Wettability Improvement with Enzymes: Wettability Improvement with Enzymes: Application to Enhanced Oil Recovery under Application to Enhanced Oil Recovery under Application to Enhanced Oil Recovery under Application to Enhanced Oil Recovery under

Conditions of the North Sea ReservoirsConditions of the North Sea Reservoirs

Fundamental Research on Surfactants and PolymersFundamental Research on Surfactants and Polymers

27 August, 201227 August, 2012

Alsu KhusainovaAlsu Khusainova

CERECenter for Energy Resources Engineering

BioRecBioRec ProjectProjectBioRecBioRec ProjectProject

Biotechnological Biotechnological Enhanced Oil RecoveryEnhanced Oil Recovery

GashydrateGashydrate Inhibition by Inhibition by Ice Structuring ProteinsIce Structuring Proteins

Microbial Induced Microbial Induced CorrosionCorrosion

Enzymatic Enzymatic Microbial Enhanced Oil RecoveryMicrobial Enhanced Oil Recovery

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Enhanced Oil RecoveryEnhanced Oil RecoveryMicrobial Enhanced Oil RecoveryMicrobial Enhanced Oil Recovery

The Main GoalThe Main Goal

To establish possible mechanisms in which h ilenzymes may enhance oil recovery

=+

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… and Also… and Also

• enzymes with maximum potential for EOR

• enzymatic action = f (T, p, ions etc. )

• synergetic effects of enzymes with surfactants and/orsynergetic effects of enzymes with surfactants and/orother EOR techniques

• enzymatic EOR biotechnology for Danish North Sea oile y at c O b otec o ogy o s o Se ofields

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What are the Enzymes?What are the Enzymes?t i t l t f li i t• protein catalysts from living systems

• recently have been introduced into the field of EOR

OxidoreductasesHydrolasesAB + H2O → AOH + BH

Carbohydrases Esterases/LipasesProteases

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Initial HypothesisInitial HypothesisInitial HypothesisInitial HypothesisEnzymes in EOREnzymes in EOR

A t surfactants A t proteinsA t catal sts Act as a surfactants Act as a proteinsAct as a catalysts

Produce additional Decrease interfacial Improve wettability Produce additional interfacially active oil

components (e.g. R-COOH)

Decrease interfacial tension (IFT) between oil

and brine

Improve wettability by adsorption of

enzymes on interfaces

Improve wettability and/or IFT

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Contact Angle MeasurementsContact Angle MeasurementsContact Angle MeasurementsContact Angle MeasurementsPlacement of the oil drop

Recording of the oil drop shape

Image processing and analysing

Obt i i f t t l lObtaining of contact angle value

Image Processing -Matlab

Image Analysis -Image J

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E i t l C ditiE i t l C ditiExperimental ConditionsExperimental Conditions• Room T and p• Brine – synthetic North Sea water

• 17 enzyme products: 15 C i l Mi2 Commercial Mixtures 1% 0.5% 0.1%

“Sandstone” Oil“Chalk” Oil Sandstone Oil

Calcite ≈ Chalk Quartz ≈Sandstone & Mica ≈ Clay

Chalk Oil

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Contact Angle: Contact Angle: Terms & Initial Terms & Initial Contact Angle: Contact Angle: Terms & Initial Terms & Initial ConditionsConditions

ΘΘ

Θ Brine

Oil

Oil – Wet StateΘ = 105-180

Intermediate – Wet StateΘ = 75-105

Water – Wet StateΘ =0-75

Minerals in Sea Water:

Anderson, 1986

5 75 5 75

Enzymatic Action:

• Calcite Θ = 38 ± 7 °• Quartz Θ = 35 ± 5 °

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Adhesion Behavior Test: Adhesion Behavior Test: TermsTermsAdhesion Behavior Test: Adhesion Behavior Test: TermsTerms

Adhesion

TemporaryAdhesion

Non-adhesion

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Adhesion MapAdhesion Map

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Contact AnglesContact Angles

Calcite in SW Θ = 38 ± 7°

Lipases/Esterases 0° (100 % reduction)

Carbohydrases No significant changes

Proteases Mixed ResultProteases Mixed Result

Oxidoreductases No significant changes

EOR-Zymax No significant changesy g g

Apollo-Greenzyme 25 % decrease

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NN S l S l GGNovozymesNovozymes Samples Samples vsvs. . GreenzymeGreenzyme

Novozymes Sample Apollo Greenzyme Sample

• Non-adhesion – CA=0° • Non-adhesion – CA> 0°

First evidence of different working mechanisms

• Spherical shape • Prolonged shape

First evidence of different working mechanisms Greenzyme – change of IFT and wettability?

Particles? Novozymes samples change of only wettability? Novozymes samples – change of only wettability?

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En me or Stabili er?En me or Stabili er?Enzyme or Stabilizer?Enzyme or Stabilizer?

%% 0 %

2-5

%2-

5 %

25-3

0

Propylene GlycolPure Lipase

• Adhesion• Non-adhesion• CA = 27°• CA (SW) = 38°

• CA = 0°• CA (enzymes product) = 0°

Enzyme Product Pure Enzyme

1 % 0.02 – 0.05 %

0.5 % 0.01 – 0.025 %

Enzyme is working Enzyme is working Component !!!Component !!!

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0.1 % 0.002 – 0.005 %Component !!!Component !!!

R f E iR f E iReference ExperimentsReference Experimentsf iSurfactant DecaneProtein

LipaseBovine Serum Albumin Sodium Dodecyl Sulfate

!!! WORKS !!!!!! WORKS !!!

0.05 - 1% 0.005-0.05% 0.001-

Apollo Greenzyme • Adhesion°

0.005%

• CA = 27°

• Non-adhesion°

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• CA = 0°

ConclusionsConclusions

• Enzymes might be of particular interest in terms of EOR

Li th t i i f th • Lipases – the most promising group of the enzymes

• Apollo-Greenzyme has potential, but very mixed result

• Preliminary mechanism proposal:

Novozymes samples change wettabilityc

Apollo-Greenzyme decreases the IFT

• Wettability might be improved due to Wettability might be improved due to

adsorption of proteins onto the oil-brine and/or brine-mineral interfaces

formation of additional interfacially active compounds formation of additional interfacially active compounds

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AcknowledgementsAcknowledgements

• zsdf

• Dr. Tonci Zunic (the Geological Museum, University of Copenhagen)

• Apollo Separation Technologies

• VH Biotechnology

Thank You!!!Thank You!!!

VH Biotechnology

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Any Questions?Any Questions?

CERECenter for Energy Resources Engineering

27-Aug-12