CN102390979A - Systems and methods of converting fuel - Google Patents
Systems and methods of converting fuel Download PDFInfo
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- CN102390979A CN102390979A CN2011102262062A CN201110226206A CN102390979A CN 102390979 A CN102390979 A CN 102390979A CN 2011102262062 A CN2011102262062 A CN 2011102262062A CN 201110226206 A CN201110226206 A CN 201110226206A CN 102390979 A CN102390979 A CN 102390979A
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- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
- C10J3/482—Gasifiers with stationary fluidised bed
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/725—Redox processes
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- 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
- C01B2203/042—Purification by adsorption on solids
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- 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
- C01B2203/042—Purification by adsorption on solids
- C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
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- 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
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- 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
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2200/00—Details of gasification apparatus
- C10J2200/09—Mechanical details of gasifiers not otherwise provided for, e.g. sealing means
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/093—Coal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0969—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1643—Conversion of synthesis gas to energy
- C10J2300/165—Conversion of synthesis gas to energy integrated with a gas turbine or gas motor
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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
- Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
Abstract
Systems and methods for converting fuel are provided wherein the system comprises at least reactors configured to conduct oxidation-reduction reactions. The first reactor comprises a plurality of ceramic composite particles, wherein the ceramic composite particles comprises at least one metal oxide disposed on a support. The first reactor is configured to reduce the least one metal oxide with a fuel to produce a reduced metal or a reduced metal oxide. The second reactor is configured to oxidize the reduced metal or reduced metal oxide to produce a metal oxide intermediate. The system may also comprise a third reactor configured to oxidize the metal oxide intermediate to regenerate the metal oxide of the ceramic composite particles.
Description
The application is an application number: 200780006757.X; Applicant: Ohio Univ; Denomination of invention: the dividing an application of the system and the method for material " transform alkene ".
The present invention relates generally to system and the method that transforms fuel, and relates generally to the oxidation-reduction reactor system that is used for the fuel conversion.
Need clean with effective energy always and produce system.The generate energy carrier for example most of business methods of steam, hydrogen, synthetic gas, liquid fuel and/or electricity based on fossil oil.In addition, the dependency of fossil oil is estimated still can continue in foreseeable future, this is owing to compare much lower cost with renewable source.Current, the carbonaceous fuel for example conversion of coal, Sweet natural gas, refinery coke generally carries out via burning or reforming process.Yet the burning of carbonaceous fuel, particularly coal is the carbon intensive process, and it is to the environmental emission great amount of carbon dioxide.In this process since coal in the complex contents thing also produce sulphur and nitrogen compound.
On the other hand, the chemical reaction between MOX and the carbonaceous fuel can provide the better mode that is stored in the energy in the fuel that reclaims.Certain methods based on the reaction of metal oxide particle and carbonaceous fuel to produce useful energy carrier.For example, people's such as Ishida U.S. Patent number 5,447,024 has been described and has wherein been used nickel oxide particle via the chemical cycle process conversion of natural gas to be become hot method, and this heat can be used for turbo.Yet, the recycling property of pure metal oxides be difference and constitute the obstacle that it uses in the commercial and industrial process.In addition, this technology has limited applicability, because it only can transform Sweet natural gas, this Sweet natural gas is more expensive than other fossil oil.The technology that another kind is known is steam-iron process, and coal deutero-producer gas and ferric oxide particles are reacted in fluidized-bed reactor to produce hydrogen with steam regeneration after a while.Yet this technology is owing to inappropriate contact of reaction solid and inter gas runs into poor gas reforming rate problem, and can not produce rich hydrogen materials flow.
Along with to the more requirement increase of cleaning and more effective fuel transformation system, produced needs to improved system and system components wherein, they will transform fuel effectively, reduce pollutent simultaneously.
In one embodiment of the invention, the system that transforms fuel is provided.This system comprises first reactor drum that comprises many ceramic composite particles, and wherein this ceramic composite particle comprises at least a MOX that is arranged on the carrier.This first reactor drum is set to reduce at least a MOX to produce reductive metal or reductive MOX with fuel.This system also comprises second reactor drum and the 3rd reactor drum; This second reactor drum is set to this reductive metal of oxidation or reductive MOX to produce metal oxide intermediate, and the 3rd reactor drum is set to make at least a MOX regeneration through this metal oxide intermediate of oxidation.
In another embodiment of the invention, the method that converts the fuel into hydrogen, CO or synthetic gas is provided.This method may further comprise the steps: in the reduction reaction between fuel and MOX MOX is reduced into reductive metal or reductive MOX; With oxygenant this reductive metal or reductive MOX are oxidized to metal oxide intermediate, also produce hydrogen, CO or synthetic gas simultaneously; With through this metal oxide intermediate oxidation being made this at least a MOX regeneration.
In another embodiment, the system that comprises the Fischer-Tropsch reaction device is provided.This Fischer-Tropsch reaction device is set to the raw materials mix deposits yields hydrocarbon fuel by contained gas fuel.This system also comprises first reactor drum that comprises many ceramic composite particles, and wherein this ceramic composite particle comprises at least a MOX that is arranged on the carrier.This first reactor drum is set to geseous fuel MOX is reduced into reductive metal or reductive MOX, and wherein this geseous fuel comprises the hydrocarbon fuel that produces through the Fischer-Tropsch reaction device at least in part.This system also comprises second reactor drum, and it is set to steam this reductive metal or the oxidation of reductive MOX to produce metal oxide intermediate.
The preparation method of ceramic composite particle is provided in another embodiment.This method comprises: make the reaction of MOX and solid support material; The mixture of heat-treated metal oxide compound and solid support material is to produce ceramic composite powder under the about 1500 ℃ temperature of about 200-; This ceramic composite powder is changed into ceramic composite particle; With in reactor drum, using before this ceramic composite particle is reduced and oxidation.
