G. Akay*, Z. Z. Noor*, M Dogru*, B. Calkan and SR Larter** *Process Intensification and Miniaturization Centre, School of Chemical Engineering and Advanced Materials, and **School of Civil Engineering and Geosciences University of Newcastle, Newcastle upon Tyne, NE1 7RU (UK) 1 Intensification of Highly Stable Water-in-Crude Oil Emulsion Separation Under Electric Field in the Presence of Micro-Cellular Demulsifiers

PROCESS INTENSIFICATION IN EMULSION SEPARATION 2

3

4 MICRO-POROUS DEMULSIFIER / ADSORBER (SULPHONATED MICRO-POROUS POLYHIPE POLYMER) (PHP)

PROCESS INTENSIFICATION IN EMULSION SEPARATION 5 PHP PHP-SO 3 Na

6 APPLICATIONS OF POLYHIPE POLYMERS (PHP) Tissue engineering Intensified oil-water emulsion separation Intensified gas / liquid separation Gas clean-up Water clean-up Nano-structured micro-porous metals Micro-bioreactors Bioprocess intensification etc

P Preparation of High Internal Phase Emulsions & POLYHIPE POLYMERS

Capillary Network New Trends in Chemical Engineering TYPES OF PORE IN POLYHIPE POLYMERS Primary Pores 0.5 < D < 300 μm Coalescence Pores Size up to ~ 10 mm Nano Pores by mixed monomer

Nano-structured Microporous Catalyst Support for Bio- and Chemical – Catalysis Nickel catalyst / support

Nano-structured Microporous Catalyst Support for Bio- and Chemical – Catalysis Nickel Catalyst / Support

PROCESS INTENSIFICATION IN EMULSION SEPARATION 11 DEMULSIFICATION OF CRUDE OIL – WATER EMULSIONS ( EFFECT OF PRESSURE / DEMULSIFIER ADSORBER )

PROCESS INTENSIFICATION IN EMULSION SEPARATION 12

PROCESS INTENSIFICATION IN EMULSION SEPARATION 13

PROCESS INTENSIFICATION IN EMULSION SEPARATION EXPERIMENTS WITH BP AMOCO VISCOUS (HARDING) CRUDE 14 Emulsion Preparation Water –in –oil emulsion (50/50) Aqueous phase is model sea water (0.6g CaCl2/L, 5.0g MgCl2 /L and 28.1g NaCl /L) Mixing at 2000 rpm for 15 minutes Stable emulsion for more than 4 weeks (no separation)

PROCESS INTENSIFICATION IN EMULSION SEPARATION Equipment for Electric Field Separation 15

PROCESS INTENSIFICATION IN EMULSION SEPARATION ELECTRIC FIELD SEPARATION 16

PROCESS INTENSIFICATION IN EMULSION SEPARATION BP AMOCO CRUDE OIL 17 EXPERIMENTAL PROCEDURE 0.5 g/kg Demulsifier/adsorber is mixed with emulsion Above mixture pumped into the electric separator while mixing Top electrode is positive (also isolated) while bottom electrode is earthed Emulsion is collected from the top and bottom and oil-water separation was measured within 10 mins, after 1 hour or 24 hours (no agitation during storage)

PROCESS INTENSIFICATION IN EMULSION SEPARATION 18 Constant Electric Field Strength (E=2.5 kV); Variable Flow Rate Immediate Separation

PROCESS INTENSIFICATION IN EMULSION SEPARATION 19 Constant Electric Field Strength (E=2.5 kV); Variable Flow Rate After 1 hour

PROCESS INTENSIFICATION IN EMULSION SEPARATION 20 Constant Electric Field Strength (E=2.5 kV); Variable Flow Rate After 24 hours

PROCESS INTENSIFICATION IN EMULSION SEPARATION 21 Constant Flow Rate (Q= 2.5 ml/min); Variable Electric Field strength Immediately after passage through the separator

PROCESS INTENSIFICATION IN EMULSION SEPARATION 22 Constant Flow Rate (Q= 2.5 ml/min); Variable Electric Field Strength 1 hour after passage through the separator

PROCESS INTENSIFICATION IN EMULSION SEPARATION 23 Scanning Electron Microscopy and EDAX Analysis PHP demulsifier absorbed several of the ionic species that were present in both phases, i.e., Na, Ca, Al, Pb and Mg as well as other compounds including Cl. Thus the demulsifier is also useful for the cleaning of the ‘produced water’ and crude oil. Therefore it is called PHP Demulsifier/Adsorber.

PROCESS INTENSIFICATION IN EMULSION SEPARATION 24 The presence of PHP demulsifier/adsorber intensifies the electric field separation at high emulsion flow rates or at low electric field strengths PHP demulsifier/adsorber also adsorbes metals as well as phenols Demulsification appears to be the result of selective adsorption of surface active species from the emulsion Synergy between the demulsifier/absorber and electric field CONCLUSIONS

PROCESS INTENSIFICATION IN EMULSION SEPARATION 25 Intensified rotating disk granulator (particle technology) Intensified separator * Electric field * Pressure * Flow field * Mixing of PHP Demulsifier/absorber Intensified rotating disk reactor for viscous reactions INTENSIFIED PROCESSING EQUIPMENT

PROCESS INTENSIFICATION IN EMULSION SEPARATION 2 Equipment -2: Rotating Porous Disk Separator and Reactor

PROCESS INTENSIFICATION IN EMULSION SEPARATION 2 TYPICAL ROTOR ELEMENT TO ACHIVE PUMPING, MIXING, SOLID CONVEYING

PROCESS INTENSIFICATION IN EMULSION SEPARATION 28 INTESIFIED ROTATING POROUS DISK SEPARATOR / REACTOR

PROCESS INTENSIFICATION IN EMULSION SEPARATION 29 ACKNOWLEDGEMENTS This research was initially supported by BNFL & Norsk Hydro CURRENT SUPPORT FROM SUSTAINABLE TECHNOLOGIES INITIATIVE (LINK): *Engineering and Physical Sciences Research Council (UK) * Department of Trade and Industry (UK) *Avecia *BLC Research *BP-Amoco * Intensified Technologies Incorporated (ITI) *Safety - Kleen Europe *Triton Chemical Systems *Willacy Oil Services Ltd *University Technology of Malaysia (for ZZ Noor)