Crystallisation and Physical

Properties of Fats
18-19 June 2008
Ghent University, Belgium

Improving the Physical and Chemical

Properties of Cocoa Butter by Selected Oil
Processing Technologies

Dr. ir. G. Calliauwa,b, ir. J. Vila Ayalaa, ir. B. Scholsa, Dr. V. Gibona,
Dr. ir. W. De Greyta, Prof. Dr. ir. I. Foubertc & Prof. Dr. ir. K. Dewettinckb

aDesmet Ballestra Group

bFTE, Ghent University

cKULeuven-Kortrijk
KULeuven-Kortrijk
De Smet Presentation 1
 Outline of the Presentation

• Introduction: Cocoa Butter Processing

• Steam Refining
• Chemical impact
• Crystallization “in process”
• Crystallization “of product”

• (Static Fractionation)
• Principle
• Process
• Product
• Conclusions
De Smet Presentation 2
 Cocoa
Oil Butter
Processing
Processing
Cleaning
Cleaning // Drying
Fermentation Drying Mechanical
Mechanical Extraction
Extraction
Meal
Meal
Roasting
Cracking
Cracking Flaking
Flaking Solvent
Solvent Extraction
Extraction
Bean
Seed
Seed
Dutching
Dehulling
Dehulling
Preparation Extraction
Crude
Crude
Oil
Oil

Speciality
Speciality Fats
Fats Hydrogenation
Hydrogenation
Degumming
Degumming
Frying
Frying oil
oil Interesterification
Interesterification
Neutralising
Neutralising
Margarine
Margarine Fractionation
Fractionation
Refined
Refined Bleaching
Bleaching
Modification Oil
Oil
Soap
Soap Winterising
Winterising

Lubricants Deodorising
Deodorising
Lubricants
Oleochemical
Biodiesel Processes Refining
Biodiesel

De Smet Presentation 3
 Oil Quality

OIL PROCESSING
Organoleptic/stability Functional Properties
-Desired taste, odour - Good melting profile
-Light color (brilliant) - Desired Plasticity
-High thermal stability
OIL - Crystallisation kinetics
-High oxidative stability
-Long shelf life QUALITY

Refining Modification

Nutritional Quality
- Balanced FA composition
- No trans FA
- High tocopherol content,…

De Smet Presentation 4
Steam Refining:
Packed Column
Principle

De Smet Presentation 5
 Steam Refining

Purpose:
1. Removal of unwanted odour and taste
2. Removal of excessive FFA (>1.75% as oleic acid)

while preserving TAG-distribution of oil, colour,

oxidative stability,…

Principle:
Stripping of volatiles with carrier gas (steam) at high
temperature (laws of Raoult & Dalton)

De Smet Presentation 6
 Steam Refining

Packed Column:

∆
∆

•Continuous countercurrent
•Short residence time

De Smet Presentation 7
Steam Refining:
Chemical Impact

De Smet Presentation 8
 Steam Refining:
Odour & Taste, TAG

• Higher temperature leads to more bland taste

Europe: residual aroma desired (e.g. 180°C)
U.S.: favouring bland taste (e.g. 200°C)

• No observable effect on TAG-distribution

TAG-ratios remain unchanged
No TFA formation
No interesterification effects

De Smet Presentation 9
 Steam Refining:
FFA-reduction
1.4
1.4

1.2
1.2 FFA
(%)
FFA-concentration (%)

1% steam
2% steam
ResidualFFA-concentration

1.0
1.0 3% steam

0.8
0.8

0.6
0.6
Residual

0.4
0.4

0.2
0.2

0.0
0.0
0 20
20 40
40 60
60 8080
Mean
Mean vapor
vapor pressure of FFA (hPa)
(mbar)
De Smet Presentation 10
 Steam Refining:
FFA-reduction
Dijkstra equation ( PO)u ( Pv S − PO)
V2 = V1
Steam (%) Transfer units u R² ( Pv S )u +1 − ( PO)u +1
1 1.70 ± 0.18 0.974
2 2.04 ± 0.10 lower model quality 0.994

