XIV th AOCS LA Congress on Oils and Fats

October 18, 2011 Cartagena, Colombia

Eur.Ing. M.Hendrix, Dr. V.Gibon, Dr.Ir. G.Calliauw, Dr.Ir. M. Kellens

Desmet Ballestra Group, Belgium
De Smet Presentation 1
 OIL PROCESSING

Cleaning
Cleaning // Drying
Drying Mechanical
Mechanical Extraction
Extraction
Meal
Meal
Cracking
Cracking Flaking
Flaking Solvent
Solvent Extraction
Extraction
Seed
Seed
Dehulling
Dehulling Crude
Crude
Preparation Extraction 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 2
 Hydrogenation Fractionation
Catalyst Refining

Hydrog. Crystallisation Filtration

Oil Olein
RB(D)
Oil

Oils & Fats

Filtration
Bleaching Stearin

Hydrogen Deodorisation

Modification
C. Interesterification Food processing
E. Interesterification
acid Catalyst
Catalyst
C.I.E. E.I.E.
Oil Oil

mixing Pack bed

reactor
Bleaching Deodorisation
De Smet Presentation 3
 FAT MODIFICATION

HYDROGENATION DRY FRACTIONATION

chemical physical (fully reversible)
• Saturation of FA • Redistribution of TAG
• Fully hydro or low trans fats
• ... Vanaspati

INTERESTERIFICATION
enzymatic (chemical)
• No change of fatty acid profile
• Redistribution of FA on glycerol.

Desmet Ballestra Presentation 4

 FRACTIONATION TECHNOLOGIES

1) Solvent fractionation
- Fat dissolved in a solvent: acetone, hexane, isopropyl alcohol, …
- Continuous process
- Diluted conditions:
No liquid oil occlusion.
Low intersolubility: low tendency to form co-crystals -> good selectivity.
High degree of crystallization (no viscosity problems): single operation.

High costs (large volumes of solvent, explosion proof)

High energy consumption (cooling at low temperature, evaporation of solvent)
Environnemental issues (use of organic solvent)
Not healthy (organic solvents)

Still applied for some Specialty Fats (Shea Butter stearin, high grade HPMF)

De Smet Presentation 5
 Continuous Solvent Fractionation: Principle

Eg. PKO Eg. hexane condenser

Solvent
hexane
recovery
Vacuum pump

Vacuum belt filter

Stearin Olein

refinery refinery
Cooler
crystalliser Olein
miscella Stearin

De Smet Presentation 6
 FRACTIONATION TECHNOLOGIES

2) Detergent fractionation
- Aqueous crystallization using surfactant (SDS) and electrolyte (MgSO4).
- Crystals easily suspended in aqueous phase.
- Light liquid oil separated from heavy water phase containing crystals
(centrifugation).
- Continuous.
High costs (chemicals)
Environnemental issues (effluent problems)
Contamination (in finished products)

Still applied in some fatty acid fractionation plants (production of oleic acid)

De Smet Presentation 7
 Continuous Wet Fractionation: Principle

Mixing tank
Centrifuge

Crystallisers
Water
wetting agent
electrolyte

feed tank
Decanters
Fatty acids
60-70°C

Water phase Stearic acid Oleic acid

To distillation To distillation
8
 FRACTIONATION TECHNOLOGIES

3) Dry fractionation
- Very Economical and « green » technology (environmental friendly):
no effluent, no chemicals, no solvent, no losses.
- Controlled crystallization from the melt by slow cooling.
- Crystallization in the bulk → low degree of crystallization:
multi-step operations and large range of fractions.
- Improved selectivity:
combining proper crystal development with a highly efficient separation.
- Batch.

Product/process developments tend to replace previous technologies

(solvent/detergent/panning and pressing) in favor of the dry fractionation technology

De Smet Presentation 9
DRY FRACTIONATION

De Smet Presentation 10
 FRACTIONATION TECHNOLOGIES

3b) Panning and pressing

- Oil poured in pans and stored in cold rooms to crystallize.
- Cakes wrapped in filter-clothes and stacked in hydraulic presses (HP).

