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Process%20Integrated%20Membrane%20Separation%20-%20with%20Application%20to%20the%20Removal%20of%20CO2%20from%20Natural%20Gas%20Hilde%20K.%20Engelien

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Title: Process%20Integrated%20Membrane%20Separation%20-%20with%20Application%20to%20the%20Removal%20of%20CO2%20from%20Natural%20Gas%20Hilde%20K.%20Engelien


1
Process Integrated Membrane Separation - with
Application to the Removal of CO2 from Natural
Gas Hilde K. Engelien
  • 22. March 2004
  • Department of Chemical Engineering, NTNU

2
Definition of Given Title
  • Process integrated membranes
  • Membranes integrated into a process.
  • Process integration techniques (process
    synthesis, modelling optimisation).
  • CO2 removal from natural gas
  • Have mainly looked at natural gas sweetening.
  • Other applications exists.

3
Overview of Presentation
  • Membranes
  • Principles of separation
  • Material selection
  • Types of membrane modules
  • Membrane separation for CO2 removal from natural
    gas
  • Applications for CO2 removal
  • Natural gas
  • Advantages/disadvantages
  • Current solutions some industrial examples
  • Process integration
  • Future trends developments
  • Concluding Remarks

4
Principles of Membrane Separation

Phase 2
Phase 1
(Feed)
(Permeate)
Membrane - a physical barrier from semi-permeable
material that allows some component to pass
through while others are held back.
Microfiltration Ultrafiltration Reverse
Osmosis Molecular sieving Gas separation Membrane
contactors Pervaporation
Driving force (?C, ?P, ?T, ?E)
Flux Selectivity
5
Different Membrane Structures (Selective layer)
  • Porous membrane Non-porous membrane Carrier
    membranes

Size Diffusion
solubility Affinity Ref Mulder, Basic
principles of separation technology)
(microfiltration/ultrafiltration)
(gas separation/pervaporation)
(gases/liquids)
6
Typical Membrane Structures (Gas Separation)
  • Asymmetric membranes
  • very thin non-porous layer - selective
  • thick, highly porous layer - mechanical support
  • Composite membranes
  • thin selective layer of one type polymer
  • mounted on asymmetric membrane - support

Selective layer
Nonporous layer (selectivity)
Asymmetric membrane
Porous layer (stability)
Composite membrane structure (two types of
materials)
Asymmetric membrane structure (one type of
material)
Ref. Dortmundt, 1999
7
Membranes - Material Selection
Polymers most common Inorganic more stable
hybrid
Polymer poly(ethene)
Monomer ethene
Ref. www.btinternet.com/chemistry.diagrams/polym
er.htm
8
Different Types of Membrane Modules
  • Two main categories for industrial applications
  • Spiral wound modules
  • Hollow fibre modules

Ref. Filtration Solutions Inc.
9
Different Types of Membrane Modules
  • Two main categories for industrial applications
  • Spiral wound modules
  • Hollow fibre modules

Cross section of hollow fibre
Ref. Aquilo Gas Separation
10
CO2 Removal from Natural Gas
11
Applications for CO2 Removal
  • Separation of CO2 from gas streams are required
    in
  • Purification of natural gas (gas sweetening).
  • Separation of CO2 in enhanced oil recovery
    processes (EOR).
  • Removal of CO2 from flue gas.
  • Removal of CO2 from biogas.
  • Reasons for sour gas sweetening ?
  • Impurities (CO2, H2S, H2O)
  • Increase heating value of natural gas - pipeline
    quality gas.
  • Reduce corrosion.
  • Prevention of SO2 pollution (formed during
    combustion of natural gas).
  • Methods used in gas sweetening (removal of CO2,
    H2S)
  • Absorption process using amine (conventional).
  • Cryogenic distillation.
  • Membranes.
  • Hybrid process where membrane is integrated with
    absorption unit.

12
Natural Gas
  • Natural gas Mainly methane (CH4), ethane,
    propane, butane.
  • Impurities H2O, CO2, N2 and H2S.
  • Natural gas treatment is the largest application
    of industrial gas separation. Membrane processes
    have lt 1 of this market large potentials
    ! (Baker, 2002)
  • Disposal Compression re-injection of CO2 in
    reservoir .