Describe in detail below considering and more fully to understand feature and the advantage that provides by embodiment of the present invention.
When combining following accompanying drawing to read together, can understand the following detailed description of illustrative embodiment of the present invention best, in the accompanying drawings, same structure representes with same Ref. No., and in the accompanying drawing:
Fig. 1 be according to one or more embodiments of the present invention produce the synoptic diagram of the system of hydrogen by coal;
Fig. 2 be according to one or more embodiments of the present invention produce the synoptic diagram of the another kind of system of hydrogen by coal;
Fig. 3 is use direct chemical circulation and the synoptic diagram of ash separation sieve by the another kind of system of coal generation hydrogen according to one or more embodiments of the present invention;
Fig. 4 is use direct chemical circulation and the synoptic diagram of ash separation cyclonic separator by the another kind of system of coal generation hydrogen according to one or more embodiments of the present invention;
Fig. 5 be according to one or more embodiments of the present invention produce the synoptic diagram of the another kind of system of hydrogen by coal, wherein this system is used for the 3rd reactor drum of recovery of heat;
Fig. 6 be according to one or more embodiments of the present invention produce the synoptic diagram of the another kind of system of hydrogen by coal, wherein this system is used sorbent material at first reactor drum that is used for desulfurization;
Fig. 7 be according to one or more embodiments of the present invention produce the synoptic diagram of the system of hydrogen by synthetic gas;
Fig. 8 be according to one or more embodiments of the present invention produce the synoptic diagram of the another kind of system of hydrogen by coal, wherein second reactor drum is got back in the carbonic acid gas recycling that produces in first reactor drum;
Fig. 9 be according to one or more embodiments of the present invention produce the synoptic diagram of the another kind of system of steam by coal;
Figure 10 be according to one or more embodiments of the present invention produce the synoptic diagram of another system of hydrogen by synthetic gas;
Figure 11 be according to one or more embodiments of the present invention produce the synoptic diagram of the another kind of system of hydrogen by synthetic gas, wherein this system comprises the pollutent control unit;
Figure 12 is the synoptic diagram of the synthetic bonded system of chemical cycle and fischer-tropsch (F-T) according to one or more embodiments of the present invention;
Figure 13 is the synoptic diagram of the another kind of system of the synthetic bonded of chemical cycle and fischer-tropsch according to one or more embodiments of the present invention;
Figure 14 is the synoptic diagram of the another kind of system of the synthetic bonded of chemical cycle and fischer-tropsch according to one or more embodiments of the present invention;
Figure 15 is the synoptic diagram of synthetic another system of bonded of chemical cycle and fischer-tropsch according to one or more embodiments of the present invention, and wherein this system comprises the pollutent control unit;
Figure 16 is the synoptic diagram of the another kind of system of the synthetic bonded of chemical cycle and fischer-tropsch according to one or more embodiments of the present invention, and wherein this system is operated under the situation of not using gasifier;
Figure 17 is the vehicle-mounted H on the vehicle that is used for according to one or more embodiments of the present invention
2The synoptic diagram of the chemical cycle system of storer;
Figure 18 (a) is the vehicle-mounted H that is used for Figure 17 according to one or more embodiments of the present invention
2The synoptic diagram of the reactor drum box of storage system, wherein this reactor drum box comprises the packed bed that contains Fe medium and small pellets;
Figure 18 (b) is the vehicle-mounted H that is used for Figure 17 according to one or more embodiments of the present invention
2The synoptic diagram of the another kind of reactor drum box of storage system, wherein this reactor drum box comprises the integral bed that contains the Fe medium and have the steam flow straight trough;
Figure 18 (c) is the vehicle-mounted H that is used for Figure 17 according to one or more embodiments of the present invention
2The synoptic diagram of another reactor drum module of storage system, wherein this reactor drum box comprises the integral bed that contains the Fe medium and have steam and air flow groove;
Figure 19 is the vehicle-mounted H that is used for Figure 17 according to one or more embodiments of the present invention
2The synoptic diagram of the reactor drum box of storage system, wherein this reactor drum box uses a series of integral bed reactor drums with air injection to be provided for the heat that steam forms;
Figure 20 is chemical cycle and the synoptic diagram of SOFC bonded system according to one or more embodiments of the present invention;
Figure 21 is the synoptic diagram of the reactor drum that is used for system of the present invention according to one or more embodiments of the present invention, and wherein this reactor drum is a moving-burden bed reactor, and it comprises near the annular region that is arranged in the fuel feed position;
Figure 22 is the synoptic diagram of the reactor drum that is used for system of the present invention according to one or more embodiments of the present invention, and wherein this reactor drum is a moving-bed, and it comprises annular region and inserts the cone in this moving-bed; With
Figure 23 is the synoptic diagram of another reactor drum that is used for system of the present invention according to one or more embodiments of the present invention, and wherein this reactor drum is a moving-burden bed reactor, and it comprises annular region.
With reference to Fig. 1, the present invention relates to transform the system and the method for fuel generally through the redox reaction of ceramic composite particle.As shown in Figure 1, this system comprises two main reactors, and additional reactor drum and assembly, will describe them below in detail.First reactor drum 1 that is set to carry out reduction reaction comprises many ceramic composite particles, and this ceramic composite particle has at least a MOX that is arranged on the carrier.As those of ordinary skills are familiar with, can be via any suitable solids delivery device/mechanism with ceramic composite particle supply response device.These solids delivery device possibly include but not limited to, pneumatics, transfer roller, lock hopper etc.Ceramic composite particle is described in the open application number 2005/0175533A1 of people's such as Thomas the U.S., and the document is for reference in this whole introducing.Disclosed particle and the particles synthesizing method, in another embodiment, the applicant has developed the alternative approach of making ceramic composite in Thomas, and this method can be improved the usefulness and the activity of the ceramic composite particle in the system of the present invention.Two kinds in these alternative approach is co-precipitation and spraying drying.
