EP2758638A2 - Energy storage technology for demanded supply optimisation - Google Patents
Energy storage technology for demanded supply optimisationInfo
- Publication number
- EP2758638A2 EP2758638A2 EP12775833.2A EP12775833A EP2758638A2 EP 2758638 A2 EP2758638 A2 EP 2758638A2 EP 12775833 A EP12775833 A EP 12775833A EP 2758638 A2 EP2758638 A2 EP 2758638A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- gas
- boiler
- comburant
- air separation
- comburant gas
- 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- Withdrawn
Links
- 238000004146 energy storage Methods 0.000 title claims abstract description 28
- 238000005516 engineering process Methods 0.000 title description 4
- 239000007789 gas Substances 0.000 claims abstract description 185
- 238000002485 combustion reaction Methods 0.000 claims abstract description 94
- 238000000926 separation method Methods 0.000 claims abstract description 94
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000001301 oxygen Substances 0.000 claims abstract description 79
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 79
- 238000003860 storage Methods 0.000 claims abstract description 71
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 41
- 238000010304 firing Methods 0.000 claims description 35
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 34
- 239000000446 fuel Substances 0.000 claims description 24
- 239000003245 coal Substances 0.000 claims description 23
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 230000006835 compression Effects 0.000 claims description 17
- 238000007906 compression Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 239000002803 fossil fuel Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 6
- 238000010248 power generation Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 230000001932 seasonal effect Effects 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000007774 longterm Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000004513 sizing Methods 0.000 abstract description 2
- 239000002028 Biomass Substances 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- VGPYEHKOIGNJKV-UHFFFAOYSA-N asulam Chemical compound COC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 VGPYEHKOIGNJKV-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000005431 greenhouse gas Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 2
- 229940112112 capex Drugs 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- F01K13/00—General layout or general methods of operation of complete plants
-
- 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
- F01K7/00—Steam engine plants characterised by the use of specific types of engine; Plants or engines characterised by their use of special steam systems, cycles or processes; Control means specially adapted for such systems, cycles or processes; Use of withdrawn or exhaust steam for feed-water heating
- F01K7/16—Steam engine plants characterised by the use of specific types of engine; Plants or engines characterised by their use of special steam systems, cycles or processes; Control means specially adapted for such systems, cycles or processes; Use of withdrawn or exhaust steam for feed-water heating the engines being only of turbine type
-
- 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
- F01K13/00—General layout or general methods of operation of complete plants
- F01K13/02—Controlling, e.g. stopping or starting
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B35/00—Control systems for steam boilers
-
- 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
- F23L7/00—Supplying non-combustible liquids or gases, other than air, to the fire, e.g. oxygen, steam
- F23L7/007—Supplying oxygen or oxygen-enriched air
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23N—REGULATING OR CONTROLLING COMBUSTION
- F23N3/00—Regulating air supply or draught
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04472—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using the cold from cryogenic liquids produced within the air fractionation unit and stored in internal or intermediate storages
- F25J3/04496—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using the cold from cryogenic liquids produced within the air fractionation unit and stored in internal or intermediate storages for compensating variable air feed or variable product demand by alternating between periods of liquid storage and liquid assist
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
- F25J3/04527—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general
- F25J3/04533—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general for the direct combustion of fuels in a power plant, so-called "oxyfuel combustion"
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
- F25J3/04563—Integration with a nitrogen consuming unit, e.g. for purging, inerting, cooling or heating
- F25J3/04575—Integration with a nitrogen consuming unit, e.g. for purging, inerting, cooling or heating for a gas expansion plant, e.g. dilution of the combustion gas in a gas turbine
- F25J3/04581—Hot gas expansion of indirect heated nitrogen
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04763—Start-up or control of the process; Details of the apparatus used
- F25J3/04769—Operation, control and regulation of the process; Instrumentation within the process
- F25J3/04812—Different modes, i.e. "runs" of operation
- F25J3/04836—Variable air feed, i.e. "load" or product demand during specified periods, e.g. during periods with high respectively low power costs
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04763—Start-up or control of the process; Details of the apparatus used
- F25J3/04866—Construction and layout of air fractionation equipments, e.g. valves, machines
- F25J3/04951—Arrangements of multiple air fractionation units or multiple equipments fulfilling the same process step, e.g. multiple trains in a network
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04763—Start-up or control of the process; Details of the apparatus used
- F25J3/04866—Construction and layout of air fractionation equipments, e.g. valves, machines
- F25J3/04951—Arrangements of multiple air fractionation units or multiple equipments fulfilling the same process step, e.g. multiple trains in a network
- F25J3/04963—Arrangements of multiple air fractionation units or multiple equipments fulfilling the same process step, e.g. multiple trains in a network and inter-connecting equipment within or downstream of the fractionation unit(s)
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2240/00—Processes or apparatus involving steps for expanding of process streams
- F25J2240/02—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream
- F25J2240/28—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream the fluid being argon or crude argon
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
- F25J2260/30—Integration in an installation using renewable energy
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
- F25J2260/80—Integration in an installation using carbon dioxide, e.g. for EOR, sequestration, refrigeration etc.
