CN101389734A - Systems and methods of converting fuel - Google Patents

Systems and methods of converting fuel Download PDF

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Publication number
CN101389734A
CN101389734A CN 200780006757 CN200780006757A CN101389734A CN 101389734 A CN101389734 A CN 101389734A CN 200780006757 CN200780006757 CN 200780006757 CN 200780006757 A CN200780006757 A CN 200780006757A CN 101389734 A CN101389734 A CN 101389734A
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China
Prior art keywords
reactor
metal oxide
fuel
ceramic composite
particle
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Chinese (zh)
Inventor
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
    • C10J3/725—Redox processes
    • 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
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • 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
    • C10J2300/0956—Air or oxygen enriched air
    • 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
    • C10J2300/0959—Oxygen
    • 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
    • C10J2300/0976—Water as steam

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

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

Transform the system and the method for fuel
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 cleaning and effective energy to produce system always.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 metal oxide 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 turbine.Yet, the recirculation 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, provide the system that transforms fuel.This system comprises first reactor that comprises many ceramic composite particles, and wherein this ceramic composite particle comprises at least a metal oxide that is arranged on the carrier.This first reactor is set to reduce at least a metal oxide to produce reductive metal or reductive metal oxide with fuel.This system also comprises second reactor and the 3rd reactor, this second reactor is set to this reductive metal of oxidation or reductive metal oxide to produce metal oxide intermediate, and the 3rd reactor is set to make at least a metal oxide regeneration by this metal oxide intermediate of oxidation.
In another embodiment of the invention, provide the method that converts the fuel into hydrogen, CO or synthetic gas.This method may further comprise the steps: in the reduction reaction between fuel and metal oxide metal oxide is reduced into reductive metal or reductive metal oxide; With oxygenant this reductive metal or reductive metal oxide are oxidized to metal oxide intermediate, also produce hydrogen, CO or synthetic gas simultaneously; With by this metal oxide intermediate oxidation being made this at least a metal oxide regeneration.
In another embodiment, provide the system that comprises the Fischer-Tropsch reaction device.This Fischer-Tropsch reaction device is set to produce hydrocarbon fuel by the raw mix of contained gas fuel.This system also comprises first reactor that comprises many ceramic composite particles, and wherein this ceramic composite particle comprises at least a metal oxide that is arranged on the carrier.This first reactor is set to geseous fuel metal oxide is reduced into reductive metal or reductive metal oxide, and wherein this geseous fuel comprises the hydrocarbon fuel that produces by the Fischer-Tropsch reaction device at least in part.This system also comprises second reactor, and it is set to steam this reductive metal or the oxidation of reductive metal oxide to produce metal oxide intermediate.
The preparation method of ceramic composite particle is provided in another embodiment.This method comprises: make the reaction of metal oxide 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, use before with this ceramic composite particle reduction and oxidation.
Consider feature and advantage that following detailed description will be understood more completely to be provided by embodiment of the present invention.
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, same structure represents 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 be according to one or more embodiments of the present invention use direct chemical circulation and the ash separation sieve by the synoptic diagram of the another kind of system of coal generation hydrogen;
Fig. 4 be according to one or more embodiments of the present invention use direct chemical circulation and the ash separation cyclonic separator by the synoptic diagram of the another kind of system of coal generation hydrogen;
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 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 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 is got back in the carbonic acid gas recirculation that produces in first reactor;
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 be according to one or more embodiments of the present invention chemical cycle and the synoptic diagram of the synthetic bonded system of fischer-tropsch (F-T);
Figure 13 be according to one or more embodiments of the present invention chemical cycle and the synoptic diagram of the another kind of system of the synthetic bonded of fischer-tropsch;
Figure 14 be according to one or more embodiments of the present invention chemical cycle and the synoptic diagram of the another kind of system of the synthetic bonded of fischer-tropsch;
Figure 15 be according to one or more embodiments of the present invention chemical cycle and the synoptic diagram of synthetic another system of bonded of fischer-tropsch, wherein this system comprises the pollutent control unit;