The 3rd alternative approach comprises the step with MOX and ceramic carrier material physical mixed.Randomly, can promoter material be added in the mixture of MOX and solid support material.After mixing, this mixture of thermal treatment is to produce ceramic composite powder under the about 1500 ℃ temperature of about 200-.Thermal treatment can be at rare gas element, steam, oxygen, air, H
2And its combination existence is carried out under the pressure between vacuum pressure and about 10 normal atmosphere down.This method can also comprise chemical treatment step, and the mixture of wherein handling MOX and solid support material with acid, alkali or both is with this ceramic composite powder activation.After powder production, can known by one of ordinary skill in the art method this ceramic composite powder be changed into ceramic composite particle.These methods can include, but not limited to extrude, granulation and for example granulation of pressure method.Particle can comprise different shape and form, for example, and pellet, material all in one piece or block.
Before this method is included in then in the reactor drum and uses with the step of this ceramic composite particle reduction and oxidation.This circulation is important to ceramic composite particle, because this mixing process can produce the particle of activity, intensity and stability with raising.This circulation is important activity, intensity and stability to improve them to ceramic composite particle.This processing also causes the porosity (0.1-50m that reduces
2/ g) and changes in crystal structure, this makes particle easily to reduce and oxidation, and does not lose its activity for a plurality of such reaction cycle.Do not report porosity in the Thomas patent, but claim that this particle is porous and has the mesoporosity.Though the particle synthetic is described and to be limited to spraying drying, co-precipitation and direct blending means among the application, through other technology for example the ceramic composite particle for preparing of collosol and gel, wet dipping and known other method of those of ordinary skills also can in the reactor drum of system of the present invention, use.
The MOX of ceramic composite comprises the metal that is selected from Fe, Cu, Ni, Sn, Co, Mn and its combination.Though this paper considers various compsns, ceramic composite comprises 40wt% MOX at least usually.Solid support material comprises at least a SiC of being selected from, the oxide compound of Al, Zr, Ti, Y, Si, La, Sr, Ba and the component of its combination.Ceramic composite comprises 5wt% solid support material at least.In another embodiment, particle comprises promoter material.This promotor comprises pure metal, MOX, metallic sulfide or its combination.These metal-based compounds comprise the element that one or more are selected from Fe, Ni, Sn, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, B, P, V, Cr, Mn, Co, Cu, Zn, Ga, Mo, Rh, Pt, Pd, Ag and Ru.Ceramic composite comprises 40wt% promoter material at the most.In an exemplary of ceramic composite, MOX comprises and is supported on TiO
2On the carrier, particularly comprise TiO
2And Al
2O
3The carrier of mixture on Fe
2O
3In another exemplary, ceramic composite can also comprise the Fe that is supported on YSZ (zirconium white of the Yittria stabilization) carrier
2O
3
Refer again to the reduction reaction of first reactor drum 1, first reactor drum 1 receives fuel, and this fuel is used for reducing at least a MOX of ceramic composite to produce metal or the reductive MOX that reduces." fuel " that this paper limited can comprise: the solid carbon compsn is coal, tar, resinous shale, oil-sand, tar sand, Biological resources, wax, coke etc. for example; The liquid carbon-containing compsn is gas and oil, oil, oil, diesel oil, aviation kerosene, ethanol etc. for example; With gaseous composition for example synthetic gas, carbon monoxide, hydrogen, methane, hydrocarbon gas gas (C
1-C
6), hydrocarbon vapour etc.For example, and not as restriction, the possible reduction reaction of following equation demonstration:
Fe
2O
3+2CO-＞2Fe+2CO
2
16Fe
2O
3+3C
5H
12-＞32Fe+15CO
2+18H
2O
In this embodiment, the MOX (Fe of ceramic composite
2O
3) by fuel for example, the CO reduction, and produce reductive MOX (Fe).Though Fe is produce in the reduction reaction of first reactor drum 1 main through reducing composition, FeO or have more that other reducing metal oxide of high oxidation state also is considered at this.
Shown in Figure 21-23, first reactor drum 1 can comprise moving-burden bed reactor, and this moving-burden bed reactor has the annular region 8 that around this moving-bed, produces.Though the various orientations in this ring zone 8 are possible, this ring zone 8 is usually located at the zone of wherein planning to introduce reductibility fuel.Shown in figure 22, moving-burden bed reactor can also comprise the mixing device that inserts moving-bed, and for example cone 9, radially to distribute ceramic composite particle and unconverted fuel mixed with this ceramic composite particle.Though Figure 22 shows and encircle regional 8 bonded cones 9, think that moving-burden bed reactor can comprise cone 8, but can not comprise the ring zone in some embodiments.Annular region 8 allows first reactor drum 1 solid and liquid fuel to be introduced the centre of the moving-bed of solid ceramic matrix material.In one embodiment, fuel can be by pneumatic introducing partial combustion in this ring zone 8 then.The fuel of not burning is fallen on the heap of the ceramic composite in this ring zone 8 and with them and is mixed for further reaction.Figure 21,22 and 23 has shown some diverse ways that form annular region 8.Figure 21 uses internal hopper to produce annular region.Figure 23 uses internal hopper and rotary valve to produce even the bigger mobile annular region with better control to ceramic composite particle.Figure 22 produces and is used for moving-bed mobile outer ring zone and uses mixing device, and for example cone 9 can be evenly distributed on the whole cross sections of moving-bed with axial dispersion solid so that unconverted fuel.
