CN104694169A - Systems and methods of converting fuel - Google Patents

Systems and methods of converting fuel Download PDF

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Publication number
CN104694169A
CN104694169A CN201510090781.2A CN201510090781A CN104694169A CN 104694169 A CN104694169 A CN 104694169A CN 201510090781 A CN201510090781 A CN 201510090781A CN 104694169 A CN104694169 A CN 104694169A
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China
Prior art keywords
reactor
metal oxide
fuel
ceramic composite
systems according
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范良士
P·古普塔
L·G·贝拉斯克斯巴尔加斯
李凡星
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Ohio State University
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Ohio State University
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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
    • 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
    • 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
    • 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
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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 system and way of converting fuel
The application is the applying date is on January 12nd, 2007, and application number is 200780006757.X, and denomination of invention is the divisional application of the application for a patent for invention of " system and way of converting fuel ".
The present invention relates generally to the system and way of converting fuel, and relates generally to the oxidation-reduction reactor system for converting fuel.
Need clean and effective energy generation systems always.Most of business methods of generate energy carrier such as steam, hydrogen, synthetic gas, liquid fuel and/or electricity are based on fossil oil.In addition, estimate still can continue in foreseeable future to the dependency of fossil oil, this is due to cost much lower compared with renewable source.Current, the conversion of carbonaceous fuel such as coal, Sweet natural gas, refinery coke is generally carried out via burning or reforming process.But the burning of carbonaceous fuel, particularly coal is carbon intensive process, and it is to environmental emission great amount of carbon dioxide.In this process because the complex contents thing in coal also produces sulphur and nitrogen compound.
On the other hand, the chemical reaction between metal oxide and carbonaceous fuel can provide the better mode reclaiming the energy be stored in fuel.Certain methods based on the reaction of metal oxide particle and carbonaceous fuel to produce useful energy carrier.Such as, the U.S. Patent number 5,447,024 of the people such as Ishida describes the method wherein using nickel oxide particle via chemical looping process, conversion of natural gas to be become heat, and this heat may be used for turbine.But the recirculation of pure metal oxides is difference and forms its obstacle used in commercial and industrial process.In addition, this technology has limited applicability, because it only can Reforming Natural gas, this Sweet natural gas is more expensive than other fossil oil.The technique that another kind is known is steam-iron process, wherein makes the derivative producer gas of coal and ferric oxide particles react to produce hydrogen with steam regeneration after a while in a fluidized bed reactor.But this technique runs into poor gas conversions problem due to the inappropriate contact between reaction solid and gas, and can not produce rich hydrogen stream.
Increasing along with to the requirement of more clean and more effective converting fuel system, creating the system to improving, and the needs of system components wherein, they will converting fuel, simultaneously decreasing pollution thing effectively.
In one embodiment of the invention, the system of converting fuel is provided.This system comprises the first reactor comprising many ceramic composite particles, and wherein this ceramic composite particle comprises at least one and is arranged in metal oxide on carrier.This first reactor is set to fuel reduction at least one metal oxide with the metal oxide of the metal or reduction that produce reduction.This system also comprises the second reactor and the 3rd reactor, this second reactor is set to be oxidized the metal of this reduction or the metal oxide of reduction to produce metal oxide intermediate, and the 3rd reactor is placed through this metal oxide intermediate of oxidation makes at least one metal oxide regenerate.
In another embodiment of the invention, provide the method converting the fuel into hydrogen, CO or synthetic gas.The method comprises the following steps: in the reduction reaction between fuel and metal oxide, metal oxide back is become the metal of reduction or the metal oxide of reduction; With oxygenant, the metal of this reduction or the metal oxide of reduction are become metal oxide intermediate, also produce hydrogen, CO or synthetic gas simultaneously; With by this metal oxide intermediate being oxidized, this at least one metal oxide is regenerated.
In still another embodiment, the system comprising fischer-tropsch reactor is provided.This fischer-tropsch reactor is set to produce hydrocarbon fuel by the raw mixture of air inclusion fuel.This system also comprises the first reactor comprising many ceramic composite particles, and wherein this ceramic composite particle comprises at least one and is arranged in metal oxide on carrier.This first reactor is set to, with geseous fuel, metal oxide back is become the metal of reduction or the metal oxide of reduction, and wherein this geseous fuel comprises the hydrocarbon fuel produced by fischer-tropsch reactor at least in part.This system also comprises the second reactor, and it to be set to the metal of this reduction or the metal oxide of reduction with steam to produce metal oxide intermediate.
In another embodiment, the preparation method of ceramic composite particle is provided.The method comprises: metal oxide and solid support material are reacted; At the temperature of about 1500 DEG C of about 200-, the mixture of heat-treated metal oxide compound and solid support material is to produce ceramic composite powder; This ceramic composite powder is changed into ceramic composite particle; By the reduction of this ceramic composite particle and oxidation before using in the reactor.
Consider that following detailed description in detail will understand the feature and advantage that are provided by embodiment of the present invention more completely.