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- 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
- Y02E20/32—Direct CO2 mitigation
-
- 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
- Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
Definitions
- the invention relates to a thermal power plant having either an oxyfuel firing capability or a partial oxyfuel firing capability, and preferably combined with biomass firing technology, and to a gas supply system for, control system for and method of operation of the same.
- the invention in particular relates to a gas supply system for, control system for and a method of operation of a thermal power plant suitable for flexible operation in response to varying demand.
- Oxyfuel firing is a means of firing the fuel with an oxygen enriched comburant gas.
- oxygen required to burn the fuel is supplied by using atmospheric air as a comburant gas.
- a supply of gas with a higher oxygen content, and in particular a mixture of substantially pure 0 2 and recycled C0 2 is used as a comburant gas.
- the oxyfuel combustion process seeks to produce combustion products that are highly concentrated in C0 2 and in particular consist essentially of C0 2 and water to facilitate carbon capture and mitigate the C0 2 emissions. To effect this, the combustion air supply must first be is separated prior to supply to the furnace in a suitable air separation unit (ASU).
- ASU air separation unit
- the separated gaseous oxygen is intended for supply to the combustion process.
- the separated nitrogen/argon mix may be expanded and vented to atmosphere or stored in storage tanks for later expansion and venting.
- the liquid oxygen may be cryogenically stored in an embedded or external liquid oxygen (LOX) storage facility.
- Liquid air may be stored in an embedded or external liquid air (LA) storage facility.
- ASU air separation unit
- CPU compression and purification unit
- FIG. 1 An example of the current state of the art technology is presented on figure 1.
- the figure comprises one ASU unit producing 0 2 for one Boiler/Turbine Unit, and one CPU unit.
- the ASU and Boiler/Turbine Unit and CPU are sized accordingly to coupled operation at steady state with reference to the nominal steady state Boiler/Turbine Unit 0 2 requirement.
- 0 2 production in the example ASU is equal to the nominal steady state Boiler/Turbine Unit 0 2 requirement of 100 kg/s.
- the Boiler/Turbine Unit is producing at this steady state full load 170 kg/s of C0 2 , and this amount is compressed in CPU.
- the electrical energy required to power the ASU Unit is extracted from the Boiler/Turbine Unit.
- FIG. 2 Another example of the current state of the art is presented on figure 2.
- the ASU unit is sized accordingly to full Boiler/Turbine Unit oxygen requirement 100 kg/s with embedded LOX storage to for example boost ASU response time.
- the electrical energy required to power the ASU Unit is extracted from the Boiler/Turbine Unit.
- FIG 3. Another example of current the current state of the art is presented on figure 3.
- the ASU is sized accordingly to full Boiler/Turbine Unit oxygen requirement 100 kg/s and is supported with external LOX storage to for example boost ASU response time.
- the electrical energy required to power the ASU Unit is extracted from the Boiler/Turbine Unit.
