WO2006112724A2 - Procede de production d'energie electrique et de co2 a partir d'une charge d'hydrocarbures - Google Patents

Procede de production d'energie electrique et de co2 a partir d'une charge d'hydrocarbures Download PDF

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Publication number
WO2006112724A2
WO2006112724A2 PCT/NO2006/000142 NO2006000142W WO2006112724A2 WO 2006112724 A2 WO2006112724 A2 WO 2006112724A2 NO 2006000142 W NO2006000142 W NO 2006000142W WO 2006112724 A2 WO2006112724 A2 WO 2006112724A2
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Prior art keywords
stream
rich
air
oxygen
outlet
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PCT/NO2006/000142
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English (en)
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WO2006112724A3 (fr
Inventor
Gelein De Koeijer
Erling Rytter
Børge Rygh SIVERTSEN
Henrik Kobro
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Statoil Asa
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Publication of WO2006112724A2 publication Critical patent/WO2006112724A2/fr
Publication of WO2006112724A3 publication Critical patent/WO2006112724A3/fr
Priority to NO20075953A priority Critical patent/NO20075953L/no

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
    • F02C3/00—Gas-turbine plants characterised by the use of combustion products as the working fluid
    • F02C3/20—Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products
    • F02C3/22—Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products the fuel or oxidant being gaseous at standard temperature and pressure
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    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0233—Chemical processing only
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    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0251—Physical processing only by making use of membranes
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    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0259—Physical processing only by adsorption on solids
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    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
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    • C01B13/0229—Purification or separation processes
    • C01B13/0288—Combined chemical and physical processing
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    • 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
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    • 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
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    • 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
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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    • 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
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    • 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
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    • C01B2203/0405—Purification by membrane separation
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    • 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
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
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    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
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    • 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
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/048—Composition of the impurity the impurity being an organic compound
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    • 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
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0816—Heating by flames
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    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0046—Nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C2900/00—Special features of, or arrangements for combustion apparatus using fluid fuels or solid fuels suspended in air; Combustion processes therefor
    • F23C2900/99011—Combustion process using synthetic gas as a fuel, i.e. a mixture of CO and H2
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23L—SUPPLYING AIR OR NON-COMBUSTIBLE LIQUIDS OR GASES TO COMBUSTION APPARATUS IN GENERAL ; VALVES OR DAMPERS SPECIALLY ADAPTED FOR CONTROLLING AIR SUPPLY OR DRAUGHT IN COMBUSTION APPARATUS; INDUCING DRAUGHT IN COMBUSTION APPARATUS; TOPS FOR CHIMNEYS OR VENTILATING SHAFTS; TERMINALS FOR FLUES
    • F23L2900/00—Special arrangements for supplying or treating air or oxidant for combustion; Injecting inert gas, water or steam into the combustion chamber
    • F23L2900/07002—Injecting inert gas, other than steam or evaporated water, into the combustion chambers
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • 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
    • Y02P20/10—Process efficiency
    • 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
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the present invention relates to a process for production of electric energy and CO 2 and an electric power plant for performing the process.
  • a major technical problem associated herewith is the difficulty of separating nitrogen from carbon dioxide.
  • One solution to this problem is a pre-combustion plant, where the CO 2 is removed from a synthesis gas, and where the remaining hydrogen is used for electricity production. The nitrogen-CO 2 mixture is prevented from being formed in this process.
  • WO 00/18680 discloses a process for preparing a hydrogen rich gas and a carbon dioxide rich gas at high pressure comprising separation of synthesis gas obtained by autothermal reforming, air-fired steam reforming or partial oxidation. Further this publication teaches the use of nitrogen for diluting the hydrogen before combustion. How this nitrogen stream is obtained or the quality thereof is not described.
  • WO 99/41188 teaches the use of steam reforming in connection with a hydrogen fueled power plant. Further this publication teaches separating of the obtained synthesis gas into a hydrogen rich stream and a carbon dioxide rich stream with chemical absorption. Part of the obtained hydrogen is used as fuel for heating the steam reformer by combusting the hydrogen with air.
  • JP2003081605 discloses a hydrogen manufacturing method with a steam reformer.
  • the aim of the process is to use the cooling energy present in liquefied natural gas (LNG) to obtain liquid carbon dioxide and hydrogen.
  • LNG liquefied natural gas
  • the obtained synthesis gas is separated by pressure swing adsorption into a hydrogen rich stream and a rest stream at atmospheric pressure.