3 1.93 ± 0.09 0.995

Bailey equation P .O V
S = . ln 1
Steam (%) A B E (%) R² E . Pv V2
1 1.40 ± 0.06 0.136 ± 0.011 82 0.992
2 lower model quality
1.33 ± 0.03 0.272 ± 0.014 91 0.992
3 1.33 ± 0.02 0.393 ± 0.018 90 0.999
Extended Bailey equation V 2 = y 0 + a exp( −bPv )
Steam (%) A B y0 E (%) R²
1 1.40 ± 0.05 0.138 ± 0.012 0.03 ± 0.02 83 0.993
2 1.32 ± 0.04 0.288 ± 0.021 0.04 ± 0.02 96 0.996
3 1.32 ± 0.02 0.390 ± 0.014 0.01 ± 0.03 94 0.999

FFA-removal can be described by various physical/mathematical models

De Smet Presentation 11
 Steam Refining:
Colour of Cocoa Butter
250
Natural
240 Alkalized
Bleached Alkalized
Crude Natural
230 Crude Alkalized
Crude Bleached Alkalized Depending on feedstock
220
pre-treatment and process
210 conditions:
Total Color (-)

200

190 Heat bleaching

180
Heat darkening
170

110
Heat bleaching
100
150 160 170 180 190 200 210 220 230

Deodorization Temperature (°C)

De Smet Presentation 12
 Steam Refining:
Theobromine & Caffeine

100
Free Fatty Acids At mild temperatures:
Theobromine
Residual concentration in CB (%)

80 Caffeine Removal of T & C > FFA

60

40

20
Deposit of T & C in vapour

0 condensation system
140 160 180 200 220 240 260 280

Stripping Temperature (°C)

De Smet Presentation 13
Steam Refining:
Crystallization
‘in process’

De Smet Presentation 14
 Steam Refining:
Theobromine & Caffeine

1e+6
Theobromine in FAD
Theobromine in CB
Caffeine in FAD
1e+5 Caffeine in CB

Adjustment of
Solubility (ppm)

1e+4
scrubber
x3 temperatures to
1e+3
solve T&C in FAD

1e+2

+ 40°C
1e+1
40 60 80 100 120 140 160

Temperature (°C)

De Smet Presentation 15
Steam Refining:
Crystallization
of Product

De Smet Presentation 16
Steam Refined Cocoa Butter:
Non-isothermal crystallization

• DSC
• 3 repetitions
• 3 factors
Temperature
Steam
FFA

• 8 parameters
• FMLR

De Smet Presentation 17
 Steam Refined Cocoa Butter:
Non-isothermal crystallization

• Models show…
I.C. Temperature (°C) Steam (%) FFA (%) R²
Heat (J/g) 74.53 0.0320* n.s. n.s. 0.22
Crystallization

Start temperature (°C) 15.05 0.0235* n.s. 1.163 0.19

Onset temperature (°C) 18.07 n.s. n.s. -0.043* 0.43
Peak max 1 (°C) 13.39 n.s. 0.185 0.376* 0.26
Peak max 2 (°C) 2.09 n.s. n.s. n.s. -
Heat (J/g) 86.27 n.s. n.s. -3.01* 0.31
Melting

Onset temperature (°C) 11.01 0.0097 n.s. 0.982* 0.23

Peak max (°C) 26.23 -0.0129 -0.022 -1.422* 0.53

•I.C.: intercept
•n.s.: not significant
•*most significant variable as indicated by ANOVA

…overall low influence, FFA most significant

De Smet Presentation 18
 Steam Refined Cocoa Butter:
Isothermal crystallization at 20°C
50

45

• XRD-measurements show: 40

Isotherm al time (min)

35

30
25

Inten
1. Two-step crystallization: to ’ 20

si ty
140

(a.u.)
120

1 00

80

60

40

2. Earlier formation of in strongly refined CB 20

17 18 19 20 21 22 23 24 25

2θ (°)

