Microchannel Emulsification

OVERVIEW ON THE APPLICATION OF MEMBRANE EMULSIFICATION IN THE FOOD INDUSTRY Dr Henelyta Ribeiro Dr Jo Janssen

Prof Dr Peter Bongers

Unilever R&D Vlaardingen

NanoMemCourse: “Nanostructured Materials and Membrane for Food Processing” 15th – 24th September 2010, Cetraro/Rende, Italy

Outline  Membrane Emulsification (ME) Processes:  Cross-Flow (XME)  Dead-End (PME)  Rotating (RME)  Vibrating (VME)  Microchannel (MCE)

 Production of Particulate Systems by ME  Potential Benefits of ME in the Food Industry Unilever Confidential

2

Conventional Membrane Emulsification Processes Cross-flow system

Stirring system

Membrane vibrating or rotating system

Unilever Confidential

Dead-end system

3

Vladisavljević & Williams. Adv. Colloid Interface Sci., 113, 1-20, 2005.

Parameters influencing ME

Ex. Cross-flow system


4

Charcosset. J. Food Eng., 92, 241-249, 2009.

Membranes Applied in ME  O/W Emulsion (Hydrophilic Membrane)      

SPG (best performance) Polypropylene Polyvinylidene fluoride (PVDF) Poly(tetrafluoroethylene) (PTFE) Polyamid 6,6 (Nylon) Metallic

 W/O Emulsion (Hydrophobic Membrane)  Hydrophilic membranes ca be made hydrophobic by chemical surface modification, especially organic silane coupling agents (non-food grade)


5

Energy Density x Sauter diameter


6

Schuchmann. In: Product Design and Engineering, Vol. 1: Basics and Technologies, Wiley-VCH Verlag, 63-93, 2007.

Dead-End or Premix ME


7

Badolato et al. Congres Mondial de L’Emulsion (CME), Lyon, 2006.

Dead-End or Premix ME Droplet break-up in PME


8

Vladisavljević et al. J Membrane Sci, 284, 373-383, 2006.

Novel Methods Rotating Membrane Emulsification

Windhab. Chemie Ingenieur Technik, 78, 1230, 2006.

Vladisavljević & Williams. J Colloid Int Sci, 229, 396-402, 2006.


9

Novel Methods Vibrating Membrane Emulsification


10 Kelder et al. J Membrane Sci, 304, 50-59, 2007.

Microchannel Emulsification


11

Kobayashi & Nakajima. In: Micro Process Engineering, Wiley-VCH, 149-171, 2006.

MC Plates Asymmetric Straight-Through Continuous phase

Grooved

Dispersed phase

Disperse Disperse phase phase Microchannel Microchannel

Terrace Slit Channel

Continuous phase


Well

12

Droplet Generation by MCE Refined soybean oil was used as the dispersed phase, and Milli-Q water containing 1 wt% sodium dodecyl surface (SDS), as the continuous phase


13

Ribeiro et al. In: Membrane for Food Application, Wiley-VCH, 129-158, 2010.

Influence of Dispersed Phase Flow Rate on the Droplet Size Effect of the dispersed-phase flow rate on the size and size distribution of the produced O/W emulsions. Refined soybean oil was used as the dispersed phase, and Milli-Q water containing 1 wt% sodium dodecyl surface (SDS), as the continuous phase.


14


Microstructure of some Typical Food Products


15

Spread and Whipped Cream Freeze Fracture TEM

5 m

20 m

Crystalline fat at the water/oil interface in a fat continuous low fat spread.

Air cell in a whipped cream, showing crystalline fat droplets stabilizing the foam structure.


16 Norton et al. AIChE Journal, 52, 1632-1640, 2006.

Ice Cream Confocal Microscopy

160 m

125 m

Ice cream showing phase separation Air bubble in ice cream with deof the biopolymers in the matrix phase emulsified fat particles. (green is the milk protein and red is Unilever Confidential the polysaccharide).

17

Norton et al. AIChE Journal, 52, 1632-1640, 2006.

Mayonnaise Confocal Microscopy

80 m Confocal micrograph of low fat mayonnaise showing oil droplets (green) and swollen starch phase (red). Unilever Confidential

18 Norton et al. AIChE Journal, 52, 1632-1640, 2006.

Production of Particulate Systems by ME

O/W Emulsion

W/O Emulsion

W/O/W Emulsion

Other Examples: - Solid lipid microparticles - Foams - Gel particles (eg. Calcium alginate) - Protein microspheres Unilever Confidential

19

Direct Membrane Emulsification Low fat confectionary via encapsulation

Source: MicroPore Technologies


20

Direct Membrane Emulsification W/O/W Emulsion Particle containing Active Molecule


21

Nakashima et al. Adv Drug Deliv Rev, 45, 47-56, 2000.