In first reactor drum 1, after the reduction, will be transported to second reactor drum 2 with the experience oxidizing reaction through the reductive metal or through the reductive metal oxide particle then.Can have second reactor drum 2 with first reactor drum, 1 same reactor type or differential responses device type be set to this through the reductive metal or through the oxidation of reductive MOX to produce metal oxide intermediate.This paper employed " metal oxide intermediate " is meant the oxidation state that has than through reductive metal or burning object height, and the MOX of the oxidation state lower than the MOX of ceramic composite.For example, and not as restriction, the possible oxidizing reaction of following equation demonstration:
3Fe+4H
2O-＞Fe
3O
4+4H
2
3Fe+4CO
2-＞Fe
3O
4+4CO
At this to use Fe
2O
3Ceramic composite as MOX is in the instance of center, and the oxidation in using second reactor drum of steam comprises the gained mixture of metal oxide intermediate with generation, and this midbody mainly comprises Fe
3O
4Fe
2O
3Also possibly exist with FeO.In addition, though H
2O, particularly steam are the oxygenants in this instance, but also consider many other oxygenants, for example, and CO, O
2, air and other compsn well known to those of ordinary skill in the art.
With reference to the solid fuel conversion embodiment of Fig. 1, this system comprises two moving-burden bed reactors 1 and 2.First reactor drum 1 that limits moving-bed is operated as follows: let solid (Fe
2O
3And coal) move down by intensive fill pattern, simultaneously gas for example, H
2, steam, CO, CO
2Or its combination moves up.This movement definition of solid and gas is the counter current contact pattern.Introducing contains Fe from the top via gravity raw material machine
2O
3Ceramic composite particle, simultaneously introduce solid fuel, for example coal in the low zone, raw material position of the ratio ceramic composite particle of first reactor drum 1.Usually, reactor drum is operated down at about 1200 ℃ temperature of about 400-and about 1-about 150 atmospheric pressure; Yet, those skilled in the art will also recognize that the temperature and pressure beyond these scopes possibly be desirable, this depends on the assembly of reaction mechanism and reaction machine mechanism.In the embodiment of Fig. 1, the coal that will grind formation through the pneumatic transport of adopting oxygen or carbonic acid gas or steam is introduced.After coal being transported to first reactor drum 1, coal is with devolatilization and form charcoal.All right and the Fe of this volatile matter
2O
3Reaction forms CO
2And water.The exit gas compsn of first reactor drum 1 can mainly comprise CO
2And steam.Subsequently, can be with CO
2Supply with condensing surface 4 with separate vapour and CO with steam
2The CO that after water condensation, obtains
2Will be purer and can be isolated under the ocean or in the geological formations or improve oil recovery, and be not discharged in the atmosphere and cause the greenhouse of the earth to warm.
The charcoal that forms during the coal devolatilization reacts when its in first reactor drum 1, flow downward red stone of Shi Zehui and partial reduction.In order to improve and the reaction of the charcoal of red stone, introduce small quantity of hydrogen in the moving-bed bottom to cause as its formation H during with the red stone reaction of partial reduction
2O.The H that produces
2O will react with the charcoal that flows downward, and cause it to be gasificated into H
2And CO.The hydrogen that forms will be somebody's turn to do through the reductive red stone with further reduction with the red stone reaction of this partial reduction then, thereby improve charcoal-red stone speed of reaction.The hydrogen of introducing at reactor bottom will guarantee that also ferric oxide particles major part when they leave first reactor drum 1 is reduced into Fe.Under some situation, have a mind to let some carbon in the particle keep unconverted in second reactor drum, to use steam to produce CO.At some under other the situation, can be with the excessive Fe that contains
2O
3Ceramic composite particle insert in first reactor drum 1 to improve speed of reaction.
Can contain the Fe particle through reductive and introduce second reactor drum 1 what leave then.As such in first reactor drum 1, second reactor drum 2 can also comprise the moving-bed with gas and solid counter current contact pattern.Steam this reactor bottom introduce and when the particle that contains reductive Fe moves down in second reactor drum, 2 inside it with this particulate oxidation.In this embodiment, the product of formation is a hydrogen, and it is discharged from the top of second reactor drum 2 subsequently.To show in other embodiment that except hydrogen for example CO and synthetic gas also are possible to product.Though Fe
2O
3It is possible being formed in second reactor drum 2, but the solid product of this reactor drum estimates it mainly is metal oxide intermediate Fe
3O
4The Fe that produces in second reactor drum 2
2O
3Amount depend on employed oxygenant, and the amount of supplying with the oxygenant of second reactor drum 2.The vapor condensation that exists in then can the hydrogen gas product with reactor drum 2 is to provide rich hydrogen materials flow.Can above-mentioned first reactor drum 1 be got back at least a portion recycling of this rich hydrogen materials flow.Except using the type of reactor identical with first reactor drum 1, second reactor drum 2 can be similarly the about 1200 ℃ temperature of about 400-with approximately operate under the 1-about 150 atmospheric pressure.