Figure 16 be according to one or more embodiments of the present invention chemical cycle and the synoptic diagram of the another kind of system of the synthetic bonded of fischer-tropsch, wherein this system is operated under the situation of not using gasifier;
Figure 17 is the vehicle-mounted H on the vehicle of being 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 box of storage system, wherein this reactor 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 box of storage system, wherein this reactor 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 module of storage system, wherein this reactor 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 box of storage system, wherein this reactor box use is a series of has the integral bed reactor of air injection to be provided for the heat that steam forms;
Figure 20 be according to one or more embodiments of the present invention chemical cycle and the synoptic diagram of Solid Oxide Fuel Cell bonded system;
Figure 21 is the synoptic diagram of the reactor that is used for system of the present invention according to one or more embodiments of the present invention, and wherein this reactor 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 that is used for system of the present invention according to one or more embodiments of the present invention, and wherein this reactor is a moving-bed, and it comprises annular region and inserts cone in this moving-bed; With
Figure 23 is the synoptic diagram of another reactor that is used for system of the present invention according to one or more embodiments of the present invention, and wherein this reactor 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 by the redox reaction of ceramic composite particle.As shown in Figure 1, this system comprises two main reactors, and additional reactor and assembly, will describe them below in detail.First reactor 1 that is set to carry out reduction reaction comprises many ceramic composite particles, and this ceramic composite particle has at least a metal oxide 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 may 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 metal oxide and ceramic carrier material physical mixed.Randomly, promoter material can be added in the mixture of metal oxide 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 wherein the mixture of handling metal oxide and solid support material with acid, alkali or both is with this ceramic composite powder activation.After powder production, can this ceramic composite powder be changed into ceramic composite particle by the known method of those of ordinary skills.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 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, by 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 of system of the present invention, use.
The metal oxide of ceramic composite comprises the metal that is selected from Fe, Cu, Ni, Sn, Co, Mn and its combination.Though this paper considers various compositions, ceramic composite comprises 40wt% metal oxide 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, metal oxide, metallic sulfide or its combination.These metal matrix 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 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 1, first reactor 1 receives fuel, and this fuel is used for reducing at least a metal oxide of ceramic composite to produce metal or the reductive metal oxide that reduces.The ＂ fuel ＂ that this paper limited can comprise: the solid carbon composition is coal, tar, resinous shale, oil-sand, tar sand, Biological resources, wax, coke etc. for example; The liquid carbon-containing composition 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 metal oxide (Fe of ceramic composite 2O 3) by fuel for example, the CO reduction, and produce reductive metal oxide (Fe).Though Fe is produce in the reduction reaction of first reactor 1 main through reducing composition, FeO or have more that other reducing metal oxide of high oxidation state also is considered at this.
First reactor 1 and second reactor 2 can comprise that various suitable reactors are to allow between gas and the solid counter current contact generally.This can use moving-burden bed reactor, a series of fluidized-bed reactor, kiln, fixed-bed reactor, their combination, or known other realization of those of ordinary skills.
Shown in Figure 21-23, first reactor 1 can comprise moving-burden bed reactor, and this moving-burden bed reactor has the annular region 8 that produces around this moving-bed.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.As 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 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.
First reactor 1 can be with being fit to resist the high various durable materials structures that arrive at least 1200 ℃ temperature.The carbon steel that has refractory masses on the includable side of this reactor is so that further minimum heat losses.This structure also allows the surface temperature of reactor quite low, thereby improves the creep resistance of carbon steel.Also can adopt other alloy that environment is fit to that is present among the various reactors, particularly when with them when being set to help intraware heat passage in solid flow or the raising moving-bed embodiment.The interconnection of various reactors can have lock hopper design or rotation/star valve designs to guarantee good sealing.Other interconnection that also can use those skilled in the art to determine easily.
