WO2017146589A1 - Hydrogen production from natural gas in combination with injection of co2 for enhanced oil recovery - Google Patents

Hydrogen production from natural gas in combination with injection of co2 for enhanced oil recovery Download PDF

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Publication number
WO2017146589A1
WO2017146589A1 PCT/NO2017/050047 NO2017050047W WO2017146589A1 WO 2017146589 A1 WO2017146589 A1 WO 2017146589A1 NO 2017050047 W NO2017050047 W NO 2017050047W WO 2017146589 A1 WO2017146589 A1 WO 2017146589A1
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Prior art keywords
gas
hydrogen
porous tube
natural gas
tube
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PCT/NO2017/050047
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French (fr)
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Torkild Reime REINERTSEN
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Hydrogen Mem-Tech As
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Publication of WO2017146589A1 publication Critical patent/WO2017146589A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B01D63/062—Tubular membrane modules with membranes on a surface of a support tube
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B01D71/0223—Group 8, 9 or 10 metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • C01B3/505—Membranes containing palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/108—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/06—Specific process operations in the permeate stream
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/13—Use of sweep gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2696—Catalytic reactions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0277—Hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/24—Mixing, stirring of fuel components
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/548—Membrane- or permeation-treatment for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention relates to a membrane module for separation of hydrogen and CO 2 in a gas mixture, a system and a method for separation of hydrogen and CO 2 from natural gas, and more particular a method and system for treatment of natural gas and for improved extraction of an oil reservoir.
  • Hydrogen plays an important role as energy carrier, e.g. as
  • WO 2007/129024 A1 is used to produce energy in a gas turbine, high
  • the CO 2 rich retentate can be re-injected into the oil or gas reservoir for increasing the extraction efficiency.
  • a main object of the present invention is to overcome the disadvantages mentioned above. More particularly, the present invention aims at providing a solution for an environmentally use of natural gas in the exploitation of oil fields and suitable methods and technical equipment for efficient on-site treatment of the extracted gas. In particular, the present invention aims at providing an alternative method for the known methods of pressure maintenance in oil fields under exploitation.
  • the present invention aims to provide an improved, space and cost- efficient method and apparatus for the production of pure hydrogen and CO 2 from natural gas.
  • the present invention aims at producing pure hydrogen in high concentration.
  • a further object is simplified transport of hydrogen from the installation, either in a pure form for later use, or mixed with natural gas and transported together with the natural gas.
  • the present invention relates to a membrane module for separation of hydrogen and CO 2 in a gas mixture as defined in claim 1 .
  • Said membrane module comprises
  • a pressure tank with an inlet and outlet for the gas at opposing sides of the tank, - at least one porous tube coated with a palladium-silver membrane, the tube longitudinally extending inside the tank, the tube being closed at the end in vicinity to the outlet of the pressure tank and being in fluid connection to a permeate outlet in the other end,
  • the present invention relates to a method as defined in claim 2.
  • the method according to the present invention comprises the following steps:
  • the CO 2 rich retentate produced in the separation process can be injected into the oil reservoir the natural gas has been extracted from, or to other suitable reservoirs in the vicinity.
  • a pipe of smaller diameter can be installed inside the porous tube to supply gas through said smaller pipe to flush permeate of hydrogen out of the porous tube.
  • the membrane module can comprise a pressure tank with an inlet and outlet for the gas at opposing sides of the tank, at least one porous tube coated with a palladium- silver membrane, the tube longitudinally extending inside the tank, the tube being sealed at the end in vicinity to the outlet of the pressure tank and being in fluid connection to an permeate outlet in the other end, a longitudinally extending sweep pipe having a smaller diameter than the porous tube and being centrally installed inside the porous tube, with a sweep gas inlet at one end and an opening for sweep gas release in vicinity to the closed end of the porous tube to supply sweep gas through said smaller pipe for flushing the hydrogen permeate out of the porous tube.
  • the retentate Prior to injection of the CO 2 rich retentate into the oil reservoir, the retentate is processed in a combustion process for removal of remnants of hydrogen and hydrocarbons.
  • the energy of the remnants removed in the combustion process can be supplied and used as energy in the reforming process of natural gas.
  • Hydrogen produced in the separation process can be exported to be used as an energy source for power production.
  • the hydrogen produced in the separation process may be exported to a consumer in a pure form for later use, or the hydrogen can be mixed with natural gas and transported together with the natural gas in existing pipelines.
  • the present invention relates to a system as defined in claim 10.
  • the system according to the present invention comprises the elements: means for reforming of natural gas extracted from an oil reservoir followed by water gas shift to obtain a gas mixture comprising hydrogen and CO 2 , at least one membrane module comprising a porous tube coated with a palladium-silver membrane for separation of hydrogen and CO 2 in the gas mixture, and means for injection of CO 2 rich retentate produced in the separation process into an oil reservoir with need for increased pressure.
  • the system may further comprise means for processing the CO 2 rich retentate in a combustion process for removal of remnants of hydrogen and hydrocarbons.
  • a line can be connected between the means for processing the CO 2 rich retentate in the combustion process and the means for reforming of natural gas, for supply of energy in the reforming process of natural gas.
  • the means for injection of CO 2 rich retentate may comprise a multiple-step process centrifugal compressor to increase the pressure of the CO 2 retentate to a pressure higher than the pressure in the reservoir.
  • the membrane module may comprise a cylindrical pressure tank with a number of porous tubes, whereby each of the porous tubes is coated with a very thin palladium- silver membrane and each of the tubes comprises different parts which are separated from each other by spreader plates.
  • a pipe of smaller diameter can be installed inside the porous tube, and said smaller pipe is arranged to receive gas to flush permeate of hydrogen out of the porous tube.
