EP1951616A2 - Verfahren zur herstellung von synthetischem gas unter verwendung eines von mindestens einer gasturbine erzeugten sauerstoffhaltigen gases - Google Patents

Verfahren zur herstellung von synthetischem gas unter verwendung eines von mindestens einer gasturbine erzeugten sauerstoffhaltigen gases

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Publication number
EP1951616A2
EP1951616A2 EP06808332A EP06808332A EP1951616A2 EP 1951616 A2 EP1951616 A2 EP 1951616A2 EP 06808332 A EP06808332 A EP 06808332A EP 06808332 A EP06808332 A EP 06808332A EP 1951616 A2 EP1951616 A2 EP 1951616A2
Authority
EP
European Patent Office
Prior art keywords
gas
duct
opening
combustion
turbine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06808332A
Other languages
English (en)
French (fr)
Inventor
Daphné KOH
Pascal Avart
Bhadra Grover
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP1951616A2 publication Critical patent/EP1951616A2/de
Withdrawn legal-status Critical Current

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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • 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
    • C—CHEMISTRY; METALLURGY
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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
    • 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
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    • C01—INORGANIC CHEMISTRY
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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
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • 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
    • F02C6/00—Plural gas-turbine plants; Combinations of gas-turbine plants with other apparatus; Adaptations of gas-turbine plants for special use
    • F02C6/04—Gas-turbine plants providing heated or pressurised working fluid for other apparatus, e.g. without mechanical power output
    • F02C6/10—Gas-turbine plants providing heated or pressurised working fluid for other apparatus, e.g. without mechanical power output supplying working fluid to a user, e.g. a chemical process, which returns working fluid to a turbine of the plant
    • 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
    • F02C6/00—Plural gas-turbine plants; Combinations of gas-turbine plants with other apparatus; Adaptations of gas-turbine plants for special use
    • F02C6/18—Plural gas-turbine plants; Combinations of gas-turbine plants with other apparatus; Adaptations of gas-turbine plants for special use using the waste heat of gas-turbine plants outside the plants themselves, e.g. gas-turbine power heat plants
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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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
    • C01B2203/0205—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
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide 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
    • C01B2203/0205—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
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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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
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation 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
    • C01B2203/04—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
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • 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
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/146—At least two purification steps in series
    • C01B2203/147—Three or more purification steps in series
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
    • 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
    • C01B2203/16—Controlling the process
    • C01B2203/1695—Adjusting the feed of the combustion
    • 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
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/84—Energy production
    • 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
    • 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
    • Y02E20/14—Combined heat and power generation [CHP]
    • 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 the production of synthesis gas and electricity in which the oxidant required for combustion to enable the synthesis gas formation reaction consists of an oxygen gas produced by at least one gas turbine.
  • a synthesis gas is a gaseous mixture which contains at least CO, H 2 , CH 4 , CO 2 , N 2 , Ar and H 2 O obtained by steam reforming (SMR).
  • the present invention relates to syngas production sites in which at least one gas turbine is also present.
  • gas turbine a device comprising at least one air compressor, a combustion chamber and an expansion turbine.
  • the site may include several gas turbines.
  • the produced compressed air is introduced with at least one fuel into the combustion chamber of the turbine and the product combustion gases pass through the expansion turbine to produce electricity by means of a compressor. alternator.
  • these gases then pass through a heat recovery boiler to produce steam.
  • the fuel of the gas turbine is usually natural gas, but may include hydrogen or synthesis gas from the synthesis gas production unit or a hydrocarbon liquid fuel.
  • the object of the present invention is to provide a synthesis gas production process having improved energy efficiency by combining the production process of the synthesis gas and a cogeneration unit.
  • the invention relates to a method for supplying the combustion device of the combustion device of a synthesis gas production unit with the exhaust gas. produced by a gas turbine, wherein the flow rate of the exhaust gas introduced into the combustion device is controlled according to the value of the oxygen concentration and / or the pressure value within the furnace of the synthesis gas production unit.
  • FIG. 1 to 3 are schematic views of at least three variants of the synthesis gas production method according to the invention also producing electricity and preheated air,
  • FIGS. 4 to 8 are diagrams of the device for delivering a turbine exhaust gas and a secondary oxygen gas in a synthesis gas reactor and in the heat recovery unit connected with the unit of synthesis gas production.