Ref. Australian Petroleum Cooperative Research
Centre
13
Typical Natural Gas Plant - Possible Membrane
Applications
Ref. UOP
14
CO2 Separation Using Membranes
  • Mechanism of separation diffusion through a
    non-porous membrane
  • A pressure driven process - the driving force is
    the partial pressure difference of the gases in
    the feed and permeate.
  • Selectivity - separation factor, ? (typical
    selectivity for CO2/CH4 is 5-30)
  • Permeability solubility (k) x diffusivity (D)
  • Either high selectivity or high permeability -
    use highly selective thin membranes.
  • Commercial membranes polymer based (cellulose
    acetate)
  • Selective removal of fast permeating gases from
    slow permeating gases.
  • The solution-diffusion process can be
    approximated by Ficks law

15
CO2 Removal from Natural Gas Current Membrane
Solutions
  • Membranes (Baker, 2002)
  • 8-9 polymer materials used for 90 of total gas
    separation membranes.
  • Several hundred new polymers reported
    (academia/patents) in the last few years.
    Problem maintaining properties during real
    operation.
  • Most gas separation modules are hollow-fibre
    modules.
  • Three markets
  • Low gas volumes (e.g. treatment of offgas) -
    better than conventional amine absorption units.
  • Moderate gas volumes - competitive with amine
    systems.
  • Higher volumes - not competitive with current
    amine systems. Problem low selectivity and flux.
  • Hybrid solution with conventional amine
    absorption technology.
  • Feed treatment - extend membrane life (condensing
    liquids, particles causing blockage and well
    additives can harm the membrane).

16
CO2 Separation Using Membranes Advantages
Disadvantages
  • Advantages (compared with absorption units)
  • Simpler process solutions
  • Smaller lighter systems (offshore)
  • Cleaner
  • Less chemical additives
  • Lower energy consumption
  • Simultaneous removal of CO2, H2S and water vapour
  • No fire or explosion hazards
  • Less maintenance
  • Lower capital and operating costs (small to
    medium scale)
  • Ability to treat gas at wellhead
  • Disadvantages
  • Low selectivity flux - large scale systems not
    economically viable (yet).
  • Thermal stability of polymer membranes.
  • Degradation lifetime of membrane.
  • Unmature technology (in industrial terms,
    compared with existing solutions)

A better environmental solution than
conventional absorption units
17
Natural Gas Processing Plant Qadirpur, Pakistan
  • In 1999 Largest membrane based natural gas plant
    in the world (Dortmundt, UOP, 1999).
  • Design 265 MMSCFD natural gas at 59 bar.
  • CO2 content is reduced from 6.5 to less than 2
    using a cellulose acetate membrane.
  • Feed treatment feed heaters.
  • Also designed for gas dehydration.
  • Plant processes all available gas.
  • Plans for expansion to 400 MMSCFD.

18
Membrane plant, Qadirpur, Pakistan
(Dortmundt, UOP, 1999)
19
Examples of Membranes In Gas Industry
  • Plants using membranes for CO2 removal
  • Kadanwari, Pakistan - 2 stage unit for treatment
    of 210 MMSCFD gas at 90 bars
  • Taiwan (1999) - 30 MMSCFD at 42 bar.
  • EOR facility, Mexico - processes 120 MMSCFD gas
    containing 70 CO2
  • Slalm Tarek, Egypt - 3 two-stage units each
    treating 100 MMSCFD natural gas at 65 bar.
  • Texas, USA - 30 MMSCFD of gas containing 30 CO
    at 42 bar.
  • Companies with membranes for CO2 removal
  • NATCO Group (Cyanara membranes)
  • Aker Kværner Process Systems
  • Air Liquid
  • UOP

20
Process Integrated Membranes
21
Process Integrated Membrane Membrane Gas/Liquid
Contactors
  • Process integrated membrane and absorption unit
    (developed by Kværner Process Systems).
  • Membrane acts as barrier surface area.
  • Increased mass transfer area.
  • Used for natural gas treatment, dehydration and
    removal of CO2 from offgas.

Ref. Aker Kværner Process Systems
  • There are several tests sites for this system
    (Falk-Pedersen)
  • Large laboratory unit at SINTEF.
  • Large scale pilot unit at Kårstø (exhaust gas
    treatment from gas engine)
  • Pilot unit at gas terminal in Scotland - testing
    different membranes.