In order to make the MOX regeneration of ceramic composite, this system is used the 3rd reactor drum 3, and it is set to metal oxide intermediate is oxidized to the MOX of this matrix material.With reference to embodiment Fig. 1, the 3rd reactor drum 3 can comprise and is used for the inflation line or the pipe of oxidized metal oxide intermediate.With reference to Fig. 5 embodiment, the oxidation of metal oxide intermediate can be carried out in HRU 3.Following equation has been listed a kind of possible oxidation mechanism in the 3rd reactor drum 3:
2Fe
3O
4+0.5O
2-＞3Fe
2O
3
With reference to the embodiment of Fig. 1, Fe
3O
4Product can be oxidized to Fe in Solid Conveying and Melting system 6
2O
3For solid transportation, can use different mechanisms.Fig. 1 shows and uses through the air operated pneumatic conveyor as transport system.Also can use band conveyer, chapelet, conveyer-screw, moving-bed and fluidized-bed reactor to transport solid.Gained consumed surplus airflow and particle separation and reclaim its high-grade-heat content be used to produce steam.After regeneration, ceramic composite particle is not degenerated and is kept complete particle functionality and activity.In another embodiment, particle can experience many reprocessing cycle, for example, 10 or more times reprocessing cycle, even greater than 100 reprocessing cycle, it is functional and can not lose.This system can be used the existing system that relates to minimal design change, thereby makes economical.
The iron particle that leaves first reactor drum 1 can also comprise ash content and other unwanted by product.If do not remove at first reactor drum 1 or after 2 stages of second reactor drum and to deash, then this ash content possibly keep gathering in system.Be used for being familiar with for those of ordinary skills except that the many devices and the mechanism of ash content.For example, can deash with respect to removing in any stream of solids of size from system of ferric oxide particles based on ash content.If will grind coal as fuel source, then it will produce thin ash particles, and general size is less than 100 μ m.The size of ceramic composite particle can change based on the redox reaction that employed metal component and ceramic composite are used for.In one embodiment, particle comprises the size of the about 50mm of about 0.5-.As a result, simple screening, for example, the simple screening under the high temperature can reach removing of ash content.Size and density variation in the simple screening use sepn process between needs and the unwanted solid particulate.Other method, for example mechanical process and can be used to separate ash and unwanted material based on the method for weight or magnetic.Tripping device, for example cyclonic separator is with further discussing in the latter embodiments.
Heat integration and recovery of heat in system and all system components are highly desirable.It is the steam demand generation steam of second reactor drum 2 that heat integration in the system concentrates on especially.This steam can easily use hydrogen, the CO that leaves reactor drum 1,2,3 respectively
2With obtainable senior thermogenesis in the surplus airflow of consumption.In above-mentioned technology, also hope to produce pure oxygen.In order to produce this pure oxygen, can use at least a portion of this hydrogen.
The residence time in each reactor drum is depended on the size and the composition of each ceramic composite particle, as those of ordinary skills are familiar with.For example, the residence time that comprises the reactor drum of Fe Base Metal oxide compound can be about 20 hours of about 0.1-.
As stated, except ash content, can also there be other unwanted element.Trace elements such as Hg, As, Se are not expected at the following and Fe of high temperature of this technology
2O
3Reaction.As a result, their expections are present in the CO that is produced
2In the materials flow.If CO
2Plan then must from this materials flow, remove these trace elementss as commodity.Various refining plants, for example mercury is removed device and is considered at this.If let this CO
2Materials flow is put in the atmosphere, and needs are taked similar selection, and this depends on the rules and regulations that existed at that time.If CO is isolated in decision
2So that long-term good storage for example is isolated in the dark geological formations, then can remove these unwanted elements.In addition, can isolate CO via the mineral substance chelating
2, this possibly more cater to the need than geological storage, because safer and more easy to control.In addition, isolate CO
2Have global CO
2Credit trading has economic interests, and this possibly be highly gainful.
In addition, sulphur can constitute another kind of unwanted element, in this system, must it be considered.In the solid fuel conversion embodiment, be present in sulphur expection and Fe in the coal
2O
3Reaction also forms FeS.It will with reactor drum 2 in steam reaction after as H
2S discharges and will pollute hydrogen stream.During water of condensation from this steam, this H
2The major part of S is got off condensation.Remaining H
2S can use routine techniques such as amine gas washing or use the high temperature of Zn, Fe or Cu base adsorbent to remove.The another kind of method of removing desulfuration will comprise the introducing sorbent material, for example, and CaO, MgO etc.In addition, shown in the embodiment of Fig. 6, can sorbent material be introduced first reactor drum 1 to remove desulfuration and to prevent it and the Fe association.Can use ash separation device from system, to remove sorbent material.
Though the embodiment of system of the present invention relates to generation hydrogen, it possibly be desirable further handling to produce ultra-high purity hydrogen.As those of ordinary skills were familiar with, some carbon or derivatives thereofs possibly change 2 and pollute hydrogen stream over to from reactor drum 1.Depend on desired hydrogen purity, it possibly be necessary to reach ultra-high purity that hydrogen is used transformation absorption (PSA) device.In the solid fuel conversion embodiment, the tail gas of PSA device possibly have the value that acts as a fuel and can be recycled in first reactor drum 1 with coal, produces efficient with the hydrogen in the improved system.
With reference to Fig. 2, the hydrogen that produces in second reactor drum 2 can provide additional benefit for system.For example, hydrogen can be supplied with the power generation part 10 that is set to produced by the hydrogen gas product of second reactor drum 2 electricity.As those of ordinary skills were familiar with, power generation part 10 can comprise air 12, gas-turbine 14, steam turbine, generator 16, fuel cell etc.In another embodiment, can be with unconverted H
2Be recycled to the region intermediate of reactor drum 2 from fuel cell, this helps to improve fuel cell efficiency and reduces fuel cell size simultaneously.Thereby, improve the efficient of whole system.