- Fossil fuel thermal power plants have a particular role in a practical mixed supply grid. Typically they are not run continuously at full load. Instead, their output will vary, partly in response to changes in supply or demand within the grid so that the grid supply is maintained. Operation in this way in response to diurnal and seasonal changes in demand, and periods of downtime, can reduce load factors over a period to 80% or less. If the ASU is designed for operation at 100% nominal boiler demand this leads to an excess of capacity, and increases both capex and opex costs for the plant.
- a comburant gas supply system for a combustion boiler/ turbine of a thermal power plant comprising: an air separation module to separate and output an oxygen rich gas from an input air supply;
- a comburant gas storage module fluidly connected to the output of the air separation module for storage in liquid state of separated oxygen rich gas; a comburant gas supply module to supply the oxygen rich gas to the combustion boiler selectively from the air separation system and/ or the comburant gas storage system;
- the air separation module has an oxygen rich gas output capacity based on one or both of:
- a combustion boiler/ turbine system of a thermal power plant comprising a combustion boiler for combustion of a fuel in the presence of an oxygen rich comburant gas; a steam turbine unit driven thereby; and a comburant gas supply system as above described fluidly linked to supply comburant gas to the combustion boiler to support combustion of the fuel.
- a combustion boiler/turbine system of a thermal plant comprising a combustion furnace for combustion of a fuel in the presence of an oxygen rich comburant gas to provide heat input to the industrial process; and a comburant gas supply system as above described fluidly linked to supply comburant gas to the combustion furnace to support combustion of the fuel.
- a combustion boiler/turbine system of a thermal power plant comprising a combustion boiler for combustion of a fuel in the presence of an oxygen rich comburant gas; a gas turbine unit driven thereby; and a comburant gas supply system as above described fluidly linked to supply comburant gas to the combustion boiler to support combustion of the fuel.
- the air separation module is not, as is conventional in the art, sized to the full nominal comburant gas requirement of the combustion boiler/ turbine unit with which is it designed to be used.
- the air separation module is sized to a percentage of the full nominal comburant gas requirement of the boiler/ turbine unit to which it supplies oxygen rich comburant gas, which percentage is related to a predetermined operational load factor of the combustion boiler/ turbine unit over a suitable operating period. Additionally the air separation module size may be changed to offer longer term energy storage than previous load factor based sizing.
- the ASU unit is utilizing electrical energy from grid that comes from renewable sources or other low cost sources. It in neither rated to the full nominal comburant gas requirement of the combustion boiler/ turbine unit nor limited to operation during periods in the operational cycle when the boiler/ turbine unit is operational.
- the air separation module is supported, variation in comburant gas requirement of the boiler/ turbine unit over the operating period is accommodated, and supply up to the nominal full load comburant gas requirement of the boiler/ turbine unit is enabled by use of the comburant gas storage module selectively to store excess separated oxygen rich gas or be a source of supply of additional separated oxygen rich gas to the comburant gas supply module.
- the air separation module it is not necessary for the air separation module to be sized, as is conventionally the case, with respect to the full capacity nominal comburant gas demand level of the boiler/ turbine unit to which it ultimately supplies oxygen rich comburant gas. It is merely necessary that it is sized in conjunction with a comburant gas storage module to be able to supply the comburant gas requirement of the boiler/ turbine unit over a load cycle based on a typical load factor for the cycle. Both capex and opex costs can be reduced relative to air separation modules which are conventionally sized and coupled to the nominal operational load of the boiler/ turbine unit.
- Nitrogen/argon separated in the ASU unit can be stored in compressed form in tanks for later expansion and stored energy recovery on demand.
- the air separation module produces an oxygen rich comburant gas from an input supply of air, in particular preferably to support oxyfuel firing of a carbonaceous fuel in the associated boiler/ turbine unit, and the comburant gas storage module stores this gas if required.
- the air separation module may be provided with at least one and preferably a plurality of air separation unit compressors, for example producing an oxygen rich comburant gas by cryogenic separation.
