperature (°C)

64.670.663.858.457.756.457.859.553.1

Exo Up Universal V3.0G TA Instruments

I.V.

53.1

56.4

57.7

57.8

58.4

59.5

63.8

64.6

70.6

Palm Oleins: Palm Mid Fractions:

-0.6

-0.4

-0.2

0.0

0.2

0.4

0.6

He

at

Flo

w (

W/g

)

-40 -20 0 20 40 60

Temperature (°C)

48.335.145.6

Exo Up Universal V3.0G TA Instruments

I.V.

35.1

45.6

48.3

15

16

17

18

19

20

21

22

23

24

25

26

500

1000

1500

2000

2500

3000

Intensity (AU)

2 theta

-35°C

-10°C

5°C

10°C

15°C

22°C

LMP

• Series of Oleins, Superoleins and Topolein with increased IV.

• Better relationship between IV and CP.

IV 56.4 57.7 57.8 58.4 59.5 63.6 64.6 70.6

CP ( C) 9.2 5.0 7.4 4.4 4.0 3.7 3.1 -2.5

« HMP »

• DSC :

Only LMP

« HMP » shoulder is nevertheless observed for lower IV oleins (higher CP).

Three sub-peaks in LMP for oleins, two for superoleins and one for topolein.

Total melting H : 64.0 (+/- 2.0) J/gr (54.0 J/gr for Topolein).

Olein IV 53.1; CP 6.5 C :

Liquid fraction from Hard PMF IV 35.1.

sub- , sub- 1, , ’2 , ’1

sub- , sub- 1, , ’2

sub- , sub- 1,

IV 33.8 34 35.6 46.8

% LMP 26.3 27.4 29.7 50

% HMP 40.2 57.3 53.1 50

% VHMP 33.6 15.3 17.2 -

DP ( C) 55.1 53.8 53.8 42

Total melting H :

IV 33.8 : 85.5 J/gr

IV 35.6 : 71.4 J/gr

See below

IV 56.4 57.7 59.5 63.8 64.6 70.6

OOO 4.2 4.3 5.8 6.2 5.7 12.0

POO 25.5 26.5 31.9 31.3 33.4 35.1

POP 30.7 29.3 28.9 22.8 17.8 6.5

PPP 1.2 0.5 0.0 0.0 0.0 0.0

SSS 1.5 0.5 0.0 0.0 0.0 0.0

SUS 49.1 47.7 44.0 37.8 34.6 16.6

SUU 42.6 45.4 47.5 53.0 56.3 65.6

UUU 6.7 6.4 8.5 9.2 9.1 17.8

• TAG’s composition :

LMP HMP

sub- , , ’1

sub- , sub- 1, , ’2 , ’1

• Two Soft PMF and one Hard PMF.

IV 48.3 45.6 35.1

DP ( C) 30.2 28.3 35.6

• DSC:

Soft PMF’s: LMP + « HMP » shoulder.

Hard PMF: LMP and HMP.

« HMP »

See below

Soft PMF’s :

(IV 48.3) :

LMP : 2.9 C, 11.7 C, 16.9 C.

« HMP » : 26.2 C.

Total melting H : 74.5 J/gr.

(IV 45.6) :

LMP : 12.6 C, 18.2 C.

« HMP » : 26.2 C.

Total melting H : 67.6 J/gr.

Hard PMF:

LMP: 14.5 C

HMP : 24.4 C + shoulder at 33.6 C

% LMP / % HMP : 60% / 40 %

Total melting H : 76.4 J/gr.

IV 48.3 45.6 35.1

OOO 3.5 2.5 1.7

POO 18.0 14.7 5.6

POP 39.7 49.5 65.5

PPP 2.1 1.3 3.0

POS 13.2 9.0 10.3

PPS 0.7 0.3 0.7

SOS 1.9 1.4 1.4

PSS 0.0 0.0 0.1

SSS 2.8 1.6 3.8

SUS 63.5 70.6 85.4

SUU 28.8 24.0 8.6

UUU 4.9 3.8 2.1

• TAG’s composition :

15

16

17

18

19

20

21

22

23

24

25

26

500

1000

1500

2000

2500

3000Intensity (AU)

2 theta

-35 °C

-10 °C

-2 °C

4 °C

9 °C

15 °C

20 °C

30 °C

Palm Oil Palm Stearin Soft PMF Hard PMF

15

16

17

18

19

20

21

22

23

24

25

26

500

1000

1500

2000

2500

3000Intensity (AU)

2 theta

-35 °C

0 °C

8 °C

20 °C

29 °C

Palm Olein Palm Superolein Palm Topolein

3 sub-peaks in LMP 2 sp 1 sp

Palm Oils : Two main populations of intersoluble co-crystals. LMP = sub- , sub- 1, , ’2 . HMP = ’1 , ’1 + ↓ LMP = UUU + SUU. HMP = SUS + SSS.

Palm Stearins : Three main populations of intersoluble co-crystals. LMP = sub- , sub- 1, , ’2 . HMP = ’1 . VHMP = LMP = UUU + SUU HMP = SUS. VHMP = SSS.

Palm Oleins : One main population of intersoluble co-crystals with sub-populations. LMP = sub- , sub- 1, , ’2 , ’1 ↓ LMP = UUU + SUU + SUS.

3 sub-populations below IV 60. 2 sub-populations for IV 63-65. 1 sub-population for IV +/- 70. Relationship with SUS content.

Palm Mid Fractions : Soft PMF : One main population of intersoluble co-crystals with sub-populations : 3 or 2 (SUS + SUU and UUU↓) + HMP shoulder (SUS + SSS).

Hard PMF: Two main populations of intersoluble co-crystals : LMP (SUS) + HMP (SUS + SSS).

15

16

17

18

19

20

21

22

23

24

25

26

500

1000

1500

2000

2500

3000

Intensity (AU)

2 theta

-35 °C

-22 °C

-8 °C

-1 °C

2 °C

15 °C

15

16

17

18

19

20

21

22

23

24

25

26

500

1000

1500

2000

2500

3000

Intensity (AU)

2 theta

-35 °C

-9 °C

2 °C

5 °C

VLI : very low intensity VHI : very high intensity LI : low intensity HI : high intensity

15

16

17

18

19

20

21

22

23

24

25

26

500

1000

1500

2000

2500

3000

Intensity (AU)

2 theta

-35 °C

-9 °C

0 °C

2.5°C

5.5°C

8 °C

12 °C