adewole j. k.: membrane separation technology in enhanced oil recovery (eor)

This presentation should be cited as: Adewole (2012) Referenced as:Jimoh K. Adewole (2012), Opportunities for Membrane Separation in Enhanced Oil Recovery, KFUPM Research Institute Technical Seminar Series 2011 –2012, Delivered on May 21st, 2012.

OPPORTUNITIES FOR MEMBRANE SEPARATION

IN ENHANCED OIL RECOVERY

BYADEWOLE Jimoh K.

Center for Petroleum & Minerals, Research InstituteKing Fahd University of Petroleum and Minerals

Dhahran, Saudi Arabia

OutlinesNeeds for Research in Membrane TechnologyEnhanced Oil RecoveryMembrane Separation TechnologySome Success Stories of MGSChallenges in Membrane Material Development for Gas SeparationSome BreakthroughsResearch Areas of ExplorationsConcluding RemarksAcknowledgementReferences

Tuesday, May 22, 2012 3Adewole J. K., CPM-KFUPM

4

0

20

40

60

80

100

120

140

0 5000 10000 15000 20000 25000 30000 35000 40000 45000GDP / Capita (US$)

Ene

rgy

Con

sum

ptio

n (‘0

00 K

WH

r / C

apita

)

Energy Consumption per Capita vs. GDP per Capita (Ghosh, 2008)

Ukraine

Russia

US

Kazakhstan Czech Republic

Malaysia

TurkeyBrazil

RomaniaThailandChina Egypt PhilippinesIndonesia

India

Italy

FranceGermany

UKJapan

Canada

80% of Global Population

NEEDS FOR RESEARCH IN MS

Tuesday, May 22, 2012 Adewole J. K., CPM-KFUPM

5

World Population

Year 2007 = 6.7billions

Developed Countries = 1.2

billions

Year 2050 = 9.2 billion

Year 2050; Asia = 5.3 billion

World Energy Demand

Energy Increase (UBE)= 7.7

Asia Growing Econs

Asia Visions to join More

Developed Countries

Energy Increase (CE) = 5.5

World Energy Scenario in 2050 (Koros et al., 2009)



6

2050

To be Effective

Membrane must be Introduced prior to Energy inefficient thermally intensive process.

5x increase in global commodities ≈ 66% increase in current energy consumption

Industrial Separation

Industrial Sector Consumes 33% Total Energy ConsumptionSeparation Process Consumes 40% Industrial Energy NeedsEquivalent to 13.2% of total Energy Consumption

Valuable savings

Achieved using available gas separation membranes units while

aggressively pursuing development of more novel materials

NEEDS FOR RESEARCH IN MSIndustrial Energy Consumption in 2050 (Koros et al., 2009)


Suspended Particles and Macromolecular Solutes ProcessingFlash Evaporation 73kwh/m3

MF/UF 7.6Kwh/m3

Thermal Distillation Plant 78.5Kwh/m3

State-of-the-art Seawater RO 6.7Kwh/m3

Cryogenic Distillation 0.302Kwh/lb propylene prod

50millions gallons/day Seawater Processing

Propylene/Propane Separation

Vapor Permeation Membrane 0.050Kwh/lb propylene prodSources: Koros et al., (2009); Humphrey & Keller (1997); Eykamp (1997); Blume (2004); Gottschlich & Jacobs (1998); Collings et al. (2004)


7

Adewole J. K., CPM-KFUPM

Economic Comparison: Dew point ControlPropane Refrigeration 0.165 $/inlet Mscf

Membrane 0.098 $/inlet Mscf

Sources: Private Study by Purvin and Gertz, June 1999, MTR, USA



9

Enhanced Oil Recovery

EOR METHODS

Other/Unconventional

Thermal EOR

Chemical EOR

Classifications (Al-Mjeni et al., 2011)

(Most Common Classification from

Literature)

Solvent/Miscible


10

CO2-EOR ?