- oxygen rich gas is intended to cover any gas having a proportion of oxygen which is greater than atmospheric air it will be appreciated that in practice for oxyfuel firing a comburant gas that is substantially free of nitrogen and in particular a comburant gas that is substantially pure oxygen will be preferred.
- the air separation module is adapted to produce and supply gas that is substantially free of nitrogen and in particular that is substantially pure oxygen to the comburant gas storage module and/ or comburant gas supply module.
- the air separation module comprises one or more cryogenic air separation units as will be familiar.
- the underlying inventive concept of the invention lies in the determination of a suitable size (that is, a suitable oxygen rich gas production capacity) for an air separation module in accordance with the invention, which is determined not with reference to 100% nominal boiler comburant demand for a steady state operation (and still less with reference to a higher maximum boiler demand) but is rather determined with reference to an adjusted demand that takes account of a boiler load factor over a suitable pre-determined period of time and/ or that takes account of an energy storage demand.
- a suitable size that is, a suitable oxygen rich gas production capacity
- a minimum size for an air separation module, and a minimum comburant gas supply capacity can be determined as the product of a nominal steady state comburant gas demand for the associated boiler/turbine unit and a boiler/turbine unit load factor and the energy storage requirement. In a preferred case, this may be the optimal size, although some additional capacity may be provided for other operational reasons. This allows the air separation unit to be smaller than it would be if sized for full nominal boiler steady state demand and reduces both build and operational costs.
- an air separation module in accordance with the invention may be sized to no more than 90% of the nominal boiler steady state operation comburant demand if the Boiler/Turbine Unit is operating over the period of time with load factor 0.8 and 10% of Boiler/Turbine Unit capacity is required as additional immediate demanded energy storage.
- the invention does not exclude the possibility that an air separation module may still embody the principles of the invention but be sized to be larger than this, for example to accommodate a maximum boiler demand that is higher than the steady state demand and/or to enable the storage of an excess of comburant gas in the comburant gas storage module, which may for instance be used in conjunction with the air separation unit as a source of energy storage to provide demand. Both of these principles are known in the prior art.
- the essence of the invention remains that the operation parameters to be determined for the air separation module are de-coupled from those to be determined with reference to steady state operation of the boiler/turbine system, and instead adjusted to take account of the applicable load factor for the boiler/turbine system and/ or required additional energy storage capacity.
- an air separation module is sized with reference to a nominal boiler comburant demand at steady state adjusted for a load factor over a period of time and/ or required additional energy storage capacity. Its associated comburant gas storage module is sized accordingly to accommodate fluctuations in demand over that period of time and if required to provide long term comburant storage.
- the air separation module and associated gas storage module should optimally be sized at least to a sufficient level to effect at least the following:
- the air separation module is capable of producing at least the total volume of comburant gas needed to meet the total demand of the associated boiler/turbine unit across the time period; b) that in combination with the comburant gas storage module, supply of comburant gas is enabled which meets at least the nominal steady state demand of the associated boiler/turbine unit at any time during the said period when it is operating at full steady state load.
- a load factor is determined across a suitable period of operation, for example over a full cycle to accommodate changes in daily/ seasonal/ annual demand, period of scheduled down-time etc.
- An air separation module has a design capacity designed with reference to the nominal demand of a boiler/turbine system with which it is intended to be used adjusted to reflect a design load factor of the boiler/turbine system.
- the design process first involves determining such a load factor over a suitable period of time.
- a suitable period of time might be a period from 24 hours up to a year, and might include periods in between.
- An air separation module in accordance with the invention might therefore have a gas output capacity based on no more than 80% of the nominal steady state demand rating of the combustion boiler/turbine. In many other systems, designed for less the continuous operation, load factors may be considerably less than 80%, for example as low as 50%.
- the combustion furnace comprises one or more burners for the combustion of carbonaceous fuel for example including carbonaceous fossil fuel, for example including coal, and for example pulverised coal, but also for example including gas, and for example including oil, and for example including biomass, and for example including distillate, and any combination of same.