  • the rest stream is combusted using pure oxygen or high-density oxygen for heating the steam reformer.
  • a CO 2 rich exhaust is produced which is cooled by the cooling energy.
  • the pure or high-density oxygen is produced by cryogenic air separation also using the cooling energy.
  • the use of hydrogen as fuel in a power plant is not disclosed.
  • US6296686 disclose a process for providing an endothermic reaction including transporting oxygen from an air stream through an oxygen selective membrane.
  • Heat is provided by combusting a fuel with either the oxygen transported through the membrane or the rest of the air stream.
  • the object of the process is to provide syngas with a H 2 /C0 molar ratio that requires more heat then the reformation itself can provide and at the same time minimize the formation of NO x .
  • the flue gas comprises a mixture of combustion products including CO 2 and nitrogen from the air stream.
  • the aim of the present invention is to provide a new precombustion process for power production which is applicable for different hydrocarbon feedstocks, which is energy efficient and which comprises recovery of produced CO 2 in form of a CO 2 rich stream that can be stored or used elsewhere. Further the aim is to provide a process that utilizes combustion heat from combusting a rest stream from separation of synthesis gas for heating a steam reformer.
  • the main product from the synthesis gas separation is a carbon lean fuel, which mainly consists of hydrogen.
  • the aim is to provide a process which can be adapted to, at the same time, produce a nitrogen rich stream, preferably oxygen free, for diluting the hydrogen rich and carbon lean fuel before or during combustion to control combustion temperature and formation of nitrogen oxides.
  • the present invention provides a process for production of electric energy and CO 2 from a hydrocarbon feedstock comprising steam reforming of the feedstock producing synthesis gas, wherein the synthesis gas is separated into a hydrogen rich and carbon lean stream and a rest stream, said hydrogen rich and carbon lean stream is combusted with compressed air for producing a combustion product which is expanded in a turbine generating electric energy, said rest stream is recirculated as fuel for producing heat for said steam reforming, characterised in that air is separated into an oxygen rich stream and a nitrogen rich stream, where said oxygen rich stream is used for combusting said rest stream creating a CO 2 rich combustion product.
  • the present invention provides an electric power plant comprising a steam reformer with an inlet for a hydrocarbon feedstock including water and/or steam and an outlet for synthesis gas, said outlet for synthesis gas is in communication with a hydrogen separation unit having an outlet for a hydrogen rich and carbon lean stream and an outlet for a rest stream, said outlet for a hydrogen rich and carbon lean stream is in communication with a combustion chamber for combusting hydrogen with compressed air having an outlet connected to a turbine for generating electric power, said outlet for a rest stream is in communication with a combustion unit heat transferringly connected to said steam reformer, characterised in that the plant further comprises an air separation unit with an outlet for an oxygen rich stream and an outlet for a nitrogen rich stream, wherein said outlet for an oxygen rich stream is in communication with the combustion unit and said combustion unit has an exhaust outlet for a CO 2 rich combustion product.
  • hydrocarbon feedstock is meant to include natural gas, LNG, gasoline, nafta, methane, oil, and bio gas, preferable natural gas.
  • figure 1 is a schematic flow sheet of a first embodiment of the present invention
  • figure 2 is a schematic flow sheet of a second embodiment of the present invention
  • figure 3 is a schematic flow sheet of a third embodiment of the present invention.
  • FIG. 1 illustrates a first embodiment of the present invention.
  • an air stream 40 enters a compressor 5 generating a compressed air stream 45 which is entered into a combustion chamber 4.
  • the compressor 5 may consist of more than one compressor units.
  • a hydrogen rich stream 26 is lead into the combustion chamber 4.
  • Combustion of hydrogen creates exhaust stream 27 which is expanded in a turbine 6.
  • a generator 12 is coupled to the turbine 6.
  • Preferably the generator, the turbine and the compressor are connected to a common shaft.
  • An expanded exhaust stream 28 that leaves the turbine is preferably past into a heat recovery steam generator (HRSG) 7, where the heat contained in the exhaust is used for generating steam which is used for production of electric energy in steam turbines.
  • HRSG heat recovery steam generator
  • the exhaust stream 28 and possible cooled exhaust stream 29 do not contain more carbon dioxide than the amount that is economically viable or is set by regulators.
  • the combustion product when using hydrogen as fuel is water which can be released to the surrounding environment without causing environmental problems.
  • a hydrocarbon feedstock together with steam and/or water is fed to the power plant through conduit 20, it is preferable heated in heat exchanger 30 and enters a steam reformer 1 through conduit 21.