  • the membrane module in the system can comprise a pressure tank with an inlet and outlet for the gas at opposing sides of the tank, at least one porous tube coated with a palladium-silver membrane, the tube longitudinally extending inside the tank, the tube being sealed at the end in vicinity to the outlet of the pressure tank and being in fluid connection to an permeate outlet in the other end, a longitudinally extending sweep pipe having a smaller diameter than the porous tube and being centrally installed inside the porous tube, with a sweep gas inlet at one end and an opening for sweep gas release in vicinity to the closed end of the porous tube to supply sweep gas through said smaller pipe for flushing the hydrogen permeate out of the porous tube.
  • membrane modules can be arranged in parallel or in series dependent on demand to production capacity and purity of the permeate.
  • a main advantage of the present invention is a reduction in required space for the installation which makes it possible to arrange the system according to the present invention on site and at locations with limited space. This can typically be vessels or existing offshore platforms at sea.
  • Another advantage of the use of the membrane module according to the present invention is a highly efficient production of pure hydrogen.
  • the sweep gas in the membrane module according to the present invention not only a high total pressure in the permeate is obtained but also an improved hydrogen flux through the palladium-silver membrane and from the membrane is achieved. Thereby, it is possible to obtain high concentrations of pure hydrogen in the permeate.
  • the hydrogen flux through the membrane is mainly dependent on the hydrogen pressure on the surface of the membrane and not the gas pressure as such.
  • the diffusion away from the membrane is generally a slower process than the diffusion through the membrane. A fast and efficient removal of the hydrogen molecules from the membrane surface is therefore very important.
  • Figure 1 shows a flow chart in accordance with the present invention for the production of hydrogen and CO 2 and the use of CO 2 for storage and pressure increase in an oil reservoir.
  • Figure 2 shows a perspective view of a cylindrical membrane module for hydrogen/ CO 2 separation according to the present invention.
  • Figure 3A to 3C shows different cross-sectional views of the cylindrical membrane module of Fig. 2.
  • Figure 4 shows a simplified schematically cross sectional view of the separating part of a membrane module according to the present invention comprising a pressure tank with a membrane tube comprising an inserted sweep gas pipe inside.
  • the arrows indicate flow directions of the different gas mixtures and components.
  • the basis for the system according to the present invention is an oil reservoir 5 with a need for pressure support (Fig. 1 ).
  • This oil reservoir 5 must be suitable to retain CO 2 in accordance with established criteria for this purpose.
  • natural gas obtained from a reservoir 5 for natural gas is reformed to obtain hydrogen and CO 2 by natural gas reforming 4.
  • the production site for synthesis gas is arranged as close as practically possible to the reservoir 5, either on a nearby offshore installation which treats natural gas or on a land-based installation in close vicinity.
  • the synthesis gas can be converted to a gas mixture comprising mainly hydrogen and CO 2 .
  • This mixture typically has a pressure of 30-40 barg.
  • the gas mixture is thereafter separated into hydrogen and CO 2 in a separation step 1 0 by use of a membrane module 20 comprising thin palladium-silver-membranes of typically 2.5 ⁇ thickness.
  • a membrane module 20 comprising thin palladium-silver-membranes of typically 2.5 ⁇ thickness.
  • the use of the membrane module 20 in the separation step makes it practically and commercially feasible to install such a membrane separation unit land-based, but more preferred is a location directly on an offshore installation.
  • the membrane module can effectively be used to separate hydrogen (permeate 6) from the remaining gas in the gas mixture (retentate 7) after the water gas shift process in the natural gas reforming step 4.
  • the obtained retentate 7 after the membrane separation step 1 0 comprises minor amounts of combustible gases such as hydrogen, methane and others. It is therefore preferred, but optionally, that the retentate 7 is further treated in a combustion process 2 whereby the remaining combustible gases are removed.
  • the energy 8 from this combustion process 2 is preferably used to supply the processing facilities with energy e.g. the reforming step 4 of the natural gas, whereby the need for additional energy production from gas turbines is reduced, which again results in an overall reduction of CO 2 emission from the facility.
  • the processed retentate 7 will mainly comprise CO 2 .
  • CO 2 By compressing the obtained retentate 7 in a compression step 3 and using the already existing infrastructure, or new installations, all CO 2 produced in the facility, can be injected back into the mentioned oil reservoir 5 which has a need for increased pressure and which is suitable to retain the injected CO 2 .
  • the CO 2 produced in the facility can be injected back into other suitable oil reservoirs, and not only the reservoir 5 from where the natural gas has been obtained. Thereby the proportion of oil extraction in an oil reservoir can be increased, which will be an economical advantage for the proprietor of this reservoir.
  • the produced hydrogen gas 6 (permeate) can have many different applications either alone or in combination with other gases.
  • the hydrogen gas 6 can e.g. be used as an energy source in gas turbines for power production in the facility or in the installation.
  • Another preferred use is to compress the hydrogen gas and admix it to a defined proportion of the remaining natural gas from the installation or facility. Thereafter, this refined gas can be exported to the end-user through the existing pipelines. The combustion of the refined gas by the end-user will result in a reduced emission of CO 2 compared to common natural (non- refined) gas.
  • Another preferred use is to compress the hydrogen gas and to transport it in pure form to the end-user by ship, pipe line, road transport, or a combination of these.
  • system and method according to the present invention is typically based on the following steps, using the means as disclosed below:
  • the reforming step 4 of natural gas to a gas mixture comprising hydrogen and CO 2 can be achieved in different ways, which are all well known to the skilled person.
  • the most common method is steam reforming where the natural gas is heated to higher temperatures, typically to 700-850 ° C, in the presence of steam and a catalyzer. Thereafter, the resulting gas mixture undergoes several steps of water gas shift to obtain an optimal amount of hydrogen.
  • a common disadvantage with this technology is a large footprint and that it is a technology causing comparable high costs.
  • the membrane separation step 10 preferably uses a membrane module 20 according to the present invention which comprises a cylindrical pressure tank 21 (Fig. 2 and 3A-3C).
  • a preferred length of the cylindrical pressure tank 21 is 2 to 3 meters with a diameter of 1 - 3 meters.
  • a number of porous tubes 22, typically having a diameter of 25 mm, are arranged inside this cylinder 21 .