High labour intensive work (partially resolved by the introduction of

continuous belts and automated high pressure membrane press
filters)

Still applied in some lauric fractionation plants (palm kernel stearin based CBS)

De Smet Presentation 11
 Panning and Pressing

Cold room with belt conveyors

Panning &
Block crystallisation
pressing:
conventional PKO
process vs
mechanised Cake breaker, mincer & monopump
system 30 bar filter press
Cake wrapping

Hydraulic presses melting

unwrapping
Semi-
Manual automatic
Olein Stearin Stearin Olein
De Smet Presentation 12
 FRACTIONATION or WINTERIZING

Same principles and similar process (Cooling till Crystallisation)

Winterization: Producing liquid oil with improved cold-tolerance
Fractionation: Separating and recovering any desired oil portion
for multi purpose needs

Winterizing = Fractionation Fractionation = Winterization

Winterization = removing minorcomponents (waxes, traces of sat glyc)
Applied on: Sunflower oil, Corn germ oil, …
continuous (< 0.5% solids)
Ricebran oil, Cottonseed oil
batch (> 2% solids)
Fish Oil, and Brush hydrogenated Fractionation !
batch (>5% solids)
Brush hydrogenated SBO Fractionation !
batch (continuous) (5-10% solids)
De Smet Presentation 13
 Dewaxing and Winterising

Dewaxing: used for removal of bulk waxes

< 200 ppm waxes
after degumming / neutralisation
centrifugal separation
continuous process

Winterisation : improvement of cold stability (at 0°C)

< 50 ppm waxes
after bleaching / deodorisation
separation by filtration
with or without filter aid
continuous or batch process

De Smet Presentation 14
 Continuous dry winterising process
Sunflower and Corn Oil

Horizontal leaf filters

Filter aid

Cold water

Flow meter Filter aid Spent filter aid

Winterised
Oil Oil

Spent filter aid

Cold water
Vertical leaf filters

warm water
Crystalliser

Maturator
De Smet Presentation 15
 Continuous dry winterising process
Sunflower and Corn Oil

Continuous
Leaf
filters

crystalliser
maturator

De Smet Presentation 16
 Dry winterizing process, and Fractionation
Continous and Batch

Oil

Filter Membrane filter press

aid

Cold water

Crystalliser Crystalliser Crystalliser

1 2 3
Olein stearin

Polish Polish
filtration filtration
Spent filter aid
warm water

Maturator

De Smet Presentation 17
 Example for Rice Bran and Cotton Seed oil

Cotton seed oil:

Dewaxing and fractionation in 1 step
Tank crystallisers working in batch
Horizontal Leaf filters, with heating

Batch Tank crystallisers Heated Hor. Leaf Filter

De Smet Presentation 18
DRY FRACTIONATION PRINCIPLES

Crystallisation

Filtration

De Smet Presentation 19
 DRY FRACTIONATION PRINCIPLES

CRYSTALLISATION
[ SSS-SSU-SUU-UUU ] [ SSS-SSU ] + [ SUU-UUU ]
FILTRATION

Purpose : - improvement cold stability (“winterising”)

- improvement oxidative stability (separation S from U)
- change physical properties

De Smet Presentation 20
 DRY FRACTIONATION PRINCIPLES

SSU / SSS

Solid Stearin

OIL Crystallisation Filtration

SSS / SSU/
80 Liquid Olein
SUU / UUU rpm PALM OIL FRACTIONATION
COOLING CURVE

SUU / UUU
70
Viscosity
60
Temperature (°C)

50 Oil temp

40

30 Water

20
Solid Fat Content
10

0 1 2 3 4 5 6
Time (hrs)

De Smet Presentation 21
 DRY FRACTIONATION PRINCIPLES

Fractional crystallization / Separation

• Crystallization from the melted state
• Adapted cooling speed is requested for the best selectivity.
• Steps are :
Full melting to destroy the « thermal memory » of the fat
Crystal initiation or nucleation (in super-cooling conditions)
Crystal growth (removal of heat release and control of viscosity)