3. Slightly higher angles in SAXS for in strongly refined CB

4. Slightly sooner occurrence of ’

• Modeling the ’ isothermal crystallization with

Foubert-model:
( ( ) )
1
(1 − n ) (( n − 1 )K (t − t _ ind ))
f ( t ) = a F 1 − 1 + 0 . 99 −1 e 1− n

De Smet Presentation 19
 Steam Refined Cocoa Butter:
Isothermal crystallization at 20°C

• When plotted as function of FFA, models show…

86
Up to 12% more heat release by ‘-crystals 0 .4 0
(J/g)

84

for 1.4% FFA removed

time t_ind a(h)
at equilibrium F

08.3
26

80
Induction

0 .3 2
Reduced induction times
Heat release

78

76
0 .2 8

74
Overall, increasing rate constants 0 .0
0 .0 0 .2
0 .2 0 .4
0 .4 0 .6
0 .6 0 .8
0 .8 1 .0
1 .0 1 .21 .2 1 .41 .4

FFFFAA-co
-connce
cen n tra
tra tiotio
n ninincoco
coco
a a
b ubtte
u tte r (%
r (% ) )

De Smet Presentation 20
 Steam Refined Cocoa Butter:
At Equilibrium

• ‘Equilibrium’ after tempering (40h at 24-26°C)

• XRD-measurements show overall presence V

• However, PLM shows:

high FFA

low FFA

De Smet Presentation 21
 Steam Refined Cocoa Butter:
SFC-values at 20, 25 and 30°C

90

80
Solid Fat Content at equilibrium (%)

70

60

S F C a t 2 0 °C
50 S F C a t 2 5 °C
S F C a t 3 0 °C

40

30
1 .4 1 .2 1 .0 0 .8 0 .6 0 .4 0 .2 0 .0

F F A -co n ce n tra tio n in co co a b u tte r (% )

De Smet Presentation 22
 Steam Refined Cocoa Butter:
Predicting SFC?

Process conditions FFA SFC

80
SFC at equilibrium (%)

75

70

40

35
0 20 40 60
Mean vapor pressure of FFA (mbar)

De Smet Presentation 23
 Conclusions
or
• Final Remarks
• The Wrap-up
• The Endtro
• Take Home Messages
• Food for Thought

De Smet Presentation 24
 The Endtro

Current situation for CB:

supply
FFA

1.75% time

demand

• Two-way expanding playing field for steam refining

• Need for efficient FFA-removal in short residence time
De Smet Presentation 25
 Acknowledgements

Prof. Dr. Johan Wouters & ing. Bernadette Norberg

(CBS, FUNDP, Namur) for the use of their XRD-facilities

Further reading
•Calliauw, G., Vila Ayala, J., Gibon, V., Foubert, I., Dewettinck, K., Wouters, J. & De
Greyt, W. (2008) Models for FFA-removal and phase behaviour changes of cocoa
butter by packed column steam refining. Journal of Food Engineering (available
online)

•Vila Ayala, J., Calliauw, G., Foubert, I., Dewettinck, K., Dyer, B. & De Greyt, W. (2007).
Impacts of bleaching and packed column steam refining on cocoa butter properties.
Journal of American Oil Chemists' Society, 84, 1069-1077.
De Smet Presentation 26
 Crystallisation and Physical
Properties of Fats
18-19 June 2008
Ghent University, Belgium

Improving the Physical and Chemical

Properties of Cocoa Butter by Selected Oil
Processing Technologies

Dr. ir. G. Calliauwa,b, ir. J. Vila Ayalaa, ir. B. Scholsa, Dr. V. Gibona,
Dr. ir. W. De Greyta, Prof. Dr. ir. I. Foubertc & Prof. Dr. ir. K. Dewettinckb

aDesmet Ballestra Group

bFTE, Ghent University

cKULeuven-Kortrijk
KULeuven-Kortrijk
De Smet Presentation 27