WO2004042200A1 - Gas turbine power plant and method of operating the same - Google Patents

Gas turbine power plant and method of operating the same Download PDF

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Publication number
WO2004042200A1
WO2004042200A1 PCT/EP2003/050782 EP0350782W WO2004042200A1 WO 2004042200 A1 WO2004042200 A1 WO 2004042200A1 EP 0350782 W EP0350782 W EP 0350782W WO 2004042200 A1 WO2004042200 A1 WO 2004042200A1
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WIPO (PCT)
Prior art keywords
membrane
gas turbine
partial oxidation
power plant
oxidation reactor
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PCT/EP2003/050782
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French (fr)
Inventor
Timothy Griffin
Daniel Holmberg
Dieter Winkler
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Alstom Technology Ltd
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Publication date
Application filed by Alstom Technology Ltd filed Critical Alstom Technology Ltd
Priority to AU2003298266A priority Critical patent/AU2003298266A1/en
Priority to EP03795991A priority patent/EP1561010B1/en
Priority to CA2505354A priority patent/CA2505354C/en
Publication of WO2004042200A1 publication Critical patent/WO2004042200A1/en
Priority to US11/123,128 priority patent/US7363764B2/en
Priority to NO20052767A priority patent/NO337677B1/en

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Classifications

    • 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
    • F02C3/30—Adding water, steam or other fluids for influencing combustion, e.g. to obtain cleaner exhaust gases
    • C—CHEMISTRY; METALLURGY
    • 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
    • C01B13/0248—Physical processing only
    • C01B13/0251—Physical processing only by making use of membranes
    • 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
    • C01B3/386—Catalytic partial combustion
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K23/00—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids
    • F01K23/02—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled
    • F01K23/06—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle
    • F01K23/10—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle with exhaust fluid of one cycle heating the fluid in another cycle
    • 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
    • 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
    • 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
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • 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
    • C01B2203/0465—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
    • C01B2203/08—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
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0883—Methods of cooling by indirect heat exchange
    • 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
    • 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
    • C01B2203/86—Carbon dioxide sequestration
    • 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
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry

