Novel Formulations and Process for
Development of Microencapsulated Krill Oil
L Sanguansri*, Z Shen, S Bhail, LJ Cheng, DY Ying and MA Augustin
CSIRO ANIMAL, FOOD AND HEALTH SCIENCES
AAOCS Omega 3 symposium - Omega-3 Hot Topics: Science, Supply and Sources
6-8 November 2013, Newcastle, NSW, Australia
Outline

Introduction

Why Krill Oil

Our strategy

Results

Summary
2 | Luz Sanguansri
Why Krill Oil

Krill oil (KO) is a premium source of marine omega-3 fatty acids

KO has a unique combination of omega-3 phospholipids and
astaxanthin

KO has inherent emulsifying power due to its phospholipids

Long chain omega-3 fatty acids in KO is susceptible to oxidation

KO has strong flavour and odour-might be unpleasant to some people
(challenge)

Market for KO is expected to be the fastest growing segment in the
global omega-3 ingredient market
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*Frost & Sullivan, June 2011
Previous experience with different ω-3 oils
- using standard emulsion preparation procedure
- using heated protein-CHO as encapsulant
Powder with
different oil
TG
P1
PL
Emulsion
size
(D, 0.5) µm
Powder
IP (hr)
@ 80°C
Omega-3
(DHA/ EPA)
(g/100 g oil)
Total fat
(g/100 g
powder)
Surface fat
(g/100 g
powder)

0.35
23.2
42 (15/27)
50
0.37
P2

0.12
11.8
55 (22/33)
50
0.31
P3

1.20
~1.4
30 (10/20)
50
16.12
P4

0.45
60.5
30 (25/5)
50
0.62

Oil rich in PL has larger emulsion particle size and higher powder surface fat than
triglyceride oils using the same formulation and process conditions
4 | Luz Sanguansri
Typical major lipid components of krill oil,
algal oil and fish oil
Krill Oil
Triacylglycerol
Diacylglycerol
Monoacylglycerol
Free fatty acids
Total neutral lipids
Phosphatidylcholin
Lyso-phosphatidylcholin
Phosphatidyletanolamin
Total polar lipids
Astaxanthin
40%
1.2%
<1%
4.2%
46.8%
35%
3.1%
2.1%
40.0%
>200 ppm
Algal Oil Fish Oil
94.0%
3.0%
<1%
<1%
97.0%
Triacylglycerol
Phospholipid
99%
<1%
99.0%
EPA
KO has ≤40% TAG and ≤40% phospholipids compared to other marine oils
(algal oils and fish oils) with >90% TAG
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DHA
Our strategy

Capitalise on the inherent emulsifying properties of krill oil
phospholipids

Capitalise on the anti-oxidative properties of heated proteincarbohydrates as encapsulant