22
Membrane Gas/Liquid Contactors
  • Benefits
  • Reduction of size and weight (important
    offshore).
  • Wide range of liquid and gas flows (separation of
    gas/liquid phase).
  • Lower capital costs compared with alternative
    schemes.
  • Reduction in energy (if membranes are integrated
    with the stripping unit).
  • Reduction in solvent losses.
  • No entrainment, flooding or channelling.
  • Performance is insensitive to motion.
  • Santos Gas Plant, Queensland, Australia
  • Australia's largest gas producer.
  • Novel polymide membrane facility for CO2 removal
    (installed Dec. 2003).
  • Uses the gas/liquid contactor.
  • Problem benzene/toluene/xylene in gas stream - a
    dewpoint control unit is installed to ensure that
    BTX are at acceptable levels.

23
Process Integration for Membrane Applications
  • Design.
  • Modelling optimisation.
  • Superstructure approach for optimisation.

Process synthesis and optimisation methods are
important for development of efficient membrane
structures for specific separation tasks.
24
Process Integration Used in Membrane Applications
  • Design.
  • Modelling optimisation.
  • Superstructure approach for optimisation.
  • Design decisions for membrane systems
  • Operating conditions (temperature, pressure,
    flow).
  • Module configuration (parallel, series, single
    stage, multiple stage, recyle).
  • Membrane material (organic, inorganic, mixed, ).

Single stage scheme
Two-step scheme
Two-stage scheme
25
Process Integration for Membrane Applications
  • Design.
  • Modelling optimisation.
  • Superstructure approach for optimisation.
  • Modelling of membrane designs for gas (Pettersen,
    Lien, 1993, 1994, 1995)
  • Parametric study.
  • Algebraic model (analogous with counter-current
    heat exchanger). Looked at single stage and
    multiple stages, effects of recycle and bypass
    configurations.
  • Classification modules - suitable for recovery of
    fast or slow permeating component.
  • Common design approach sequential procedures
  • Module configurations are selected a priory.
  • Optimisation on selected module to determine the
    operating conditions.
  • Resulting flowsheet may be sub-optimal.

26
Process Integration for Membrane Applications
  • Design
  • Modelling optimisation.
  • Superstructure approach for optimisation.
  • Membrane system design for multicomponent
  • gas mixtures via MINLP (Qi, Henson, 2000)
  • Superstructure
  • Consists of membrane units, compressors, stream
    mixers and splitters.
  • Used to represent the possible network
    configurations of a membrane system.
  • Case study CO2 and H2S separation from natural
    gas using spiral-wound membranes.
  • Simultaneous optimisation of flowsheet in terms
    of total annual process costs.

27
Process Integration for Membrane Applications
  • Design
  • Modelling optimisation.
  • Superstructure approach for optimisation.
  • Optimal design of membrane systems (Mariott,
    Sørensen, 2003)
  • Detailed rigorous mathematical models for the
    membrane separation.
  • Superstructure representation of the membrane
    system.
  • Optimisation using generic optimisation algorithm
    for pervaporation pilot plant (ethanol/water).
  • Significant improvement in design.
  • Favourable compared with conventional MINLP
    solution methods.
  • Generic algorithms can be a basis for an
    effective powerful tool for optimal design of
    membrane systems.

28
Process Integration for Membrane Applications
  • Design
  • Optimisation
  • Superstructure approach
  • A targeting approach to the synthesis of membrane
    networks for gas
  • separations (Kookos, 2002)
  • Superstructure representation.
  • Hollow-fibre membrane system.
  • Uses the upper bound trade-off curve
    (relationship between permeability and
    selectivity for membranes).
  • Configuration and membrane properties are
    optimised together.
  • Find the optimal membrane permeability and
    selectivity and the optimum structure.

29
Future Development
30
Problems/Challenges
  • Increasing selectivity without productivity loss
    (flux) - larger volume application will then be
    possible.
  • Maintaining membrane properties under real
    conditions
  • Loss of stability performance at high T and
    high P.
  • Maintaining membrane properties in the presence
    of aggressive feeds.
  • Condensing heavy hydrocarbons - can degrade the
    performance of the membrane.
  • Thermal stability (of polymer membranes) -
    inorganic membranes would be better.
  • Economic competitiveness for large scale systems.
  • Improving lifetime of membrane.
  • Commercialisation - getting the industry to
    accept membranes.

31
Future High Performance Membranes Selectivity
vs. Permeability Upper Bound
CO2/CH4 selectivity vs. CO2 permeability
  • Upper bound for selectivity vs. permeability.
  • Current selectivity of CO2/CH4 membranes is
    typically 5-30.
  • High performance membranes will move the upper
    bound upwards.
  • Higher selectivity and permeability
  • will
  • reduce area (capital cost).
  • reduce loss of methane in permeate (profit).