Definitions

  • the invention relates to a method of operating a gas turbine power plant according to claim 1 and a gas turbine power plant according to claim 9.
  • This present invention is related to make use of so-called partial oxidation (POX) of the natural gas to syngas consisting of CO and H 2 .
  • the oxygen required for this partial oxidation is provided by a ceramic, air separation membrane, thermally integrated into the process.
  • This syngas would then be water gas shifted to produce even more hydrogen and convert the CO to CO 2 , and finally use the produced hydrogen as fuel in a gas turbine.
  • MCM ixed Conducting Membrane
  • the driving force is a difference in oxygen partial pressure between the permeate and retentate sides of the membrane.
  • the transport process also requires high temperatures, i.e. > 700°C.
  • the surfaces of the permeate side of the membrane that containing the syngas is coated with catalytic material to promote the formation of synthesis gas 17 ⁇ and, in particular, hydrogen.
  • Catalyst materials used for autothermal reforming are Rh, Ru, Co, Fe or bimetallic combinations thereof
  • the air stream from the compressor can be lead to a catalytic burner where the air is heated by means of catalytic combustion.
  • the fuel for the catalyst is either hydrogen or natural gas.
  • hydrogen is preferred to avoid producing CO 2 .
  • the reason for using a catalytic burner is to increase the average temperature in the membrane/POX reactor thereby increasing the oxygen flux through the membrane. Also, the temperature gradient in the reactor will be lower and thus the thermal stresses for the reactor will decrease.
  • the syngas coming from the membrane/POX reactor consisting of hot steam, H 2 and CO can enter a low temperature heat exchanger, where the syngas mixture is cooled down by an incoming stream of the compressed air from the compressor.
  • a medium temperature heat exchanger to raise the temperature of the mixture of steam and natural gas before the mixture enters the membrane/POX reactor. This would flatten out the temperature profile in the membrane/POX reactor and thus lower the temperature gradients in this.
  • the hot flue gases of the gas turbine can be utilised in a heat recovery steam generator producing steam for the bottoming steam cycle and producing more power in a steam turbine and electricity in a generator.
  • Fig. 1 illustrates a gas turbine power plant according to the present inven- tion
  • Fig.2 illustrates the partial oxidation of the membrane/partial oxidation reactor.
  • Fig. 1 shows a syngas based low emission power according to the present invention.
  • Air 1 is fed through a compressor 2 before the compressed air 3 is fed at least through a membrane/partial oxidation (POX) reactor 4.
  • POX membrane/partial oxidation
  • the membrane/POX reactor 4 After the membrane/POX reactor 4 the air is burned in a combustion chamber 5 together with hydrogen 6.
  • the flue gases are then expanded in a turbine 7, which is driving the compressor 2 and producing electricity in a generator 8.
  • the hot flue gases 9 are utilised in a heat recovery steam generator 10 producing steam for the bottoming steam cycle 11 and producing more power in a steam turbine 12 and electricity in a generator 13.
  • the three reactions combine to produce a mixture of H2, CO and CO 2 ; the overall heat balance and product mixture is dictated by the amount of oxygen (and endothermic reactions) that is present.
  • the design of the membrane/POX reactor 4 is such that the overall process is autothermal, and the membrane temperature is of ca. 800 °C.
  • the membrane/POX reactor 4 would be combined to both work as an oxygen transferring membrane and as well as doing the partial oxidation.
  • One membrane type that can be used to separate the oxygen from the air is a so-called "Mixed Conducting Membrane" (MCM). These materials consist of complex crystalline structures, which incorporate oxygen ion vacancies (5-15%).
  • the transport principle for oxygen transport through the membrane 18 is adso ⁇ tion on the surface followed by decomposition into ions, which are transported through the membrane by sequentially occupying oxygen ion vacancies.
  • the ion transport is counterbalanced by a flow of electrons in the opposite direction.
  • the driving force is a difference in oxygen partial pressure between the permeate and retentate sides of the membrane 18.
  • the transport process also requires high temperatures, i.e. > 700°C.
  • the surfaces of the permeate side of the membrane 18 that containing the syngas 17 ⁇
  • catalytic material to promote the formation of synthesis gas 17 ⁇ and, in particular, hydrogen.
  • Catalyst materials used for autothermal re- forming are Rh, Ru, Co, Fe or bimetallic combinations thereof (e.g. Co/Fe).
  • the air stream from the low temperature heat exchanger 19 can then be lead to a catalytic burner 20 where the air is heated by means of catalytic combustion.
  • the fuel for the catalytic burner 20 is either hydrogen 21 or natu- ral gas 14. Use of hydrogen 21 is preferred to avoid producing CO 2 .
  • the reason for using a catalytic burner 20 is to increase the average temperature in the membrane/POX reactor 4, increasing the oxygen flux through the membrane 18. Also, the temperature gradient in the reactor 4 will be lower and thus the thermal stresses for the reactor 4 will decrease.
  • This catalytic burner 20 can also be used to help control process conditions within the MCM reactor during start up or to address instabilities within the membrane/POX reactor 4 associated with the autothermal reforming and potential catalyst deactivation.
  • the temperature of the MCM reactor will be very sensitive to the amount of O 2 present and we could have some strange transients during start up. A quick reacting catalytic burner 4 running on H2 could help for process control.
  • the syngas 17 ⁇ After the syngas 17 ⁇ has been cooled down in the low temperature heat exchanger 19, the syngas 17 ⁇ is then further cooled down in a CO shift reactor 22, lowering the temperature further to about 200-300°C. Depending on the chosen cooling temperature, water will condense out or not. Since a low temperature favours the CO shift reaction it might be wise to keep the temperature low. This will also lower the water consumption for the cycle since the condensed water 23 can be re-injected in the bottoming steam cycle 11.
  • the medium used for the cooling is boiler feed water 241, 24 2 from a bottoming steam and water cycle 11.
  • the CO shift reactor 22 is in other words used to convert CO and water to CO2 and more hydrogen. Also this reaction is mildly exothermic, leading to that some of the water condensed out during the cooling (or all water if the cooling temperature is high) is evaporated again, taking heat from the exo- thermic process described above.
  • the syngas 17 2 consists ideally of H 2 , CO 2 and H 2 O. This syngas 17 2 is then lead to some kind of CO 2 abso ⁇ tion equipment 25, based on either chemical or physical abso ⁇ tion.
  • the CO 2 removal rate in this kind of equipment is around 90 %.
  • Low pressure steam 26 needed for the CO 2 removal is extracted from the steam turbine 12, and the condensed water 27 is lead back to the feed water tank of the steam cycle 11.
  • the removed CO 2 28 is further compressed by means of inter-cooling in a compressor 29, producing liquid CO 2 30 that might be deposited or used in for instance enhanced oil recovery.
  • the syngas 17 3 mainly consisting of H 2 , H 2 O and some remaining CO 2 is lead to a combustion chamber 5, to be burned together with air from the first side of the membrane/POX reactor 4.
  • the water in the syngas 17 3 helps control the combustion temperature and thus lowers NO ⁇ formation.
  • a part of the resulting syngas 17 3 comprising hydrogen 6 from the CO 2 removal equipment 25 can as well be burned in the catalytic burner 20.

