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
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 3 *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 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) P1 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
Typical major lipid components of krill oil, algal oil and fish oil Krill Oil Algal Oil Fish Oil Triacylglycerol 40% 94.0% 99% Diacylglycerol 1.2% 3.0% Monoacylglycerol <1% <1% Free fatty acids 4.2% <1% <1% Total neutral lipids 46.8% 97.0% 99.0% Phosphatidylcholin 35% Lyso-phosphatidylcholin 3.1% Phosphatidyletanolamin 2.1% Total polar lipids 40.0% Astaxanthin >200 ppm Phospholipid Triacylglycerol EPA DHA KO has 40% TAG and 40% phospholipids compared to other marine oils (algal oils and fish oils) with >90% TAG 5
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 6
CSIRO s Krill Oil Microencapsulation Technology - Emulsification and Spray Drying Process Strategy 1 Krill Oil Strategy 2 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 Preparation of phospholipid rich interface Protein + carbohydrate solution Adjust ph as required ± Heat Treatment Add krill oil and homogenise Standard emulsion preparation steps 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 7 CSIRO s Patented Technology
Particle size distribution and zeta-potential of KO in H2O emulsions (Strategy 1) Volume (%) 10% KO emulsion: neat or in 1% Protein, 2.5% Protein or 3% Heated Protein-CHO 16 14 12 10 8 6 4 2 0 0.01 0.1 1 10 100 Particle size (µm) Zeta-potential (mv) KO emulsions (ph 8) ph 8.0 10% KO neat -50.40±3.3 10% KO in 1% Protein 1-25.9±1.0 10% KO in 2.5% Protein 1-19.3±0.6 10% KO in 3% Heated Protein 2 -CHO -49.6±3.03 For comparison: 10% fish oil in 3% Heated Protein 2 -CHO -36.5±1.0 1 Isolectric Point = 7-9 (almost no charge at ph8) 2 Isoelectric Point = 4-5 (negative charge at ph8) Emulsion stabilised by Protein 1 has weaker charge of the oil-water interface Emulsion stabilised by Heated protein 2 -CHO (MRP) as encapsulant maintained the strong charge of the oilwater interface 8
% Remaining of EPA % Remaining of DHA GC area of propanal(x10-4) Stability of Krill Oil emulsions during accelerated storage at 40 C KO emulsion 17.5 months at 4 C Analysis of remaining EPA during storage Analysis of remaining DHA during storage Propanal Headspace Analysis during storage 100 90 80 70 60 50 100 90 80 70 60 50 300000 250000 200000 150000 100000 50000 0 Day 11 Day 18 Day 25 Day 11 Day 18 Day 25 Day 11 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 9
CSIRO s Krill Oil Microencapsulation Technology - Strategy 1 vs. Strategy 2 Strategy 1 Krill Oil Strategy 2 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 Spray dry at 180/80 C Inlet/outlet temperature Spray dried Powder: Krill Oil embedded in Proteincarbohydrate Matrix Same formulation, Different process Different in zeta potential (different oil-water interface) Protein + carbohydrate solution Adjust ph as required ± Heat Treatment Add krill oil and homogenise Krill oil-in-water Emulsion Spray dry at 180/80 C Inlet/outlet temperature Spray dried Powder: Krill Oil embedded in Proteincarbohydrate Matrix 10 CSIRO s Patented Technology
Propanal GC area (x10-4) Percentage remaining of LC-n-3 PUFAs Stability of Krill oil powder during storage at 40 C 16 100 14 12 10 90 80 8 70 6 4 2 0 50% KO P1 50% KO P2 50% KO P3 50% KO P4 Day 0 Day 17 Day 28 60 50 EPA DHA EPA DHA EPA DHA Day 0 day 17 Day 28 50% KO P1 50% KO P2 50% KO P3 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 11
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 into proteincarbohydrate High temperature & high shear Mixing Extrude through a die Add protein-carbohydrate solution (60 C) into emulsion Dry Mix until homogeneous Apply secondary coating (optional) Krill Oil-in-water Emulsion ± additives Spray dry at 180/80 C Inlet/outlet temperature Extruded Pellet: Krill Oil embedded in Proteincarbohydrate Matrix Spray dried Powder: Krill Oil embedded in Proteincarbohydrate Matrix 12 CSIRO s Patented Technology
Extruded samples with Krill Oil (non-expanded) KO emulsion embedded in different matrices LF1: KO in water emulsion (protein-cho blend matrix) LF1: KO in water emulsion (heated protein-cho matrix) LF1: KO in water emulsion (protein matrix) LF1: KO in water emulsion (carbohydrate matrix) LF2: KO in MRP emulsion + PP (carbohydrate matrix) LF3: KO in MRP emulsion (carbohydrate matrix) KO Content (% dry basis) Ratio of DHA/EPA 8.82 0.51 14.14 0.52 15.16 0.52 11.88 0.50 9.73 0.50 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 13
Extruded snacks with Krill Oil (expanded) KO emulsion embedded in a snack formulation KO Content (% dry basis) Ratio of 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
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
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 Research Team Leader, Food Systems Engineering Tel: +61 3 9731 3228 Email: luz.sanguansri@csiro.au Web: www.csiro.au