G. Akay, Z. Z. Noor, M Dogru*, B. Calkan and SR Larter** *Process Intensification and Miniaturization Centre, School of Chemical Engineering and Advanced

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

OBJECTIVES 1. Breakdown (separation) of the emulsion (CRUD) produced during nuclear reprocessing. 2. To develop an INTENSIFIED (very fast and small volume) oil – water separation process for applications in CRUDE OIL PRODUCTION under DOWNHOLE and SUBSEA conditions. 3. Equipment development for the above.


3

EMULSION SEPARATION TECHNIQUES

ESTABLISHED METHODS

Chemical Demulsifiers

Hydrocyclones

Electric Field

Membranes

NOVEL METHODS

High Pressure

Novel Micro-porous Polymeric Demulsifiers

COMBINED METHODS FOR SYNERGY

(Demulsifier + Electric Field + Pressure)


4

MICRO-POROUS DEMULSIFIER / ADSORBER

(SULPHONATED MICRO-POROUS POLYHIPE POLYMER)

(PHP)


5

PHP PHP-SO3Na

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

PolyHIPE Polymer (PHP)

Polymerisation

High Internal Phase Emulsion

with ε>74%

Pore wall with interconnecting holes (interconnects)

Monomer Aqueous phase

Concentrated emulsion with dispersed phase volume (ε)=74%

Emulsion

Add more aqueous phase

Figure 1.12 Schematic diagram of PHP formation (Adapted from Bryon, 2000).


Polymerisation


with ε>74%




Emulsion



Polymerisation


with ε>74%




Emulsion


Figure 1.12 Schematic diagram of PHP formation (Adapted from Bryon, 2000).

PPreparation of High Internal Phase Emulsions & POLYHIPE POLYMERS

CapillaryNetwork

New Trends in Chemical Engineering

TYPES OF PORE IN POLYHIPE POLYMERS

Primary Pores0.5 < D < 300 μm

Coalescence PoresSize up to ~ 10 mm

Nano Poresby 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


11

DEMULSIFICATION OF CRUDE OIL – WATER EMULSIONS

( EFFECT OF PRESSURE / DEMULSIFIER ADSORBER )


12

NEED FOR NOVEL OIL - WATER

SEPARATION TECHNIQUES

Crude oil contains 10 – 90 % dispersed water

Current technology is designed for onshore

applications

Offshore separation requires small

processing equipment

Current technology is ineffective for highly

viscous crude or when high levels of

indigenous surfactants are present.


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REASONS FOR INTENSIFICATION IN CRUDE OIL PRODUCTION

Reduction of Environmental Impact

Reduction of Crude Oil/ Water Pumping Cost

Utilisation of the Potential Energy at Downhole /

Subsea Conditions

(High Pressure and Temperature)

Lower Capital and Running Costs

Small Offshore Processing Equipment

Oil-in-Water Emulsions are More Common & Environment

Restriction More Strict


EXPERIMENTS WITH BP AMOCO VISCOUS (HARDING) CRUDE

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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)


Equipment for Electric Field Separation

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ELECTRIC FIELD SEPARATION

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BP AMOCO CRUDE OIL

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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)


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0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

100.0

2.0 4.0 6.0 8.0 10.0

Emulsion Flow Rate (mL/min)

Without Addition ofPHP Demulsifeir

With Addition ofPHP Demulsifi er

Constant Electric Field Strength (E=2.5 kV); Variable Flow RateImmediate Separation


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0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

100.0

2.0 4.0 6.0 8.0 10.0

Emulsion Flow Rate (mL/min)

Without Addition of PHPDemulsifier

With Addition of PHP Demulsifier

Constant Electric Field Strength (E=2.5 kV); Variable Flow Rate

After 1 hour


20

0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

100.0

2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0

E mulsion Flow Rate (mL/min)

Without Addition ofPHP Demulsifeir

With Addition of PHPDemulsifi er

Constant Electric Field Strength (E=2.5 kV); Variable Flow Rate

After 24 hours


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0

10

20

30

40

50

60

70

80

90

100

1.0 2.0 3.0 4.0 5.0

Electric Field Stregth (kV)

WithoutAddition ofDemulsifier

With Addition ofDemulsifier

Constant Flow Rate (Q= 2.5 ml/min); Variable Electric Field strength Immediately after passage through the separator


22

0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

100.0

1.0 2.0 3.0 4.0 5.0

Electr ic Field Strength (kV)

Without Addition of PHPDemulsifi er

With addition of PHP Demulsifi er

Constant Flow Rate (Q= 2.5 ml/min); Variable Electric Field Strength 1 hour after passage through the separator


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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.


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• 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


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• 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


2

OIL

EMULSION DEMULSIFIER

Retantatefor

analysis

Demulsifierfor

analysis

Emulsion-DemulsifierSeparator

RetantateRecycle

WATER

Rotating Porous Disk-CDDM-Separator in Shear Flow Configuration

Porous Disk

Porous Disk (Stationary)

(Rotating)

Equipment -2: Rotating Porous Disk Separator and Reactor


2

TYPICAL ROTOR ELEMENT TO ACHIVE PUMPING, MIXING, SOLID CONVEYING


28

INTESIFIED ROTATING POROUS DISK SEPARATOR / REACTOR


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ACKNOWLEDGEMENTS

This research was initially supported by BNFL & Norsk Hydro

CURRENT SUPPORT FROMSUSTAINABLE 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)

Documents

G. Akay*, Z. Z. Noor*, M Dogru*, B. Calkan and SR Larter** *Process Intensification and Miniaturization Centre, School of Chemical Engineering and Advanced

G. Akay, Z. Z. Noor, M Dogru*, B. Calkan and SR Larter** *Process Intensification and Miniaturization Centre, School of Chemical Engineering and Advanced