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

Abstract

It is disclosed a method of operating a gas turbine power plant and gas turbine power plant wherein hydrogen (6) for the combusting process is produced by feeding natural gas (14) mixed with steam (15) through a membrane/partial oxidation reactor (4) and converting the natural gas (14) at least to H2 and CO. Thereby oxygen is transferred from the compressed air (3) through the membrane (18) of the membrane/partial oxidation reactor (4) and the oxygen is used for the partial oxidation process of the natural gas (14). The process is followed by converting the syngas in a CO shift reactor (22) and a CO shift reactor (22) to a C02 removal equipment (25) to mainly hydrogen (6).

Description

Gas turbine power plant and method of operating the same
FIELD OF THE INVENTION
The invention relates to a method of operating a gas turbine power plant according to claim 1 and a gas turbine power plant according to claim 9.
BACKGROUND OF THE INVENTION
In the last years different projects were launched with the aim to develop emission free gas turbine based processes using semi-closed cycles with CO2/H2O mixtures as working fluid. Methods of operating such power plants are known from for example from EP-A1-0 939 199 and EP-A1-0 953 748. In these processes the fuel, usually natural gas, reacts with technically pure oxygen generated either in an external air-separation unit or internally in an integrated membrane reactor. One major disadvantage of using air-separation units for these kind of processes is that they consume a great amount of en- ergy, thus penalising the efficiency and power output of the plant. From the literature it can be found that the energy demand for air-separation units is as high as 0.3 kWh/kg O2 produced. The energy consumption for separating the oxygen from the air can be decreased very much if oxygen-separating mem- branes are used. Also this technique has a few disadvantages, namely: metal to ceramic sealing is needed that can withstand temperatures > 800°C, the turbine inlet temperature (TIT) and the ceramic sealing temperature are linked, which limits the maximum TIT and thus lowers the performance of the plant and one needs to separate large amounts of air, corresponding to the total O2 required for full oxidation of fossil fuel powering the gas turbine.
SUMMARY OF THE INVENTION
It is therefore the aim of the present invention to provide a method of operating a gas turbine power plant and a gas turbine power plant which avoids the disadvantages of the prior and increasing the overall efficiency of the power plant.
A method of operating a gas turbine power plant according to the features of claim 1 and a gas turbine power plant according claim 9 was found.
This present invention is related to make use of so-called partial oxidation (POX) of the natural gas to syngas consisting of CO and H2. The oxygen required for this partial oxidation is provided by a ceramic, air separation membrane, thermally integrated into the process. This syngas would then be water gas shifted to produce even more hydrogen and convert the CO to CO2, and finally use the produced hydrogen as fuel in a gas turbine.
By doing this, one would overcome the temperature limit previously set by the membrane. The membrane reactor unit would be combined to both work as an oxygen transferring membrane and as a reactor for the partial oxidation. One membrane type that can be used to separate the oxygen from the air is a so-called "Mixed Conducting Membrane" (MCM). These materials consist of complex crystalline structures, which incorporate oxygen ion vacancies (5- 15%). The transport principle for oxygen transport through the membrane is adsorption on the surface followed by decomposition into ions, which are transported through the membrane by sequentially occupying oxygen ion vacancies. The ion transport is counterbalanced by a flow of electrons in the opposite direction completing the circuit. The driving force is a difference in oxygen partial pressure between the permeate and retentate sides of the membrane. The transport process also requires high temperatures, i.e. > 700°C. In an embodiment of the present invention the surfaces of the permeate side of the membrane that containing the syngas is coated with catalytic material to promote the formation of synthesis gas 17ι and, in particular, hydrogen. Catalyst materials used for autothermal reforming are Rh, Ru, Co, Fe or bimetallic combinations thereof