When reading together in conjunction with the following drawings, can understand the following detailed description of illustrative embodiment of the present invention best, in the accompanying drawings, the same Ref. No. of same structure represents, and in accompanying drawing:
Fig. 1 is the schematic diagram being produced the system of hydrogen by coal according to one or more embodiments of the present invention;
Fig. 2 is the schematic diagram being produced the another kind of system of hydrogen by coal according to one or more embodiments of the present invention;
Fig. 3 is the direct chemical cycle of use according to one or more embodiments of the present invention and ash separation sieve are produced the another kind of system of hydrogen schematic diagram by coal;
Fig. 4 is the direct chemical cycle of use according to one or more embodiments of the present invention and ash separation cyclonic separator are produced the another kind of system of hydrogen schematic diagram by coal;
Fig. 5 is the schematic diagram being produced the another kind of system of hydrogen by coal according to one or more embodiments of the present invention, and wherein this system uses the 3rd reactor being used for recovery of heat;
Fig. 6 is the schematic diagram being produced the another kind of system of hydrogen by coal according to one or more embodiments of the present invention, and wherein this system uses sorbent material in for the first reactor of desulfurization;
Fig. 7 is the schematic diagram being produced the system of hydrogen by synthetic gas according to one or more embodiments of the present invention;
Fig. 8 is the schematic diagram being produced the another kind of system of hydrogen by coal according to one or more embodiments of the present invention, wherein the second reactor is got back in the carbonic acid gas recirculation produced in the first reactor;
Fig. 9 is the schematic diagram being produced the another kind of system of steam by coal according to one or more embodiments of the present invention;
Figure 10 is the schematic diagram being produced another system of hydrogen by synthetic gas according to one or more embodiments of the present invention;
Figure 11 is the schematic diagram being produced the another kind of system of hydrogen by synthetic gas according to one or more embodiments of the present invention, and wherein this system comprises pollutant catabolic gene assembly;
Figure 12 is the schematic diagram that chemical cycle according to one or more embodiments of the present invention and fischer-tropsch (F-T) synthesize the system combined;
Figure 13 is the schematic diagram of the another kind of system that chemical cycle is according to one or more embodiments of the present invention combined with Fiscber-Tropscb synthesis;
Figure 14 is the schematic diagram of the another kind of system that chemical cycle is according to one or more embodiments of the present invention combined with Fiscber-Tropscb synthesis;
Figure 15 is the schematic diagram of another system that chemical cycle is according to one or more embodiments of the present invention combined with Fiscber-Tropscb synthesis, and wherein this system comprises pollutant catabolic gene assembly;
Figure 16 is the schematic diagram of the another kind of system that chemical cycle is according to one or more embodiments of the present invention combined with Fiscber-Tropscb synthesis, and wherein this system operates when not using gasifier;
Figure 17 is the vehicle-mounted H on vehicle according to one or more embodiments of the present invention 2the schematic diagram of the chemical looping system of storer;
Figure 18 (a) is the vehicle-mounted H for Figure 17 according to one or more embodiments of the present invention 2the schematic diagram of the reactor box of storage system, wherein this reactor box comprises the packed bed containing Fe medium and small pellets;
Figure 18 (b) is the vehicle-mounted H for Figure 17 according to one or more embodiments of the present invention 2the schematic diagram of the another kind of reactor box of storage system, wherein this reactor box comprises containing Fe medium and the integral bed with steam flow straight trough;
Figure 18 (c) is the vehicle-mounted H for Figure 17 according to one or more embodiments of the present invention 2the schematic diagram of another reactor module of storage system, wherein this reactor box comprises containing Fe medium and the integral bed with steam and air flow groove;
Figure 19 is the vehicle-mounted H for Figure 17 according to one or more embodiments of the present invention 2the schematic diagram of the reactor box of storage system, wherein this reactor box uses the heat that a series of integral bed reactor with air sparging is formed to be provided for steam;
Figure 20 is the schematic diagram of the system that chemical cycle is according to one or more embodiments of the present invention combined with Solid Oxide Fuel Cell;
Figure 21 is the schematic diagram of the reactor for system of the present invention according to one or more embodiments of the present invention, and wherein this reactor is moving-burden bed reactor, and it comprises the annular region be arranged near fuel feed position;
Figure 22 is the schematic diagram of the reactor for system of the present invention according to one or more embodiments of the present invention, and wherein this reactor is moving-bed, and it comprises annular region and inserts the cone in this moving-bed; With
Figure 23 is the schematic diagram of another reactor for system of the present invention according to one or more embodiments of the present invention, and wherein this reactor is moving-burden bed reactor, and it comprises annular region.
Generally with reference to Fig. 1, the present invention relates to the system and way of the redox reaction converting fuel by ceramic composite particle.As shown in Figure 1, this system comprises two main reactors, and additional reactor and assembly, will describe them in detail below.The first reactor 1 being set to carry out reduction reaction comprises many ceramic composite particles, and this ceramic composite particle has at least one and is arranged in metal oxide on carrier.As would be familiar to one of ordinary skill in the art, can via any suitable solids delivery device/mechanism by ceramic composite particle supplied reactor.These solids delivery device may include but not limited to, pneumatics, transfer roller, lock hopper etc.Ceramic composite particle is described in the U.S. Published Application No 2005/0175533A1 of the people such as Thomas, and the document is for reference in this overall introducing.Except particle disclosed in Thomas and particles synthesizing method, in another embodiment, the applicant has developed the alternative approach manufacturing ceramic composite, and the method can improve usefulness and the activity of the ceramic composite particle in system of the present invention.Two kinds in these alternative approach is co-precipitation and spraying dry.
3rd alternative approach comprises the step by metal oxide and ceramic carrier material physical mixed.Optionally, promoter material can be added in the mixture of metal oxide and solid support material.After blending, at the temperature of about 1500 DEG C of about 200-this mixture of thermal treatment to produce ceramic composite powder.Thermal treatment can at rare gas element, steam, oxygen, air, H 2and its combination exist under carry out under pressure between vacuum pressure and about 10 normal atmosphere.The method can also comprise chemical treatment step, wherein with acid, alkali or both process the mixture of metal oxide and solid support material to be activated by this ceramic composite powder.After powder production, by method known to persons of ordinary skill in the art, this ceramic composite powder can be changed into ceramic composite particle.These methods can include, but not limited to extrude, granulation and pressure method such as granulation.Particle can comprise different shape and form, such as, and pellet, material all in one piece or block.
The step that this ceramic composite particle reduces and is oxidized before then comprising use in the reactor by the method.This circulation is important to ceramic composite particle, because this mixing process can produce have the activity of raising, the particle of strength and stability.This circulation is important activity, strength and stability to improve them to ceramic composite particle.This process also causes the porosity (0.1-50m reduced 2/ g) and changes in crystal structure, this makes particle easily to reduce and to be oxidized, and does not lose its activity for multiple such reaction cycle.Do not report porosity in Thomas patent, but claim that this particle is porous and has mesoporosity.Although the description of particle synthesis is limited to spraying dry, co-precipitation and direct blending means in the application, also can be used in the reactor of system of the present invention by other technology ceramic composite particle that such as prepared by collosol and gel, wet dipping and other method known to persons of ordinary skill in the art.