  • the invention therefore relates to a process for producing synthesis gas at an industrial site comprising at least one gas turbine in which the oxygen gas produced by the gas turbine is recovered in the combustion reaction implemented for the production of gas.
  • synthesis according to the invention, the oxidant necessary for combustion to allow the formation reaction of the synthesis gas consists of an oxygen gas produced by at least one gas turbine.
  • the equipment for obtaining the raw synthesis gas may be a steam reforming reactor (SMR), followed by a secondary reforming reactor, or a partial oxidation reactor (POX) using hydrocarbons to produce the feed gas.
  • SMR steam reforming reactor
  • POX partial oxidation reactor
  • the raw synthesis gas comprises hydrogen, carbon monoxide, carbon dioxide and other compounds. It can also be a reactor for implementing an ATR process or a convective reforming process.
  • synthesis gas production reactions are carried out at high temperature, which requires combustion within a reactor for the implementation and maintenance of the synthesis reaction.
  • This combustion requires the presence of an oxidizer, which is according to the invention, at least partly derived from the gas turbine.
  • This combustion is implemented by means of burners fed by the exhaust gas of the turbine and by an oxidizer.
  • the latter is usually natural gas, but it can also be a liquid or solid containing hydrocarbons.
  • this oxidant is an oxygenated gas that is all or part of the exhaust gas of the gas turbine.
  • the gas turbine produces an exhaust gas generally comprising 13% to 16% by volume of oxygen on wet gas.
  • the exhaust gases are recovered and introduced into the burners of the SMR, ATR, POX or convective reformer for the implementation of the combustion required for the reaction. of synthesis gas production. These exhaust gases generally have a temperature of between 450 ° C. and 650 ° C.
  • a direct consequence of the implementation of the process according to the invention is that the heat produced during the combustion to allow the reaction of formation of the synthesis gas can then be used to produce steam or preheated air.
  • the synthesis gas production process produces an excess of heat compared to a process using only air for the combustion implemented in the production of syngas.
  • This excess heat can be valorized by heating any type of fluid, and in particular, water or water vapor or air by contacting within a heat exchanger of these fluids with the synthesis gas produced and / or the fumes produced by the combustion in the synthesis gas reactor and / or the fumes produced by combustion in the gas turbine.
  • a portion of the oxygen gas produced by the gas turbine may be used in a heat recovery unit.
  • the gas turbine produces an amount of oxygen gas greater than that required for combustion to allow the formation reaction of the synthesis gas.
  • the excess of oxygenated gas can then be used as an oxidant in the combustion implemented by a heat recovery unit.
  • the heat recovery unit may be the combustion gas heat recovery zone of the synthesis gas production device. This zone is present at all synthesis gas production sites and makes it possible to recover the heat of the exhaust gases produced by the combustion which allows the formation reaction of the synthesis gas.
  • the combustion implemented within this zone is that of the hydrocarbons used in the production of the synthesis gas and the oxygen gas produced by the gas turbine.
  • the heat recovery unit may also be a steam generating unit (so-called "Heat Recovery Steam Generator” or HRSG).
  • HRSG Heat Recovery Steam Generator
  • the steam produced can be used to create electricity by means of a steam turbine, or it can be used for an industrial process using steam (it is then an exported product of the site).
  • the heat recovery unit can also be an air preheater (so called "Air Preheater”).
  • the compressed air by the compressor of the gas turbine may be heated in an exchanger incorporated in the convective zone of the equipment for producing the synthesis gas.
  • the flow rate of the turbine exhaust gas introduced into the burners of the synthesis gas production unit is controlled.
  • This control can be done by at least one control means placed on the device for distributing the exhaust gas from the turbine to the combustion device: it can be a valve or a shutter with variable closure placed on the distribution duct of the this gas, or it may be an exhaust fan placed at the outlet of the exhaust gas of the synthesis gas production unit.
  • This exhaust fan creates a vacuum within the combustion furnace of the synthesis gas production unit indirectly inducing a suction of the turbine exhaust gas in the burners of the synthesis gas production unit.