  • the steam reformer synthesis gas is formed and the synthesis gas 22 is optionally cooled in a heat exchanger 31 before it optionally enters a shift reactor unit 2 as stream 23.
  • the shift reactor unit can comprise of one or several stages, e.g. high and low temperature shift reactors.
  • the synthesis gas is shifted by forcing at least part of the CO and H 2 O to form CO 2 and H 2 .
  • the optionally shifted synthesis gas 24 is optionally cooled in a heat exchanger 32 before it is fed as stream 25 into a hydrogen separation unit 3, like a distillation unit, a membrane unit or a pressure swing adsorption (PSA) unit, preferably a PSA unit.
  • the separated hydrogen forms the carbon lean fuel stream 26 to the combustion chamber 4, which may contain maximum 20 mol% CH 4 , CO or CO 2 , but preferably less than 10 mol%.
  • a rest stream 50 containing CO 2 , CO, H 2 O, H 2 and CH 4 is optionally compressed in compressor 60.
  • compressor 60 The work needed to be performed by compressor 60 will depend on the pressure of the rest stream 50, the higher the pressure of stream 50 the less work compressor 60 has to perform.
  • Compressed rest gas 51 is optionally preheated in heat exchanger 35 before it enters a combustion unit 11 as stream 52.
  • the rest stream 52 is combusted in the combustion unit 11 to heat the steam reformer 1. The combustion supplies the necessary extra energy needed for the steam reforming process.
  • An air stream 41, optionally partly compressed in compressor 5 or another compressor is optionally past through a heat exchanger 37 before it enters an air separation unit 9 as stream 42.
  • air is separated into an oxygen rich and nitrogen lean stream 43 and a nitrogen rich stream 19.
  • the oxygen rich and nitrogen lean stream 43 preferably contains more than 90 mol% oxygen.
  • the nitrogen rich stream 19 comprises preferably less than 10 mol% oxygen.
  • Stream 19 may optionally as a whole or partially be expanded in the turbine 6 for generating electricity (not shown on figure 1).
  • the oxygen rich stream 43 is optionally compressed in compressor 62 creating stream 44, which is optionally heated in heat exchanger 33 before it enters the combustion unit 11 as stream 46.
  • Conduit 57 supplies the air separation unit 9 with heat, electricity and/or natural gas depending on the technology used for air separation.
  • the exhaust 53 from the combustion unit 11 will contain predominantly H 2 O and CO 2 , and preferably less than 10 mol% uncombusted fuel and nitrogen.
  • the exhaust is preferably cooled in heat exchanger 36 and a cooled CO 2 rich stream 54 may be compressed in compressor 61 to obtain a compressed supercritical or liquefied CO 2 stream 55 that can be stored, injected into oil or gas containing formations to enhance production or used in any other way.
  • water can be removed from stream 54 as liquid water stream 56, for instance by inserting a condenser (not shown) downstream from the heat exchanger 36.
  • a condenser (not shown) downstream from the heat exchanger 36.
  • uncombusted fuel and nitrogen are present in stream 53, they can optionally be removed in a compression process e.g. by a relatively small distillation unit (not shown).
  • the work needed to be performed by compressor 61 will depend on the pressure of the steam 53.
  • the pressure of stream 53 depends on the pressure of the rest stream 50 and of the oxygen rich stream 46.
  • it may optionally first be expanded in a CO 2 ZH 2 O turbine (not shown) that generates extra electricity.
  • H 2 O can be partially removed and the CO 2 recompressed.
  • This option is preferred if the pressure and temperature of stream 53 are high, preferably above 4 bar and 900 °C respectively.
  • the efficiency of this CO 2 /H 2 O turbine can be optionally increased by combusting the uncombusted fuel (not shown).
  • the air separation unit 9 comprises an oxygen transfer membrane.
  • the membrane is preferably operated at an increased temperature. This may be obtained by passing the optionally compressed air stream 41 through a optional heat exchanger 37.
  • the air stream 42 is brought into contact with the oxygen transfer membrane.
  • Oxygen present in the air stream is transferred through the membrane and leaves the unit as oxygen rich stream 43, which may be pure oxygen.
  • the oxygen depleted air stream leaves the unit 9 as nitrogen rich stream 19.
  • the oxygen transfer membrane can consist of any material capable of transferring oxygen.
  • Known oxygen transfer membranes comprise a membrane preferably arranged on a support material.