Optionally, prior to entering the membrane reactor, the air stream from the compressor can be lead to a catalytic burner where the air is heated by means of catalytic combustion. The fuel for the catalyst is either hydrogen or natural gas. Thereby the use of hydrogen is preferred to avoid producing CO2. The reason for using a catalytic burner is to increase the average temperature in the membrane/POX reactor thereby increasing the oxygen flux through the membrane. Also, the temperature gradient in the reactor will be lower and thus the thermal stresses for the reactor will decrease.
With advantage the syngas coming from the membrane/POX reactor consisting of hot steam, H2 and CO can enter a low temperature heat exchanger, where the syngas mixture is cooled down by an incoming stream of the compressed air from the compressor. One other possibility would be to use a medium temperature heat exchanger to raise the temperature of the mixture of steam and natural gas before the mixture enters the membrane/POX reactor. This would flatten out the temperature profile in the membrane/POX reactor and thus lower the temperature gradients in this.
After the expansion the hot flue gases of the gas turbine can be utilised in a heat recovery steam generator producing steam for the bottoming steam cycle and producing more power in a steam turbine and electricity in a generator.
BRIEF DESCRIPTION OF THE DRAWINGS Preferred embodiments of the invention are illustrated in the accompanying drawings, in which
Fig. 1 illustrates a gas turbine power plant according to the present inven- tion and
Fig.2 illustrates the partial oxidation of the membrane/partial oxidation reactor.
The drawings show only the parts important for the invention. Same elements will be numbered in the same way in different drawings.
DETAILED DESCRIPTION OF THE INVENTION
Fig. 1 shows a syngas based low emission power according to the present invention. Air 1 is fed through a compressor 2 before the compressed air 3 is fed at least through a membrane/partial oxidation (POX) reactor 4. After the membrane/POX reactor 4 the air is burned in a combustion chamber 5 together with hydrogen 6. The flue gases are then expanded in a turbine 7, which is driving the compressor 2 and producing electricity in a generator 8. After the expansion the hot flue gases 9 are utilised in a heat recovery steam generator 10 producing steam for the bottoming steam cycle 11 and producing more power in a steam turbine 12 and electricity in a generator 13.
As can be seen from Fig. 1, natural gas 14 is being mixed with superheated intermediate pressure steam 15 and is then lead to the membrane/POX reactor 4. One possibility here would be to use a medium temperature heat exchanger 16 to raise the temperature of the mixture of steam 15 and natural gas 14. This would flatten out the temperature profile in the membrane/POX reactor 4 and thus lower the temperature gradients in this. Since the tem- perature involved is not too high (<900°C), it might be possible to use a metal heat exchanger. As seen in Fig. 2, in the membrane/POX reactor 4, oxygen is transferred through a membrane 18 from a first side to a second side and is partially oxidised (as well as reformed with steam) on the membrane 18 surface with the natural gas 14 by the following reactions:
CH4 + 0.5O2 = 2H + CO + 35.67 kJ/mol
CH4 + H2O => CO + 3H2 - 205 kJ/mol
CO + H2O => CO2 + H2 + 41.15 kJ/mol
In sum, the three reactions combine to produce a mixture of H2, CO and CO2; the overall heat balance and product mixture is dictated by the amount of oxygen (and endothermic reactions) that is present. The design of the membrane/POX reactor 4 is such that the overall process is autothermal, and the membrane temperature is of ca. 800 °C. The membrane/POX reactor 4 would be combined to both work as an oxygen transferring membrane and as well as doing the partial oxidation. One membrane type that can be used to separate the oxygen from the air is a so-called "Mixed Conducting Membrane" (MCM). These materials consist of complex crystalline structures, which incorporate oxygen ion vacancies (5-15%). The transport principle for oxygen transport through the membrane 18 is adsoφtion on the surface followed by decomposition into ions, which are transported through the membrane by sequentially occupying oxygen ion vacancies. The ion transport is counterbalanced by a flow of electrons in the opposite direction. The driving force is a difference in oxygen partial pressure between the permeate and retentate sides of the membrane 18. The transport process also requires high temperatures, i.e. > 700°C. In an embodiment of the present invention the surfaces of the permeate side of the membrane 18 (that containing the syngas 17ι) is coated with catalytic material to promote the formation of synthesis gas 17ι and, in particular, hydrogen. Catalyst materials used for autothermal re- forming are Rh, Ru, Co, Fe or bimetallic combinations thereof (e.g. Co/Fe).