  • the flow rate of the exhaust gas introduced into the combustion device is controlled so that the oxygen concentration downstream of the combustion chamber of the synthesis gas production unit is between 2 and 3. % by volume of dry gas and / or that the pressure within the furnace of the synthesis gas production unit is between 5 mm and -15 mm of water.
  • a pressure and / or oxygen concentration sensor is generally placed downstream of the combustion chamber of the synthesis gas production unit so as to measure this concentration and this pressure. This sensor is connected to the means (s) for controlling the flow of the exhaust gas to be introduced into the retro-feedback combustion device so as to control the introduction of the exhaust gas from the turbine to this concentration and / or this pressure.
  • the invention advantageously uses this property to ensure the introduction of the gas turbine exhaust gases into the burners.
  • the combustion chamber of the synthesis gas production unit these are easily aspirated; no compression means are needed to introduce them into the burners.
  • the oxygenated gas used in the combustion chamber may be atmospheric air.
  • This air is usually introduced by means of a fan blowing ("forced draft fan" in English). Prior to its introduction into the reactor, this air is preferably heated to the temperature of the oxygen gas leaving the gas turbine, which is of the order of 450 0 C to 650 ° C, for example by means of burners.
  • the secondary oxygenated gas may also be oxygen under pressure from an air separation unit ("Air Separation Unit" (ASU) in English), which amounts to implementing an oxy combustion. This oxygen can also be introduced into the secondary reformer of the synthesis gas production device.
  • ASU Air Separation Unit
  • the method also provides that:
  • atmospheric air is introduced into the heat recovery zone of the combustion gas and / or into a steam production unit.
  • the atmospheric air is heated before being introduced into the combustion chamber of the synthesis gas production unit, into the heat recovery zone of the combustion gas and / or into a production unit of the combustion gas. steam.
  • Atmospheric air is usually heated by means of a burner.
  • the atmospheric air introduced into the heat recovery zone of the combustion gas and / or into a steam generating unit can be heated by means of a burner fed by at least a portion of the exhaust gas produced by the device. of synthesis gas production. The recirculation of this exhaust gas increases the production of steam while reducing the partial pressure of NO x .
  • the invention then relates to an oxidizer supply device of the combustion device of a synthesis gas production unit by the exhaust gas produced by a gas turbine for carrying out the controlled feed method described. previously.
  • This device consists of at least two ducts:
  • the first conduit comprising: an opening cooperating with the gas turbine and allowing the introduction of the exhaust gas into said first duct,
  • the second conduit comprising: . an opening cooperating with the first duct and allowing the introduction of the exhaust gas into said second duct,
  • an opening for introducing the secondary oxygen gas into said second conduit an opening control means for introducing the secondary oxygenated gas into the second conduit, allowing either opening or closing of the opening
  • an opening allowing the evacuation of the oxygenated gas present in the second duct towards the combustion chamber of the synthesis gas production device, means for regulating the flow of exhaust gas.
  • One of the means of controlling the opening for introducing the secondary oxygenated gas is a hatch.
  • the hatch makes it possible to open or close the said opening: it is open to introduce the secondary oxygenated gas into the duct and it is closed to prevent the introduction of the secondary oxygenated gas into the duct.
  • Another means of controlling the opening for the introduction of secondary oxygen gas is an air blower ("air blowers").
  • the means of regulating the flow of exhaust gas in the second conduit is generally composed of flaps ("inlet guide born” or “louvers” in English).
  • the regulation can go as far as the total stopping of the exhaust flow of the turbine.
  • the means for regulating the exhaust gas flow rate of the gas turbine (3) in the second duct is slaved to a pressure sensor and / or oxygen concentration located downstream of the combustion chamber of the synthesis gas production unit.
  • the invention also relates to a variant of the preceding device for the distribution of the exhaust gas of the turbine and a secondary oxygen gas in the combustion device of the synthesis gas production unit and furthermore in the zone of heat recovery from the flue gas and / or to a steam generating unit.
  • the device comprises three ducts and: the first duct comprises another opening cooperating with the third duct and allowing the evacuation of the gas present in the first duct towards the third duct; the third duct comprises:
  • an opening allowing the introduction of the secondary oxygenated gas into said second conduit
  • an opening control means for introducing the secondary oxygenated gas into the third duct, allowing either opening or closing of the opening
  • an opening allowing the evacuation of the oxygenated gas present in the third duct to the heat recovery zone of the combustion gas and / or to the steam production unit.