  • the membranes that exist today are made of ceramic materials. The membranes can transfer oxygen to a larger absolute pressure on the permeate side than on the retentate side.
  • a concentration gradient will work as the driving force.
  • the stream 43 will contain oxygen and CO 2 and/or steam. If the membrane is swept with CO 2 this will not interfere with the ability of the process to produce a CO 2 rich stream 55, but it only means that a part of the produced CO 2 is recycled. If steam is used for sweeping the stream 53 will contain more H 2 O then without steam sweeping.
  • the rest stream 50 from the hydrogen separation unit can contain some H 2 O, and H 2 O is produced by the combustion. That is if the intent of the process is a pure CO 2 stream some conventional equipment for water separation, like a condenser, must be enclosed downstream from combustion unit 11. If the membrane is swept with steam, this equipment will have to handle somewhat larger amounts of water/steam.
  • the air separation unit 9 comprises a material that physically or chemically absorbs/adsorbs oxygen selectivly. Oxygen is adsorbed and released in a pressure swing operation.
  • the oxygen adsorbing capacity of the material is best at high temperature (500-1000 0 C). This for instance might be achieved by heating the air stream 41 in heat exchanger 37.
  • the adsorbing material can be swept with a CO 2 rich stream like stream 53 or 54, or a steam stream, possibly produced in one of the heat exchangers 31, 32 or in the HRSG system 7.
  • the stream 43 will contain oxygen and CO 2 and/or steam.
  • the separation unit preferably comprises at least two adsorbent beds operated in a dual mode, when adsorption takes place in the first one, desorption takes place in the second one and vice versa.
  • a separation process is known as a Ceramic Autothermal Recovery (CAR).
  • the air separation unit 9 comprises an air separation membrane more permeable to either nitrogen or oxygen.
  • the driving force for the air separation with an air separation membrane is a pressure gradient over the membrane.
  • the air separation unit 9 is a cryogenic air separation unit.
  • compressed air 41 is preferably cooled in heat exchanger 37 before it enters the separation unit 9.
  • the separation of the synthesis gas in a pressure swing adsorption unit 3 is preferably operated in such a way that the rest stream 50 leaving the unit 3 is at a pressure higher than atmospheric pressure, preferably it has a pressure of 1-20 bar, more preferred 1-5 bar.
  • a rest stream with an elevated pressure has the advantage that less work must be performed by compressor 60.
  • Using a rest stream 50 with an elevated pressure is preferably combined with a cryogenic air separation unit.
  • FIG. 2 illustrates a second embodiment of the present invention.
  • the figure shows the power plant according to figure 1 with the same reference numbers, but the power plant further comprises a low temperature catalytic combustion unit 8.
  • At least a part of the nitrogen rich stream 19 from the air separation unit 9 enters combustion unit 8 as stream 19' .
  • any oxygen present in the stream is combusted by using a part 26' of the hydrogen rich stream 26.
  • an oxygen free stream 18 is produced which is used for diluting the rest of the hydrogen rich stream 26 before or in the combustion chamber 4.
  • the fuel stream 90 is cooled in a cooler 38 before it enters the combustion chamber 4 as stream 91. Diluting the hydrogen stream has the advantage that the combustion temperature is more easily controlled and thereby the unwanted generation of nitrogen oxides can be limited.
  • the process performed in the combustion unit 8 is stimulated low temperature combustion, where an oxygen containing nitrogen stream and a hydrogen stream are combusted to form an oxygen free nitrogen stream also containing some H 2 O for diluting the main hydrogen stream.
  • a control system for controlling the flow of the different streams can be installed.
  • the flow of the main hydrogen stream may be controlled by a valve arrange upstream or downstream from the point where the main hydrogen fuel stream is diluted. In one embodiment all valves and other control means can be arranged upstream from the turbine which allows for use of a conventional turbine.
  • stream 19" it is also an option as illustrated by stream 19" to use at least part of the nitrogen rich stream for diluting the fuel and/or cooling of the combustion chamber 4 by adding the stream directly into the chamber 4. Further at least part of the nitrogen rich stream 19 may as illustrated by stream 19'" be expanded in the turbine 6, and thereby act as blade cooling. Any remaining nitrogen rich stream may leave the plant as vent stream 19*.
  • FIG. 3 illustrates a third embodiment of the present invention.
  • the figure shows the power plant according to figure 2, using the same reference numbers for the same units.
  • the air separation unit is a CAR unit, consisting of O 2 absorbent unit 81 and preferably regenerative heaters/coolers 80 and 82.