In first reactor 1, after the reduction, will be transported to second reactor 2 with the experience oxidizing reaction through the reductive metal or through the reductive metal oxide particle then.Can have second reactor 2 with first reactor, 1 same reactor type or different reactor type be set to this through the reductive metal or through the oxidation of reductive metal oxide to produce metal oxide intermediate.The employed ＂ metal oxide intermediate of this paper ＂ is meant the oxidation state that has than through reductive metal or burning object height, and the metal oxide of the oxidation state lower than the metal oxide 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 metal oxide is in the example of center, and the oxidation in using second reactor of steam comprises the gained mixture of metal oxide intermediate with generation, and this intermediate mainly comprises Fe 3O 4Fe 2O 3Also may exist with FeO.In addition, though H 2O, particularly steam are the oxygenants in this example, but also consider many other oxygenants, for example, 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 first reactor, the 1 following operation of moving-bed: allow 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.Contain Fe via gravity raw material machine from the top introducing 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 1.Usually, reactor is in the about 1200 ℃ temperature of about 400-with approximately operate under the 1-about 150 atmospheric pressure; Yet, 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 embodiment of Fig. 1, the coal that will grind formation by the pneumatic transport of adopting oxygen or carbonic acid gas or steam is introduced.After coal being transported to first reactor 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 composition of first reactor 1 can mainly comprise CO 2And steam.Subsequently, can be with CO 2Supply with condenser 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 flow downward in first reactor 1 ferric oxide of Shi Zehui and partial reduction.In order to improve and the reaction of the charcoal of ferric oxide, introduce small quantity of hydrogen in the moving-bed bottom to cause as its formation H during with the ferric oxide 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 then will with the ferric oxide reaction of this partial reduction with further reduction this through the reductive ferric oxide, thereby improve charcoal-ferric oxide speed of reaction.The hydrogen of introducing at reactor bottom will guarantee that also ferric oxide particles major part when they leave first reactor 1 is reduced into Fe.In some cases, have a mind to allow some carbon in the particle keep unconverted in second reactor, to use steam to produce CO.In some other cases, can be with the excessive Fe that contains 2O 3Ceramic composite particle insert in first reactor 1 to improve speed of reaction.
Can contain the Fe particle through reductive and introduce second reactor 1 what leave then.As in first reactor 1, second reactor 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, 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 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 2, but the solid product of this reactor estimates it mainly is metal oxide intermediate Fe 3O 4The Fe that produces in second reactor 2 2O 3Amount depend on employed oxygenant, and the amount of supplying with the oxygenant of second reactor 2.The vapor condensation that exists in then can the hydrogen gas product with reactor 2 is to provide rich hydrogen materials flow.At least a portion recirculation of this rich hydrogen materials flow can be got back to above-mentioned first reactor 1.Except using the type of reactor identical with first reactor 1, second reactor 2 can be similarly operated under the about 1200 ℃ temperature of about 400-and about 1-about 150 atmospheric pressure.
In order to make the metal oxide regeneration of ceramic composite, this system is used the 3rd reactor 3, and it is set to metal oxide intermediate is oxidized to the metal oxide of this matrix material.With reference to embodiment Fig. 1, the 3rd reactor 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 heat reclamation device 3.Following equation has been listed a kind of possible oxidation mechanism in the 3rd reactor 3:
2Fe 3O 4+0.50 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 by 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 1 can also comprise ash content and other unwanted by product.If do not remove at first reactor 1 or after 2 stages of second reactor and to deash, then this ash content may 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.Simple screening use need in the sepn process and unwanted solid particulate between size and density variation.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 will further be discussed in the embodiment of back.
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 2 that heat integration in the system concentrates on especially.This steam can easily use hydrogen, the CO that leaves reactor 1,2,3 respectively 2With obtainable senior thermogenesis in the surplus airflow of consumption.In above-mentioned technology, also wish 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 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 of Fe Base Metal oxide compound can be about 20 hours of about 0.1-.
As mentioned above, 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 allow 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 may 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 may be highly gainful.
In addition, sulphur can constitute another kind of unwanted element, it must be considered in this system.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 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 be removed.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, sorbent material can be introduced first reactor 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 may be desirable further handling to produce ultra-high purity hydrogen.As those of ordinary skills were familiar with, some carbon or derivatives thereofs may change 2 and pollute hydrogen stream over to from reactor 1.Depend on desired hydrogen purity, it may 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 may have the value that acts as a fuel and can be recycled in first reactor 1 with coal, produces efficient with the hydrogen in the improved system.
With reference to Fig. 2, the hydrogen that produces in second reactor 2 can provide additional benefit for system.For example, hydrogen can be supplied with the power generation part 10 that is set to be produced by the hydrogen gas product of second reactor 2 electricity.As those of ordinary skills were familiar with, power generation part 10 can comprise air compressor 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 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, provide the another kind of coal converting system similar to Fig. 1.With this CO 2A part of recirculation return carrier gas as coal injection.Two reactors are 400-1200 ℃ of operation and by from the rare gas element of air separation plant N for example down 2The reductive metallic particles is transported to second reactor 2.The hydrogen that produces in second reactor 2 also can be used to transport the reductive metal oxide particle.From this nitrogen, isolate this reductive metal and import second reactor 2 to produce H with steam reaction 2The H that produces 2May comprise H owing to the sulphur in the coal 2S, and may be attached to this particle and form MeS.As shown, 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 will be through using the ash separation system of filter screen.In this embodiment, because wearing and tearing, most of ash content and metal oxide particle isolated be used for regeneration, to use feeding device simultaneously, for example, pneumatic conveyor sends back to remaining metal oxide particle in the inlet of first reactor 1 by air, there, also may 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 2.Be oxidized to metal oxide intermediate in second reactor 2 after, 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 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 as gradation device or common known other device of those of ordinary skills.
