AOCS Shortcourse - Fundamentals of Oilseed and Edible Oil Processing and Refining

November 17-18, 2014 – Crowne Plaza, Shangai Pudong - Shangai, China

Fat Modification Processes:

Dry Fractionation, Chemical and Enzymatic
Interesterification and Hydrogenation

Ir. Jan De Kock & Dr. Ir. Wim Degreyt

Desmet Ballestra Group

Zaventem, Belgium
E-mail : [email protected]
Presentation outline

1. What about fat modification?

2. Dry Fractionation

3. Chemical & Enzymatic Interesterification

4. Hydrogenation

5. Conclusions
 Total Yearly Edible Oil Production : 169 Mio tons
- Oversupply LIQUID oils

- Oil Modification required for use in food

Rape Oil, 14%
Rapeseed oil (14%)

Palm Oil, 28%

Palm Oil (28%)

Others24%
Others, (24%)

SunflowerSun
Oil Oil,
(7%)7%

CNO&PKO, 5%
CNO + PKO (5%)
Soya Oil, 22%
Soybean Oil (27%)
Source : FAOSTAT

3
Oils & Fats Processing
Preparation
Extraction
Cleaning /
Drying Mechanical Meal
Extraction
Seed Cracking
Solvent
Dehulling Crude Oil
Extraction
Flaking
Refining

Shortening Modification Degumming

Hydrogenation Neutralising
Salad /
Edible
Frying oil Interesterification Bleaching
Oil
Fractionation Winterising
Margarine
Deodorising
Oils & Fats – Market situation
Oils & Fats – New quality criteria

HEALTH CONCERNS
OIL QUALITY
Nutritional qualities
“STANDARDS” Balanced FA composition
“NEW” High vitamin content (tocos …)

Low or zero trans FA

OIL CONCERNS
No contaminants
Organoleptic properties/oxidative stability No fat degradation products
Bland taste, odourless
ENVIRONMENTAL ISSUES
Light and brilliant colour
No effluent; no waste
Good oxidation parameters (PV and An-V)
No chemicals; no solvent
Good shelf life
Low risk
Good cold stability Lower oil losses
Trans-Fatty Acids

* Double bond naturally occurring in

CIS TRANS cis configuration
CIS
* cis-trans isomerization occurs
mainly during partial hydrogenation

* ‘Natural’ trans fatty acids are formed in

the rumen of ruminants and can be found
in milk fats and animal fats
Trans-Fatty Acids : General characteristics

* Geometrical structure comparable to

Saturated Fatty acids
* trans isomers have higher melting point
C18:1cis (oleic acid) : 14°C
C18:1trans (elaidic acid) : 43.7°C
* Generally unwanted in food fats because
of negative nutritional properties
* Sometimes desired in confectionery fats
(CBR) for typical melting characteristics
Trans-Fatty Acids : Nutritional aspects
• Convincing evidence that consumption of trans FA gives
- increase of total/LDL cholesterol in blood (dose dependent)
- increased risk for coronary heart disease

• Ruminant (natural) versus Industrial trans FA

- No evidence that nutritional properties are different

• Dietary recommendations
- As low as possible (EFSA)
- < 1% Energy equals approx. max. 2 g trans FA/day (FAO)
Low trans Food Fats
Regulatory situation
• Max. trans levels in Food (fats) are set in various countries
• In US, Preliminary determination of FDA : trans FA are not GRAS

Trans Fatty Acids are banned from Food Fats

Partial hydrogenation replaced by dry fractionation and

(chemical/enzymatic) interesterification
Oils & Fats – Why Modification?
MOST EDIBLE OILS HAVE LIMITED APPLICATIONS AS FUNCTIONAL INGREDIENT IN FOOD
PRODUCTS IN THE ORIGINAL FORM

MODIFICATION TECHNOLOGIES ARE APPLIED TO EXTEND AND INCREASE

THEIR USE IN FOOD FORMULATION

THIS IS ACHIEVED BY PHYSICAL OR CHEMICAL MODIFICATIONS OF THE

TRIACYLGLYCEROL COMPOSITION

HISTORICALLY, THIS WAS MOSTLY DONE BY PARTIAL, SELECTIVE HYDROGENATION

NOWADAYS, HYDROGENATED PRODUCTS ARE MORE AND MORE REPLACED BY LOW

OR NON TRANS PRODUCTS

The alternative: FRACTIONATION & INTERESTERIFICATION

TECHNOLOGIES!!
Oil Modification Technologies

INTERESTERIFICATION HYDROGENATION
- Chemical or Enzymatic process - Chemical process
- No change of FA profile - Saturation/isomerization
- Random triglyceride composition - Formation of trans FA