Miscible Fluid Displacement

Global Warming

Available CO2 Pipeline

Cheap Sources of CO2

(Environment)

(Transportation)

(Availability)

(Rooted in the early Stages of Industrial Revolution)

Level of Toxicity

(Gas Properties)

Enhanced Oil Recovery


11

Partial separation of a mixture of two or morecomponents by use of a semi-permeable barrier

Figure: Basic Membrane Separation

Membrane Separation Technology

Driving Forces:Hydrostatic Pressure

Concentration

Electrical Potential


Semi-Permeable Barrier

Membrane

Organic

Glassy Rubbery

Inorganic/ Carbon Liquid

Hybrid Membrane (Provide Property and Processing Advantages)


Organic Membrane Separation

Figure: Motion of molecules with the polymer cavities (Xiao et al., 2009)


Glassy & Rubbery Polymers

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Glassy MembranesFast Gas Slow Gas

HexanePropaneH2O

Ethane

CO2

MethaneHydrogen

Nitrogen

HydrogenCO2H2O

Nitrogen

MethaneEthane

PropaneHexane

Rubbery Membranes Fast Gas Slow Gas

Source: MTR Inc., USA


15

P1 D1 . S1

P2 D2 . S2

=

Permeability = Diffusivity * Solubility (P) (D) (S)

Membrane Selectivity

Solution-Diffusion Mechanism

Adsorption at high pressure side

Diffusion through the membrane

Desorption at low pressure side

Membrane Selectivity; Measure of Separation Performance


16

Module housing

SpacerMembraneSpacer

Feed flow

Permeate flow after passing through membrane

Feed flow

Feed flowPermeate flow

Residue flow

Residue flow

Membrane Modules

Spiral Wound Membrane ModuleHollow Fiber

Source: MTR Inc, Aquilo Gas Separation

Cross Section representation


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Advantages of Membrane Separation

• Offshore production platform applications

• Minimal or no operator attention

• Small footprint, low weight

• Low maintenance

• Lower capital and operating costs


Types Possible EOR Application

Reverse Osmosis /Hyper filtration

Miscible Gas, Smart Water, Thermal

Nano filtration Smart Water, Thermal, Microbial

Ultra filtration/ Micro filtration Chemical, Thermal

Types of Membrane Separation

Membrane Distillation Gas Enrichment Unit for Miscible Gas flooding

Gas Separation Gas Enrichment Unit for Miscible Gas flooding


19

Some Success Stories of MGS

Plant Initial Cap

(MMscfd)

Expanded Cap(MMscfd)

Pressure

(bar)CO2 Mole% Year of

Comm

Kelly-Snyder Field 70 600 N/A 87 2006CakerawalaProduction Platform

N/A 700 N/A 37

Qadirpur, Pakistan 265 500 59 6.5 1999Taiwan 30 ─ 42 ─ 1999Kadanwari, Pakistan 210 ─ 90 ─ N/AEOR facility, Mexico 120 ─ N/A 70 N/ASlalm & Tarek, Egypt 100 ─ 65 N/ATexas, USA 30 ─ 42 30 N/ASource: Koros et al., (2009); and Engelien, (2004); Dortmundt, UOP, (1999)

Membrane Gas Separation Plants

Adewole J. K., CPM-KFUPM

Figure: Enhanced Oil Recovery System in Mexico (UoP)

Commissioned July 1997120 MMSCFD inlet gas 70% CO2. Outlet gas 93% CO2 and is reinjected.

EOR Gas Enrichment Unit

Some Success Stories of MGS


Customized EOR GE Unit: Membrane for CO2 Removal From Reformer Gas by MTR Inc, USA

Some Success Stories of MGSEOR Gas Enrichment Unit


22

Challenges in Material Development for Polymeric MGS

Low Productivity

Balanced Permeability & Selectivity

Physical Aging

Plasticization &Conditioning


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The first challengeGas Transport through membrane began 1950 Emergence of High Flux asymmetric Loeb-Sourirajan membranes –

selective top thin layer (0.1micron) and porous support in 1980Could not be used for GS due to surface defectSolved using thin layer of silicone rubber coating

Low Productivity

Membrane Permeability Selectivity (CO2/CH4)

Celuose Acetate 8.9 20-25


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Permeability and Permselectivity for pure gases at feed pressure of 3.5 bar; membrane thickness of 20 μm (Bernardo et al., 2009)

Commercial Membranes with High CO2 Permeability have Emerged

Low Productivity

0

100

200

300

400

500

600

Cellulose Accetae

Cytop Hyflon AD 60

Hyflon AD 80

Teflon AF 1600

Per

mea

bilit

y (b

arre

r)

05

101520253035404550

Cellulose Accetae

Cytop Hyflon AD 60

Hyflon AD 80

Teflon AF 1600

Per

mse

lect

ivit

y


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Robeson (1991) Upper Bound Curves Discovered with an Empirical Correlation to Represent a General Trade-Off

Figure: Trade-off for CO2/CH4 gas pair in DABA containing polyimides

Better Balance of Selectivity & Permeability

Materials that do notobey the simple rules areneeded to achieve higherselectivity/permeabilitycombination


26

Robeson’s Upper Bound Curves was further studied and

modified by Freeman (1999).