Melting Crystal initiation Crystal growth

De Smet Presentation 22
 Oil crystallisation
DRY FRACTIONATION curve
PRINCIPLES

80
PALM OIL FRACTIONATION
COOLING CURVE
70 Crystallisation
= exothermic
60
Temperature (°C)

50

40
H cooling =
30
0.5 kCal / °C.kg
cooling
20 nucleation

10 crystallisation
H crystallisation =
agglomeration
50 kCal / kg
0 1 2 3 4 5 6
Time (hrs)
Oil temp rpm
Viscosity Water temp Solid Fat Content
De Smet Presentation 23
 Crystallization Theory
Fatty acid arrangement

3 3 3
1 3 1 1 1

FA1 C T
FA2 C A
FA3 C
G

2 2 2 2
Fork Chair Chair Chair
SSS SUTS SUCS

S: saturated; U:unsaturated; T:trans; C:cis

De Smet Presentation 24
 Crystallization Theory
TAG arrangement

L-2 L-2 L-3 L-3

SSS SUTS

SSS SUCS
De Smet Presentation 25
 Crystallization Theory
Crystal structure

a>b>c
c

c
b
a b
a

De Smet Presentation 26
 Crystallizaton Theory
Crystal morphology

Ideal Non ideal

defects
Needle
Spherulite

De Smet Presentation 27
 DRY FRACTIONATION PRINCIPLES

- Determined by cooling profile

- Complex: polymorphism (α, β’, β)

intersolubility (phase behaviour liquid vs solid state)

- Stages: Supercooling nucleation

Crystal growth

Maturation / Agglomeration

- two approaches: slow crystallisation / long cooling cycle

fast crystallisation / short cycle

De Smet Presentation 28
 DRY FRACTIONATION PRINCIPLES
Crystallization and seperation

Liquid Nucleation Crystallisation

Separation Agglomeration Maturation

Stearin Olein
De Smet Presentation 29
 DRY FRACTIONATION PRINCIPLES

Fractional crystallization / Separation

•Centrifugal separators: nozzle centrifuge or centrifugal decantor
difference in density liquid vs solid 0.05 kg/l
Filtration: difference in permeability, macromolecular crystals vs molecular liquid
• Vacuum filters: rotary drum or belt filter

•Membrane press filters: 15 bar or 30 bar squeezing pressure

Mixed pack plate design
for 6-30 bar
15-30 mm gap
25-50 mm gap

De Smet Presentation 30
Vacuum Belt Filter
Florentine

Scraping of the
stearin cake

De Smet Presentation 31
Vacuum Drum Filter

Hyd Fish
Oil Frac

Filtration rate dependent

(limited filtration surface !!)
De Smet Presentation 32
 DRY FRACTIONATION PRINCIPLES

Fractional crystallization / Separation

Membrane press filters:
- higher flexibility
- less dependent on filtration rate
(large surface)
- less sensitive to crystal morphology
changes
- higher olein yield / better quality stearin
- better protection against oxidation
- less energy consumption Bigger size → 25m3

Any development Bigger plates → 2x2m

in press filtration?
Higher pressure → 50 bar
De Smet Presentation 33
 MEMBRANE PRESS FILTER

Crystallized oil between membranes and plates

MEMBRANE PLATE MEMBRANE

FILTER CLOTH

Central feed

Corner feed

De Smet Presentation 34
 MEMBRANE PRESS FILTER

Squeezing section Olein flow

De Smet Presentation 35
Membrane Press Filter

Inflatable Chamber
membrane
10-50 mm
Central
feed

Membrane
KM – UM Chamber
KX
Corner plate
Membrane RCplate
Plate
feed

De Smet Presentation 36
 Membrane Press Filter
Filtration sequence

Filling Squeezing

Slurry

filling O
L
cake squeezing E
I
Mixed pack design cake blowing N
for 6-30 bar

cake discharge

STEARIN
De Smet Presentation 37
 MEMBRANE PRESS
Membrane Press FilterFILTER

Top bar
Cake
discharge

std 10  50%
extension

Cake
discharge
Side bar
De Smet Presentation 38
MEMBRANE PRESS FILTER

Stearin hopper

De Smet Presentation 39
 Seperation Technology
Comparison

Press
Press filtration
filtration Centrifugation Vacuum filtration
Filtration data (standard 6 bar)
(16 bar) (drum / belt)