With reference to Fig. 5 embodiment, using the 3rd reactor 3 be the fluidized-bed form to reclaim the particle that heat leaves second reactor with further oxidation is metal oxide intermediate, for example Fe 3O 4In other embodiment and accompanying drawing, this reactor is shown as from the wherein introducing air of second reactor, 2 to first reactors 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 heat reclamation device 3 from the outlet of second reactor 2, there, introduce oxygen or air this particle is oxidized to again their highest oxidation state, the i.e. metal oxide of ceramic composite, for example Fe 2O 3Except oxidation conversion, also produce heat in this course, and the particulate temperature may increase hastily also.Particle with remarkable higher temperature can be introduced again 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 particle with high heat capacity, in an exemplary, use have high thermal conductivity carrier for example SiC may be desirable.
Shown in the embodiment of Fig. 6, can be with sorbent material, for example modified calcium carbonate or calcium oxide or calcium hydroxide inject first reactor 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.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 the about 1mm of about 100 μ m-in some exemplary, and this depends on the size of ceramic composite particle in the system.Spent sorbents (after sulphur is captured) will be isolated and regenerated then so that be further used for first reactor 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, provide the system implementation scheme of reformed gas fuel generally.As shown in Figure 9, can be with the CO that in first reactor 1, produces 2A part separately and with steam introduce second reactor 2.By control steam and CO 2Feed rate, can obtain to have different H 2Synthetic gas with the CO ratio.This synthetic gas can being introduced gas-turbine, can be used for chemical/liquid fuel with generating or it synthetic.Be used for synthetic the H of fischer-tropsch in order to produce with about 2:1 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 describe in detail below and discuss and the synthetic bonded system of the present invention of fischer-tropsch.Can also change H by the interlude that will a part of output after water condensation be recycled to second reactor 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 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.Reductive metal and metallic sulfide may be introduced second reactor 2 with steam reaction.Product materials flow in this system may comprise H 2And H 2S.Can use conventional washer technology to extract H out 2S and may obtain rich H 2Materials flow.By 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 1.Because H 2S and steam/CO 2Between balance, H 2S and Hg can not react with the particle in first reactor 1.As a result, pollutent will with CO 2Come out also can be isolated together from first reactor 1 together.Only also therefore pure metal particles will enter second reactor 2, rich H 2Materials flow can produce not using low temperature sulphur and mercury to remove under the situation of device.In addition, can use ceramic composite particle (it is no longer valid in the technology of first and second reactors) the replaced C aO of activity with degeneration or size to remove H 2S, for example, to level less than 30ppm.
With reference to Figure 13, the chemical cycle system as hydrogen generator can 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 1 is the part of the by product and the unconverted synthetic gas of F-T reactor 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 100 with the raising transformation efficiency, or, also it can be recycled to gasifier to make more synthetic gas.In addition, can be simultaneously obtain the steam of second reactor, because normally height heat release of F-T reaction from gasifier and F-T reactor 100.The H of second reactor 1 that can comprise number of C O and produce by the chemical cycle reactor 2The product recycled back is to regulate the H of F-T raw material 2/ CO compares about 2:1.In some embodiments, can after leaving gasifier 30 and be transported to gas-cleaning installation 22, the cleaning synthetic gas carry out this adjusting.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 recirculation is got back in the F-T reactor 100.By with C 1-C 4By product and unconverted synthetic gas change into the H of the raw material that is F-T reactor 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 hydrocracking with F-T reactor 100.If after hydrocracking, 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 1, use hot gas purification and remaining pollutent to come out and can not be attached on the particle from first reactor 1.At this, will be from a part of CO of first reactor, 1 generation 2Introduce product refining plant or CO 2Tripping device is to extract pure basically CO from the discharge air-flow of first reactor 1 2Then that this is pure basically CO 2Introducing is introduced second reactor 2 to form H with steam 2/ CO ratio is the cleaning 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 synthetic gas productivity of first reactor with further raising chemical cycle system.With reference to Figure 16, the F-T system can be combined with coal converting system rather than synthetic gas.In this embodiment, sorbent material can be infeeded this system to extract sulphur out.F-T synthetic by product can also be infeeded first reactor 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 by 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.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 2.