Discovered that to surpass the upper bound emphasis should be

placed on increasing the selectivity by:

Inter-chain spacing

Chain stiffness

Better Balance of Selectivity & Permeability


27

Robeson’s Empirical Model Revisited with more data in 2008

Figure: Robeson's trade-off for CO2/CH4 gas pair polyimides

Better Balanced of Selectivity & Permeability

17 years later few membranes are above the 1991 Robeson’s Upper Bound Limit


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Recent Report on Surpassing of Upper Bound Limit

Better Balanced of Selectivity & Permeability

Figure: Robeson's trade-off for CO2/CH4 gas pair for microporous Thermally Rearranged polybenzimidazole (TR-PBI) membrane heat treated at 450oC (Han et al., 2010).


29

Pressure dependent phenomena Caused by the dissolution of certain penetrants within the polymer matrix Disruption of the chain packing and enhance inter-segmental mobility of

polymer chains (Xiao et al., 2009 ). Induced by condensable gases and vapours encountered in gas

separation involving aggressive feed streams, such as CO2 in natural gas (Qiu et al., 2011 and Wind et al, 2004).

Causes an increase in permeability and a decrease in selectivity as the partial pressure of plasticizing penetrant rises beyond a critical level.

Plasticization and Conditioning

Plasticization ?


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Plasticization and ConditioningInfluence of upstream pressure on permeability coefficients(a) Low-sorbing gases(b) Plasticization of a rubbery polymer (c) dual-mode behavior in a glassy polymer (d) dual-mode behavior at low pressure (<10 atm) and plasticization at higher pressure

Matteucci et al. (2006)


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Pressure at which the permeability starts to increase with increasing pressure. Pressure at which gas permeability exhibits a minimum value (Xiao et al.,

2009; and Scholes et al., 2010)


Plasticization Pressure

Decline in membrane performance Increase in methane loss Decline in process reliability (Wind, 2004)

Effects of Plasticization


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Sorbing sizeable quantities of penetrant into glassy polymer Glassy state is altered Polymers do not return to their original state after removal of the

penetrant (Murphy et al., 2009)


Conditioning in Glassy Polymer

EffectsPermanent changes to the morphology and transport properties of

membrane due to irreversible volume dilation (Xiao et al., 2009 )Gas separation performance becomes time-dependentAffect the reliability of this performance and hinder commercialization of

membrane for industrial separation (Xiao et al. 2009)


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Flow CapacityMax: 8 MMSCFD Operated: 2.5-3.0 MMSCFD Pressure ratingMax: 1250 psig Operated: 475 psig TemperatureMax: 135oF Operated: 100-125oF


Membrane Material research Inc, USA

Industrial Example


34

Physical Aging due to nonequilibrium state of glassy polymers

Diffusion of FreeVolume and latticecontraction (physicalAging) (Xiao et al.,2009)

Physical Aging


35

Some BreakthroughsSuggested Methods for Improved Separation Performance

Crosslinking and Thermal Treatment (Qiu et al., 2011; & Kanehashi, et al.,2010)

•Decarboxylation-induced thermal cross linking•Cross-linking by diamino compounds at ambient temperature•Monoesterification & transesterification reaction of carboxylic acid•Imide ring opening reactions•Diols-alder type cyclization reactions


36

Some BreakthroughsSuggested Methods for Improved Separation PerformanceCopolymerization (Xiao et al., 2009)Template Polymerization & Use of Porogens (Askari et al., 2012 ) Thermal Rearrangement (Park et al., 2010; Park et al.,2007; Tullos

et al., 1999)Polymer Blending (Xiao et al., 2009)Mixed Matrix (Adewole et al., 2011; Koros et al., 2009; and Chung

et al., 2007)Grafting of Polymer Backbone (Pixton & Paul,1995; and Scholes et

al., 2010)Dual-layer hollow fiber spinning process (Hosseini et al., 2010)


37

Some Breakthroughs

120oC, 24hr 180oC, 24hr 300oC, 20hr

330oC, 20hr 350oC, 1hr 370oC, 1hr

150 140190

290330

450

14 45 48 48 48 48

Separation Performance of Decarboxylation-induced Thermal Crosslinking of Hollow Fiber 6FDA-DAM:DABA (3:2) Membrane for

Pure CO2 Gas (Qiu et al., 2011)

Permeability PermSelectivity Plasticization Pressure(barrer) (bar)