IV palm oil 52 52 52
IV olein 57 57 57
IV stearin 34
32 38 40
SFC slurry 12% 12% 12%
SFC cake 55%
65% / 41%
Yield olein 78%
82% 74-75% 71%

De Smet Presentation 40
 Membrane Press Filter
Effect squeezing and cake thickness

Commodity
fractions Squeezing SFC(1) Yield IV
pressure cake stearin olein stearin olein
50 mm(2)
% % % %
6 bar 55 23.6 76.4 39.7 57.1
15 bar 61 20.0 80.0 36.6 57.1
30 bar(3)
65 18.3 81.7 34.7 57.1
25 mm(2)
% % % %
6 bar 60 20.6 79.4 36.8 57.2
15 bar 66 18.8 81.2 34.9 57.2

30 bar 70 16.2 83.8 32.1 57.2

(1): SFC measured by NMR directly after cake discharge
Specialty (2): chamber width (3): no empty chamber guaranteed
fractions
De Smet Presentation 41
 DRY FRACTIONATION PRINCIPLES

Crystallisers
Crystallisers
Membrane press
filter (MPF)

MPF
Stearin
melting
tanks
(Buffer tank)
olein tanks

De Smet Presentation 42
 DRY FRACTIONATION TECHNOLOGIES

Labo and Pilot plants are essential tools in Fractionation technology

De Smet Presentation 43
 TECHNOGICAL DEVELOPMENTS:
NEW CRYSTALLIZERS
MOBULIZER (low shear)

MOVING COOLING BUNDLES

De Smet Presentation 44
 TECHNOGICAL DEVELOPMENTS:
NEW CRYSTALLIZERS

Low Shear Crystallizer

(special cooling surface Near static crystallization
configuration)

De Smet Presentation 45
TECHNOGICAL DEVELOPMENTS:
NEW CRYSTALLIZERS
AGITATOR (blades)
TIRTIAUX CRYSTALLIZER
(high shear)

STATIC COOLING BUNDLES

De Smet Presentation 46
 TECHNOGICAL DEVELOPMENTS:
Vertical Tube Crystalliser

New generation dynamic

crystallisers used in oil
fractionation with
improved cooling surface
configuration

Vert. cooling tubes

Vert. cooling fins

TX (DB)
De Smet Presentation 47
 TECHNOGICAL DEVELOPMENTS:
CRYSTALLIZERS
AGITATOR
CONCENTRIC CRYSTALLIZER
(high shear)

CONCENTRIC COOLING WALLS

De Smet Presentation 48
 TECHNOGICAL DEVELOPMENTS:
NEW CRYSTALLIZERS
3 hr 23°C 1 hr 17°C
Cocoa PLM PLM Palm Kernel Oil
Palm kernel
butter oil

25 µm

LM
Free
liquid
Entrained
liquid
> 40% SFC

De Smet Presentation 49
TECHNOGICAL DEVELOPMENTS:
NEW CRYSTALLIZERS
STATOLIZER (static)

BLOCK CRYSTALLIZATION

(soft) CAKE DISCHARGE

De Smet Presentation 50
 TECHNOGICAL DEVELOPMENTS:
NEW CRYSTALLIZING SYSTEMS
dynamic Static 4-6 hr
1002D1 1002D2
static
1001
1002S1 1002S2

PKO
F1057/82C
K

PF1002D
Dynamic 2-3 hr PF1002S
1016

F1082B

F1082S PF1082D
T
PF1082ST

De Smet Presentation 51
CRYSTALLIZERS OF FIRST GENERATION

TUBULAR CRYSTALLIZERS
Also functional in FA fractionation

De Smet Presentation 52
CRYSTALLIZERS OF FIRST GENERATION

CONTUBE CRYSTALLIZERS

De Smet Presentation 53
 COOLING CURVES
FOR CRYSTALLIZATION

The oil can be cooled according to :

a) Differential temperature profile : T water = f (T oil)
b) Fixed cooling water temperature profile : T oil = f (T water)
a) DT oil water – T oil – T water controls b) T water control