DRY FRACTIONATION
- Physical and Fully Reversible
- No solvents, No chemicals
- Yielding (min.) 2 fractions with different TAG compos.
Outline Presentation

1. What about fat modification?

2. Dry Fractionation

3. Chemical & Enzymatic Interesterification

4. Hydrogenation

5. Conclusions
Dry Fractionation
Principle
• Controlled cooling of a melted fat in a special designed crystallizer
• Separation of crystals and liquid oil (filtration or centrifugation)
• Gives two fractions : Solid (‘Stearin’) and Liquid (‘Olein’)

Process characteristics
• Physical and fully reversible process
• No solvents, no additives, no chemicals : ‘Green Process’
• No yield loss, no post-treatment required
Dry Fractionation : Applications
Food Oleochemistry Biofuel

OIL (TAG) FATTY ACIDS (FA)

METHYL ESTERS (FAME)

- Stearin - « stearic » acid

- « stearic » FAME
- Olein - « oleic » acid
- « oleic » FAME

To improve cold stability = winterization

To improve physical properties
 Dry Fractionation Process
Physical separation of triglycerides
Sat-Sat-Sat Sat-Unsat-Sat Sat-Unsat-Unsat Unsat-Unsat-Unsat Feedstock
SSS SUS SUU UUU

Crystallization + Separation
Sat-Sat-Sat Sat-Unsat-Sat Sat-Unsat-Unsat Unsat-Unsat-Unsat
SSS SUS + SUU UUU

STEARIN OLEIN

- Good physical properties - Good cold stability

- Use in margarines or as shortening - Use as salad oil or frying oil
Dry Fractionation Process

SSU / SSS

Solid Stearin

OIL Crystallisation Filtration

SSS / SSU/
80 Liquid Olein
SUU / UUU rpm PALM OIL FRACTIONATION
COOLING CURVE
70
Viscosity
SUU / UUU
60
Temperature (°C)

50 Oil temp

40

30 Water

20
Solid Fat Content
10

0 1 2 3
Time (hrs)
17
4 5 6
Dry Fractionation : Different Crystallizers
High Shear Crystallizers : (1) Tirtiaux type

Agitation
Blades

Static cooling Bundles or Fins

 Dry Fractionation : Different Crystallizers
High Shear Crystallizers
(2) Concentric crystallizer (3) Tubular crystallizer

AGITATOR

CONCENTRIC
COOLING WALLS
Dry Fractionation : Different Crystallizers
Low Shear Crystallizer : MOBULIZER

MOVING COOLING BUNDLES

 MOBULIZER = Moving Bundle Crystallizer

- Crystallizer with integrated cooling-agitation,

- Shear on crystals is minimized, but homogenuous cooling
with low speed Moving Bundle covering total volume

MOVING COOLING BUNDLES

STATOLIZER = ‘STATIC’ Crystallizer
Static Crystallisation Dynamic pre-crystallisation

Oil Transfer

Cake release Cake Fluidisation Filtration

Dry Fractionation : Separation of fractions
1. Vacuum Filters : Rotary drum or belt
* Continuous filtration

2. Centrifugal Separation
* Nozzle centrifuges or centrifugal decanters

3. Membrane press filters

* Most applied filters in dry fractionation
* Highest olein yield and best stearin quality
* Discontinuous filtration (filtration cycle)
Dry Fractionation : Membrane Press Filter
Discontinuous filtration

1. Filling (2-3 bar) 2. Squeezing (6-30 bar) 3. Filter opening

Olein collection Stearin collection
Dry Fractionation : Membrane Press Filter
Membrane plate Filter plate

FILTER CLOTH Inflatable

membrane

Membrane Filter
plate plate

Chamber (10-50 mm width)

filled with crystallized oil
Dry Fractionation : new developments

Continuous crystallization = iConFrac™

Liquid oil
feed

Crystallized slurry
Crystallization in Batch: “Reaction in Time”

Temperature: 60°C Temperature: 22°C

Solid Fat Content: 0% Solid Fat Content: 10%
Viscosity: 50 cP Viscosity: 350 cP
 Continuous Crystallization: “Reaction in Space”

Temperature: 40°C Achieved with MOBULIZER

Solid Fat Content: 0%
Viscosity: 60 cP

- Gentle, laminar mixing

- Good heat transfer

Temperature: 22°C
Solid Fat Content: 10%
- Internal baffles for better horizontal mixing
Viscosity: 350 cP
1000 tpd flowchart (Palm Olein - IV 56 production)