  • This device is adapted to the implementation of the method for controlling the introduction, into the combustion chambers of a device for producing synthesis gas, of the oxygen gas required for combustion to enable the formation reaction of the gas of previously defined synthesis. It makes it possible to choose the nature of the oxygenated gas to be introduced into the combustion chamber of the synthesis gas unit and into the boiler of the steam production unit.
  • the opening control means for introducing the oxygenated gas into the third conduit is of the same type as that described for the second conduit.
  • the third conduit may also include means for regulating the flow of the exhaust gas; this means of regulation is generally composed of shutters ("inlet guide varies" or "louvers" in English).
  • the first conduit of the variant of the device may comprise a means for sharing the exhaust gas of the gas turbine between the second conduit and the third conduit, and, preferably, this sharing means is slaved to a concentration sensor.
  • oxygen located downstream of the combustion chamber of the synthesis gas production unit.
  • the first conduit comprises an opening allowing the evacuation of the oxygenated gas present in this conduit to the atmosphere.
  • the evacuation of the gas present in the first conduit to the atmosphere is provided when the gas turbine is in partial load or failed and does not produce exhaust gas.
  • the partial or total evacuation of the gas may also be provided when the gas turbine is operating but when the synthesis gas production device is partially loaded or stopped.
  • the preceding device usually comprises burners ("duct burners" in English) placed in the second and third ducts. These burners can heat the oxygenated gases, which is particularly useful when the oxygen gas is atmospheric air or oxygen, or when it is desired to increase the steam production by heating the main oxygen gas present in the third conduit. So, the burners are generally placed in the second and third ducts downstream of the opening allowing the introduction of the secondary oxygenated gas into the ducts relative to the direction of flow of the secondary oxygen gas in the ducts.
  • the first conduit comprises an opening allowing the evacuation of the oxygenated gas present in the conduit to the atmosphere.
  • This opening which allows the evacuation of the oxygen gas present in the duct to the atmosphere, generally cooperates with a duct comprising a means for regulating the flow of exhaust gas.
  • FIG. 1 to 8 illustrate the device and the method according to the invention.
  • the numbers have the following meaning:
  • FIG. 1 is a schematic view of the synthesis gas production process according to the invention, further allowing the production of electricity, steam and preheated air.
  • the synthesis gas 1 is produced from hydrocarbons 18 in the unit 7 either by steam reforming, or by partial oxidation or gasification, or by autothermal or secondary reforming, or by convective reforming, or by reforming by heat exchange with a hydrocarbon fuel.
  • Combustion uses as oxidant an oxygenated gas 21 which is partly the exhaust gas produced by the gas turbine 3.
  • This gas turbine is fed with hydrocarbons 18 identical to those used for the gas formation reaction. of synthetic or different hydrocarbons 71, it produces electricity 38 and / or compressed air 35.
  • the heat generated by the combustion to allow the formation reaction of the synthesis gas in the combustion chamber of the unit 7 is recovered in the heat recovery zone of the combustion gas 5 which produces steam 6 and heats the compressed air 35 producing preheated air 27, the latter coming from the compressed air 35 produced by the compressor of the gas turbine 3.
  • the steam 6 comes to add to that 61 already produced by the unit 17 of recovery of the synthesis gas production device, said unit 17 being intended to recover the residual heat in the cooled synthesis gas 19.
  • Part 22 of the exhaust gas of the gas turbine 2 from the gas turbine 3 feeds the heat recovery unit 5, especially during the triggering of the synthesis gas production unit 7.
  • atmospheric air 8 is used as the oxidant in the combustion chambers of the unit 7 and / or in the heat recovery zone of the combustion gas 5.
  • This air 8 is generally preheated by means of the burners 120 and 20, fed by the fuel 18 and / or 71.
  • the exhaust gas 2 of the turbine 3 is discharged by means of the stack 40.
  • a portion 121 of the steam 12 produced by the vapor recovery unit 17 and the heat recovery zone of the combustion gas 5 can be directly exported, while another part 41 is exported after having been expanded in the steam turbine 50 to produce more electricity 39 and steam condensates 51.