The syngas 17ι now consisting of hot steam, H2 and CO enters a low temperature heat exchanger 19 , where the syngas 171 mixture is cooled down by an incoming stream of the compressed air 3 from the compressor 2. Optionally, the air stream from the low temperature heat exchanger 19 can then be lead to a catalytic burner 20 where the air is heated by means of catalytic combustion. The fuel for the catalytic burner 20 is either hydrogen 21 or natu- ral gas 14. Use of hydrogen 21 is preferred to avoid producing CO2. The reason for using a catalytic burner 20 is to increase the average temperature in the membrane/POX reactor 4, increasing the oxygen flux through the membrane 18. Also, the temperature gradient in the reactor 4 will be lower and thus the thermal stresses for the reactor 4 will decrease. This catalytic burner 20 can also be used to help control process conditions within the MCM reactor during start up or to address instabilities within the membrane/POX reactor 4 associated with the autothermal reforming and potential catalyst deactivation. The temperature of the MCM reactor will be very sensitive to the amount of O2 present and we could have some strange transients during start up. A quick reacting catalytic burner 4 running on H2 could help for process control.
After the syngas 17ι has been cooled down in the low temperature heat exchanger 19, the syngas 17ι is then further cooled down in a CO shift reactor 22, lowering the temperature further to about 200-300°C. Depending on the chosen cooling temperature, water will condense out or not. Since a low temperature favours the CO shift reaction it might be wise to keep the temperature low. This will also lower the water consumption for the cycle since the condensed water 23 can be re-injected in the bottoming steam cycle 11. The medium used for the cooling is boiler feed water 241, 242 from a bottoming steam and water cycle 11. During the cooling of the syngas 17ι in the CO shift reactor 22, the syngas 17ι undergoes the following reaction:
CO + H2O => H2 + CO2 + 41.15 kJ/mol
The CO shift reactor 22 is in other words used to convert CO and water to CO2 and more hydrogen. Also this reaction is mildly exothermic, leading to that some of the water condensed out during the cooling (or all water if the cooling temperature is high) is evaporated again, taking heat from the exo- thermic process described above. After the CO shift reactor 22 the syngas 172 consists ideally of H2, CO2 and H2O. This syngas 172 is then lead to some kind of CO2 absoφtion equipment 25, based on either chemical or physical absoφtion. The CO2 removal rate in this kind of equipment is around 90 %. Low pressure steam 26 needed for the CO2 removal is extracted from the steam turbine 12, and the condensed water 27 is lead back to the feed water tank of the steam cycle 11. The removed CO2 28 is further compressed by means of inter-cooling in a compressor 29, producing liquid CO2 30 that might be deposited or used in for instance enhanced oil recovery.
After removing most of the CO2, the syngas 173 mainly consisting of H2, H2O and some remaining CO2 is lead to a combustion chamber 5, to be burned together with air from the first side of the membrane/POX reactor 4. The water in the syngas 173 helps control the combustion temperature and thus lowers NOχ formation. A part of the resulting syngas 173 comprising hydrogen 6 from the CO2 removal equipment 25 can as well be burned in the catalytic burner 20.
REFERENCE NUMBERS
Air Compressor
Compressed air
Membrane/partial oxidation (POX) reactor
Combustion chamber
Hydrogen
Gas turbine
Generator
Hot flue gases
Heat recovery steam generator
Bottoming steam cycle
Steam Turbine
Generator
Natural gas
Superheated steam
Medium temperature heat exchanger 2, 173 Syngas
Membrane
Low temperature heat exchanger
Catalytic burner
Hydrogen
CO shift reactor
Condensed water
Boiler feed water
CO2 absoφtion equipment Low pressure steam
Condensed water
CO2
Compressor
Liquid CO2