  • the number of tubes 22 are chosen such that an optimal utilization of the space in the cylindrical pressure tank 21 is achieved.
  • Each of the porous tubes 22 comprises for instance four to six parts which are screwed to each other (Fig. 3B). At each of the attachment points there is a spreader plate 24 with a defined number of holes, covering the cross sectional area of the cylindrical tube of the pressure tank 21 .
  • the spreader plates 24 function as a mechanical support on the tube's side wall and ensure that there is a turbulent flow through the cylindrical tube 21 .
  • All parts of the porous tube 22 are coated by a palladium-silver membrane, which is typically 2.5 ⁇ thick.
  • Each tube 22 is sealed in their ends. In each of the porous tubes 22, it is arranged a sweep pipe 26 with a smaller diameter, typically a diameter of 10 mm, which is open in the end.
  • the permeate 6 hydrogen
  • a suitable gas 27 e.g. steam or nitrogen
  • the permeate 6 hydrogen
  • This particular construction allows a very efficient separation of the gas mixture.
  • the number of membrane modules 20 arranged in parallel or serial is determined by the requirement of the facility for production capacity (amount of kilos hydrogen per time unit) and purity of the permeate.
  • the afforded space for the membrane unit is comparable small. This allows it to be used in facilities with very limited space such as offshore platforms and oil rigs.
  • the membrane module 20 comprises several parts connected by respective flange connections (Fig. 3 A). As seen, the membrane module 20 comprises a lower flange 40 for connection to a foundation or similar, or other parts of the plant.
  • the membrane module 20 comprises a lower flange 40 for connection to a foundation or similar, or other parts of the plant.
  • membrane module 20 further comprises several flanges in the upper part, i.e. a lower upper flange 42, a middle upper flange 44, and a flange 46 at the top.
  • the porous tubes 22 can, as mentioned, consist of several parts, connected by spreader plates 24, and where the tubes 22 at top are connected or suspended to a head plate 50 with several apertures 50a (Fig. 3B).
  • the porous tubes 22 can be mounted to the head plate 50 in a similar pattern as the apertures 50a.
  • the head plate 50 is preferable connected in the lower upper flange 42.
  • the pipes 26 of smaller diameter can in a similar manner be connected or suspended to a head plate 52 with apertures 52a, in where said head plate 52 is connected in the middle upper flange 44 and with the pipes 26 inserted in the porous tubes 22 (Fig. 3A and C).
  • the pipes 26 of smaller diameter can be mounted to the head plate 52 in a similar pattern as the apertures 52a.
  • the membrane module 20 further comprises among others a sweep gas inlet 30 at the top of the module, i.e. an inlet for instance for inert gas (Fig. 3A).
  • a hydrogen outlet 36 is located in the upper part of the module.
  • FIG 4 shows schematically in a cross sectional simplified view the separating part of a membrane module 20 according to the present invention also indicating the main gas flows through the parts of the membrane module 20.
  • the membrane tube 22 is, as described above, inside the cylindrical pressure tank 21 of the membrane module 20.
  • the membrane module in Figure 4 is only shown with one porous membrane tube 22.
  • the cylindrical pressure tank 21 has an inlet (not shown) in its upper part for the gas mixture 33 obtained after the water shift reaction and an outlet 34 in the bottom for release of the retentate 7.
  • the gas mixture 33 passes on its way through the tank 21 along the outside of the porous membrane tube 22 covered with the palladium-silver membrane.
  • the porous tube 22 extends longitudinally inside the pressure tank 21 .
  • the tube 22 is sealed at the end 23 which is located in vicinity to the outlet 34 of the pressure tank 21 and is in fluid connection to a permeate outlet 36 in the other end.
  • Hydrogen (permeate) 6 comprised in the gas mixture 33 can pass through the highly hydrogen-selective membrane around tube 22 following the concentration
  • the membrane module 20 is provided with a longitudinally extending sweep gas pipe 26 which is opened in the bottom end 25.
  • This pipe has a smaller diameter than the tube 22 and is arranged centrally inside the porous tube 22. It has a sweep gas inlet at one end (not shown) and an opening 25 for sweep gas 27 release in vicinity to the sealed end 23 of the porous tube 22.
  • the function of the sweep pipe 26 is to supply sweep gas 27 through said smaller pipe 26 for flushing the hydrogen permeate 6 out of the porous tube 22. Thereby, the sweep gas 27 is first flushed through the pipe 26 and flows thereafter along the inner side of the porous membrane module 22 thereby taking the permeated hydrogen with it to said permeate outlet (not shown).
  • Providing the sweep gas 27 in thin pipes 26 extending to the bottom of the porous membrane tubes 22 and being open in their extreme ends 25, has mainly two effects:
  • the membrane 22 is flushed over the whole surface and the partial pressure of hydrogen in the permeate is lowest in the area where the partial pressure in the supplied gas is lowest. This results in a particular high flux through the membrane 22.
  • the amount of "dead space volume" on the inner side of the membrane tubes 22 is minimized. Thereby, the flow velocity of the sweep gas 27 is optimized and is highest possible.
  • a main advantage of the use of the membrane module 20 according to the present invention is a highly efficient production of pure hydrogen 6 using counter current flow.
  • the sweep gas 27 in the membrane module 20 according to the present invention not only a high total pressure in the permeate is obtained but also an improved hydrogen flux through the palladium-silver membrane 22 and from the membrane 22 is achieved. Thereby, it is possible to obtain high concentrations of pure hydrogen 6 in the permeate/sweep gas 6,27.
  • the hydrogen flux through the membrane 22 is mainly dependent on the hydrogen pressure on the surface of the membrane 22 and not the gas pressure as such.
  • the diffusion away from the membrane 22 is generally a slower process than the diffusion through the membrane 22.
  • a fast and efficient removal of the hydrogen molecules from the membrane surface is therefore very important for an efficient separation and to achieve high concentrations of pure hydrogen in the permeate. This is achieved by the membrane module according to the present invention.