  • An air stream 70 is compressed in compressor 68 and enters optionally an air heater 69 as stream 71.
  • the heated air stream 72 is entered into the CAR unit where it is heated further in heater 80.
  • Oxygen is absorbed from the air stream as it passes through 81. Heat is recovered in cooler 82 before the oxygen depleted air and nitrogen rich stream 19 leaves the air separation unit.
  • the stream is optionally cooled further in heat exchanger 83 and optionally compressed in compressor 67 before it is optionally used as stream 19', 19" and/or 19'".
  • Oxygen is released from the absorbent unit 81 by using a sweep stream 92.
  • the stream is heated in heater 82.
  • the oxygen rich steam is preferably cooled in cooler 80 before it leaves the air separation unit as stream 43.
  • the stream 43 is compressed and cooled further before it is fed to the combustion unit 11.
  • the sweep stream is obtained from the exhaust stream 53 which preferable is cooled in cooler 64, compressed in compressor 65 and heated in heat exchanger 65 before it is used. The rest of the exhaust stream 53 treated as discussed above.
  • optimised operation conditions for a power plant according to the present invention will in every case depend on the equipment that is used.
  • the following examples show the conditions and results for one system. It will be obvious for a technician skilled in the art that these can vary considerably within the scope of the present invention. The examples are not to be considered limiting for the present invention.
  • the operation conditions of the power plant illustrated on figure 2 are as follows:
  • Air at 15 °C is added to the compressor 5 until the compressed air reaches 17 bara. Thereafter the air 45 is combusted with a fuel 91, which enters at 954 0 C and contains 43 mol% hydrogen, 50 mol% nitrogen, and 0.1 mol% CH 4 .
  • the nitrogen rich hot air 19' added to the catalytic combustor 8 is at 900 0 C, 18.8 bara, and contains 5 mol% O 2 . Vent stream 19* is not present in this case.
  • the exhaust 28 into the HRSG 7 is 581 °C, and leaves at 98 0 C as stream 29.
  • Air separation unit 9 is in this case an Oxygen Transfer Membrane unit, which is swept with a stream containing 41 mol% H 2 O and 56 mol% CO 2 (not shown in figure 2). It enters at 975 °C and 2.0 bara, and is taken from stream 53 (which is first cooled, recompressed and reheated, not shown in figure 2). The minimum ratio of the O 2 pressures in the air and sweep gas is 5.
  • the PSA 3 operates at 50 0 C, producing a rest stream 50 at 1.0 bara with 16 mol% CH 4 , 56% mol% CO 2 , 22 mol% H 2 and 4 mol% CO.
  • the temperature of the synthesis gas 24 out of the shift reactors 2 is 250 °C.
  • the synthesis gas 22 out of the steam reformer is 900 0 C and contains 50 mol% H 2 , 17 mol% CO, 26 mol% H 2 O and 5.5 mol% CH 4 .
  • the entrance conditions of the stream 21 into the steam reformer 1 are 550 °C, 32.5 bara and a steam- to-carbon ratio of 1.8.
  • the temperature of the combustion 11 increases from 650, stream 52, to 1000 °C, stream 53. Compressor 62 is not present in this case.
  • the oxygen rich stream 43 is at 900 0 C, 1.0 bara, containing 80 mol% O 2 , 11 mol% CO 2 and 8 mol% H 2 O.
  • the CO 2 stream 55 is compressed to 110 bara.
  • the operation conditions of the power plant illustrated on figure 3 are as follows: Air at 15 0 C is added to the compressor 5 until the compressed air reaches 17 bara. Thereafter the air is combusted with a fuel, which enters at 280 °C, stream 91 and contains 61 mol% hydrogen, 35 mol% nitrogen, and 0.9 mol% CH 4 .
  • the nitrogen rich hot air 19' added to the catalytic combustor 8 is at 570 °C, 19 bara, and contains 2.5 mol% O 2 . Vent stream 19* is present in this case, while combustion cooling 19" and turbine cooling 19" ' are not.
  • the exhaust 28 into the HRSG 7 is 570 °C, and leaves at 99 °C as stream 29.
  • Air separation unit 80/81/82 is in this case a CAR unit, which is swept with stream 92 containing 2.7 mol% H 2 O, 94 mol% CO 2 , and 2.5 mol% N 2 .
  • the stream enters at 90 °C and 2.2 bara, and is taken from stream 53 after cooling in heat exchanger 64.
  • Energy input stream 57 consists of natural gas and LP steam.