30
Upper bound (1991)
(Ref Koros, 2000)
32
Future Trends and Developments
  • For improved thermal chemical stability of
    polymer membranes
  • New polymers with different side-chains or
    different backbones .
  • Cross-linked polymers.
  • Plasma treatment.
  • New materials (move into large-scale gas
    separations)
  • New polymer structures with higher selectivity
    permeability.
  • Facilitated transport membranes - high
    selectivity.
  • Mixed matrix materials - blends of inorganic
    materials (e.g. molecular sieving) domains in
    polymers.
  • Combination of cross-linking and mixed matrix
    material.
  • Membranes tailored for specific separation tasks.
  • Inorganic materials.
  • Process Integration
  • Rigorous models.
  • Optimisation of whole structure (module design).

33
Concluding Remarks
  • Looked at
  • Introduction to principles of membrane
    separation, material selection types of
    membrane modules.
  • Membranes for the use of CO2 removal from natural
    gas.
  • Small scale better than conventional absorption
    process.
  • Medium scale Competitive with conventional
    absorption process.
  • Large scale future applications along with
    development of membranes.
  • Industrial examples.
  • Process integrated membrane gas/liquid contactor.
  • Optimisation of membrane structures
    (superstructure approach).
  • Problems and challenges.
  • Future trends and development.
  • Membrane technology and industrial applications
    is a growing industry !

34
Future CO2 Separation Going to Mars ?
Ref. NASA Space Research
35
Acknowledgements
  • Taek-Joong Kim, Department of Chemical
    Engineering, NTNU
  • Jon A. Lie, Department of Chemical Engineering,
    NTNU
  • Arne Lindbråthen, Department of Chemical
    Engineering, NTNU
  • Olav Falk-Pedersen, Aker Kværner Process Systems,
    Norway
  • Mike Entwistle, Aker Kværner Australia

36
References
  • Textbooks
  • Basic Principles of Membrane Technology,
    Mulder, M., 2nd. Edt., Kluwer Academic
    Publishers, 1996
  • Polymer gas separation membranes, Paul, D.R.,
    Yampolskii, Y.P., CRC Press, 1994
  • General Papers
  • Baker, R.W., Future directions of membrane gas
    separation technology, Ind. Eng. Chem. Res.,
    2002, 41, 1393-1411
  • Koros, W.J., Mahajan, R., Pusing the Limits on
    Possibilities for Large Scale Gas Separation
    Which Strategies ?, J. Membrane Science, 175,
    2000, 181-196
  • Tabe-Mohammadi, A., A Review of the Applications
    of Membrane Separation Technology in Natural Gas
    Treatment, Separation Science and technology,
    34, 10,1999, 2095-2111
  • Dortmund, D., Doshi, K., Recent Developments in
    CO2 Removal Membrane Technology,
    http//www.uop.com/gasprocessing/TechPapers/CO2Rem
    ovalMembrane.pdf
  • Lee, A.L., Feldkirchner, H.L., Gamez, J.P.,
    Meyer, H.,S., Membrane process for CO2 removal
    tested at Texas plant, Oil Gas Journal, 1994,
    92, 5, 90-93
  • Leiknes, T.O., Gas transfer and degassing using
    hollow fibre membranes, Dr. ing. thesis,
    Department of Hydraulic and Environmental
    Engineering, NTNU, Norway, ISBN 82-471-5391-2.
  • Hagg, M.B., Membrane purification of chlorine
    gas, Dr. ing. thesis, Department of Chemical
    Engineering, NTNU, Norway, ISBN
  • Ali, S., Boblak, P., Capili, E., Milidovich, S.,
    Membrane Separation and Ultrafiltration,Laborato
    ry for Process and Product Design, University of
    Illinois, , http//vienna.che.uic.edu/teaching/che
    396/sepProj/FinalReport.pdf
  • Lindbråthen, A., Ottøy, M., Natural Gas
    Dehydration and Purification by Membranes,
    Report, 1999, Telemark Tekniske Industrielle
    Utviklingssenter.
  • Drioli, E., Romano, M., Progress and new
    perspectives on integrated membrane operation for
    sustainable industrial growth, Ind. Eng., Chem.
    Res., 2001, 40, 1277-1300

37
References
  • Lokhandwala, K.A., Jacobs, M.L., Membranes for
    fuel gas conditioning, Hydrocarbon Engineering,
    May 2000
  • Echt, W., Hybrid systems combining technologies
    leads to more efficient gas conditioning, 2002
    Laurance Reid Gas Conditioning Conference,
    http//www.uop.com/gasprocessing/TechPapers/Hybrid
    Systems.pdf
  • Koros., W.J., Fleming, G.K., Review
    Membrane-based gas separation, J. Membrane
    Science, 83, 1993, 1-80