The metal oxide of ceramic composite comprises the metal being selected from Fe, Cu, Ni, Sn, Co, Mn and its combination.Although consider various composition herein, ceramic composite comprises at least 40wt% metal oxide usually.Solid support material comprises at least one and is selected from SiC, the component of the oxide compound of Al, Zr, Ti, Y, Si, La, Sr, Ba and its combination.Ceramic composite comprises at least 5wt% solid support material.In another embodiment, particle comprises promoter material.This promotor comprises pure metal, metal oxide, 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, metal oxide comprises and is supported on TiO 2on carrier, particularly comprise TiO 2and Al 2o 3mixture carrier on Fe 2o 3.In another exemplary embodiment, ceramic composite can also comprise the Fe be supported on YSZ (zirconium white of Yittria stabilization) carrier 2o 3.
Refer again to the reduction reaction of the first reactor 1, the first reactor 1 receives fuel, and this fuel is used for reducing at least one metal oxide of ceramic composite to produce metal or the metal oxide of reduction of reduction." fuel " as defined herein can comprise: solid carbonaceous composition is coal, tar, resinous shale, oil-sand, tar sand, Biological resources, wax, coke etc. such as; Liquid carbonaceous composition thing is gas and oil, oil, oil, diesel oil, aviation kerosene, ethanol etc. such as; With gaseous composition such as synthetic gas, carbon monoxide, hydrogen, methane, gaseous hydrocarbon gases (C 1-C 6), hydrocarbon vapour etc.Such as, and not conduct restriction, following equation shows possible reduction reaction:
Fe 2O 3+2CO->2Fe+2CO 2
16Fe 2O 3+3C 5H 12->32Fe+15CO 2+18H 2O
In this embodiment, the metal oxide (Fe of ceramic composite 2o 3) by fuel such as, CO reduces, and produce the metal oxide (Fe) of reduction.Although Fe is produce in the reduction reaction of the first reactor 1 main through reducing composition, FeO or other reducing metal oxide with more high oxidation state are also considered at this.
First reactor 1 and the second reactor 2 can comprise various suitable reactor to allow overall countercurrent contact between gas and solid.This can use moving-burden bed reactor, a series of fluidized-bed reactor, kiln, fixed-bed reactor, their combination, or known to persons of ordinary skill in the art other realizes.
As shown in figures 21-23, the first reactor 1 can comprise moving-burden bed reactor, and this moving-burden bed reactor has the annular region 8 produced around this moving-bed.Although the various orientations in this ring region 8 are possible, this ring region 8 is usually located at the region of wherein intending to introduce reductibility fuel.As shown in figure 22, moving-burden bed reactor can also comprise and inserts the mixing device of moving-bed, such as cone 9, radially to distribute ceramic composite particle and being mixed with this ceramic composite particle by unconverted fuel.Although Figure 22 shows the cone 9 be combined with ring region 8, think that moving-burden bed reactor can comprise cone 8, but ring region can not be comprised in some embodiments.Annular region 8 allows the first reactor 1 that solid and liquid fuel are introduced the centre of the moving-bed of solids ceramic composites.In one embodiment, fuel can be introduced pneumatically then partial combustion in this ring region 8.The heap that the ceramic composite in this ring region 8 fallen by the fuel do not burnt is mixed for further reaction with them.Figure 21,22 and 23 shows some diverse ways forming annular region 8.Figure 21 uses internal hopper to produce annular region.Figure 23 uses internal hopper and rotary valve to produce the even larger annular region flowing of ceramic composite particle to better control.Figure 22 produces the external annular region for gas solid downflow and uses mixing device, and such as cone 9 can be evenly distributed on the whole cross sections of moving-bed with axial dispersion solid so that unconverted fuel.
First reactor 1 can with being applicable to resisting the high various durable materials structures arriving the temperature of at least 1200 DEG C.The includable side of this reactor has the carbon steel of refractory masses, to make further minimum heat losses.This structure also allows the surface temperature of reactor quite low, thus improves the creep resistance of carbon steel.Also can adopt other alloy that environment is applicable to be present among various reactor, particularly when by them as when being set to the intraware helping solid flow or improve heat trnasfer in moving-bed embodiment.The interconnection of various reactor can have lock hopper design or rotation/star valve design to ensure good sealing.Other interconnection that those skilled in the art also can be used easily to determine.
After reduction in the first reactor 1, then the second reactor 2 is transported to experience oxidizing reaction by through the metal of reduction or the metal oxide particle through reducing.Can have and be set to this metal through reducing or the metal oxide through reducing with the second reactor 2 of the first reactor 1 same reactor type or different reactor type to produce metal oxide intermediate." metal oxide intermediate " used herein refers to the oxidation state had than the metal through reducing or burning object height, and the metal oxide of the oxidation state lower than the metal oxide of ceramic composite.Such as, and not conduct restriction, following equation shows possible oxidizing reaction:
3Fe+4H 2O->Fe 3O 4+4H 2
3Fe+4CO 2->Fe 3O 4+4CO
At this to use Fe 2o 3as in example centered by the ceramic composite of metal oxide, the oxidation in the second reactor using steam comprises the gained mixture of metal oxide intermediate by producing, this intermediate mainly comprises Fe 3o 4.Fe 2o 3also may exist with FeO.In addition, although H 2o, particularly steam are oxygenants in this example, but also consider other oxygenants many, such as, and CO, O 2, air and other composition 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.Limit the first reactor 1 of moving-bed to operate as follows: allow solid (Fe 2o 3and coal) move down by intensive fill pattern, gas is such as simultaneously, H 2, steam, CO, CO 2or its combination moves up.This movement definition of solid and gas is countercurrent contact mode.Introduce containing Fe from top via gravity raw material machine 2o 3ceramic composite particle, simultaneously introduce solid fuel, such as coal in the region that the feed location of the ratio ceramic composite particle of the first reactor 1 is low.Usually, reactor operates at the temperature and the about 150 atmospheric pressure of about 1-of about 1200 DEG C of about 400-; But those skilled in the art will also recognize that the temperature and pressure beyond these scopes may be desirable, this depends on the assembly of reaction mechanism and reaction machine mechanism.In the implementation of figure 1, by adopting the pneumatic transport of oxygen or carbonic acid gas or steam to be introduced by the coal grinding formation.After the coal is delivered to the first reactor 1, devolatilization is formed charcoal by coal.This volatile matter can also and Fe 2o 3reaction forms CO 2and water.The exit gas composition of the first reactor 1 mainly can comprise CO 2and steam.Subsequently, can by CO 2with steam supply condenser 4 with separate vapour and CO 2.The CO obtained after condensation of water 2will be purer and can be isolated under the ocean or in geological formations or improve oil recovery, and not to be discharged in air and to cause the greenhouse of the earth to warm.