De Smet Presentation 54
 COOLING CURVES
FOR CRYSTALLIZATION
80
PALM OIL FRACTIONATION
COOLING CURVE
70 Crystallisation
= exothermic
60
Temperature (°C)

50

40
H cooling =
30
0.5 kCal / °C.kg
cooling
20 nucleation

10 crystallisation
H crystallisation =
agglomeration
50 kCal / kg
0 1 2 3 4 5 6
Time (hrs)
Oil temp rpm
Viscosity Water temp Solid Fat Content
De Smet Presentation 55
 COOLING CURVES
Oil controlled Curve

Dynamic
crystallizer with
vertical cooling
plates /coils
(Fractionnement
Tirtiaux)

oil temperature
controlled

De Smet Presentation 56
 PRODUCT DEVELOPMENT

Oleo-
Food Bio-fuel
chemistry

Oil FFA FAME

Dry Fractionation Dry Fractionation Dry Fractionation

Oleins Oleic Acid Oleic FAME

Stearins Stearic Acid Stearic FAME

De Smet Presentation 57
 PRODUCT DEVELOPMENT
Food

Palm Oil SUPERSTEARIN

SUPERSTEARIN

IV
IV 17-21
12-14
Solid route
STEARIN
STEARIN

IV 32-36
PALM
PALM OIL
OIL SOFT
SOFT STEARIN
STEARIN

IV 40-42 HARD
HARD PMF
PMF
IV 51-53

P.M.F.
IV 32-36 HPMF route
P.M.F.

IV 42-48
OLEIN
OLEIN

IV 56-59 RECYCLING

SUPEROLEIN
SUPEROLEIN

TREE
TREE OF OF PALMOIL
PALMOIL IV 64-66 TOPOLEIN
TOPOLEIN
(( IV=
IV= Iodine
Iodine Value
Value ))
FIG 2 Liquid route
IV 70-72

De Smet Presentation 58
 PRODUCT DEVELOPMENT
Food

Solid route: Re-fractionation of Palm Stearin for Super Stearin

RBD Palm Oil

Stearin IV ~ 52
Olein
IV ~ 33-34 ~ 20% ~ 80% Frying oil
IV ~ 56
PPP ~ 25% 15 bar
POP ~ 28%

Super Stearin
~ 70% ~ 30% IV ~ 12-14
30 bar PPP ~ 65%
Soft Stearin POP ~ 10%
IV ~ 41-43 SFC@10°C: ~ 95%
PPP ~ 10% SFC@40°C: ~ 85%
POP ~ 34% Margarine and baking fats SFC@60°C: ~ 20%
SFC@10°C: ~ 75% Dairy substitutes
« Low trans » substitute of hydrogenated products
SFC@25°C: ~ 43%
Hardstock for margarines
SFC@40°C: ~ 16%

De Smet Presentation 59
 PRODUCT DEVELOPMENT
Food

HPMF route: basestock for CBE RBD Palm Oil

IV ~ 52
Stearin ~ 80%
Olein Frying oil
~ 20%
IV 33-34 IV ~ 56
15 bar
~ 45% ~ 55%
15 bar
Soft PMF Super olein
Palm Stearin re-fractionation
IV ~ 45 IV ~ 64-65
~ 10% ~ 90% Salad oil
15 bar
Topped PPP Topped Soft PMF
IV ~ 25 IV ~ 47
~ 35% ~ 65%
30 bar
Mid olein
Hard PMF
IV ~ 52-53
IV ~ 35 SFC*@30°C: ~ 43%
Basestock for CBE DAG < 3% SFC*@35°C: ~ 2%
PPP < 2 % SFC*@40°C: ~ 0%
POP ~ 65-67% * IUPAC tempered

De Smet Presentation 60
 PRODUCT DEVELOPMENT
Food

Liquid route: improved cold stability

RBD Palm Oil

IV ~ 52
Stearin Olein Frying oil
~ 20% ~ 80%
IV 33-34 IV ~ 56
15 bar
~ 43% ~ 57%
15 bar
Soft PMF Recycling
Super olein
IV ~ 45 Salad oil
IV ~ 64-65
~ 50% ~ 50%