- the comburant gas supply module is adapted to supply comburant gas to the burners to support the combustion of the fuel in use. Suitable fuel supply means supply fuel to the combustion site for oxyfuel combustion in familiar manner.
- the air separation module provides in the typical case the sole source of comburant gas supply to the combustion boiler/turbine system.
- the invention embodies all arrangements of apparatus, whether comprising single air separation units and single boilers or plural separation units and/or plural boilers working cooperatively together, where the air separation system is sized in accordance with the principles of the invention with reference to a demand rating for the combustion boiler/turbine system adjusted to a suitable load factor across a pre-determined operating period.
- the combustion boiler/turbine system of the invention further comprises a carbon dioxide compression and storage module for the compression and storage of at least some of the carbon dioxide produced by combustion of fuel in the combustion boiler.
- Suitable compression and storage units will be well known from the art. Since it is a principle of the invention that the operational capacity and parameters of the air separation system have been decoupled from those of the boiler/turbine system, it follows that the specific operational parameters and capacity of the carbon dioxide compression and storage module are not specifically pertinent to the invention. However, in the preferred case, a carbon dioxide compression and storage module will be provided which has a compression capacity determined by and coupled to the boiler output, and for example to the output of combustion C0 2 at least at nominal steady state capacity. Thus, the compression and storage unit is not decoupled in the same way from the boiler capacity but is preferably rated at least with reference to the required capture rate of nominal boiler demand.
- the carbon dioxide compression and storage module is rated to a compression capacity which will enable a nominal carbon emissions rate of zero or less during steady state operation of the boiler/ turbine. It follows that in the case where a boiler is designed for firing using fossil fuels with nominal 100% emissions contribution, the compression and storage module should be rated for a compression volume that is equal to that of the total furnace CO2 emission volume at steady state operation. Where a boiler is rated for a fuel mix, such as a mixed fossil fuel and bio-mass firing, or a pure bio-mass firing, which has a reduced or zero nominal emissions contribution, two possibilities arise.
- a carbon dioxide compression and storage unit may be reduced in size accordingly, so as to compress and store just that quantity of carbon dioxide produced from the boiler which is sufficient to give a zero nominal emissions for the system, with the remaining CO2 being vented to atmosphere, for example via a stack, or the carbon dioxide compression and storage system may have a greater design capacity, producing a system with a negative emissions rate.
- a thermal power plant comprises a power generation unit having a comburant gas supply system in accordance with the first aspect of the invention and/ or a combustion boiler/ turbine system in accordance with the second aspect of the invention.
- a method of operation of a thermal power plant having an air separation module for the separation of an oxygen rich comburant gas supply for oxyfuel firing of fossil fuel an oxygen rich comburant gas storage facility is provided, the method characterized by the steps of: providing a combustion boiler/turbine system of a thermal power plant having a combustion boiler for combustion of a fuel in the presence of an oxygen rich comburant gas;
- an air separation module to separate and output an oxygen rich comburant gas from an input air supply
- a comburant gas storage module fluidly connected to the output of the air separation module for storage in liquid state of separated oxygen rich gas
- a comburant gas supply module to supply the oxygen rich gas to the combustion boiler selectively from the air separation system and/ or the comburant gas storage system
- the air separation module is operated at an oxygen rich gas separation capacity based on the said comburant gas demand of the combustion boiler/turbine adjusted to take account of the said determined load factor and/ or said required energy storage capacity.
- an air separation module is provided and operated at an output capacity which is decoupled from the demand capacity of the boiler/turbine at steady state, and is less or more than 100% of the said steady state demand, but is instead adjusted to take account of the load factor and/ or required energy storage capacity.
- a minimum output capacity of the air separation module is preferably determined as the product of the nominal steady state comburant gas demand and the load factor and the required energy storage capacity.