With reference to Fig. 3, the another kind of coal converting system similar with Fig. 1 is provided.With this CO
2A part of recycling return carrier gas as coal injection.Two reactor drums are 400-1200 ℃ of operation and through from the rare gas element of air separation plant N for example down
2The reductive metallic particles is transported to second reactor drum 2.The hydrogen that produces in second reactor drum 2 also can be used to transport the reductive metal oxide particle.From this nitrogen, isolate this reductive metal and import second reactor drum 2 to produce H with steam reaction
2The H that produces
2Possibly comprise H owing to the sulphur in the coal
2S, and possibly be attached to this particle and form MeS.As shown in, can use conventional sulphur washing and brushing device 22 to remove H
2S also produces pure H
2Oxidation particle from 2 outlets of second reactor drum will pass through the ash separation system of using filter screen.In this embodiment; Because wearing and tearing, most of ash content and metal oxide particle isolated be used for regenerating, will use feeding device simultaneously; For example; Pneumatic conveyor sends back to remaining metal oxide particle in the inlet of first reactor drum 1 through air, there, also possibly supply with additional ceramic composite.The employed additional ceramic composite particle of this paper is meant fresh granules, and they are used for substituting particulate or the ceramic composite particle that becomes too small or invalid owing to wearing and tearing and passivation.Typical additional ceramic composite rate will be less than 2% of particle flow speed in the system.
With reference to Fig. 4, different Solid Conveying and Melting systems, and different ash separation device can be used for coal direct reaction body system.At this, use chapelet at N
2In the environment reductive metallic particles is transferred to second reactor drum 2.After in second reactor drum 2, being oxidized to metal oxide intermediate, consequently this particle is oxidized when arriving cyclonic separator to use the pneumatic conveyor that adopts air that this metal oxide intermediate is delivered to cyclonic separator 3.Can adopt cyclonic separator that particle separation is gone out simultaneously and import first reactor drum owing to the particulate and the coal ash of wearing and tearing are removed with air with additional metal oxide particle.Additional speed is equally less than 2% of particle flow speed in the system.Other device also can be used for ash separation like gradation device or common known other device of those of ordinary skills.
With reference to Fig. 5 embodiment, using the 3rd reactor drum 3 be the fluidized-bed form to reclaim the particle that heat leaves second reactor drum with further oxidation is metal oxide intermediate, for example Fe
3O
4In other embodiment and accompanying drawing, this reactor drum is shown as from the wherein introducing air of second reactor drum, 2 to first reactor drums 1 or the supply line of oxygen.It will be reactant transport device, fast fluidized bed, fluidized-bed, lifter or transported pneumatically system.At this, with metal oxide intermediate Fe for example
3O
4Inject HRU 3 from the outlet of second reactor drum 2, there, introduce oxygen or air this particle is oxidized to again their highest oxidation state, the i.e. MOX of ceramic composite, for example Fe
2O
3Except oxidation conversion, also produce heat in this course, and the particulate temperature possibly increase hastily also.Can the particle with remarkable higher temperature be introduced first reactor drum 2 again and be kept at the heat that the heat in this particle will provide reduction reaction to need at least in part.For particle with high heat capacity, in an exemplary, use have high thermal conductivity carrier for example SiC possibly be desirable.
Shown in the embodiment of Fig. 6, can be with sorbent material, for example modified calcium carbonate or quicklime or calcium hydroxide inject first reactor drum 1 to remove desulfuration from coal.CaCO
3Injection rate will be about 1%-about 15% of metal oxide flow rate in this system; Yet this injection rate changes according to the composition of employed coal.Natural manganese dioxide also can be used as sorbent material.Generally, the size of absorbent particles is less than ceramic composite particle, and in the certain exemplary embodiment, can have the particle size of the about 1mm of about 100 μ m-, and this depends on the size of ceramic composite particle in the system.Spent sorbents (after sulphur is captured) will be isolated and regenerate then so that be further used for first reactor drum 1 with ash content.In this embodiment, can under the situation that does not need washer, produce pure H
2
With reference to Fig. 7-9, the system implementation scheme of reformed gas fuel is provided generally.As shown in Figure 9, can be with the CO that in first reactor drum 1, produces
2A part separately and with steam introduce second reactor drum 2.Through control steam and CO
2Feed rate, can obtain to have different H
2Synthetic gas with the CO ratio.Can this synthetic gas being introduced gas-turbine, can be used for chemical/liquid fuel with generating or it synthetic.Be used for synthetic about 2: 1 H that has of fischer-tropsch in order to produce with the generation liquid fuel
2The synthetic gas of/CO ratio, typical steam and CO
2The feed rate ratio should be about 2: 1.To more detail below and discuss and the synthetic bonded system of the present invention of fischer-tropsch.Can also change H through the interlude that will a part of output after water condensation be recycled to second reactor drum 2
2The output ratio of/CO.This will allow more water gas shift reactions with unconverted CO
2Change into CO.
Shown in Fig. 9 embodiment that synthetic gas transforms, in second reactor drum 2, make reductive metallic particles and air combustion.The heat that can use the water extraction generation is to produce high-temperature steam.Steam can be used for generating then or it can be used for from resinous shale extraction heavy oil.In the embodiment of Figure 10, system must be considered the following fact: the H in the crude synthesis gas
2S will form metallic sulfide with metal reaction.Maybe with reductive metal and metallic sulfide introduce second reactor drum 2 with steam reaction.Product materials flow in this system possibly comprise H
2And H
2S.Can use conventional washer technology to extract H out
2S and possibly obtain rich H
2Materials flow.Through using gas fuel, for example synthetic gas replaces solid fuel, can avoid ash separation process.