The charcoal formed during coal devolatilization reacts when its flow downward in the first reactor 1 ferric oxide of Shi Zehui and partial reduction.Reacting with the charcoal of ferric oxide to improve, bottom moving-bed, introducing a small amount of hydrogen form H to cause when the ferric oxide of itself and partial reduction reacts 2o.The H produced 2o reacts with the charcoal flowed downward, and causes it to be gasificated into H 2and CO.Then ferric oxide with this partial reduction react to reduce this ferric oxide through reducing further by the hydrogen formed, thus raising charcoal-ferric oxide speed of reaction.Guarantee ferric oxide particles major part when they leave the first reactor 1 is also reduced into Fe by the hydrogen introduced at reactor bottom.In some cases, some carbon in particle is had a mind to allow to keep unconverted to use steam to produce CO in the second reactor.In some other cases, excessive can be contained Fe 2o 3ceramic composite particle insert in the first reactor 1 to improve speed of reaction.
Then the Fe particle that contains through reduction left can be introduced the second reactor 1.As in the first reactor 1, the second reactor 2 can also comprise the moving-bed with gas and solid countercurrent contact mode.Steam this reactor bottom introduce and when containing the particle of Fe reduced when the second reactor 2 inside moves down it by this particulate oxidation.In this embodiment, the product of formation is hydrogen, and it is discharged from the top of the second reactor 2 subsequently.To show that product such as CO and synthetic gas is also possible in addition to hydrogen in other embodiment.Although Fe 2o 3it is possible for being formed in the second reactor 2, but the solid product of this reactor estimates mainly metal oxide intermediate Fe 3o 4.The Fe produced in second reactor 2 2o 3amount depend on used oxygenant, and the amount of oxygenant of supply the second reactor 2.Then can by the vapor condensation existed in the hydrogen gas product of reactor 2 to provide rich hydrogen stream.The recirculation at least partially of this rich hydrogen stream can be got back to above-mentioned first reactor 1.Except using the type of reactor identical with the first reactor 1, the second reactor 2 can operate similarly at the temperature and the about 150 atmospheric pressure of about 1-of about 1200 DEG C of about 400-.
In order to make the metal oxide of ceramic composite regenerate, this system uses the 3rd reactor 3, and it is set to metal oxide metal oxide intermediate being oxidized to this matrix material.With reference to embodiment Fig. 1, the 3rd reactor 3 can comprise inflation line for oxidized metal oxide intermediate or pipe.With reference to Fig. 5 embodiment, the oxidation of metal oxide intermediate can be carried out in heat reclamation device 3.Following equation lists a kind of possible oxidation mechanism in the 3rd reactor 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 system 6 2o 3.For solid transportation, different mechanisms can be used.Fig. 1 shows and uses by air operated pneumatic conveyor as transport system.Also band conveyer, chapelet, conveyer-screw, moving-bed and fluidized-bed reactor can be used to carry out transport solid.The remaining airflow of gained consumption and particle separation are reclaimed its high-grade-heat content for generation of 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, and such as, 10 or more reprocessing cycle, are even greater than 100 reprocessing cycle, and can not lose that it is functional.This system can use the existing system relating to minimal design change, thus makes economy.
The iron particle leaving the first reactor 1 can also comprise ash content and other unwanted by product.If the first reactor 1 or after the second reactor 2 stage not except deashing, then this ash content may keep in system assemble.For except many devices of ash content and mechanism by those of ordinary skill in the art are familiar with.Such as, can based on ash content relative to the size of ferric oxide particles from any stream of solids system except deashing.If will grind coal to be used as fuel source, then it will produce thin ash particles, and general size is less than 100 μm.The size of ceramic composite particle can change based on the redox reaction used for used metal component and ceramic composite.In one embodiment, particle comprises the size of the about 50mm of about 0.5-.As a result, simply sieve, such as, the simple screening under high temperature can reach the removing of ash content.Simple screening uses in sepn process the size and density variation that need between unwanted solid particulate.Other method, such as mechanical process, and can be used to separate ash and unwanted material based on the method for weight or magnetic.Tripping device, such as cyclonic separator is discussed further by the embodiment below.
Heat integration in system and all system components and recovery of heat are highly desirable.Heat integration in system concentrate on especially be the second reactor 2 steam demand produce steam.This steam easily can use the hydrogen, the CO that leave reactor 1,2,3 respectively 2with obtainable senior thermogenesis in the remaining airflow of consumption.In above-mentioned technique, also wish to produce pure oxygen.In order to produce this pure oxygen, this hydrogen can be used at least partially.
The residence time in each reactor depends on size and the composition of each ceramic composite particle, as would be familiar to one of ordinary skill in the art.Such as, the residence time comprising the reactor of Fe metal oxides can be about 20 hours of about 0.1-.
As mentioned above, other unwanted element can also be there is in addition to ash.Trace elements as Hg, As, Se do not expect under the high temperature of this technique with Fe 2o 3reaction.As a result, their expections are present in produced CO 2in stream.If CO 2intend to be used as commodity, then must remove these trace elementss from this stream.Various refining plant, such as mercury removing device is considered at this.If allow this CO 2stream is put in air, and take similar selection by needing, this depends on the rules and regulations existed at that time.If determine isolation CO 2so that storage good for a long time, such as, be isolated in dark geological formations, then can remove these unwanted elements.In addition, CO can be isolated via mineral sequestration 2, this more may cater to the need than geological storage, because safer and more easy to control.In addition, CO is isolated 2have global CO 2credit trading has economic interests, and this may be highly gainful.