In the embodiment of Figure 17, provide the additional purpose of system of the present invention.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 be by the isolator of good design or the temperature in the maintenance of the recovery of heat in other zone of the system module.This module will be made of each different shells and each shell can be that the packed bed of pellet or it can be materials 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 made keeps less than 10mm.Figure 18 (a)-(c) and Figure 18 show module, promptly have some examples of the reactor that contains the Fe medium, and described 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.By 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 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 Solid Oxide Fuel Cell.In fact, this Solid Oxide Fuel Cell is served as second reactor 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 recirculation 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.
Should be noted that; term such as ＂ be ＂ preferably, and the ＂ general ＂ of ＂, ＂ and the common ＂ of ＂ generally is not used for limiting scope of invention required for protection or hints that some feature is crucial, main and even is important the structure or the function of invention required for protection at this.On the contrary, the outstanding alternative or additional feature that can be used for maybe can being not used in particular of the present invention only planned to be used in these terms.
For describing and limiting purpose of the present invention, should be noted that term ＂ basically ＂ be 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 revising and change under the situation of the scope of the invention that does not break away from the appended claims qualification.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 (54)

1. transform the system of fuel, comprising:
First reactor that comprises many ceramic composite particles, this ceramic composite particle comprises at least a metal oxide that is arranged on the carrier, and wherein this first reactor is set to should reduce to produce reductive metal or reductive metal oxide by at least a metal oxide with fuel;
Be set to this reductive metal of oxidation or reductive metal oxide to produce second reactor of metal oxide intermediate; With
Be set to by this metal oxide intermediate of oxidation so that this at least a metal oxide regenerated the 3rd reactor.
2. according to the system of claim 1, wherein this first reactor is set to produce carbonic acid gas, steam or its combination, and second reactor is set to produce H 2, CO, synthetic gas, heat or its combination.
3. according to the system of claim 1, the oxygenant that wherein is used for oxidation step comprises steam, carbonic acid gas, air, oxygen or its combination.
4. according to the system of claim 3, wherein use CO 2Agent produces synthetic gas with steam oxidation.
5. according to the system of claim 4, wherein by a part of recirculation with second reactor product, or the CO of second reactor is imported in control 2H with the amount of steam oxidation agent control synthetic gas 2/ CO ratio.
6. according to the system of claim 1, wherein this ceramic composite particle comprises promotor.
7. according to the system of claim 1, wherein this fuel comprises solid fuel, liquid fuel, geseous fuel or its combination.
8. according to the system of claim 1, also comprise be set to remove deash, the tripping device of charcoal or unwanted material.
9. system according to Claim 8, wherein this ash separation device comprises cyclonic separator, filter screen, gradation device or its combination.
10. according to the system of claim 1, wherein this first and second reactor is set to operate under the atmospheric pressure of about 1 normal atmosphere-about 150.
11. according to the system of claim 1, wherein this first and second reactor is set to operate under the about 1200 ℃ temperature of about 400-.
12. according to the system of claim 1, wherein this metal oxide comprises and is supported on TiO 2Fe on the carrier 2O 3, this metal oxide intermediate comprises Fe 3O 4
13. according to the system of claim 1, also comprise the power generation part that is communicated with second reactor fluid, this power generation part is set to be produced by the product of second reactor.
14. according to the system of claim 1, also comprise at least one heat exchanger that is set to heat the raw material that comprises water, steam and its combination, to pass through to use thermogenesis steam from first reactor, second reactor or both product materials flows.
15. according to the system of claim 1, wherein this first reactor and second reactor comprise at least one moving-burden bed reactor, a series of fluidized-bed reactor, kiln, fixed-bed reactor or its combination.
16. according to the system of claim 15, wherein this moving-burden bed reactor limits the counter current contact between gas and the solid.
17. according to the system of claim 1, wherein this first reactor is a moving-burden bed reactor, it comprises that the mixing device that inserts this moving-bed is radially to distribute ceramic composite particle and unconverted fuel mixed with this ceramic composite particle.
18. according to the system of claim 1, wherein this first reactor is the moving-burden bed reactor that is limited to the annular region that produces around the moving-bed, this annular region is the position of introducing fuel.
19., also comprise the transfer roller or the Pneumatic feeding device that are set to solid fuel is transported to first reactor according to the system of claim 1.