Cross Flow Membrane Emulsification Production of Whey protein-based Foams


22 Bals & Kulozik, Int Dairy J, 13, 903-908, 2003.

Dead-End Membrane Emulsification Carotenoid-loaded O/W Emulsion Water and emulsifiers

M

Pre-emulsion

N2 O/W Pre-emulsion Water

T = 140°C - 210 °C

Oil + Astaxanthin

T  20°C

TI Heat exchanger

Nylon membrane (Hydrophilic)

T  35 °C

t2s

Astaxanthin crystals in Oil

O/W Fine emulsion

ON

268,24 g

CAstaxanthin = 1 mmol/L Unilever Confidential

23 Ribeiro et al. J Food Sci, 70, E117-E123, 2005.

Dead-End Membrane Emulsification Carotenoid-loaded O/W Emulsion

After 2. Cycle d3,2 (m)

Sauter Diameter after n Cycles 1,0 1,1 1,3 1,4 1,5 1,7 1,8 1,9 2,0 2,2 >2,2

After 1. Cycle d3,2 (m) 0,9 1,0 1,1 1,3 1,4 1,5 1,6 1,8 1,9 2,0 >2,0

After 3. Cycle d3,2 (m)

Unilever

0,8 0,9 1,0 1,2 1,3 1,4 1,6 1,7 1,8 1,9 Confidential>1,9

24

Dead-End Membrane Emulsification Carotenoid-loaded O/W Emulsion – Droplet size distribution after n cycles 100

Q 3 / Vol %

80

• Nylon Membrane • Pore diameter = 0.8 µm

60

j = 40 %

40

DP = 10 bar after 1. cycle after 2. cycle after 3. cycle

20

0 0.01

0.1

1

Droplet Size x / µm Unilever Confidential

10

100 25

Dead-End Membrane Emulsification Production of W/O/W Emulsion containing Biopolymer-gelled Water Droplets


26 Surh et al. J Agric Food Chem, 55, 175-184, 2007.

Microchannel Emulsification (Unilever)

Unilever Confidential Pulido-de-Torres et al., Nanotech 2006, Boston.

27

Microchannel Emulsification Disperse oil phase: Soybean oil + β-Carotene

Microscope video system

-caroteneloaded O/W emulsion

Continuous phase: Water + 1 % Sucrose laureate

Concβ-carotene = 3.3 g/Loil

MC Module

MC Platte

TMC Platte = 39 ºC


28

Ribeiro & Nakajima, Congres Mondial de L’Emulsion (CME), Lyon, 2006.

Microchannel Emulsification Asymmetric Straight-Through MC Plate

Grooved MC Plates

Flow rate Cont. phase = 20 mL/h

Flow rate Cont. phase = 10 mL/h

Flow rate Disp. phase = 0.5 mL/h

Flow rate Disp. phase = 0.1 mL/h

d = 27 μm Unilever Confidential CV = 2.8 %

d = 9 μm29 CV = 5.2 %

Microchannel Emulsification Straight-Through MC Plate Generation of soybean oil-inwater emulsion droplets stabilized by proteins from MCEs: (a) and (b) Generation of uniform droplets. (c) Unstable generation of nonuniform droplets.

(d) Wetting of the dispersed phase on the chip surface.


30



(a) Optical micrograph of W/O emulsion droplets generated by MCE. (b) Images of a giant vesicle observed by bright-field light microscopy (left) and by fluorescence microscopy (right). Unilever Confidential

31



(a) Schematic drawing of the production of a W/O/W emulsion by MCE. (b) Optical micrograph of the generation of uniform soybean oil droplets containing aqueous droplets from MCs. (c) Optical micrograph of the generated oil droplets containing many sub-micron aqueous droplets. The volume fraction of the internal water phase in the oil droplets was 30%. Unilever Confidential 32 Ribeiro et al. In: Membrane for Food Application, Wiley-VCH, 129-158, 2010.

Potential Benefits of ME in the Food Industry


33

Pros x Cons  Pros  Low energy input process (104 to 106 J/m3)  Low shear  Production of narrow droplet size distribution

 Cons  Low flow rate due to irregular microstructure and surface properties  Particulate fouling blocks the membrane pores  Emulsifiers can change the wetting properties of the membrane Unilever Confidential

34

Challenges  Industrial Perspective  Operability of the process     

Increase flux Reduce membrane fouling Easy control & scale-up Easy cleaning process Sustainable technical solution

 Environmental friendly process  Reduction of energy costs  Chemical consumption  Pollution Unilever Confidential  Waste

35

Back Slides

Economic Outlook 

For Unilever, the economic outlook concerns different aspects:

- Can the technology be scaled-up in an economically acceptable way?

- Can it be implemented in the business? - What are the potential benefits in the Unilever product portfolio (food and HPC)?

- Which other applications can be conceived, and can contribute to a successful marketing of the membrane process as such? Unilever Confidential

37

Conventional Membrane Emulsification Processes


38

Lambrich & Schubert. J Membrane Sci, 257, 76-84, 2005.