TO FILTRATION

SIC SIC
SIC SIC

PF1002A1 PF1002A2 PF1002A3 PF1002A4

DN100
MF1082A
FIC

TIC
TIC
PF1078C LAS

F1081B2
Operating PF1078D
PF1078A
F1082A
PF1078D TI PF1078C
PF1050/81B2

Outgoing Palm
TI

F1081B1
4 Units Parallel PF1050/82A

Olein LICA

RBD Palm Oil PF1001A2

500 tpd flowchart (Palm Olein IV 58- 60 production)

TO FILTRATION

SIC SIC
SIC SIC

PF1002A1 PF1002A2 PF1002A3 PF1002A4

DN100
MF1082A
FIC

TIC
TIC
PF1078C LAS

F1081B2
Operating PF1078D
PF1078A
F1082A
PF1078D TI PF1078C
PF1050/81B2

Outgoing Palm
TI

F1081B1
2x2 Units in series PF1050/82A

Olein LICA

For more delicate products

RBD Palm Oil PF1001A2 (superolein production)
250 tpd flowchart (Palm Olein - IV 62 production)

TO FILTRATION

SIC SIC
SIC SIC

PF1002A1 PF1002A2 PF1002A3 PF1002A4

DN100
MF1082A
FIC

TIC
TIC
PF1078C LAS

F1081B2
Operating PF1078D
PF1078A
F1082A
PF1078D TI PF1078C
PF1050/81B2

Outgoing Palm
TI

F1081B1
4 Units in series PF1050/82A

Olein LICA

For more delicate products

RBD Palm Oil PF1001A2 (or olein refractionation)
Process Performance- Palm olein IV 56-58
Up to 15 % higher
throughput
Up to 2 % netto 45% less 35% less 25% better
120 increased yield steam electricity filtration

100

80

60 Batch
Continuous

40

20

0
Capacity Yield S team Electrical Filter Factor

iConFrac™
 iConFrac is a Proven Industrial Technology
First results New Sales in Malaysia, New Sales in Indonesia,
presented at Africa, South America India, South America
PIPOC 3500 tpd 4000 tpd
CFD simulations

2005-2010 2011 2012 2013

Pilot tests
Start-up Start-up
First Industrial Plant Second Industrial Plant
750tpd 500tpd
Europe Indonesia

33
Dry Fractionation – Product development
Multi-stage Fractionation of Refined Palm Oil
New developments :
1. Refractionation of palm stearin
2. Refractionation of super olein
3. Production of good quality H-PMF
RBD Palm Oil
IV ~ 52

1 Stearin
IV 32-36
Olein
IV ~ 56-58

Super olein
Soft PMF
IV ~ 42-48 3 IV ~ 64-66 2
Salad oil
30 bar

Hard PMF Mid olein

IV 32-36 IV ~ 52-53
Palm Oil Fractionation – Product development
1 Palm stearin refractionation
RBD Palm Oil
IV ~ 52
PPP ~ 5% & POP ~ 28%
Stearin
~ 20% ~ 80% Olein
IV ~ 33-34 Frying oil
15 bar IV ~ 56
PPP ~ 25% & POP ~ 28%

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

RBD Palm Oil

IV ~ 52
Olein
Stearin ~ 20% ~ 80%
CP: 10°C Frying oil
IV ~ 56
IV 33-34
15 bar

~ 45% ~ 55%

15 bar
Soft PMF Super olein CP: 4°C Salad oil
IV ~ 45 IV ~ 64-65

Margarine fat ~ 50% ~ 50%

< 15 bar

Recycling CP: -5°C

« PMF » Top olein
IV ~ 56-58 IV ~ 72-73 Salad oil
Palm Oil Fractionation – Product development
3 Production of good quality Hard PMF
Soft PMF
Reblending to IV ~ 45
palm stearin ~ 10% ~ 90%
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

- Traditionally done with solvent fractionation

- Challenge to produce good quality H-PMF via dry fractionation
(fractionation route; crystallizer design ,yield vs quality)
Palm Kernel Oil Fractionation
Single stage fractionation
Crude Palm Kernel oil
IV ∼ 18

Statoliser
18°C SFC-content
60-65 % 35-40 % °C %
20 98
PK Olein PK Stearin CBS 25 92
IV < 25 IV =7 IV ∼1 30 50
35 5
Full Hydrogenation