  • Another portion 14 of the produced vapor 12 forms a mixture 48 with the hydrocarbons 18 prior to introduction into the unit 7.
  • an exhaust gas 37 is produced which is exhausted by the fan 29 to the exhaust stack 401.
  • the cooled synthesis gas 19 is purified in the exhaust gas elimination unit 40.
  • a portion 283 or all 280 of the CO 2 removed can be recycled to the synthesis gas production device by mixing with the hydrocarbons and the vapor 14.
  • the other portion 284 or all 280 of the CO 2 removed can be compressed and liquefied for export.
  • a portion 34 of the low CO 2 synthesis gas is used as fuel in the gas turbine 3.
  • the remainder of the low CO 2 synthesis gas 192 is purified in the purification unit 26 which adjusts the ratio.
  • the purified synthesis gas 28 can also be introduced into separation units 261 of H 2 and CO so as to produce on the one hand purified hydrogen 281 for export or compression and on the other hand purified CO 282 for export or compression.
  • the purge gas mixture from the separation units 261 is used as fuel in the combustion chamber of the synthesis gas production device.
  • an analyzer 100 measures the concentration of oxygen pressure in the downstream zone of the combustion chamber and a pressure sensor 104 measures the oxygen concentration at the outlet of the furnace 7.
  • the control means the exhaust gas flow rate of the gas turbine 103 is controlled by a feedback control 101, at the values given by the analyzer 100 and the sensor 100 and increases or decreases the flow rate of the exhaust gas 2 of the gas turbine 3 so as to maintain the pressure and the oxygen concentration of the synthesis gas production unit within normal operating limits.
  • the exhaust fan 29 of the combustion products 37 of the synthesis gas production unit is controlled by a feedback control 102, at the values given by the sensor 104 and the analyzer 100 and increases or decreases its speed. so as to influence the flow rate of the exhaust gas 2 of the gas turbine 3.
  • FIG. 2 is a schematic view of a synthesis gas production process such as that of FIG. 1, except that this method comprises a steam generating unit 13 fed with hydrocarbon fuels 42 and a part 22 of the gas of FIG. Oxygen exhaust 2 from the gas turbine 3.
  • the steam generating unit 13 is generally a boiler burning heavy or solid fuels 42 that can not be used in the gas turbine 3 or in the gas production device.
  • the steam generating unit 13 produces steam, a part 47 of which is mixed with the steam 12 produced by the steam recovery unit 17 of the synthesis gas production device, and the other part 43 is mixed with the steam 41 expanded by the turbine 50.
  • the exhaust gases 44 of the steam generating unit 13 are mixed with the combustion products 37 of the unit 7.
  • the production of synthesis gas can continue even if the gas turbine is stopped, through the use of atmospheric air. It is also possible to decouple the gas turbine from the synthesis gas production unit by means of the exhaust stack 40. For example, even if the synthesis gas production unit stops operating, the Gas turbine can still be used to produce electricity and steam.
  • FIG. 3 is a schematic view of a synthesis gas production process such as that of FIG. 1, except that this process comprises a single oxygenated gas conduit. This scheme is used when the heat required for the combustion required for the synthesis gas formation reaction is sufficiently supplied by all the oxygen gas of the gas turbine.
  • FIG. 4 is a schematic view corresponding to the method of FIG. 1 detailing the device for distributing the main oxygenated gas and the secondary oxygenated gas in the combustion chamber of the synthesis gas production device 7.
  • the three ducts 9, 91 and 92 allow to distribute the oxygenated exhaust gas 2 of the turbine
  • the opening 10 makes it possible to introduce the oxygenated gas 2 of the gas turbine 3 into the duct 9, the opening 161 and the opening 211 respectively making it possible to introduce a portion 21 of the oxygenated gas 2 into the duct 91; and a portion 22 of the oxygenated exhaust gas 2 in the conduit 92,
  • flaps 16 and 4 make it possible to regulate the flow rate of gas 21 and gas 22,
  • the opening 11 and the opening 112 make it possible, respectively, to introduce the atmospheric air 8 into the duct 91 and into the duct 92,
  • traps 111 and 113 make it possible to choose the introduction of either oxygenated gas 21 or 22 or atmospheric air 8 into their respective ducts 91 or 92,
  • the burners 120 and 20 make it possible to heat the gas flowing in the ducts 91 and 92,
  • the opening 162 makes it possible to evacuate the gas present in the duct 91 towards the combustion chamber of the synthesis gas production device 7,
  • the opening 212 makes it possible to evacuate the gas present in the conduit 92 towards the heat recovery zone of the combustion gas 5,
  • the opening 151 makes it possible to evacuate the oxygenated gas present in the duct 9 towards the atmosphere by means of the chimney 40, flaps 15 making it possible to regulate this flow.