Apply chemistry and emulsion/material science capabilities to
design the oil-water interface and microcapsule properties
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CSIRO’s Krill Oil Microencapsulation Technology
- Emulsification and Spray Drying Process
Strategy 1
Strategy 2
Krill Oil
Mix water and Krill Oil using high shear
mixer
Adjust pH as required
Neat Krill Oil-in-water Emulsion
Add protein-carbohydrate solution
(60°C) into emulsion
Preparation of
phospholipid
rich interface
Protein + carbohydrate
solution
Adjust pH as required
± Heat Treatment
Standard
emulsion
preparation
steps
Add krill oil and homogenise
Mix until homogeneous
Krill Oil-in-water Emulsion
Krill oil-in-water Emulsion
Spray dry at 180/80°C
Inlet/outlet temperature
Spray dry at 180/80°C
Inlet/outlet temperature
Spray dried Powder:
Krill Oil embedded in Proteincarbohydrate Matrix
Spray dried Powder:
Krill Oil embedded in Proteincarbohydrate Matrix
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CSIRO’s Patented Technology
Particle size distribution and zeta-potential of KO
in H2O emulsions (Strategy 1)
Zeta-potential
(mV)
10% KO emulsion: neat or in 1% Protein, 2.5% Protein or 3%
Heated Protein-CHO
16
KO emulsions (pH 8)
14
Volume (%)
12
10
8
6
4
2
0
0.01
0.1
1
Particle size (µm)
10
100
pH 8.0
10% KO neat
-50.40±3.3
10% KO in 1% Protein1
-25.9±1.0
10% KO in 2.5% Protein1
-19.3±0.6
10% KO in 3% Heated Protein2-CHO
-49.6±3.03
For comparison:
10% fish oil in 3% Heated Protein2-CHO
1Isolectric Point
-36.5±1.0
= 7-9 (almost no charge at pH8)
4-5 (negative charge at pH8)
2Isoelectric Point =
• Emulsion stabilised by Protein1 has weaker charge of the oil-water interface
• Emulsion stabilised by Heated protein2 -CHO (MRP) as encapsulant maintained the strong charge of the oilwater interface
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KO emulsion 17.5 months at 4°C
Stability of Krill Oil emulsions
during accelerated storage at 40°C
Analysis of remaining EPA during storage
Analysis of remaining DHA during storage
Propanal Headspace Analysis during storage
100
% Remaining of EPA
90
80
70
60
300000
90
80
70
60
50
50
Day 11
Day 18
Day 25
Day 11
GC area of propanal(x10-4)
% Remaining of DHA
100
250000
200000
150000
100000
50000
0
Day 18
Day 25
• pH has no significant effect on oxidation of neat KO in water emulsion during storage
• Encapsulation significantly improved the stability of krill oil-in-water emulsions during
storage
• Heated protein-CHO (MRP) encapsulant provided the best protection from oxidation
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Day 11
Day 18
Day 25
CSIRO’s Krill Oil Microencapsulation Technology
- Strategy 1 vs. Strategy 2
Strategy 1
Strategy 2
Krill Oil
Protein + carbohydrate
solution
Mix water and Krill Oil using high shear
mixer
Adjust pH as required
Adjust pH as required
Neat Krill Oil-in-water Emulsion
± Heat Treatment
Add protein-carbohydrate solution
(60°C) into emulsion
Add krill oil and homogenise
Mix until homogeneous
Krill Oil-in-water Emulsion
Spray dry at 180/80°C
Inlet/outlet temperature
Spray dried Powder:
Krill Oil embedded in Proteincarbohydrate Matrix
10 | Luz Sanguansri
Same formulation,
Different process
Different in zeta potential
(different oil-water interface)
Krill oil-in-water Emulsion
Spray dry at 180/80°C
Inlet/outlet temperature
Spray dried Powder:
Krill Oil embedded in Proteincarbohydrate Matrix
CSIRO’s Patented Technology
Stability of Krill oil powder during storage at
40°C
100
14
12
10
8
6
4
2
0
50% KO P1
Day 0
50% KO P2
50% KO P3
50% KO P4
Day 17
Day 28
Percentage remaining of LC-n-3 PUFAs
Propanal GC area (x10-4)
16
90
80
70
60
50
EPA
DHA
Day 0
50% KO P1
EPA
DHA
EPA
day 17
50% KO P2
50% KO P3
DHA
Day 28
50% KO P4
P1 10% KO neat + maltodextrin (Strategy 1)
P2 10% KO in 1% protein + maltodextrin (Strategy 1)
P3 10% KO in 3% heated protein-carbohydrates + maltodextrin (Strategy 1)
P4 10% KO in 3% heated protein-carbohydrates + maltodextrin (Strategy 2)
Heated protein-CHO (MRP) encapsulant provided the best
protection from oxidation during storage
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CSIRO’s Microencapsulation Technology
- Embedding and Extrusion process
Krill Oil
Mix water and Krill Oil using high
shear mixer
Adjust pH as required
Neat Krill Oil-in-water Emulsion
Add protein-carbohydrate
solution (60°C) into emulsion
Mix until homogeneous
Krill Oil-in-water Emulsion ± additives
Spray dry at 180/80°C
Inlet/outlet temperature
Add into proteincarbohydrate
High
temperature &
high shear
Mixing
Extrude through a die
Dry
Apply secondary coating
(optional)
Extruded Pellet:
Krill Oil embedded in Proteincarbohydrate Matrix
Spray dried Powder:
Krill Oil embedded in Proteincarbohydrate Matrix
12 | Luz Sanguansri
CSIRO’s Patented Technology
Extruded samples with Krill Oil (non-expanded)
KO emulsion embedded in
different matrices
KO Content
(% dry basis)
Ratio of
DHA/EPA
LF1: KO in water emulsion
(protein-CHO blend matrix)
8.82
0.51
LF1: KO in water emulsion
(heated protein-CHO matrix)
14.14
0.52
LF1: KO in water emulsion
(protein matrix)
15.16
0.52
LF1: KO in water emulsion
(carbohydrate matrix)
11.88
0.50
LF2: KO in MRP emulsion + PP
(carbohydrate matrix)
9.73
0.50
LF3: KO in MRP emulsion
(carbohydrate matrix)
7.10
0.50
Up to 15% krill oil was embedded in protein matrix
Krill oil emulsions were stable during high temperature & high shear extrusion
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Extruded snacks with Krill Oil (expanded)
KO emulsion embedded in
a snack formulation
KO Content
Ratio of
(% dry basis) DHA/EPA
KO in water emulsion
7.76
0.51
KO in MRP emulsion + PP
8.53
0.51
KO in MRP emulsion
3.92
0.50
Up to 8.5% krill oil was embedded in extruded expanded snacks
Krill oil emulsions were stable during extrusion of expanded snacks
14 | Luz Sanguansri
Summary

Microencapsulation enhanced the oxidative stability of krill oil
emulsions and spray dried KO powder during storage

The encapsulant formulation and order of processing affect the
oil-water interface and stability during storage

Protein or protein-carbohydrate encapsulants enhanced the
oxidative stability of KO during storage

Heated protein-carbohydrate encapsulant provided the best
protection from oxidation in emulsion and powder

Stabilised KO emulsions are stable to high temperature and high
shear extrusion
15 | Luz Sanguansri
Acknowledgement

Keith Pitts – for the production of extruded samples

Michael Mazzonetto – for production of krill oil powders
Thank you
CSIRO ANIMAL, FOOD AND HEALTH SCIENCES | PREVENTATIVE HEALTH FLAGSHIP
Luz Sanguansri | Research Team Leader, Food Systems Engineering
Tel: +61 3 9731 3228 | Email: [email protected]
Web: www.csiro.au