In addition, sulphur can form another kind of unwanted element, it must be considered in this system.In solid fuel conversion embodiment, be present in the sulphur expection in coal and Fe 2o 3react and form FeS.It using with the steam reaction in reactor 2 after as H 2s discharges and will pollute hydrogen stream.During water of condensation from this steam, this H 2condensation is got off by the major part of S.Remaining H 2s can use routine techniques as amine gas washing or use the high temperature of Zn, Fe or Cu base adsorbent to be removed.Except the another kind of method of desulfuration will comprise introducing sorbent material, such as, CaO, MgO etc.In addition, as with the embodiment of fig. 6, sorbent material can be introduced the first reactor 1 to remove desulfuration and to prevent itself and Fe from associating.Ash separation device can be used from system to remove sorbent material.
Although the embodiment of system of the present invention relates to generation hydrogen, process may be desirable to produce ultra-high purity hydrogen further.As would be familiar to one of ordinary skill in the art, some carbon or derivatives thereofs may proceed to 2 from reactor 1 and pollute hydrogen stream.Depend on required hydrogen purity, use pressure-variable adsorption (PSA) device may be necessary to reach ultra-high purity to hydrogen.In solid fuel conversion embodiment, the tail gas of PSA device may have the value as fuel and can be recycled in the first reactor 1 together with coal, with the hydrogen generation efficiency in improved system.
With reference to Fig. 2, the hydrogen produced in the second reactor 2 can provide additional benefit for system.Such as, hydrogen can be used for the power generation part 10 being set to be produced by the hydrogen gas product of the second reactor 2 electricity.As would be familiar to one of ordinary skill in the art, power generation part 10 can comprise air compressor 12, gas-turbine 14, steam turbine, generator 16, fuel cell etc.In another embodiment, can by unconverted H 2be recycled to the region intermediate of reactor 2 from fuel cell, this helps to improve fuel cell efficiency and reduces fuel cell size simultaneously.Thus, improve the efficiency of whole system.
With reference to Fig. 3, provide the another kind of coal converting system similar to Fig. 1.By this CO 2a part of recirculation return as coal injection carrier gas.Two reactors operate and pass through the rare gas element such as N from air separation plant at 400-1200 DEG C 2the metallic particles of reduction is transported to the second reactor 2.The hydrogen produced in second reactor 2 also may be used for the metal oxide particle transporting reduction.From this nitrogen, isolate the metal of this reduction and input the second reactor 2 to produce H with steam reaction 2.The H produced 2h may be comprised due to the sulphur in coal 2s, and this particle may be attached to and form MeS.As shown, conventional sulphur washing and brushing device 22 can be used to remove H 2s also produces pure H 2.The oxidation particle exported from the second reactor 2 will pass through the ash separation system using filter screen.In this embodiment, due to wearing and tearing, most of ash content and metal oxide particle are isolated for regeneration, feeding device will be used simultaneously, such as, remaining metal oxide particle sends back in the entrance of the first reactor 1 by air by pneumatic conveyor, there, also may supply supplementary ceramic composite.Supplementary ceramic composite particle used herein refers to fresh granules, and they are used for substituting due to wearing and tearing and passivation and becoming too small or invalid particulate or ceramic composite particle.Typical ceramic composite rate of supplementing will be less than 2% of particle flow rate in system.
With reference to Fig. 4, different solid conveying system, and different ash separation device may be used for coal direct reaction body system.At this, use chapelet at N 2in environment, the metallic particles of reduction is transferred to the second reactor 2.Be oxidized to metal oxide intermediate in the second reactor 2 after, consequently this particle is oxidized when arriving cyclonic separator to use the pneumatic conveyor of employing air this metal oxide intermediate to be delivered to cyclonic separator 3.Particulate due to wearing and tearing can be removed with coal ash together with air, adopt cyclonic separator particle separation gone out and input the first reactor together with supplementary metal oxide particle simultaneously.Supplementary speed is less than 2% of particle flow rate in system equally.Other device other device as grain classifier or those of ordinary skill in the art are usually known also may be used for ash separation.
With reference to Fig. 5 embodiment, the 3rd reactor 3 in fluidized-bed form is used to reclaim heat such as, to be oxidized the particle and metal oxide intermediate that leave the second reactor further, Fe 3o 4.In other embodiment and accompanying drawing, this reactor is shown as the supply line of wherein introducing air from the second reactor 2 to the first reactor 1 or oxygen.It will be reactant transport device, fast fluidized bed, fluidized-bed, lifter or pneumatic conveying system.At this, by metal oxide intermediate such as Fe 3o 4inject heat reclamation device 3 from the outlet of the second reactor 2, there, introduce oxygen or air this particle to be oxidized to again their highest oxidation state, i.e. the metal oxide of ceramic composite, such as Fe 2o 3.In addition to the oxidation conversion, also produce heat in this course, and the temperature of particle also may increase hastily.The particle with remarkable higher temperature can be reintroduced back to the first reactor 2 and be kept at the heat that the heat in this particle will provide reduction reaction to need at least in part.For the particle with high heat capacity, in an exemplary embodiment, the carrier such as SiC with high thermal conductivity is used may to be desirable.
As with the embodiment of fig. 6, can by sorbent material, such as modified calcium carbonate or calcium oxide or calcium hydroxide inject the first reactor 1 to remove desulfuration from coal.CaCO 3injection rate is by the about 1%-about 15% for metal oxide flow rate in this system; But this injection rate changes according to the composition of used coal.Magnesium oxide also can be used as sorbent material.Generally, the size of absorbent particles is less than ceramic composite particle, and can have the particle size of about 100 μm-about 1mm in some example embodiments, and this depends on the size of ceramic composite particle in system.Spent sorbents (after sulfur capture) will be isolated and then be regenerated to be further used for the first reactor 1 together with ash content.In this embodiment, pure H can be produced when not needing washer 2.