Done with Static crystallizer

 Palm Kernel Oil Fractionation
Two stage fractionation

Crude Palm Kernel oil

IV ∼ 18

Statoliser
Single stage
22°C SFC-content
71-73 % 27-29 % °C %
20 94
PK Olein PK Stearin 25 84
IV ∼ 23 IV ∼5,0 CBS
30 56
35 1

To refractionation Direct use –

No hydrogenation
 Palm Kernel Oil Fractionation
Two stage fractionation : Olein refractionation

Crude Palm Kernel Olein

IV ∼ 23

Statoliser
Second Step stage
22°C SFC-content
81-83 % 17-19 % °C %
20 96
PK Olein PK Stearin CBS 25 84
IV ∼ 28 IV ∼7 IV ∼1 30 38
35 5
Coating fats, filling creams
Full Hydrogenation
Basestock for interesterification
Presentation outline

1. What about fat modification?

2. Dry Fractionation

3. Chemical & Enzymatic Interesterification

4. Hydrogenation

5. Conclusions
Interesterification: Principle
Enzyme
Oil blend NaOCH3
Interesterified oil
R1R1R1 R 2 R 2 R 2
R1R1R1 + R 2 R 2 R 2 R1R1R2 R 2 R 2 R1
R1R2R1 R 2 R 1 R 2
R2R1R1 R 1R 2 R 2

- Rearrangement of FA (Random TAG composition)

- No change of the FA profile (no trans formation)
- One feedstock gives one interesterified oil
- Chemical catalyst or enzyme (irreversible)
 Interesterification: Objectives
- Improve melting curve (steeper and/or lower melting point)
- Improve physical properties (e.g. plasticity)
- Combine properties of the oil blend
Palm Oil/Fully Hydro Palm Kernel Oil (60/40 w/w) Palm Stearin/Coconut Oil (50/50 w/w)
SFC (%)

SFC (%)
90 90
80 Blend 1 80 Blend 2
CIE blend 1 CIE blend 2
70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 5 10 15 20 25 30 35 40 45 0 5 10 15 20 25 30 35 40 45 50
Temperature (°C) Temperature (°C)
Chemical Interesterification Process

NB, NBD, Drying + De-

RBD Reaction Bleaching Deodorizing
activation

1 2 3 4
- Feedstock : neutralized, bleached or fully refined
1 Drying + Interesterification
* Drying at 120-150°C & 20 mbar to moisture < 100 ppm
* Reaction : 30 min. at 90-120°C & 50 mbar with 0.05-0.1% NaOCH3
2 Catalyst inactivation with water or citric acid solution
3 Bleaching (to remove color bodies and soaps)
4 Deodorization (FFA & FAME stripping, off-flavor removal)
Oil losses during Chemical Interesterification
- Losses from catalyst addition
* 1 mole NaOCH3 gives 1 mole soap and 1 mole FAME
* Hence, 0.1% NaOCH3 gives 1% (soap +FAME)
* Soap is converted in FFA during catalyst inactivation with citric acid
* FFA and FAME are both removed during deodorization (stripping)

- Losses during bleaching & deodorization

* Bleaching : 0.3 x amount of bleaching earth
* Deodorization : 1.3 x (FFA + FAME)

- For CIE with 0.1% and post-bleaching with 0.5% BE

* HIGH OIL LOSSES : 1.5% on incoming oil
Standard Chemical Interesterification

POST-TREATMENT
 Enzymatic Interesterification

LIPOZYME TL IM
• Triacylglycerolhydrolase (also named Lipase)
• Obtained Thermomyces lanuginosus (in past from pancreas)
• Thermo-stable (max 75°C)
• Kosher and Halal approved

= Immobilized enzyme (on silica carrier)

700 μm
• Stabilizes the enzyme
• Allows use in fixed bed reactors
• Gives higher enzyme life time (lower enzyme cost)
Enzymatic Interesterification Process
Contact
NB, NBD, with Lipase Deodorizing
RBD TL IM (NZ)

Feedstock : Fully refined oil (blend)

Enzyme is inactivated by oxidation products and acids.
Enzyme is not sensitive for FFA and water
Required feedstock quality
- Moisture : max. 300 ppm
- Soaps : max. 5 ppm
- Peroxide value : max. 1 meq O2/kg
- p-anisidine value : max. 5
- Water extract of oil : 6.0 < pH < 9.0
Enzymatic Interesterification Process
Contact
NB, NBD, with Lipase Deodorizing
RBD TL IM (NZ)