- the method can in an alternative be seen as a method of determination of a design capacity of an air separation module as above described, with reference to the demand capacity of a combustion boiler which it is to supply with comburant gas, which method comprises the steps of:
- the method comprises determining a design output for the air separation module which is less than the nominal comburant gas demand of the combustion boiler at steady state, but which is at least the mean comburant gas demand of the boiler over the pre-determined operating period when due account is taken of the load factor and required energy storage capacity.
- the method is in particular a method of operation of a thermal power plant comprises a power generation unit having a comburant gas supply system in accordance with the first aspect of the invention and/ or a combustion boiler/ turbine system in accordance with the second aspect of the invention, and preferred features will be understood by analogy.
- the step of determining a load factor adjusted demand is preferably determined as the product of the nominal steady state comburant gas demand and the load factor.
- the oxygen rich comburant gas is suitable for oxyfuel firing of carbonaceous fuel and is for example preferably substantially free of nitrogen and more preferably substantially pure oxygen. It is a requirement of the invention that the comburant gas production capacity of the air separation module is decoupled from the demand requirement of the boiler and is instead reduced with reference to a load factor adjusted demand and/ or increased to provide required energy storage capacity. In effect, the load factor and/ or storage capacity adjusted demand sets a minimum requirement for the production capacity of the air separation module.
- the air separation module may still be provided with a higher capacity, for example to accommodate peak demand levels above nominal or to provide an energy storage flexibility in which the air separation module is run at a higher capacity during periods of lower power demand.
- the method of operation may additionally comprise: tending to reduce the works power of the air separation module in response to an increased grid demand and balancing the same by comburant gas from storage to make up the required supply for oxyfuel firing; or tending to increase the works power of the air separation module in response to a reduced grid demand and balancing the same by supplying the resultant excess to the storage.
- the air separation system is operated at reduced power at times of higher grid demanded output, and this reduced power reduces the overall works power of the plant in order to supply additional power to the grid without the need to vary the power output of the generation plant.
- the energy stored in compressed nitrogen/argon form in tanks could be recovered when demanded.
- a thermal power plant comprises a power generation unit having an oxyfuel firing system including an air separation system as above described.
- Figures 1 to 3 are schematic diagrams of prior art systems in which an air separation unit is sized at least to 100% nominal boiler comburant demand;
- FIGS 4 to 8 are schematic diagrams of embodiments of the invention in which an air separation unit is sized at less than 100% nominal boiler comburant demand but rather at a comburant demand adjusted by a boiler load factor determined over a suitable period of time.
- FIGS 1 to 3 are schematic diagrams of prior art systems and have been discussed in that context hereinabove.
- the figure shows for clarity one ASU unit producing 0 2 for one Boiler/Turbine Unit, and one CPU unit.
- the ASU and Boiler/Turbine Unit and CPU are sized in coupled manner for steady state operation, whereby production in the ASU is equal to the boiler/ turbine steady state requirement of 100 kg/s.
- the Boiler/Turbine Unit produces 170 kg/s of C0 2 , and this amount is compressed in CPU.
- FIGS 4 to 8 are schematic diagrams of embodiments of the invention in which a similar ASU unit producing 0 2 for a similar Boiler/Turbine Unit is sized at less than 100% nominal Boiler/Turbine Unit 0 2 demand but rather at demand level adjusted by a boiler load factor determined over a suitable period of time.
- BLF - Boiler/Turbine Load Factor over the assumed period of time (for example, a daily cycle, a seasonal cycle, an annual cycle, with or without account taken of downtime);
- 02Dem - is the Boiler Nominal Comburant demand.
- the LOX storage may be sized accordingly.
- the ASU could be oversized to accommodate a maximum boiler demand that is higher than nominal demand. Additionally the LOX storage could be oversized to accommodate a maximum boiler demand that is higher than nominal demand.
- FIG 4. A possible embodiment of the invention is presented on figure 4.
- the figure again shows for clarity one ASU unit producing 0 2 for one Boiler/Turbine Unit, and one CPU unit.
- the ASU Unit is sized to 80% of the Boiler/Turbine Unit nominal Oxygen requirement and is supported by embedded in ASU LOX Oxygen storage.