With reference to Figure 11 embodiment, the use sorbent material for example hot gas desulfurizer of CaO is used for a large amount of H in the crude synthesis gas
2S removes and goes to less than 100ppm.Then should pretreated synthetic gas and steam and appropriate amount (usually＜15%) CO
2The bottom of mixing and introducing first reactor drum 1.Because H
2S and steam/CO
2Between balance, H
2S and Hg can not react with the particle in first reactor drum 1.As a result, pollutent will with CO
2Come out also can be isolated together from first reactor drum 1 together.Only also therefore pure metal particles will get into second reactor drum 2, rich H
2Materials flow can produce not using low temperature sulphur and mercury to remove under the situation of device.Ceramic composite particle (it is no longer valid in the technology of first and second reactor drums) the replaced C aO that in addition, can use activity with degeneration or size is to remove H
2S, for example, to level less than 30ppm.
With reference to Figure 13, can the chemical cycle system as steam iron generator be connected with fischer-tropsch (F-T) synthetic system generally, to produce chemical substance or liquid fuel.The synthetic gas that derives from modern gasifier can not provide the enough H that satisfy the synthetic needs of F-T usually
2Concentration (H
2/ CO=2: 1).The raw material of first reactor drum 1 is the part of the by product and the unconverted synthetic gas of F-T reactor drum 100.In another embodiment, this raw material can comprise the product of a part from the refining system.The rest part of this by product and unconverted synthetic gas is recycled to F-T reactor drum 100 with the raising transformation efficiency, or, also can it be recycled to gasifier to make more synthetic gas.In addition, can be simultaneously obtain the steam of second reactor drum, because normally height heat release of F-T reaction from gasifier and F-T reactor drum 100.The H of second reactor drum 1 that can comprise number of C O and produce by the chemical cycle reactor drum
2The product recycled back is to regulate the H of F-T raw material
2/ CO compared about 2: 1.In some embodiments, can, the cleaning synthetic gas carry out this adjusting after leaving gasifier 30 and be transported to gas-cleaning installation 22.In this case, use stoichiometric by product and unconverted synthetic gas to be used for the H of gas regulation with generation
2, this ratio of being about to is adjusted to about 2: 1, simultaneously remaining air-flow recycling is got back in the F-T reactor drum 100.Through with C
1-C
4By product and unconverted synthetic gas change into the H of the raw material that is F-T reactor drum 100
2, improved system efficient and selectivity of product widely.The working pressure of chemical cycle system will with the F-T resemble process, for example, in be pressed into about 20 normal atmosphere.
The embodiment of describing among Figure 12 and 14 embodiment and Figure 13 is similar; One of them main difference is that all by products all are used for producing H
2The H of excessive amount
2Can be used for wax product hydrogen cracking with F-T reactor drum 100.If after hydrogen cracking, still remain excessive H
2, then generally can use gas turbine or fuel cell to come to be factory application or energy market generating.
In the F-T of Figure 15 embodiment, before first reactor drum 1, use hot gas purification and remaining pollutent to come out and can not be attached on the particle from first reactor drum 1.At this, will be from a part of CO of first reactor drum, 1 generation
2Introduce product refining plant or CO
2Tripping device is to extract pure basically CO from the discharge air-flow of first reactor drum 1
2Then that this is pure basically CO
2Introducing is introduced second reactor drum 2 to form H with steam
2/ CO ratio is about 2: 1 cleaning synthetic gas.Then this synthetic gas is used for F-T reactor drum 100 to produce liquid fuel or chemical substance.Also the synthetic gas productivity of first reactor drum with further raising chemical cycle system is got back in the by-product stream recycling of F-T reactor drum 100.With reference to Figure 16, can the F-T system be combined with coal converting system rather than synthetic gas.In this embodiment, can sorbent material be infeeded this system to extract sulphur out.Can also F-T synthetic by product be infeeded first reactor drum 1 to make more synthetic gas.In this solid fuel conversion embodiment, do not need gasifier; Therefore, system can comprise still less equipment, thereby reduces cost and invest improved system efficient simultaneously.
In all F-T embodiments, can through from the high-temperature steam of chemical cycle system of the present invention or gasifier with a part of steam superheated that produces in the F-T reactor drum.This superheated vapour can comprise various uses, for example, drives the raw material that steam turbine is used for parasitic energy or is used as reactor drum 2.
In the embodiment of Figure 17, the additional purpose of system of the present invention is provided.In this embodiment, with metal oxide particle Fe for example
2O
3Be processed into the vehicle-mounted H in the vehicle 230
2The module of storer or packed bed in the cylindrical shell or material all in one piece.At this, in central equipment 210 with the processing of this module with use carbonaceous fuel for example synthetic gas it is reduced into its metallic forms.Then this reductive module is distributed to fuel station 200 and be installed in the automobile 230 to substitute useless module.Steam will obtain and will be introduced into the model to react to produce H with the reductive particle from PEM fuel cell or hydrogen internal combustion engine
2Drive automobile.The representative temperature of reaction will be approximately 250-700 ℃, because reaction is heat release.Can keep the temperature in the module through the isolator or the recovery of heat in other zone of system of good design.This module will be made up of each different shells and each shell can be that packed bed or it of pellet can be a material all in one piece.In an exemplary, material all in one piece can have the small channel of diameter 0.5-10mm, and the thickness of while by the wall that particle is processed keeps less than 10mm.Figure 18 (a)-(c) and Figure 18 show module, promptly have some instances of the reactor drum that contains the Fe medium, and said medium has the packed bed of (a) small pellets; (b) has the integral bed of the straight line raceway groove that is used for steam; (c) has the integral bed of the raceway groove that is used for steam and air.
Figure 18 c and Figure 18 b show air will flow through some raceway grooves simultaneously vapour streams cross remaining raceway groove.Through this flow arrangement, the raceway groove of air process is used for the heat of adjacent channel with generation, thereby keeps them to be in the temperature (250-700 ℃) for hydrogen manufacturing needs.Figure 19 shows a kind of possible configuration of the shell design of using shown in Figure 18 (c).At this, with different outer cover packagings in module and be connected to each other and be used for the fuel cell of automobile 230 or the H of oil engine constantly to produce
2Can use special monolith design and connectivity scenario strictly that air and steam raceway groove is separated from one another.