  • a preferred production method for very thin metal membranes such as the above mentioned palladium-silver membrane which may used in the system and method according to the present invention, is disclosed in NO 304 220 and EP2083938 B1 . There it is also disclosed a method to arrange the membrane around a porous tube. Combustion 2 of the residual product
  • the energy 8 of these remnants is used for example by a combustion process 2 of the remnants before the subsequent injection of the retentate 7 into the oil reservoir 5.
  • the technology used for combustion 2 will depend on the concentration of combustible gases in the retentate 7. As the applied technology is well known to the skilled person in this field, it is not described in more detail.
  • the pressure of the gas must be higher than the pressure in the reservoir 5. This is typically achieved by a multiple-step process of compression 3 using a centrifugal blower. This technique and the necessary means are well known to the skilled person and a detailed disclosure is therefore not necessary to provide.

Abstract

The present invention relates to a membrane module for the separation of hydrogen from CO2 in a gas mixture, a method and system for treatment of natural gas and for improved extraction of an oil reservoir comprising the following steps: extracting natural gas from an oil reservoir (5), reforming (4) of the natural gas followed by water gas shift to obtain a gas mixture comprising hydrogen and CO2, separation of hydrogen and CO2 in the gas mixture using at least one membrane module (20) comprising a porous tube (22) coated with a palladium-silver membrane, and injection (3) of CO2 rich retentate produced in the separation process (10) into an oil reservoir with need for increased pressure. The hydrogen produced in the separation process can be transported to the consumer in a pure form for later use or it can be mixed with natural gas and transported together with the natural gas in existing pipelines.

Description

Hydrogen production from natural gas in combination with injection of C02 for enhanced oil recovery.
Field of the invention
The present invention relates to a membrane module for separation of hydrogen and CO2 in a gas mixture, a system and a method for separation of hydrogen and CO2 from natural gas, and more particular a method and system for treatment of natural gas and for improved extraction of an oil reservoir. Background of the invention
There is an increased interest on global basis for use of hydrogen as an energy resource. Hydrogen plays an important role as energy carrier, e.g. as
environmentally friendly fuel. In addition, hydrogen can be important for storage of energy gained from environmentally friendly, but instable, productions methods for electrical power, such as windmills and solar cells.
At the same time, there is an increasing focus on problems related to the emission of CO2 from human activity. Extrapolative scenarios for the energy demands on global basis show that hydrocarbon-based resources such as oil and gas will still be important for a long time. Therefore, achieving a carbon dioxide-neutral use of these resources is of great importance.
A common challenge for the oil industry is that long-term oil fields which have been used for several years, loose their pressure. As a consequence, the possibility for further production is no longer present, even though the reservoir itself still contains a large amount of oil. Different methods are used today to maintain the pressure in oil reservoirs over a longer period. One of these methods is based on the injection of water or gas into the reservoir to maintain the pressure. It is well known that the injection of carbon dioxide into a reservoir can be used to increase the pressure. As a consequence, the injection will also contribute to a removal of carbon dioxide from the carbon cycle. In this way, a larger part of the existing oil fields can be exploited with the existing infrastructure. At the same time, carbon dioxide can be stored on a permanent basis in the bedrocks, being structures which have kept the natural gas for millions of years. A challenge for the described method is that many of the oil fields, which could be used for this type of injections, are offshore, while the main sources for carbon dioxide are typically land-based. Thus, the mentioned strategy in reality affords large investments, both for capturing of the gas from point sources on land, as well as the transport via pipes to the reservoirs which are suitable for injection. WO 2007/129024 A1 discloses a method for the production of natural gas from an oil or gas field. The natural gas is reformed in a water gas shift reaction. Thereafter, the reformed gas is further treated to separate hydrogen and CO2. This includes a method for hydrogen production, whereby hydrogen and CO2 in a gas mixture are separated in a reactor by means of a palladium-silver membrane on a porous pipe. A sweep gas is used to flush out the separated hydrogen. As the separated hydrogen in WO 2007/129024 A1 is used to produce energy in a gas turbine, high
concentrations of purified hydrogen in the fuel gas are not desirable or afforded. The CO2 rich retentate can be re-injected into the oil or gas reservoir for increasing the extraction efficiency.
Objects of the present invention
A main object of the present invention is to overcome the disadvantages mentioned above. More particularly, the present invention aims at providing a solution for an environmentally use of natural gas in the exploitation of oil fields and suitable methods and technical equipment for efficient on-site treatment of the extracted gas. In particular, the present invention aims at providing an alternative method for the known methods of pressure maintenance in oil fields under exploitation.
Furthermore, the present invention aims to provide an improved, space and cost- efficient method and apparatus for the production of pure hydrogen and CO2 from natural gas. In particular, the present invention aims at producing pure hydrogen in high concentration.
A further object is simplified transport of hydrogen from the installation, either in a pure form for later use, or mixed with natural gas and transported together with the natural gas.
Summary of the invention
In a first aspect the present invention relates to a membrane module for separation of hydrogen and CO2 in a gas mixture as defined in claim 1 . Said membrane module comprises
- a pressure tank with an inlet and outlet for the gas at opposing sides of the tank, - at least one porous tube coated with a palladium-silver membrane, the tube longitudinally extending inside the tank, the tube being closed at the end in vicinity to the outlet of the pressure tank and being in fluid connection to a permeate outlet in the other end,
- a longitudinally extending sweep pipe having a smaller diameter than the porous tube and being centrally installed inside the porous tube, with a sweep gas inlet at one end and an opening for sweep gas release in vicinity to the closed end of the porous tube to supply sweep gas through said smaller pipe for flushing the hydrogen permeate out of the porous tube.
In a second aspect the present invention relates to a method as defined in claim 2. The method according to the present invention comprises the following steps:
extracting natural gas from an oil reservoir, reforming of the natural gas followed by water gas shift to obtain a gas mixture comprising hydrogen and CO2, separation of hydrogen and CO2 in the gas mixture using at least one membrane module comprising
a porous tube coated with a palladium-silver membrane, and injection of CO2 rich retentate produced in the separation process into an oil reservoir with need for increased pressure.