- the Boiler/Turbine Unit operates only with coal and with a determined load factor 0.8 over an operating period.
- the CPU Unit is sized for full mass of the Boiler/Turbine C0 2 gas emission at 170 kg/s of C0 2 . Compressing and storing emissions from firing the coal results in unit having nominal zero emissions.
- the ASU Unit is sized to 60% of the Boiler/Turbine Unit nominal Oxygen requirement and is supported by LOX Oxygen storage external to the ASU.
- the Boiler/Turbine Unit is designed for firing with 50% of coal and 50% of biomass and operates with load factor 0.6 over an operating period.
- the CPU Unit is sized for full C0 2 gas volume from coal firing and full C0 2 gas volume from biomass firing in the Boiler/Turbine Unit to total gas emission at 128 kg/s of C0 2 . Compressing and storing emissions from firing the biomass results in unit having negative emissions.
- the ASU Unit is sized to 75% of the Boiler/Turbine Unit nominal Oxygen requirement and is supported by LOX Oxygen storage external to the ASU.
- the Boiler/Turbine Unit is designed for firing with 50% of coal and 50% of biomass and operates with load factor 0.75 over an operating period.
- the CPU Unit is sized for C0 2 gas storage of 68 kg/s of C0 2 . Gas emission at 68 kg/s of C0 2 is released to atmosphere via the stack.
- the CPU Unit is sized for C0 2 gas storage of the emissions from the Boiler/Turbine Unit attributable to coal firing only. Compressing and storing emissions from firing the coal results in unit having near zero nominal emissions.
- FIG. 7 Another possible embodiment of the invention is presented on figure 7.
- the ASU Unit is sized to 50% of the Boiler/Turbine Unit nominal Oxygen requirement and is supported by LOX Oxygen storage external to ASU.
- the Boiler/Turbine Unit fires only biomass and operates with load factor 0.5 over an operating period.
- the CPU Unit is sized for full C0 2 gas volume from the biomass firing in the Boiler/Turbine Unit at 170 kg/s of C0 2 . Compressing and storing emissions from firing the biomass results in unit having negative emissions.
- FIGS. 4 to 7 show for simplicity a schematic in which a single ASU unit produces 0 2 for a single Boiler/Turbine Unit, and emissions therefrom are shown compressed by a single CPU unit it will be understood that this is by may of illustration only, and that the invention embodies any combination of plural ASU modules and/ or plural boiler/ turbine modules and/ or where applicable plural CPU modules to give the required capacities, and in particular to meet the requirement that an air storage system produces 0 2 or other oxygen rick comburant gas for a boiler/ turbine system at less than 100% nominal demand but rather at demand level adjusted by a boiler load factor determined over a suitable period of time.
- the illustrated embodiment has four Boiler/Turbine Units A, B, C, and D, and one common LOX storage.
- Boiler/Turbine Unit A fires 50% of coal and 50% of biomass and operates with load factor 0.75 over an operating period.
- the Boiler/Turbine Unit A has one ASU unit and the ASU unit is sized to 75% of Boiler/Turbine Unit nominal Oxygen requirement and is supported by external to ASU LOX Oxygen storage.
- the CPU Unit is sized for full CO2 gas volume from firing the coal and the biomass in the Boiler/Turbine Unit A. Compressing and storing emissions from firing the coal and the biomass results in the unit having nominal negative emissions.
- Boiler/Turbine Units B and C have one shared ASU unit sized to 75% of both Boiler/Turbine Unit B and C nominal Oxygen requirements and is supported by external to ASU LOX Oxygen storage.
- Boiler/Turbine Unit B fires 50% of coal and 50% of biomass and operates with a load factor 0.75 over an operating period.
- the CPU Unit for Boiler/Turbine Unit B is sized for full from firing the coal only. CO2 gas volume attributable to firing the biomass is vented via the stack. Compressing and storing emissions from firing the coal results in the unit having nominal near zero emissions.