  • the hatches 111 and 113 are put in place so as to close the openings 11 and 112: thus, the combustion chamber of the unit 7 and the recovery zone are fed. of heat of the combustion gas 5 in exhaust gas from the turbine 3.
  • flaps 4 and 16 it is possible to distribute at will more or less exhaust gas from the turbine 3 to the duct 91 and the combustion chamber of the unit 7, or to the conduit 92 and the heat recovery zone of the combustion gas 5.
  • the flap 16 is slaved to the sensor 100 for measuring the pressure and / or the oxygen concentration of the production unit. synthesis gas by reactive control: it can be more or less open depending on this control so as to regulate the flow of the exhaust gas 2 of the turbine 3 flowing in the duct 91.
  • the hatches 111 and 113 are placed in such a way as to open the openings 11 and 112 and thus feed the combustion chamber 7 and the heat recovery zone of the combustion gas 5 with air atmospheric (secondary oxygenated gas).
  • the burners 20 and 120 can preheat the atmospheric air.
  • the flaps 4 and 16 are closed, the flaps 15 are adjusted so as to evacuate the gas from the turbine to the atmosphere through the chimney 40.
  • the hatches 111 and 113 are put in place so as to open the openings 11 and 112 and thus supply the combustion chamber 7 and the heat recovery zone of the combustion gas 5 with atmospheric air (secondary oxygenated gas).
  • FIG. 5 is a schematic view corresponding to the method of FIG. 2 detailing the device for distributing the exhaust gas 2 of the turbine 3 and the secondary oxygenated gas in the combustion chamber of the synthesis gas production device 7.
  • This diagram differs from that of Figure 4 in that it comprises a steam generating unit 13 fueled 42 and oxidant by a portion 22 of the exhaust gas 2 from the gas turbine 3.
  • the conduit 92 can supply oxygen gas to this steam generating unit 13 rather than providing oxygen gas to the heat recovery zone of the combustion gas 5.
  • FIG. 6 is a schematic view corresponding to the method of FIG. 3 detailing the device for distributing the exhaust gas 2 of the turbine 3 and the secondary oxygenated gas in the combustion chamber of the synthesis gas production device 7.
  • This diagram differs from that of Figures 4 and 5 in that it does not include conduit 92 for discharging the oxygenated gas to the heat recovery zone of the combustion gas 5 or to a steam generating unit 13.
  • FIG. 7 is a variant of the embodiment of FIG. 6 in which the opening 11, which makes it possible to introduce secondary oxygenated gas into the duct 91, is connected to a conduit 94 for the introduction of pure oxygen 174 from a ASU 172 in the conduit 91.
  • L 1 ASU 172 also supplies pure 173 to secondary reformer 171 and oxygen 175 to the oxygen export.
  • FIG. 8 is a variant of the embodiment of FIG. 4 in which part of the combustion products 30 of the synthesis gas production unit feeds the burner 20 of the duct 92 by means of a duct 300. shutters 183 can modulate the flow rate of these products of combustion 300.
  • the recirculation of the products of combustion makes it possible to reduce the temperature of the flame and to limit the production of NO x nitrogen oxides.
  • the recirculation rate of the products of combustion can vary between 15 and 20%. A reduction of approximately 40 to 55% in NO x emissions was observed.
  • the temporary or continuous use of the oxygen gas of the gas turbine in the synthesis gas production device allows the use of a single recovery section of the gas turbine. heat in said synthesis gas production device, as in Figures 1, 3, 4, 6, 7 and 8, while it is usually necessary to use two.
  • the amount of fuel used by the synthesis gas production device is reduced compared to the case where the synthesis gas production unit and the cogeneration unit are independent.
  • the amount of steam produced can be increased during use of the device according to the invention comprising three ducts by starting the post-combustion in the burners present in the third duct.