The CO2 rich retentate produced in the separation process can be injected into the oil reservoir the natural gas has been extracted from, or to other suitable reservoirs in the vicinity. A pipe of smaller diameter can be installed inside the porous tube to supply gas through said smaller pipe to flush permeate of hydrogen out of the porous tube.
The membrane module can comprise a pressure tank with an inlet and outlet for the gas at opposing sides of the tank, at least one porous tube coated with a palladium- silver membrane, the tube longitudinally extending inside the tank, the tube being sealed at the end in vicinity to the outlet of the pressure tank and being in fluid connection to an permeate outlet in the other end, a longitudinally extending sweep pipe having a smaller diameter than the porous tube and being centrally installed inside the porous tube, with a sweep gas inlet at one end and an opening for sweep gas release in vicinity to the closed end of the porous tube to supply sweep gas through said smaller pipe for flushing the hydrogen permeate out of the porous tube. Prior to injection of the CO2 rich retentate into the oil reservoir, the retentate is processed in a combustion process for removal of remnants of hydrogen and hydrocarbons. The energy of the remnants removed in the combustion process can be supplied and used as energy in the reforming process of natural gas.
Hydrogen produced in the separation process can be exported to be used as an energy source for power production.
The hydrogen produced in the separation process may be exported to a consumer in a pure form for later use, or the hydrogen can be mixed with natural gas and transported together with the natural gas in existing pipelines. In a third aspect the present invention relates to a system as defined in claim 10. The system according to the present invention comprises the elements: means for reforming of natural gas extracted from an oil reservoir followed by water gas shift to obtain a gas mixture comprising hydrogen and CO2, at least one membrane module comprising a porous tube coated with a palladium-silver membrane for separation of hydrogen and CO2 in the gas mixture, and means for injection of CO2 rich retentate produced in the separation process into an oil reservoir with need for increased pressure.
The system may further comprise means for processing the CO2 rich retentate in a combustion process for removal of remnants of hydrogen and hydrocarbons.
A line can be connected between the means for processing the CO2 rich retentate in the combustion process and the means for reforming of natural gas, for supply of energy in the reforming process of natural gas.
The means for injection of CO2 rich retentate may comprise a multiple-step process centrifugal compressor to increase the pressure of the CO2 retentate to a pressure higher than the pressure in the reservoir. The membrane module may comprise a cylindrical pressure tank with a number of porous tubes, whereby each of the porous tubes is coated with a very thin palladium- silver membrane and each of the tubes comprises different parts which are separated from each other by spreader plates.
A pipe of smaller diameter can be installed inside the porous tube, and said smaller pipe is arranged to receive gas to flush permeate of hydrogen out of the porous tube.
The membrane module in the system can comprise a pressure tank with an inlet and outlet for the gas at opposing sides of the tank, at least one porous tube coated with a palladium-silver membrane, the tube longitudinally extending inside the tank, the tube being sealed at the end in vicinity to the outlet of the pressure tank and being in fluid connection to an permeate outlet in the other end, a longitudinally extending sweep pipe having a smaller diameter than the porous tube and being centrally installed inside the porous tube, with a sweep gas inlet at one end and an opening for sweep gas release in vicinity to the closed end of the porous tube to supply sweep gas through said smaller pipe for flushing the hydrogen permeate out of the porous tube.
Several membrane modules can be arranged in parallel or in series dependent on demand to production capacity and purity of the permeate.
In accordance with the present invention, it is possible to produce pure hydrogen and CO2 from natural gas in a closed cycle. A main advantage of the present invention is a reduction in required space for the installation which makes it possible to arrange the system according to the present invention on site and at locations with limited space. This can typically be vessels or existing offshore platforms at sea.
Another advantage of the use of the membrane module according to the present invention is a highly efficient production of pure hydrogen. By using the sweep gas in the membrane module according to the present invention not only a high total pressure in the permeate is obtained but also an improved hydrogen flux through the palladium-silver membrane and from the membrane is achieved. Thereby, it is possible to obtain high concentrations of pure hydrogen in the permeate.
The hydrogen flux through the membrane is mainly dependent on the hydrogen pressure on the surface of the membrane and not the gas pressure as such. The diffusion away from the membrane is generally a slower process than the diffusion through the membrane. A fast and efficient removal of the hydrogen molecules from the membrane surface is therefore very important.
By producing hydrogen and collecting CO2 as close as possible to the injection point for an oil field with need for increased pressure, costs can be saved. This results in a reduced need for CO2 catch from many separate CO2 emitting sources such as gasworks. Furthermore, there is no need for transport of CO2 from these separate sources to the injection point via pipelines or other means for transport. As mentioned, the hydrogen can be transported to the consumer in a pure form for later use such as in ships and cars. It can also be mixed with natural gas and transported together with the natural gas in the existing pipelines. In this way the carbon dioxide emission can be reduced correspondingly on the consumer side. Description of the diagrams
Embodiments of the present invention will now be described, by way of example only, with reference to the following diagrams wherein:
Figure 1 shows a flow chart in accordance with the present invention for the production of hydrogen and CO2 and the use of CO2 for storage and pressure increase in an oil reservoir.
Figure 2 shows a perspective view of a cylindrical membrane module for hydrogen/ CO2 separation according to the present invention.
Figure 3A to 3C shows different cross-sectional views of the cylindrical membrane module of Fig. 2.
Figure 4 shows a simplified schematically cross sectional view of the separating part of a membrane module according to the present invention comprising a pressure tank with a membrane tube comprising an inserted sweep gas pipe inside. The arrows indicate flow directions of the different gas mixtures and components.