• Fixed bed reactors

Oil flow : top-to-bottom or bottom-to-top
• Oil flow rate
EIE is a slow reaction : approx. 1000 x slower than CIE
1.0 – 1.7 kg interesterified oil/kg enzyme
Feedstock dependent (conversion of high melting fats is slower)
• Enzyme productivity
2.5 – 4.0 ton interesterified oil/kg enzyme
Enzymatic Interesterification Process
Contact
NB, NBD, with Lipase Deodorizing
RBD TL IM (NZ)

• Post-bleaching
Not required for most of the EIE oil (98 %)
Oil for enzyme conditioning (4 kg oil/kg enzyme) has high FFA content (± 5%)
and high soap content (1000 ppm) and needs to be reprocessed
First EIE oil after enzyme conditions (20 ton/500 kg enzyme) still has
200-300 ppm soaps. It is recommended to collect this soapy oil in a separate
buffer tank and bleach it before blending it with the bulk of the EIE oil

• Post-deodorization
EIE oil requires only mild deodorization (no off-flavors, minimal FFA formation)
Standard Enzymatic Interesterification
Enzymatic Interesterification: Industrial plant

EIE plant – Skid mounted

4 x 500 kg
(48-80 ton/d)
 Chemical versus Enzymatic Interesterification
Palm Stearin / Soybean Oil (70/30 w/w)
SFC (%)

80
Initial Blend
70 Deo CIE Blend
Deo EIE Blend
60

50

40

30 Biggest Delta SFC

20
Delta SFC ~ 10%
10

0
0 5 10 15 20 25 30 35 40 45 50 55 60
Temperature (°C)
IUPAC 2.150 non tempered
Chemical versus Enzymatic Interesterification
90
Starting
Solid Fat Content [%]

80 Material
70 Immobilized
Enzyme
60
Sodium
50 Methoxide
40
30
20
10
0
0 5 10 15 20 25 30 35 40 45 50
Temperature [°C]
Palm stearin/Coconut oil (60/40)
IUPAC 2.150 non tempered
 Chemical versus Enzymatic Interesterification
+ Chemical interesterification
• Gives fully random TAG composition (determined by FA composition)
• Highly reproducible and cost-effective
• Easy (batch)
• Suitable for frequent feedstock changes

- Chemical interesterification
• Hazardous catalyst safe handling required
• Side reactions require proper post-treatment
• High oil losses due to side-reactions (soap and FAME formation)
• Risk of flavour reversion & reduced stability
• Loss in minor-components (eg. antioxidants)
 Chemical versus Enzymatic Interesterification
+ Enzymatic interesterification
• Simple, clean and safe process.
• No side reactions giving higher interesterified oil yield;
• Better quality (less DAG, better oxidative stability) than CIE
• Lower capital investment cost compared to CIE

- Enzymatic interesterification
• Feedstock quality is critical for good enzyme activity
• Enzyme activity is feedstock dependent
• Operating cost largely determined by enzyme cost (enzyme activity)
Oil Modification Processes

COST COMPARISON

Operating cost
Fractionation
Capital cost

Enzymatic IE
2.5 ton oil/kg enzyme

Chemical IE
0.1% CH3ONa

Hydrogenation
Δ IV 50
0 5 10 15 20 25 30 35 40 45 50

Cost in Europe (EUR / ton)

Presentation outline

1. What about fat modification?

2. Dry Fractionation

3. Chemical & Enzymatic Interesterification

4. Hydrogenation

5. Conclusions
Hydrogenation – Still a future ?

Only full hydrogenated fats (IV < 1) are potential feedstock

for zero trans fats

But, full hydrogenated fats mostly have a too high melting

point and can therefore not be used as such.

Full hydrogenated fats can be used in oil blends for

interesterification, but then this will have a high cost

Real potential of full hydrogenation will mainly depend on

feedstock cost (e.g. Sunflower oil vs palm oil)
Presentation outline

1. What about fat modification?

2. Dry Fractionation

3. Chemical & Enzymatic Interesterification

4. Hydrogenation

5. Conclusions
CONCLUSIONS
Dry fractionation is a powerful process to produce many
different zero trans fats starting from a given feedstock (mainly
palm and palm kernel oil).

Continuous fractionation opens the door for further more

economical processing on large scale.

Enzymatic and chemical interesterification allow to further

develop zero trans fats with the same functionality as trans-rich
partial hydrogenated fats.

Still a lot of product development work can be done by

combining
full hydrogenation, dry fractionation and interesterification
to arrive at better zero trans fats of the future !!
 Thank you
for your attention!!!

Science behind technology !

Contact:
Ir. Jan De Kock – Key Account Manager - Desmet Ballestra
Group
mail: [email protected]