With reference to Figure 20, system of the present invention can also be used for fuel cell technology.In this exemplary of Figure 20, directly the reductive metallic particles is infeeded and directly to process solid-fuelled SOFC.In fact, this SOFC serves as second reactor drum 2 in the redox system.Particle is reduced in this fuel reaction device and is introduced into fuel cell then to react and generation down at 500-1000 ℃ with oxygen or air.The particle recycling of oxidation is got back to the fuel reaction device with reduction once more.Because the applicability of system of the present invention, think that the present invention can introduce many other commercial runs.
Be noted that term like " preferably ", " generally ", " generally " with " " be not used for limiting scope of invention required for protection or hint that some characteristic is crucial, main and even is important the structure or the function of invention required for protection at this usually.On the contrary, the outstanding alternative or additional characteristic that can be used for maybe can being not used in particular of the present invention only planned to be used in these terms.
From describing and limiting the object of the invention, should be noted that term " basically " is used for representing at this can be owing to the intrinsic uncertainty of any quantitative comparison, numerical value, observed value or other expression.Term " basically " this also be used for representing quantificational expression can with the discrepant degree of given reference, and can not cause the variation of the basic function of in question theme.
Though at length and with reference to specific embodiments of the present invention described the present invention, it is possible obviously under the situation of the scope of the invention that does not break away from the appended claims qualification, revising and change.More particularly, though that aspects more of the present invention are thought at this is preferred or especially favourable, think that the present invention not necessarily is limited to these preferred aspects of the present invention.
Claims (15)
1. the preparation method of ceramic composite particle may further comprise the steps:
Make the reaction of MOX and solid support material;
The mixture of heat-treated metal oxide compound and solid support material is to produce ceramic composite powder under 200-1500 ℃ temperature;
This ceramic composite powder is changed into ceramic composite particle;
Before in reactor drum, using this ceramic composite particle is reduced and oxidation.
2. according to the method for claim 1, also comprise promoter material is added in the mixture of MOX and solid support material.
3. according to the process of claim 1 wherein that thermal treatment can be at rare gas element, steam, oxygen, air, H
2And its combination existence is carried out under the pressure between vacuum pressure and 10 normal atmosphere down.
4. according to the method for claim 1, comprise that also mixture chemical treatment with MOX and promotor is to activate ceramic composite powder.
Based on the process of claim 1 wherein reactions step via spray-drying, directly mix, dipping or its combination are carried out altogether.
According to the process of claim 1 wherein via extrude, granulation, peptization and its combination carry out the conversion of ceramic composite powder.
7. pass through the particle of the method preparation of claim 1.
8. according to the particle of claim 7, wherein this MOX comprises the metal that is selected from Fe, Cu, Ni, Sn, Co, Mn and its combination.
9. according to the particle of claim 7, wherein this ceramic composite comprises this MOX of 40wt% at least.
10. according to the particle of claim 7, wherein this solid support material comprises at least a SiC of being selected from, the oxide compound of Al, Zr, Ti, Y, Si, La, Sr, Ba and the component of its combination.
11. according to the particle of claim 7, wherein ceramic composite comprises 5wt% solid support material at least.
12. particle according to claim 7; Wherein this particle comprises the promotor that contains pure metal, MOX, metallic sulfide or its combination, and wherein this metal comprises that one or more are selected from the element of Fe, Ni, Sn, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, B, P, V, Cr, Mn, Co, Cu, Zn, Ga, Mo, Rh, Pt, Pd, Ag and Ru.
13. according to the particle of claim 12, wherein ceramic composite comprises 40wt% promoter material at the most.
14. according to the process of claim 1 wherein that this ceramic composite particle is pellet, material all in one piece, block or its array configuration.
15. according to the process of claim 1 wherein this particle can operate be used for 10 or more times reprocessing cycle after keep active.
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| TWI601813B (en) * | 2013-03-15 | 2017-10-11 | 拜布克 威科斯公司 | Chemical looping processes for partial oxidation of carbonaceous fuels |
| CN108085783A (en) * | 2017-12-27 | 2018-05-29 | 江西嘉捷信达新材料科技有限公司 | High tenacity carborundum and preparation method thereof |
| CN114787101A (en) * | 2019-12-13 | 2022-07-22 | 奥卢大学 | Electroceramic composite material and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI601813B (en) * | 2013-03-15 | 2017-10-11 | 拜布克 威科斯公司 | Chemical looping processes for partial oxidation of carbonaceous fuels |
| CN108085783A (en) * | 2017-12-27 | 2018-05-29 | 江西嘉捷信达新材料科技有限公司 | High tenacity carborundum and preparation method thereof |
| CN114787101A (en) * | 2019-12-13 | 2022-07-22 | 奥卢大学 | Electroceramic composite material and manufacturing method thereof |
| CN114787101B (en) * | 2019-12-13 | 2024-04-09 | 奥卢大学 | Electroceramic composite and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007082089A3 (en) | 2008-03-13 |
| CA2881661A1 (en) | 2007-07-19 |
| US20140144082A1 (en) | 2014-05-29 |
| WO2007082089A2 (en) | 2007-07-19 |
| EP1973992A2 (en) | 2008-10-01 |
| EP1973992A4 (en) | 2012-04-04 |
| CN104694169A (en) | 2015-06-10 |
| US20090000194A1 (en) | 2009-01-01 |
| CA2636325A1 (en) | 2007-07-19 |
| CA2636325C (en) | 2015-04-28 |
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