Description of preferred embodiments of the invention
The basis for the system according to the present invention is an oil reservoir 5 with a need for pressure support (Fig. 1 ). This oil reservoir 5 must be suitable to retain CO2 in accordance with established criteria for this purpose. As a first step 9 natural gas obtained from a reservoir 5 for natural gas is reformed to obtain hydrogen and CO2 by natural gas reforming 4. Preferably, the production site for synthesis gas is arranged as close as practically possible to the reservoir 5, either on a nearby offshore installation which treats natural gas or on a land-based installation in close vicinity. In combination with a so-called water gas shift reaction, the synthesis gas can be converted to a gas mixture comprising mainly hydrogen and CO2. This mixture typically has a pressure of 30-40 barg.
The gas mixture is thereafter separated into hydrogen and CO2 in a separation step 1 0 by use of a membrane module 20 comprising thin palladium-silver-membranes of typically 2.5 μιη thickness. The use of the membrane module 20 in the separation step makes it practically and commercially feasible to install such a membrane separation unit land-based, but more preferred is a location directly on an offshore installation. As a palladium-silver-membrane is only permeable for hydrogen, i.e. it is 1 00% selective for hydrogen, the membrane module can effectively be used to separate hydrogen (permeate 6) from the remaining gas in the gas mixture (retentate 7) after the water gas shift process in the natural gas reforming step 4.
Due to practical reasons, the obtained retentate 7 after the membrane separation step 1 0 comprises minor amounts of combustible gases such as hydrogen, methane and others. It is therefore preferred, but optionally, that the retentate 7 is further treated in a combustion process 2 whereby the remaining combustible gases are removed. The energy 8 from this combustion process 2 is preferably used to supply the processing facilities with energy e.g. the reforming step 4 of the natural gas, whereby the need for additional energy production from gas turbines is reduced, which again results in an overall reduction of CO2 emission from the facility.
The processed retentate 7 will mainly comprise CO2. By compressing the obtained retentate 7 in a compression step 3 and using the already existing infrastructure, or new installations, all CO2 produced in the facility, can be injected back into the mentioned oil reservoir 5 which has a need for increased pressure and which is suitable to retain the injected CO2. However, the CO2 produced in the facility can be injected back into other suitable oil reservoirs, and not only the reservoir 5 from where the natural gas has been obtained. Thereby the proportion of oil extraction in an oil reservoir can be increased, which will be an economical advantage for the proprietor of this reservoir. The produced hydrogen gas 6 (permeate) can have many different applications either alone or in combination with other gases.
The hydrogen gas 6 can e.g. be used as an energy source in gas turbines for power production in the facility or in the installation. Another preferred use is to compress the hydrogen gas and admix it to a defined proportion of the remaining natural gas from the installation or facility. Thereafter, this refined gas can be exported to the end-user through the existing pipelines. The combustion of the refined gas by the end-user will result in a reduced emission of CO2 compared to common natural (non- refined) gas. Another preferred use is to compress the hydrogen gas and to transport it in pure form to the end-user by ship, pipe line, road transport, or a combination of these.
In more detail, the system and method according to the present invention is typically based on the following steps, using the means as disclosed below:
Reforming 4 of natural gas
The reforming step 4 of natural gas to a gas mixture comprising hydrogen and CO2 can be achieved in different ways, which are all well known to the skilled person. The most common method is steam reforming where the natural gas is heated to higher temperatures, typically to 700-850 °C, in the presence of steam and a catalyzer. Thereafter, the resulting gas mixture undergoes several steps of water gas shift to obtain an optimal amount of hydrogen. A common disadvantage with this technology is a large footprint and that it is a technology causing comparable high costs.
An alternative to the steam reforming is an auto-thermal reforming, wherein the energy for the reforming process is produced by reacting the natural gas with oxygen (as air or pure oxygen) and water vapor. Likewise, this technology affords several steps of water-gas shift in order to obtain an optimal amount of hydrogen. This technology is principally cheaper and affords installations of smaller dimensions. Apart from these two common technologies, there are several other technologies under development, which may be used in the present invention as many of these require a smaller volume and space. Examples for such preferred technologies are membrane reactors, wherein all processes are arranged in one reactor and hydrogen is separated by means of membranes and different compact versions of steam reactors (e.g. plate-type, concentric annular, partial oxidation). The palladium-silver membrane module according the present invention
The membrane separation step 10 preferably uses a membrane module 20 according to the present invention which comprises a cylindrical pressure tank 21 (Fig. 2 and 3A-3C). A preferred length of the cylindrical pressure tank 21 is 2 to 3 meters with a diameter of 1 - 3 meters. A number of porous tubes 22, typically having a diameter of 25 mm, are arranged inside this cylinder 21 . Preferably, the number of tubes 22 are chosen such that an optimal utilization of the space in the cylindrical pressure tank 21 is achieved.
Each of the porous tubes 22 comprises for instance four to six parts which are screwed to each other (Fig. 3B). At each of the attachment points there is a spreader plate 24 with a defined number of holes, covering the cross sectional area of the cylindrical tube of the pressure tank 21 . The spreader plates 24 function as a mechanical support on the tube's side wall and ensure that there is a turbulent flow through the cylindrical tube 21 . All parts of the porous tube 22 are coated by a palladium-silver membrane, which is typically 2.5 μιη thick. Each tube 22 is sealed in their ends. In each of the porous tubes 22, it is arranged a sweep pipe 26 with a smaller diameter, typically a diameter of 10 mm, which is open in the end. By adding of a suitable gas 27 through this inner pipe 26 (e.g. steam or nitrogen) the permeate 6 (hydrogen) can be flushed out of the porous tube 22. This particular construction allows a very efficient separation of the gas mixture. The number of membrane modules 20 arranged in parallel or serial is determined by the requirement of the facility for production capacity (amount of kilos hydrogen per time unit) and purity of the permeate. In spite of the high membrane surface in the membrane module 20 according to the present invention which allows a high separation capacity, the afforded space for the membrane unit is comparable small. This allows it to be used in facilities with very limited space such as offshore platforms and oil rigs.