  • the PSA 3 operates at 50 0 C, producing a rest stream 50 at 1.3 bara with 29 mol% CH 4 , 53% mol% CO 2 , 15 mol% H 2 and 1 mol% CO.
  • the temperature of the synthesis gas 24 out of the shift reactors 2 is 250 0 C.
  • the synthesis gas 22 out of the steam reformer is 845 0 C and contains 44 mol% H 2 .
  • the entrance conditions of steam reformer 1 are 550 0 C, 32.5 bara and has a steam-to-carbon ratio of 1.9.
  • the temperature of the combustion outlet 53 is 920 °C. Compressor 62 and heat exchanger 63 are not present in this case.
  • the oxygen rich stream 43 is at 210 0 C, 1.2 bara, containing 25 mol% O 2 , 66 mol% CO 2 and 6 mol% H 2 O.
  • the CO 2 stream 55 is compressed to 110 bara.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne un procédé de production d'énergie électrique et de CO2 à partir d'une charge d'hydrocarbures qui consiste à reformer à la vapeur la charge produisant un gaz de synthèse. Ce gaz de synthèse est séparé en un flux riche en hydrogène, un flux pauvre en carbone et un flux restant, les flux riche en hydrogène et pauvre en carbone étant brûlés à l'air comprimé afin de fournir un produit de combustion qui se détend dans une turbine générant de l'énergie électrique, et le flux restant étant recyclé sous forme de combustible afin de produire de la chaleur destinée au reformage à la vapeur. L'invention concerne une centrale électrique permettant de mettre ledit procédé en oeuvre.
PCT/NO2006/000142 2005-04-19 2006-04-19 Procede de production d'energie electrique et de co2 a partir d'une charge d'hydrocarbures WO2006112724A2 (fr)

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NO20075953A NO20075953L (no) 2005-04-19 2007-11-19 Fremgangsmate for produksjon av elektrisk energi og CO2 fra et hydrokarbonramateriale

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NO20051891 2005-04-19
NO20051891A NO20051891D0 (no) 2005-04-19 2005-04-19 Prosess for produksjon av elektrisk energi og CO2 fra et hydrokarbon rastoff

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2299090A3 (fr) * 2009-09-18 2012-01-18 Air Products and Chemicals, Inc. Système de combustion pour turbine intégrant une membrane de transport d'ions
US8163070B2 (en) 2008-08-01 2012-04-24 Wolfgang Georg Hees Method and system for extracting carbon dioxide by anti-sublimation at raised pressure
EP2446122A4 (fr) * 2009-06-22 2015-07-15 Echogen Power Systems Inc Système et procédé pour gérer des problèmes thermiques dans un ou plusieurs procédés industriels
GB2544802A (en) * 2015-11-27 2017-05-31 Statoil Petroleum As A combustion method
EP2663524B1 (fr) * 2011-01-10 2018-12-12 Stamicarbon B.V. acting under the name of MT Innovation Center Procédé de production d'hydrogène

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WO1999041188A1 (fr) * 1998-02-13 1999-08-19 Norsk Hydro Asa Procede de production d'energie electrique et de vapeur
WO2002002460A2 (fr) * 2000-06-29 2002-01-10 Exxonmobil Research And Engineering Company Generation d'electricite avec un reacteur a membrane a echange thermique
WO2002072470A1 (fr) * 2001-02-16 2002-09-19 Norsk Hydro Asa Procede de fabrication d'un melange gazeux contenant de l'hydrogene et de l'azote

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8163070B2 (en) 2008-08-01 2012-04-24 Wolfgang Georg Hees Method and system for extracting carbon dioxide by anti-sublimation at raised pressure
EP2446122A4 (fr) * 2009-06-22 2015-07-15 Echogen Power Systems Inc Système et procédé pour gérer des problèmes thermiques dans un ou plusieurs procédés industriels
EP2299090A3 (fr) * 2009-09-18 2012-01-18 Air Products and Chemicals, Inc. Système de combustion pour turbine intégrant une membrane de transport d'ions
EP2663524B1 (fr) * 2011-01-10 2018-12-12 Stamicarbon B.V. acting under the name of MT Innovation Center Procédé de production d'hydrogène
GB2544802A (en) * 2015-11-27 2017-05-31 Statoil Petroleum As A combustion method
GB2544802B (en) * 2015-11-27 2022-08-17 Equinor Energy As Combusting fuel with oxidant

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NO20051891D0 (no) 2005-04-19

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