38

Some Breakthroughs

180oC, 24hr 330oC, 20hr 350oC, 1hr

100

250

300

37.5 30 27.569 69 55


10%CO2 /90% CH4Gas (Qiu et al., 2011)


180oC, 24hr 330oC, 20hr 350oC, 1hr

130

250 265

27 27 2655 69 69


50%CO2 /50% CH4Gas (Qiu et al., 2011)



0

10

20

30

40

50

60

Crosslinked with Ethylene glycol in

DMAc

Decarboxylation at high Temperature

+220 oC, 23hr

Decarboxylation at high Temperature+220 oC, 23hr + rapid Quenching from above Tg

Plas

ticiza

tion P

ressu

re (b

ar)

Improved Antiplasticization Resistance via Crosslinking of 6FDA-DAM-DABA (2:1) (Staudt-Bickel & Koros ,1999; and

Kratochvil & Koros, 2008)

39

Some Breakthroughs


40

Some Breakthrough

2

2.5

3

3.5

4

4.5

Mixed CH4/CO2

PureHDPE

1wt%C15A

5wt%N1.44P

Perm

eabilit

y (ba

rrer)

Mixed Matrix Polyethylene/Nanoclay for Natural Gas Tranportation at 50oC and 100bar (Adewole et al., 2012)

CO2 Transport Pipeline


41

Some Breakthroughs

Schematic of various gas transport routes through hybrid polymeric membranes (Xiao et al., 2009)


Research Areas for ExplorationDevelopment of optimum membrane configuration for

available gas separation membranesAggressive research efforts towards developing more novel

materials with better balanced of selectivity and flux, and resistance to plasticization, conditioning and aging

Evaluation of the best source of CO2 for EOR GE unitLiquid membranes from renewable sources (date seed oil)Development of methods where membranes are fabricated at

lower temperature is neededDevelopment of novel large scale membrane spinning

processes for mixed matrix (hybrid)42Tuesday, May 22, 2012 Adewole J. K., CPM-KFUPM

43

Compact enough to be driven by solar power

Light

Photosynthesis

Fuels Electricity

Photovoltaic

MFeed Retentate

Permeate

Membrane module

Research Areas for Exploration


Concluding Remarks

44

Multidisciplinary research efforts is essential

Academic-Industry collaborative research is vital

Valuable Savings can be achieved using available materials while

aggressively pursuing development of more novel materials

Developing countries such as should incorporate membrane units from

the beginning. Thermally intensive units have 30-50 years useful lives

Suggested methods should be extended to polymers that are currently

useful for gas separation in the industry


Acknowledgement

45

CPM, RI and KFUPM

Director CPM, Dr A. S. Sultan

Dr L. O. Babalola

KACST and Ministry of Petroleum & Mineral

Resources

Friends and ColleaguesTuesday, May 22, 2012 Adewole J. K., CPM-KFUPM

46

Adewole, J. K., Jensen, L., Al-Mubaiyedh, U. A., von Solms, N., & Hussein, I. A. (2011). TransportProperties of Natural Gas through Polyethylene Nanocomposites. Journal of PolymerResearch

Al-Mjeni, R., Arora, S., Cherukupalli, P., Wunnik, J., dwards, J., Febler, B. J., et al. (2011). Has the TimeCome for EOR? Oilfield Review , 22 (4), 16-34.

Partha S. Ghosh & Associates, (2008). Presntation on How Chemical Engineering will Drive the 21stCentury: The Mega Possibilities Ahead.

Bernardo, P., Drioli, E., & Golemme, G. (2009). Membrane Gas Separation: A Review/State of the Art.Ind. Eng. Chem. Res. , 48, 4638–4663.

Blume, I. (2004). Norit Ultrafiltration as Pretreatment for RO for Wastewater Reuse: The SulaibiyaProject. Presentation at Advanced Membrane Technology II Conference, . Irsee, Germany.

Collings, C. W., Huff, G. A., & Bartels, J. V. (2004). Patent No. Pat. Appl. Publ. 20040004040 A1. USA.Dortmund, D., Doshi, K., ‘Recent Developments in CO2 Removal Membrane Technology,Eykamp, W. (1997). Membrane Separation Processes. In Perry's Chemical Engineers' Handbook (7th

ed., p. Chapter 22). New York, NY: Mc Graw-Hill.Gertz, P. a. (1999, June ). Propane Refrigeration Cost. Private Study .Gottschlich, D., & Jacobs, M. L. (n.d.). Monomer Recovery Process, Membrane Technology and

Research Inc., USA, p. 14.http://www.uop.com/gasprocessing/TechPapers/CO2RemovalMembrane.pdfHumphrey, J. L., & Keller, G. E. (1997). Energy Considerations, in Separation Process Technology. New

York, NY: Mc Graw-Hill.