- Boiler/Turbine Unit C fires only coal and operates with load factor 0.75 over an operating period.
- the CPU Unit for Boiler/Turbine Unit C is sized for full C0 2 gas volume from firing the coal. Compressing and storing emissions from firing the coal results in unit having nominal near zero emissions.
- Boiler/Turbine Unit D has Oxygen supplied from multiple ASU units.
- the ASU units are different sizes, however the combined size of the ASU units is sized to 75% of Boiler/Turbine Unit D nominal Oxygen requirement and is supported by external to ASU LOX Oxygen storage.
- the Boiler/Turbine Unit D fires 50% of coal and 50% of biomass and operates with load factor 0.75 over an operating period.
- the CPU Unit for Boiler/Turbine Unit D is sized for full C0 2 gas volume from firing the coal and the biomass. Compressing and storing emissions from firing the coal and the biomass results in unit having nominal negative emissions.
- the electrical energy required to power the ASU unit is preferably supplied from a renewable energy source or a low cost energy source and is decoupled from the Boiler/Turbine Unit operation.
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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GBGB1116157.7A GB201116157D0 (en) | 2011-09-19 | 2011-09-19 | Energy storage technology for demanded supply optimisation |
PCT/GB2012/052300 WO2013041848A2 (en) | 2011-09-19 | 2012-09-18 | Energy storage technology for demanded supply optimisation |
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EP2758638A2 true EP2758638A2 (en) | 2014-07-30 |
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EP12775833.2A Withdrawn EP2758638A2 (en) | 2011-09-19 | 2012-09-18 | Energy storage technology for demanded supply optimisation |
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US (1) | US20140223909A1 (ko) |
EP (1) | EP2758638A2 (ko) |
KR (1) | KR20140060332A (ko) |
CA (1) | CA2879001A1 (ko) |
GB (1) | GB201116157D0 (ko) |
WO (1) | WO2013041848A2 (ko) |
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US20150107247A1 (en) * | 2013-10-18 | 2015-04-23 | Alstom Technology Ltd | Control system for oxy fired power generation and method of operating the same |
US20150260029A1 (en) * | 2014-03-11 | 2015-09-17 | Rachid Mabrouk | Integrated process for enhanced oil recovery using gas to liquid technology |
US10316825B2 (en) | 2015-09-02 | 2019-06-11 | Sebastiano Giardinella | Non-air compressed gas-based energy storage and recovery system and method |
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US4227374A (en) * | 1978-10-20 | 1980-10-14 | Oxley Alan J | Methods and means for storing energy |
US20070251267A1 (en) * | 2006-04-26 | 2007-11-01 | Bao Ha | Cryogenic Air Separation Process |
US20090158978A1 (en) * | 2007-12-20 | 2009-06-25 | Foster Wheeler Energy Corporation | Method of controlling a process of generating power by oxyfuel combustion |
JP5178453B2 (ja) * | 2008-10-27 | 2013-04-10 | 株式会社日立製作所 | 酸素燃焼ボイラ及び酸素燃焼ボイラの制御方法 |
JP4920051B2 (ja) * | 2009-02-25 | 2012-04-18 | 株式会社日立製作所 | 酸素燃焼ボイラプラント及び酸素燃焼ボイラプラントの運転方法 |
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- 2012-09-18 KR KR1020147008587A patent/KR20140060332A/ko not_active Application Discontinuation
- 2012-09-18 US US14/345,775 patent/US20140223909A1/en not_active Abandoned
- 2012-09-18 EP EP12775833.2A patent/EP2758638A2/en not_active Withdrawn
- 2012-09-18 CA CA2879001A patent/CA2879001A1/en not_active Abandoned
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GB201116157D0 (en) | 2011-11-02 |
US20140223909A1 (en) | 2014-08-14 |
KR20140060332A (ko) | 2014-05-19 |
WO2013041848A2 (en) | 2013-03-28 |
CA2879001A1 (en) | 2013-03-28 |
WO2013041848A3 (en) | 2014-03-13 |
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