Generally with reference to Fig. 7-9, provide the system implementation scheme of converting gaseous fuels.As shown in Figure 9, the CO that can will produce in the first reactor 1 2a part separately and introduce the second reactor 2 together with steam.By controlling steam and CO 2feed rate, can obtain and there is different H 2with the synthetic gas of CO ratio.This synthetic gas can be introduced gas-turbine and may be used for chemical/liquid fuel synthesis with generating or it.In order to produce for Fiscber-Tropscb synthesis to produce the H with about 2:1 of liquid fuel 2the synthetic gas of/CO ratio, typical steam and CO 2feed rate ratio should be about 2:1.To in detail the system of the present invention discussed and be combined with Fiscber-Tropscb synthesis be more described in detail below.H can also be changed by the interlude a part of output being after condensation of water recycled to the second reactor 2 2the output ratio of/CO.This will allow more water gas shift reactions with by unconverted CO 2change into CO.
As shown in the fig. 9 embodiment of syngas conversion, in the second reactor 2, make metallic particles and the air combustion of reduction.The heat that water extraction can be used to produce is to produce high-temperature steam.Steam then may be used for generating or it can be used for from resinous shale extraction heavy oil.In the embodiment of Figure 10, system must consider the following fact: the H in crude synthesis gas 2s will form metallic sulfide with metal reaction.The metal of reduction and metallic sulfide may be introduced the second reactor 2 with steam reaction.Product stream in this system may comprise H 2and H 2s.Conventional washer technology can be used to extract H out 2s and rich H may be obtained 2stream.By using geseous fuel, such as synthetic gas replaces solid fuel, can avoid ash separation process.
With reference to Figure 11 embodiment, the hot gas sulfur removal unit of sorbent material such as CaO is used to be used for a large amount of H in crude synthesis gas 2s is less than 100ppm except going to.Then by this pretreated synthetic gas and steam and appropriate amount (usual <15%) CO 2mix and introduce the bottom of the first reactor 1.Due to H 2s and steam/CO 2between balance, H 2s and Hg can not with the particle reaction in the first reactor 1.As a result, pollutent will with CO 2out also can be isolated together from the first reactor 1 together.Only also therefore pure metal particles will enter the second reactor 2, rich H 2stream can when do not use Sulfur-Vapor of Lower Temperature and mercury removing device produce.In addition, the ceramic composite particle of activity or the size with degeneration (it is no longer valid in the technique of the first and second reactors) can be used to replace CaO to remove H 2s, such as, to the level being less than 30ppm.
Generally with reference to Figure 13, the chemical looping system as hydrogen generator can be connected with fischer-tropsch (F-T) synthetic system, to produce chemical substance or liquid fuel.The synthetic gas deriving from modern gasifiers can not provide the enough H meeting F-T and synthesize needs usually 2concentration (H 2/ CO=2:1).The raw material of the first reactor 1 is the by product of F-T reactor 100 and a part for unconverted synthetic gas.In another embodiment, this raw material can comprise the product of a part from refinery systems.The rest part of this by product and unconverted synthetic gas is recycled to F-T reactor 100 to improve transformation efficiency, or, also it can be recycled to gasifier to manufacture more synthetic gas.In addition, the steam of the second reactor can be obtained from gasifier and F-T reactor 100, because F-T reacts normally high exothermic heat simultaneously.Some CO can be comprised and the H of the second reactor 1 produced by chemical looping reaction device 2product is recycled back, to regulate the H of F-T raw material 2/ CO compares about 2:1.In some embodiments, gasifier 30 can be left at clean synthetic gas and carry out this adjustment after being transported to gas-cleaning installation 22.In this case, use stoichiometric by product and unconverted synthetic gas to produce the H for gas regulation 2, by this proportion adjustment to about 2:1, remaining gas recirculation is got back in F-T reactor 100 simultaneously.By by C 1-C 4by product becomes the H of the raw material being F-T reactor 100 with unconverted Synthetic holography 2, can improved system efficiency and selectivity of product widely.The working pressure of chemical looping system will with F-T resemble process, such as, in be pressed into, about 20 normal atmosphere.
Figure 12 is similar to the embodiment described in Figure 13 with the embodiment of 14; One of them main difference is that all by products are all used for producing H 2.The H of excessive amount 2may be used for the wax product hydrocracking of F-T reactor 100.If still remain excessive H after hydrocracking 2, then gas turbine or fuel cell generally can be used to come for factory application or energy market generating.
In the F-T embodiment of Figure 15, before the first reactor 1, use hot gas purification remaining pollutent out can not will be attached to particle from the first reactor 1.At this, by a part of CO produced from the first reactor 1 2introduce product cleanup unit or CO 2tripping device is to extract substantially pure CO in the discharge air-flow from the first reactor 1 2.Then by this substantially pure CO 2introduce and introduce the second reactor 2 to form H together with steam 2/ CO ratio is the clean synthetic gas of about 2:1.Then this synthetic gas is used for F-T reactor 100 to produce liquid fuel or chemical substance.Also the by-product stream recirculation of F-T reactor 100 is got back to the first reactor to improve the synthetic gas productivity of chemical looping system further.With reference to Figure 16, F-T system can be combined with coal converting system instead of synthetic gas.In this embodiment, sorbent material can be fed this system to extract sulphur out.The by product that F-T synthesizes can also be fed the first reactor 1 to manufacture more synthetic gas.In this solid fuel conversion embodiment, do not need gasifier; Therefore, system can comprise less equipment, thus reduces costs and invest improved system efficiency simultaneously.
In all F-T embodiments, can by a part of steam superheated will produced in F-T reactor from the high-temperature steam of chemical looping system of the present invention or gasifier.This superheated vapour can comprise various uses, such as, drives the raw material that steam turbine is used for parasitic energy or is used as in reactor 2.