References


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Jacobs, K. A. (n.d.). New Membrane Applications in Gas Processing. Membrane Technology andResearch, Inc.

Kanehashi, S., Sato, S., & Nagai, K. (2010). Synthesis and Gas Permeability of Hyperbranched andCross - linked Polyimide Membranes. In Y. Yampolskii, & B. Freeman (Eds.), Membrane GasSeparation (pp. 3-27). John Wiley & Sons, Ltd.

Koros, W. K., Krotochvil, A., Shu, S., & Husain, S. (2009). Energy and Environmental Issues and Impactsof Membranes in Industry. In E. Drioli, & L. Giorno (Eds.), Membrane Operations InnovativeSeparations and Transformations (pp. 139-165). Weinheim: Wiley-VCH Verlag GmbH & Co.KGaA.

Kratochvil, A. M., & Koros, W. J. (2008). Decarboxylation-Induced Cross-Linking of a Polyimide forEnhanced CO2 Plasticization Resystance. Macromolecules , 41, 7920- 7927.

Matteucci, S., Yampolskii, Y., Freeman, B. D., & Pinnau, I. (2006). Transport of Gases and Vapors inGlassy and Rubbery Polymers. In Y. Yampolskii, I. Pinnau, & B. D. Freeman (Eds.), MaterialsScience of Membranes for Gas and Vapor Separation (pp. 1-40). John Wiley & Sons, Ltd.

Murphy, T. M., Offord, G. T., & Paul, D. R. (2009). Fundamentals of Membrane Gas Separation. In E.Drioli, & L. Giorno (Eds.), Membrane Operations. Innovative Separations and Transformations(pp. 63-82). Weinheim: WILEY-VCH Verlag GmbH & Co. KGaA.

Park, H. B., Han, S. H., Jung, C. H., Lee, Y. M., & Hill, A. J. (2010). Thermally rearranged (TR) polymermembranes for CO2 separation. Journal of Membrane Science , 359 , 11–24.

Park, H. B., Jung, C. H., Lee, Y. M., Hill, A. J., Pas, S. J., Mudie, S. T., et al. (2007). Polymers with cavitiestuned for fast selective transport of small molecules and ions,. Science , 318, 254–258.

References


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Paul, D., & Robeson, L. (2008). Polymer nanotechnology: Nanocomposites. Polymer , 49 , 3187–3204.Pixton, M. R., & Paul, D. R. (1995). Gas transport properties of adamantane- based polysulfones.

POLYMER , 36 (16), 3165.Qiu, W., Chen, C.-C., Xu, L., Cui, L., Paul, D. R., & Koros, W. (2011). Sub-Tg Cross-Linking of a Polyimide

Membrane for Enhanced CO2 Plasticization Resistance for Natural Gas Separation.Macromolecules , 44, 6046–6056.

Scholes, C. A., Chen, G. Q., Stevens, G., & Kentish, S. E. (2010). Plasticization of ultra-thin polysulfonemembranes by carbon dioxide. Journal of Membrane Science , 346 , 208–214.

Staudt-Bickel, C., & Koros, W. J. (1999). Improvement of CO2/CH4 separation characteristics of polyimidesby chemical crosslinking. Journal of Membrane Science , 155, 145–154.

Tullos, G., Powers, J., Jeskey, S., & Mathias, L. (1999 ). Thermal conversion of hydroxycontaining imides tobenzoxazoles: polymer and model compound study. Macromolecules , 32 , 3598–3612.

Wellington, J. M., & Ku, A. Y. (2011). Opportunities for Membranes in Sustainable Energy. Journal ofMembrane Science , 373, 1-4.

Wind, J. D., Paul, D. R., & Koros, W. J. (2004 ). Natural gas permeation in polyimide membranes. Journal ofMembrane Science , 228 , 227–236.

Xiao, Y., Low, B. T., Hosseini, S. S., Chung, T. S., & Paul, D. R. (2009 ). The strategies of moleculararchitecture and modification of polyimide-based membranes for CO2 removal from natural gas -A review. Progress in Polymer Science , 34 , 561–580.

References


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Thank YouFor

ListeningTuesday, May 22, 2012 Adewole J. K., CPM-KFUPM

50

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adewole j. k.: membrane separation technology in enhanced oil recovery (eor)

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membrane technology

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billions energy increase

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