The membrane module 20 comprises several parts connected by respective flange connections (Fig. 3 A). As seen, the membrane module 20 comprises a lower flange 40 for connection to a foundation or similar, or other parts of the plant. The
membrane module 20 further comprises several flanges in the upper part, i.e. a lower upper flange 42, a middle upper flange 44, and a flange 46 at the top. The porous tubes 22 can, as mentioned, consist of several parts, connected by spreader plates 24, and where the tubes 22 at top are connected or suspended to a head plate 50 with several apertures 50a (Fig. 3B). The porous tubes 22 can be mounted to the head plate 50 in a similar pattern as the apertures 50a. The head plate 50 is preferable connected in the lower upper flange 42.
The pipes 26 of smaller diameter can in a similar manner be connected or suspended to a head plate 52 with apertures 52a, in where said head plate 52 is connected in the middle upper flange 44 and with the pipes 26 inserted in the porous tubes 22 (Fig. 3A and C). The pipes 26 of smaller diameter can be mounted to the head plate 52 in a similar pattern as the apertures 52a. The membrane module 20 further comprises among others a sweep gas inlet 30 at the top of the module, i.e. an inlet for instance for inert gas (Fig. 3A). A middle syngas inlet 32 and lower syngas outlet 34, the syngas inlet 32 being for hydrogen and CO2 and the syngas outlet 34 being for retentate. A hydrogen outlet 36 is located in the upper part of the module.
Figure 4 shows schematically in a cross sectional simplified view the separating part of a membrane module 20 according to the present invention also indicating the main gas flows through the parts of the membrane module 20. The membrane tube 22 is, as described above, inside the cylindrical pressure tank 21 of the membrane module 20. For illustrative reasons the membrane module in Figure 4 is only shown with one porous membrane tube 22.
The cylindrical pressure tank 21 has an inlet (not shown) in its upper part for the gas mixture 33 obtained after the water shift reaction and an outlet 34 in the bottom for release of the retentate 7. The gas mixture 33 passes on its way through the tank 21 along the outside of the porous membrane tube 22 covered with the palladium-silver membrane. The porous tube 22 extends longitudinally inside the pressure tank 21 . The tube 22 is sealed at the end 23 which is located in vicinity to the outlet 34 of the pressure tank 21 and is in fluid connection to a permeate outlet 36 in the other end. Hydrogen (permeate) 6 comprised in the gas mixture 33 can pass through the highly hydrogen-selective membrane around tube 22 following the concentration
gradient/gradient in partial pressure.
Inside the porous membrane tube 22, the membrane module 20 is provided with a longitudinally extending sweep gas pipe 26 which is opened in the bottom end 25. This pipe has a smaller diameter than the tube 22 and is arranged centrally inside the porous tube 22. It has a sweep gas inlet at one end (not shown) and an opening 25 for sweep gas 27 release in vicinity to the sealed end 23 of the porous tube 22. The function of the sweep pipe 26 is to supply sweep gas 27 through said smaller pipe 26 for flushing the hydrogen permeate 6 out of the porous tube 22. Thereby, the sweep gas 27 is first flushed through the pipe 26 and flows thereafter along the inner side of the porous membrane module 22 thereby taking the permeated hydrogen with it to said permeate outlet (not shown).
Providing the sweep gas 27 in thin pipes 26 extending to the bottom of the porous membrane tubes 22 and being open in their extreme ends 25, has mainly two effects: The membrane 22 is flushed over the whole surface and the partial pressure of hydrogen in the permeate is lowest in the area where the partial pressure in the supplied gas is lowest. This results in a particular high flux through the membrane 22. Furthermore, the amount of "dead space volume" on the inner side of the membrane tubes 22 is minimized. Thereby, the flow velocity of the sweep gas 27 is optimized and is highest possible.
A main advantage of the use of the membrane module 20 according to the present invention is a highly efficient production of pure hydrogen 6 using counter current flow. By using the sweep gas 27 in the membrane module 20 according to the present invention not only a high total pressure in the permeate is obtained but also an improved hydrogen flux through the palladium-silver membrane 22 and from the membrane 22 is achieved. Thereby, it is possible to obtain high concentrations of pure hydrogen 6 in the permeate/sweep gas 6,27.
The hydrogen flux through the membrane 22 is mainly dependent on the hydrogen pressure on the surface of the membrane 22 and not the gas pressure as such. The diffusion away from the membrane 22 is generally a slower process than the diffusion through the membrane 22. A fast and efficient removal of the hydrogen molecules from the membrane surface is therefore very important for an efficient separation and to achieve high concentrations of pure hydrogen in the permeate. This is achieved by the membrane module according to the present invention.
A preferred production method for very thin metal membranes such as the above mentioned palladium-silver membrane which may used in the system and method according to the present invention, is disclosed in NO 304 220 and EP2083938 B1 . There it is also disclosed a method to arrange the membrane around a porous tube. Combustion 2 of the residual product
After the above described separation 10 of the gas mixture in CO2 and hydrogen gas, there are typically still remnants of hydrogen and hydrocarbons in the retentate 7. It is preferred that the energy 8 of these remnants is used for example by a combustion process 2 of the remnants before the subsequent injection of the retentate 7 into the oil reservoir 5. The technology used for combustion 2 will depend on the concentration of combustible gases in the retentate 7. As the applied technology is well known to the skilled person in this field, it is not described in more detail.
Compression 3 of C02
To be able to inject the CO2 retentate 7 into the oil reservoir 5, the pressure of the gas must be higher than the pressure in the reservoir 5. This is typically achieved by a multiple-step process of compression 3 using a centrifugal blower. This technique and the necessary means are well known to the skilled person and a detailed disclosure is therefore not necessary to provide.