< 15 bar

Salad oil
« PMF » Top olein
IV ~ 56-58 IV ~ 72-73

De Smet Presentation 61
 PRODUCT DEVELOPMENT
Food

Palm Kernel Oil Crude or RBD Palm Kernel Oil

IV ~ 18
Single stage Double stage
~ 37% ~ 63% ~ 28% ~ 72%
30 bar 30 bar

PK Stearin PK Olein PK Stearin PK Olein

IV ~ 7 IV ~ 24.5 IV ~ 5.5 IV ~ 23

See double stage Direct use ~ 18% ~ 82%

Hardening CBS 30 bar

PK Stearin
IV ~ 1
PK Stearin Hardening PK Stearin PK Olein
CBS IV ~ 7 IV ~ 27
IV ~ 1
Non dairy ice cream
CBS Coating fats and filling creams
Toffee and caramels
Basestock for interesterification

De Smet Presentation 62
 PRODUCT DEVELOPMENT
Food

Lard fat Crude Lard Fat

IV ~ 67
~ 40% ~ 60%

10 bar
Stearin Olein
IV ~ 51 IV ~ 78
Melting point ~ 50°C Mettler Cloud Point ~ 0°C

Fish Oil
NB Fish Oil
IV ~ 180 Winterization
~ 20% ~ 80%

10 bar
Stearin Olein
IV ~ 135 IV ~ 195
Melting point ~ 45°C Cold test @0°C: > 6 hrs

De Smet Presentation 63
 PRODUCT DEVELOPMENT
Oleo-chemistry

Tallow Fatty Acids Distilled Tallow Fatty Acids

IV ~ 56
C16:0 ~ 24%
C18:0 ~ 19%
C18:1 ~ 41%
C18:2 ~ 6%
C18:3 ~ 0.5%
50-55% 45-50 %
30 bar

Tallow Fatty Acids Stearin Tallow Fatty Acids Olein

IV ~ 20 IV ~ 97
C16:0 ~ 43 %
C16:0 < 5 %
C18:0 ~ 34 %
C18:0 ~ 1 %
C18:1 ~ 15 %
C18:1 ~ 72 %
C18:2 ~ 2 %
C18:2 ~ 10 %
C18:3 ~ 0.1 %
C18:3 ~ 1.5 %
Clear Melting Point: 53-54°C
Mettler Cloud Point < 4°C

De Smet Presentation 64
 PRODUCT DEVELOPMENT
Bio-fuel

Tallow Fat
Splitting - Distillation IV ~ 56-58
SFA ~45%
MUFA ~ 47%
Distilled Tallow Fatty Acids
PUFA ~ 8%

Dry Fractionation IV ~ 93
SFA ~ 10%
50-55%
Distilled Tallow Fatty Acids Olein 30 bar MUFA ~ 77%
PUFA ~ 13%
Acid Esterification Mettler Cloud Point < 4.5°C

Distilled Tallow Methyl Esters

CFPP < -10°C
Mettler Cloud point < - 15°C

De Smet Presentation 65
 TAKE HOME MESSAGES

• Dry fractionation:
Preferred alternative iso solvent and detergent fractionation technologies.

• Multi-step process:
Production of large varieties of fractions.

• Technological improvements:
Increased knowledge in crystallization fundamentals.
Design of new equipments:
MoBulizer (low shear crystallization).
StaTolizer (static crystallization).
Efficiency of the separation:
High pressure membrane press filters.

De Smet Presentation 66
 TAKE HOME MESSAGES

• Edible applications:
RBD Palm Oil (super stearin, CBE, salad oils).
Crude or RBD Palm Kernel Oil (CBS).

• Non edible applications (oleo-chemistry and bio-fuel industry):

FA dry fractionation for oleic acid.
Increased cold stability of FAME.

De Smet Presentation 67
 XIV th AOCS LA Congress on Oils and Fats
October 18, 2011 Cartagena, Colombia

De Smet Presentation 68