Claims

1. A method of operating a gas turbine power plant comprising the steps of
- compressing air (1) in at least one compressor (2), - feeding the compressed air (3) from the at least one compressor (2) through a first side of a membrane/partial oxidation reactor (4),
- feeding the air from the first side of the membrane/partial oxidation reactor (4) to a combustion chamber (5),
- combusting the air with hydrogen (6) thereby producing flue gases (9), - expanding the flue gases (9) in a gas turbine (7) driving at least one generator (9),
- feeding natural gas (14) mixed with steam (15) to the second side of the membrane/partial oxidation reactor (4) and converting the natural gas (14) at least to H2 and CO, whereby oxygen is transferred from the compressed air (3) through the membrane (18) of the membrane/partial oxidation reactor (4) and using the oxygen for the partial oxidation process of the natural gas (14),
- feeding the resulting syngas (17ι) to a CO shift reactor (22) thereby producing H2 and converting a majority of the remaining CO to CO2, - feeding the resulting syngas (172) from the CO shift reactor (22) to a
CO2 removal equipment (25) thereby removing CO2,
- feeding the resulting syngas (173) comprising H2 and H2O from the CO2 removal equipment (25) at least to the combustion chamber (5).
2. The method of operating a gas turbine power plant according to claim 1 , wherein the method comprises the step of burning in a catalytic burner (20) a fuel (6, 14) with the compressed air (3) from the compressor (2) and feeding the resulting gases from the catalytic burner (20) to the first side of the membrane/partial oxidation reactor (4).
3. The method of operating a gas turbine power plant according to claim 2, wherein natural gas (14) and/or part of the resulting syngas (173) com- prising Hydrogen (6) from the CO2 removal equipment (25) is burned in the catalytic burner (20). 4. The method of operating a gas turbine power plant according to claim 2, wherein comprises the step of burning in a catalytic burner (20) a fuel (6, 14) with the compressed air (3) from the compressor (2) and feeding the resulting gases from the catalytic burner (20) to the first side of the membrane/partial oxidation reactor (4) during the start up of the gas turbine power plant.
5. The method of operating a gas turbine power plant according to any of the claims 1 to 4, wherein produced syngas (17ι) coming from the second side of the membrane/partial oxidation reactor (4) is cooled by the use of compressed air coming from the compressor in a heat exchanger (19) before the syngas (17ι) is fed to the CO shift reactor (22).
6. The method of operating a gas turbine power plant according to any of the claims 1 to 4, wherein the natural gas (14) mixed with steam (15) is heated by the use of compressed air coming from the first side of the membrane/partial oxidation reactor (4) in a heat exchanger (16) before the mixture is feed to the membrane/partial oxidation reactor (4).
7. The method of operating a gas turbine power plant according to any of the claims 1 to 6, wherein the extracted CO2 from the CO2 removal equipment (25) is compressed and liquified.
8. The method of operating a gas turbine power plant according to any of the claims 1 to 7, comprising the step of feeding the hot flue gases (9) from the gas turbine (7) to a heat recovery steam generator (10), thereby producing steam and expanding the generated steam in a steam turbine (12).
9. A gas turbine power plant comprising - at least a compressor (2),
- a membrane/partial oxidation reactor (4) including two sides of the membrane (18), the membrane/partial oxidation reactor (4) connected on one end of the first side to the compressor (2),
- a combustion chamber (5) connected on the second end of the first side to membrane/partial oxidation reactor (4),
- a gas turbine (7) connected to the combustion chamber (5),
- a feed line connected to one end of the second side of the membrane/partial oxidation reactor (4),
- a CO shift reactor (22) connected to second end of the second side of the membrane/partial oxidation reactor (4) by a feed line and
- a CO2 removal equipment connected to the CO shift reactor (22) and
- a feed line at least for hydrogen (6) connected the combustion chamber (5).
10. The gas turbine power plant according to claim 9, wherein the surfaces of the membrane (18) which are connected to the second side of the membrane/partial oxidation reactor (4) is coated with catalytic material.
11.The gas turbine power plant according to claim 10, wherein the membrane (18) is coated with a catalyst material of Rh, Ru, Co, Fe or bimetallic combinations thereof.
12. The gas turbine power plant according to any of the claims 9 to 11, wherein before and/or after the membrane/partial oxidation reactor (4) a heat exchanger (16, 19) is arranged connecting the air path after the compressor (2) and/or before the combustion chamber (5) on the first side of the membrane (18) and the feed line before and/or after the second side of the membrane (18).
3. The gas turbine power plant according to any of the claims 9 to 12, wherein a catalytic burner (20) is arranged before the membrane/partial oxidation reactor (4) connected on one end of the first side of the membrane (18) and connected to the compressor (2).
PCT/EP2003/050782 2002-11-08 2003-11-03 Gas turbine power plant and method of operating the same WO2004042200A1 (en)

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EP1561010B1 (en) 2012-09-05
US7363764B2 (en) 2008-04-29
CA2505354C (en) 2012-04-03
AU2003298266A1 (en) 2004-06-07
US20050235650A1 (en) 2005-10-27
EP1561010A1 (en) 2005-08-10
NO20052767L (en) 2005-06-08
CA2505354A1 (en) 2004-05-21

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