In the embodiment of Figure 17, provide the additional purpose of system of the present invention.In this embodiment, by metal oxide particle such as Fe 2o 3be processed into the vehicle-mounted H in vehicle 230 2packed bed in the module of storer or cylindrical shell or material all in one piece.At this, in central equipment 210, this module is processed to use carbonaceous fuel such as synthetic gas that it is reduced into its metallic forms.Then the module of this reduction distributed to fuel station 200 and be installed in automobile 230 to substitute useless module.Steam will obtain from PEM fuel cell or hydrogen internal combustion engine and by be introduced in model with reduction particle reaction to produce H 2drive automobile.The representative temperature of reaction will be about 250-700 DEG C, because reaction is heat release.The temperature in module can be kept by the recovery of heat in the isolator of good design or other region of system.This module will be made up of each different shells and each shell can be the packed bed of pellet or it can be material all in one piece.In an exemplary embodiment, material all in one piece can have the small channel of diameter 0.5-10mm, and the thickness of the wall be simultaneously made up of particle keeps being less than 10mm.Figure 18 (a)-(c), and Figure 18 shows module, namely have some examples of the reactor containing Fe medium, described medium has the packed bed of (a) small pellets; B () has the integral bed of the straight channels for steam; (c) there is the integral bed of the raceway groove for steam and air.
Figure 18 c and Figure 18 b show air will flow through some raceway grooves simultaneously steam flow through remaining raceway groove.By this flow arrangement, the raceway groove of air process will produce the heat being used for adjacent channel, thus keep them to be in as hydrogen manufacturing and the temperature (250-700 DEG C) that needs.Figure 19 shows a kind of possible configuration using the shelling machine shown in Figure 18 (c).At this, will be connected to each other constantly to produce the H being used for fuel cell in automobile 230 or oil engine in different outer cover packaging to module 2.Can use special monolith design and connection scheme strictly by air and steam channels 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 metallic particles of reduction is fed and can directly process solid-fuelled Solid Oxide Fuel Cell.In fact, this Solid Oxide Fuel Cell serves as the second reactor 2 in redox system.Particle is reduced and is then introduced into fuel cell to react at 500-1000 DEG C with oxygen or air and to produce electricity in this fuel reactor.The particle recirculation of oxidation is got back to fuel reactor again to reduce.Because the applicability of system of the present invention, think that the present invention can introduce other commercial runs many.
It is noted that term is as " preferably ", " generally ", " generally " and " usually " are not used for limiting scope of invention required for protection at this or imply that some feature is crucial, mainly and even be important to the structure of invention required for protection or function.On the contrary, these terms are only intended for the outstanding alternative or additional feature that may be used for maybe can being not used in particular of the present invention.
For description and limit object of the present invention, it should be noted that term " substantially " this be used for represent can owing to any quantitative comparison, numerical value, observed value or other represent intrinsic uncertainty.Term " substantially " this be also used for representing quantificational expression can with given reference discrepant degree, and the change of the basic function of in question theme can not be caused.
Although also describe the present invention with reference to specific embodiment of the invention scheme in detail, obviously when not departing from the scope of the invention that appended claims limits, amendment and change are possible.More particularly, although aspects more of the present invention are thought preferred or especially favourable at this, think that the present invention is not necessarily limited to these preferred aspects of the present invention.

Claims (54)

1. the system of converting fuel, comprising:
Comprise the first reactor of many ceramic composite particles, this ceramic composite particle comprises at least one and is arranged in metal oxide on carrier, and wherein this first reactor to be set to this at least one metal oxide back with fuel with the metal oxide of the metal or reduction that produce reduction;
Be set to be oxidized the metal of this reduction or the metal oxide of reduction to produce the second reactor of metal oxide intermediate; With
Be placed through this metal oxide intermediate of oxidation with the 3rd reactor making this at least one metal oxide regenerate.
2. system according to claim 1, wherein this first reactor is set to produce carbonic acid gas, steam or its combination, and the second reactor is set to produce H 2, CO, synthetic gas, heat or its combination.
3. system according to claim 1, the oxygenant wherein for oxidation step comprises steam, carbonic acid gas, air, oxygen or its combination.
4. system according to claim 3, wherein uses CO 2synthetic gas is produced with steam oxidation agent.
5. system according to claim 4, wherein passes through a part of recirculation of the second reactor product, or the CO of control inputs second reactor 2the H of synthetic gas is controlled with the amount of steam oxidation agent 2/ CO ratio.
6. system according to claim 1, wherein this ceramic composite particle comprises promotor.
7. system according to claim 1, wherein this fuel comprises solid fuel, liquid fuel, geseous fuel or its combination.
8. system according to claim 1, also comprise be set to except deashing, the tripping device of charcoal or unwanted material.
9. system according to claim 8, wherein this ash separation device comprises cyclonic separator, filter screen, grain classifier or its combination.
10. system according to claim 1, wherein this first and second reactor is set to operate under about 1 normal atmosphere-about 150 atmospheric pressure.
11. systems according to claim 1, wherein this first and second reactor is set to operate at the temperature of about 1200 DEG C of about 400-.
12. systems according to claim 1, wherein this metal oxide comprises and is supported on TiO 2fe on carrier 2o 3, this metal oxide intermediate comprises Fe 3o 4.
13. systems according to claim 1, also comprise the power generation part be communicated with the second reactor fluid, and this power generation part is set to produce electricity by the product of the second reactor.
14. systems according to claim 1, also comprise at least one heat exchanger being set to heat and comprising water, steam and its raw material combined, with the thermogenesis steam by using from the first reactor, the second reactor or both product streams.
15. systems according to claim 1, wherein this first reactor and the second reactor comprise at least one moving-burden bed reactor, a series of fluidized-bed reactor, kiln, fixed-bed reactor or its combination.
16. systems according to claim 15, wherein this moving-burden bed reactor limits the counter current contact between gas and solid.
17. systems according to claim 1, wherein this first reactor is moving-burden bed reactor, it comprise insert this moving-bed mixing device radially to distribute ceramic composite particle being mixed with this ceramic composite particle by unconverted fuel.
18. systems according to claim 1, wherein this first reactor is the moving-burden bed reactor being limited to the annular region produced around moving-bed, and this annular region is the position of introducing fuel.
19. systems according to claim 1, also comprise the transfer roller or Pneumatic feeding device that are set to solid fuel is transported to the first reactor.