  • the invention makes it possible to regulate the flow rate, the temperature and the steam production pressure for export through the steam turbine.
  • the fuel and the hydrocarbon raw material and fuel used for the co-generation of electricity, steam and synthesis gas are converted with an efficiency of 80% to 90%; this conversion rate can not be achieved by an independent power generation unit.
  • the hot oxygen gas from the gas turbine helps reduce the fuel consumption required by the combustion chamber of the syngas production unit.
  • the flue gases are therefore more available to produce the extra steam that can pass through a steam turbine to produce more electricity.
  • This invention also produces preheated air which can be used in the regeneration of catalysts in certain industrial processes. In short, a strong increase in thermal and electrical efficiency is achieved by a growth in steam and electricity production divided by a decrease in gas consumption as fuel.
  • the fact that the oxygen gas from the gas turbine is hot reduces the fuel consumption in the combustion chamber of the synthesis gas production device.
  • the heat recovery zone of the flue gas can also replace a steam generating unit of a cogeneration unit. Once the heat of the oxygen gas and the flue gas is recovered, the cooled exhaust gas is sucked in by a fan and exhausted through a chimney.
  • the steam obtained in the steam recovery unit of the synthesis gas production device 17, the heat recovery zone of the combustion gas 5 and the steam production unit 13 can be introduced either into a steam turbine backpressure that produces steam and electricity, either in a steam condensing turbine producing hot water and electricity.
  • the generator of the gas turbine produces electricity that can be used by auxiliary equipment, for example fans, compressors and pumps that are in the integrated plant.
  • auxiliary equipment for example fans, compressors and pumps that are in the integrated plant.
  • the following advantages are obtained: improved efficiency of the heat recovery unit (due to the absence of nitrogen), reduction of NO x emissions, reduction of the amount of gas used as fuel
  • the invention brings flexibility to the industrial site and a range of products greater by the production of synthesis gas, CO, hydrogen, oxogas (mixture of H 2 and CO ratio), steam, hot air and electricity.
  • the synthesis gas production device may be equipped with exhaust gas treatment systems such as a selective catalytic NOx (Selective Catalytic Removal of NO x ) unit to control the content of the synthesis gas.
  • NO x Selective Catalytic Removal of NO x
  • flue gas or an exhaust gas cleaning device to remove carbon dioxide, particulates and sulfur oxides.

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EP06808332A 2005-09-19 2006-09-15 Verfahren zur herstellung von synthetischem gas unter verwendung eines von mindestens einer gasturbine erzeugten sauerstoffhaltigen gases Withdrawn EP1951616A2 (de)

Applications Claiming Priority (2)

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FR0552804A FR2890954B1 (fr) 2005-09-19 2005-09-19 Procede de production de gaz de synthese a l'aide d'un gaz oxygene produit par au moins une turbine a gaz
PCT/FR2006/050894 WO2007034107A2 (fr) 2005-09-19 2006-09-15 Procede de production de gaz de synthese a l'aide d'un gaz oxygene produit par au moins une turbine a gaz

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US (1) US20090165377A1 (de)
EP (1) EP1951616A2 (de)
JP (1) JP5215185B2 (de)
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WO (1) WO2007034107A2 (de)

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DE102009043499A1 (de) * 2009-09-30 2011-03-31 Uhde Gmbh Verfahren zum Betrieb eines IGCC-Kraftwerkprozesses mit integrierter CO2-Abtrennung
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JP5905119B2 (ja) * 2011-12-19 2016-04-20 アルストム テクノロジー リミテッドＡＬＳＴＯＭ Ｔｅｃｈｎｏｌｏｇｙ Ｌｔｄ 煙道ガス再循環を用いるガスタービン発電装置におけるガス成分制御
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FR2890954A1 (fr) 2007-03-23
WO2007034107A3 (fr) 2008-03-20
CN101309857B (zh) 2012-07-04
CN101309857A (zh) 2008-11-19
FR2890954B1 (fr) 2011-02-18
WO2007034107A2 (fr) 2007-03-29
JP2009508790A (ja) 2009-03-05
JP5215185B2 (ja) 2013-06-19
US20090165377A1 (en) 2009-07-02

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