38
References
  • Membrane Gas/Liquid Contactor
  • Grønvold, M.S., CO2 capture with membrane
    contactors, presented at the Third Nordic Mini
    symposium on Carbon Dioxide Capture and Storage,
    Trondheim, Norway, 2-3 Oct. 2003.
  • Herzog, H., Falk-Pedersen, O., The Kvaerner
    Membrane Contactor Lessons from a Case Study in
    How to Reduce Capture Costs, 5th International
    Conference on Greenhouse Gas Control
    Technologies, Cairns, Australia 13-16 August,
    2000
  • Hoff, K.A., Svendsen, H., Juliussen, O.,
    Falk-Pedersen, O., Grønnvold, M.S., Stuksrud,
    D.B., The Kvaerner/Gore Membrane Process for CO2
    removal, Presented at AIChE Annual Meeting,
    2000, Los Angeles
  • Dannstrøm, H., Stuksrud, D.B., Svendsen, H.,
    Membrane Gas/Liquid Contactors for Natural Gas
    Sweetening, http//www.gasprocessors.com/GlobalDo
    cuments/E00May_06.PDF
  • Falk-Pedersen, O., Grønnvold, M.S., Nøkleby, P.,
    Membrane gas/liquid contactors, paper received
    from O. Falk-Pedersen.
  • Optimal Design and Optimisation
  • Pettersen, T., Lien, K.M., Design studies of
    membrane permeator processes for gas separation,
    Gas. Sep. Purif., 9, 3, 151-169, 1995.
  • Pettersen, T., Lien, K.M., Insights into the
    design of optimal separation systems using
    membrane permeators, Computers Chem. Eng., 18,
    Suppl. S319-S324, 1994.
  • Pettersen, T., Lien, K.M., Design of complex ga
    separation processes, Presented at the AIChE
    Annual Meeting, St. Louis, Nov. 1993
  • Pettersen, T., Lien, K.M., Synthesis of
    separation systems using membrane permeators,
    Proceedings of PSE, 1994, 835-842.
  • Lien, K.M., Sizing and Costing of Gas Separating
    Membrane Modules - A shortcut method, Report for
    a 2-week projeck for SINTEF, Division of Applied
    Chemcistry, July 1990, Draft Version
  • Marriott, J., Sørensen, E., The optimal design
    of membrane systems,

39
References
  • Kookos, I.K., A targeting approach to the
    synthesis of membrane network for gas
    separations, j. Membrane Science, 208, 193-202,
    2002
  • Qi., R., Henson, M.A., Optimization-based design
    of spiral-wound membranes systems for CO2/CH4
    separations, Separation and Purification
    Technology, 13, 209-225, 1998
  • Qi., R., Henson, M.A., Membrane system design
    for multicomponent gas mixtures via mixed-integer
    nonlinear programming, Computers and Chemical
    Engineering, 24, 2719-2737, 2000
  • Company/Internet References
  • GE Water Technologies http//www.gewater.com/inde
    x.jsp
  • Aquilo Gas Separation bv http//www.aquilo.nl/pro
    ducts.htm
  • Australian Petroleum Cooperative Research Centre
    http//www.co2crc.com.au/geodisc.htm
  • UOP, http//www.uop.com
  • Filtration Solutions Inc., http//www.filtsol.com/
    technology/super_hydrophilic.shtml
  • NASA Space Research, http//science.nasa.gov/headl
    ines/y2003/03dec_membranes.htm
  • Aker Kværner Process Systems, http//www.kccproces
    s.com/
  • Air Liquide, http//www.medal.airliquide.com/en/me
    mbranes/carbon/natural/offshore.asp
  • NATCO Group, http//www.natcogroup.com/default.asp
  • Membrane Technology and Research Inc.,
    http//www.mtrinc.com/

40
CO2 Removal from Flue Gas Capture Storage of CO2
  • Natural gas fired power plant
  • natural gas is burnt to produce power - CO2 is
    created in the combustion
  • CO2 is separated from flue gas - then stored or
    used
  • Four possible methods for removal of CO2
  • conventional absorption
  • pressure swing absorption
  • cryogenic separation
  • membrane technology (e.g. Aker Kværner membrane
    gas/liquid contactor)

Ref. IEA
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