20. systems according to claim 1, also comprise solid fuel gasif, candle filter, mercury removing device, gas cleanup component, Pressure Swing Absorption, water gas shift reactor or their combination.
21. systems according to claim 1, wherein this first reactor comprises and is set to trap contaminants, the metal carbonate of heavy metal or its combination, metal oxide or metal hydroxides.
22. systems according to claim 1, wherein this first reactor can operate the H for the bottom reception recirculation at this reactor 2stream.
23. systems according to claim 1, wherein this first reactor can operate and receive fuel for the first reactor area below the feed zone of ceramic composite particle.
24. systems according to claim 1, wherein this first reactor can operate and comprise oxygen, CO for receiving in the position adjacent with the region intermediate feeding fuel 2, air, steam, nitrogen and its combination raw material.
25. systems according to claim 1, are wherein connected this system with Solid Oxide Fuel Cell so that the product of this fuel are recycled to the second reactor.
26. systems according to claim 1, wherein this system is communicated with fischer-tropsch reactor fluid.
27. systems according to claim 26, also comprise FF.
28. systems according to claim 1, wherein this first and second reactor comprises the packed bed in portable box form, and wherein this portable box is set to produce hydrogen and be stored in vehicle by hydrogen.
29. methods converting the fuel into hydrogen, CO or synthetic gas, comprising:
In reduction reaction between fuel and metal oxide, metal oxide back is become the metal of reduction or the metal oxide of reduction;
With oxygenant, the metal of this reduction or the metal oxide of reduction are become metal oxide intermediate, also produce hydrogen, CO or synthetic gas simultaneously; With
By making this at least one metal oxide regenerate the oxidation of this metal oxide intermediate.
30. systems, comprising:
Be set to the fischer-tropsch reactor being produced hydrocarbon fuel by the raw mixture comprising fuel;
Comprise the first reactor of many ceramic composite particles, wherein this ceramic composite particle comprises at least one and is arranged in metal oxide on carrier, wherein this first reactor to be set to fuel by this at least one metal oxide back to produce metal or the metal oxide of reduction of reduction, and wherein this fuel is made up of the hydrocarbon fuel of this fischer-tropsch reactor at least in part; With
Be set to the metal of this reduction of steam oxidation or the metal oxide of reduction to produce the second reactor of metal oxide intermediate, this oxygenant is made up of the product of this fischer-tropsch reactor at least in part.
31. systems according to claim 30, also comprise:
Gaseous fuel feed source;
Process the purification system of the hydrocarbon product produced in this system.
32. systems according to claim 30, wherein this oxygenant is steam, CO, air, O 2or its combination.
33. systems according to claim 30, the steam wherein for the second reactor comprises the steam produced in fischer-tropsch reactor or gasifier at least partly.
34. systems according to claim 30, also comprise and are placed through this metal oxide intermediate of oxidation with the 3rd reactor making this at least one metal oxide regenerate.
35. systems according to claim 30, wherein this second reactor is set to produce hydrogen or synthetic gas.
36. systems according to claim 30, the fuel wherein supplying the first reactor comprises the synthetic gas produced by the gasification of hydrocarbon fuel at least in part.
37. systems according to claim 30, are wherein recycled to the first reactor by the by product of fischer-tropsch reactor.
38. systems according to claim 30, also comprise the steam turbine that the steam being set to be produced by this system produces electricity.
39. systems according to claim 30, also comprise gaseous fuel mixing location, wherein the hydrogeneous product of geseous fuel raw material and the second reactor can be implemented to mix the geseous fuel equaling about 2:1 with the mol ratio producing hydrogen and carbon monoxide, and this geseous fuel is used for the raw mixture of this fischer-tropsch reactor.
The preparation method of 40. ceramic composite particles, comprises the following steps:
Metal oxide and solid support material are reacted;
At the temperature of about 1500 DEG C of about 200-, the mixture of heat-treated metal oxide compound and solid support material is to produce ceramic composite powder;
This ceramic composite powder is changed into ceramic composite particle;
By the reduction of this ceramic composite particle and oxidation before using in the reactor.
41., according to the method for claim 40, also comprise in mixture promoter material being added to metal oxide and solid support material.
42. according to the method for claim 40, and wherein thermal treatment is at rare gas element, steam, oxygen, air, H 2and its combination exist under carry out under pressure between vacuum pressure and be the schematic diagram for the reactor in system of the present invention, wherein this reactor is moving-burden bed reactor, and it comprises about 10 normal atmosphere of annular region near the fuel feed position that is arranged according to one or more embodiments of the present invention.
43. according to the method for claim 40, also comprises the mixture chemical treatment of metal oxide and promotor to activate ceramic composite powder.
44. according to the method for claim 40, and wherein reactions steps is carried out via spraying dry, directly mixing, total immersion stain or its combination.
45. according to the method for claim 40, wherein via extruding, granulation, efflorescence (pelletization) and its combination carry out the conversion of ceramic composite powder.
46. particles prepared by the method for claim 40.
47. according to the particle of claim 46, and wherein this metal oxide comprises the metal being selected from Fe, Cu, Ni, Sn, Co, Mn and its combination.
48. according to the particle of claim 46, and wherein this ceramic composite comprises at least this metal oxide of 40wt%.
49. according to the particle of claim 46, and wherein this solid support material comprises at least one and is selected from SiC, the component of the oxide compound of Al, Zr, Ti, Y, Si, La, Sr, Ba and its combination.
50. according to the particle of claim 46, and wherein ceramic composite comprises at least 5wt% solid support material.
51. according to the particle of claim 46, wherein this particle comprises containing pure metal, metal oxide, metallic sulfide or its promotor of combining, and wherein this metal comprises 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.
52. according to the particle of claim 51, and wherein ceramic composite comprises 40wt% promoter material at the most.
53. according to the method for claim 40, and wherein this ceramic composite particle is pellet, material all in one piece, block or its array configuration.
54. according to the method for claim 40, and wherein this particle can operate for keeping active after 10 or more time reprocessing cycle.
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US20090000194A1 (en) 2009-01-01
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