Claims

Claims
1 . A membrane module (20) for separation (10) of hydrogen and CO2 in a gas mixture wherein the module (20) comprises
- a pressure tank (21 ) with an inlet (32) and outlet (34) for the gas at opposing sides of the tank (21 ),
- at least one porous tube (22) coated with a palladium-silver membrane, the tube longitudinally extending inside the tank (21 ), the tube being closed at the end (23) in vicinity to the outlet (34) of the pressure tank (21 ) and being in fluid connection to a permeate outlet (36) in the other end,
- a longitudinally extending sweep pipe (26) having a smaller diameter than the porous tube (22) and being centrally installed inside the porous tube (22), with a sweep gas (27) inlet at one end and an opening (25) for sweep gas (27) release in vicinity to the closed end (23) of the porous tube (22) to supply sweep gas (27) through said smaller pipe (26) for flushing the hydrogen permeate out of the porous tube (22).
2. A method for treatment of natural gas and for improved extraction of an oil reservoir comprising the following steps:
- extracting natural gas from an oil reservoir (5),
reforming (4) of the natural gas followed by water gas shift to obtain a gas mixture comprising hydrogen and CO2,
separation (10) of hydrogen and CO2 in the gas mixture using at least one membrane module (20) comprising a porous tube (22) coated with a palladium-silver membrane, and
injection (3) of CO2 rich retentate produced in the separation process (10) into an oil reservoir with need for increased pressure.
3. Method according to claim 2, wherein the CO2 rich retentate produced in the separation process (10) is injected (3) into the oil reservoir (5) the natural gas has been extracted from, or to other suitable reservoirs in the vicinity.
4. Method according to claim 2 or 3, wherein a pipe (26) of smaller diameter than the porous tube (22) is being installed inside the porous tube (22), and to supply gas through said smaller pipe to flush permeate of hydrogen out of the porous tube (22).
5. Method according to any of the claims 2 to 4, wherein the membrane module comprises
- a pressure tank (21 ) with an inlet (32) and outlet (34) for the gas at opposing sides of the tank (21 ),
- at least one porous tube (22) coated with a palladium-silver membrane, the tube longitudinally extending inside the tank (21 ), the tube being sealed at the end (23) in vicinity to the outlet (34) of the pressure tank (21 ) and being in fluid connection to an permeate outlet (36) in the other end,
- a longitudinally extending sweep pipe (26) having a smaller diameter than the porous tube (22) and being centrally installed inside the porous tube (22), with a sweep gas (27) inlet at one end and an opening (25) for sweep gas (27) release in vicinity to the closed end (23) of the porous tube (22) to supply sweep gas (27) through said smaller pipe (26) for flushing the hydrogen permeate out of the porous tube (22).
6. Method according to any of the claims 2 to 5, wherein prior to injection (3) of the CO2 rich retentate into the oil reservoir (5), the retentate is processed in a combustion process (2) for removal of remnants of hydrogen and hydrocarbons.
7. Method according to claim 3, wherein the energy (8) of the remnants removed in the combustion process (2) is supplied and used as energy in the reforming process (4) of natural gas.
8. Method according to any of the claims 2 to 7, wherein hydrogen produced in the separation process (10) is exported (6) to be used as an energy source for power production.
9. Method according to any of the claims 2 to 8, wherein hydrogen produced in the separation process (10) is exported (6) to a consumer in a pure form for later use, or the hydrogen is mixed with natural gas and transported together with the natural gas in existing pipelines.
10. A system for treatment of natural gas and for improved extraction of an oil reservoir comprising the elements:
- means for reforming (4) of natural gas extracted from an oil reservoir (5) followed by water gas shift to obtain a gas mixture comprising hydrogen and CO2, - at least one membrane module (20) comprising a porous tube (22) coated with a palladium-silver membrane for separation (1 0) of hydrogen and CO2 in the gas mixture, and
- means for injection (3) of CO2 rich retentate produced in the separation process (1 0) into an oil reservoir with need for increased pressure.
1 1 . System according to claim 1 0, comprising means for processing the CO2 rich retentate in a combustion process (2) for removal of remnants of hydrogen and hydrocarbons.
1 2. System according to claim 1 0 or 1 1 , wherein a line (L1 ) is connected between the means for processing the CO2 rich retentate in the combustion process (2) and the means for reforming (4) of natural gas, for supply of energy in the reforming process (4) of natural gas.
1 3. System according to claim 1 0, wherein the means for injection (3) of CO2 rich retentate comprises a multiple-step process centrifugal compressor to increase the pressure of the CO2 retentate to a pressure higher than the pressure in the reservoir (5).
14. System according to claim 1 0, wherein the membrane module (20) comprises a cylindrical pressure tank with a number of porous tubes (22), whereby each of the porous tubes (22) is coated with a very thin palladium-silver membrane and each of the tubes comprises different parts which are separated from each other by spreader plates (24).
1 5. System according to any of the claims 1 0 to 14, wherein a pipe (26) of smaller diameter than the porous tube (22) is installed inside said porous tube (22), and said smaller pipe is arranged to receive gas to flush permeate of hydrogen out of the porous tube (22).
1 6. System according to any of the claims 1 0 to 1 5, wherein the membrane module comprises
- a pressure tank (21 ) with an inlet (32) and outlet (34) for the gas at opposing sides of the tank (21 ),
- at least one porous tube (22) coated with a palladium-silver membrane, the tube longitudinally extending inside the tank (21 ), the tube being sealed at the end (23) in vicinity to the outlet (34) of the pressure tank (21 ) and being in fluid connection to an permeate outlet (36) in the other end,
- a longitudinally extending sweep pipe (26) having a smaller diameter than the porous tube (22) and being centrally installed inside the porous tube (22), with a sweep gas (27) inlet at one end and an opening (25) for sweep gas (27) release in vicinity to the closed end (23) of the porous tube (22) to supply sweep gas (27) through said smaller pipe (26) for flushing the hydrogen permeate out of the porous tube (22).
17. System according to any of the claims 10 to 16, wherein several membrane modules (20) are arranged in parallel or in series dependent on demand to production capacity and purity of the permeate.
PCT/NO2017/050047 2016-02-25 2017-02-22 Hydrogen production from natural gas in combination with injection of co2 for enhanced oil recovery WO2017146589A1 (en)

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