20., comprise that also solid fuel gasification device, candle filter, mercury removes device, gas sweetening assembly, pressure-swing absorption unit, water gas shift reactor or their combination according to the system of claim 1.
21. according to the system of claim 1, wherein this first reactor comprises metal carbonate, metal oxide or the metal hydroxides that is set to trap contaminants, heavy metal or its combination.
22. according to the system of claim 1, wherein this first reactor can be operated the H that is used in the reception recirculation of the bottom of this reactor 2Materials flow.
23. according to the system of claim 1, wherein this first reactor can be operated first reactor area that is used for below the feed zone of ceramic composite particle and receive fuel.
24. according to the system of claim 1, wherein this first reactor can be operated and be used for comprising oxygen, CO with the region intermediate position adjacent reception that infeeds fuel 2, air, steam, nitrogen and its combination raw material.
25., wherein this system is connected with Solid Oxide Fuel Cell so that the product of this fuel is recycled to second reactor according to the system of claim 1.
26. according to the system of claim 1, wherein this system is communicated with Fischer-Tropsch reaction device fluid.
27., also comprise FF according to the system of claim 26.
28. according to the system of claim 1, wherein this first and second reactor comprises the packed bed that is portable box form, wherein this portable box is set to produce hydrogen and hydrogen is stored in the vehicle.
29. convert the fuel into the method for hydrogen, CO or synthetic gas, comprising:
In the reduction reaction between fuel and metal oxide metal oxide is reduced into reductive metal or reductive metal oxide;
With oxygenant this reductive metal or reductive metal oxide are oxidized to metal oxide intermediate, also produce hydrogen, CO or synthetic gas simultaneously; With
By this metal oxide intermediate oxidation being made this at least a metal oxide regeneration.
30. system comprises:
Be set to produce the Fischer-Tropsch reaction device of hydrocarbon fuel by the raw mix that comprises fuel;
First reactor that comprises many ceramic composite particles, wherein this ceramic composite particle comprises at least a metal oxide that is arranged on the carrier, wherein this first reactor is set to should reduce to produce reductive metal or reductive metal oxide by at least a metal oxide with fuel, and wherein this fuel is made up of the hydrocarbon fuel of this Fischer-Tropsch reaction device at least in part; With
Be set to this reductive metal of steam oxidation or reductive metal oxide to produce second reactor of metal oxide intermediate, this oxygenant is made up of the product of this Fischer-Tropsch reaction device at least in part.
31. the system according to claim 30 also comprises:
The geseous fuel supply source;
Handle the refining system of the hydrocarbon product that produces in this system.
32. according to the system of claim 30, wherein this oxygenant is steam, CO, air, O 2Or its combination.
33. according to the system of claim 30, steam to the small part that wherein is used for second reactor comprises the steam that Fischer-Tropsch reaction device or gasifier produce.
34., also comprise being set to by this metal oxide intermediate of oxidation so that this at least a metal oxide regenerated the 3rd reactor according to the system of claim 30.
35. according to the system of claim 30, wherein this second reactor is set to produce hydrogen or synthetic gas.
36. according to the system of claim 30, the fuel of wherein supplying with first reactor comprises the synthetic gas that the gasification by hydrocarbon fuel produces at least in part.
37. according to the system of claim 30, wherein the by product with the Fischer-Tropsch reaction device is recycled to first reactor.
38., comprise that also the steam that is set to be produced by this system produces the steam turbine of electricity according to the system of claim 30.
39. system according to claim 30, also comprise the geseous fuel hybrid position, wherein the hydrogeneous product of the geseous fuel raw material and second reactor can be implemented to mix the geseous fuel that equals about 2:1 with the mol ratio that produces hydrogen and carbon monoxide, and this geseous fuel is used for the raw mix of this Fischer-Tropsch reaction device.
40. the preparation method of ceramic composite particle may further comprise the steps:
Make the reaction of metal oxide 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;
Before in reactor, using this ceramic composite particle is reduced and oxidation.
41., also comprise promoter material added in the mixture of metal oxide and solid support material according to the method for claim 40.
42. according to the method for claim 40, wherein thermal treatment is at rare gas element, steam, oxygen, air, H 2And its combination exists and to carry out under the pressure between the vacuum pressure down and be the synoptic diagram that is used for the reactor of system of the present invention, wherein this reactor is a moving-burden bed reactor, and it comprises near about 10 normal atmosphere of annular region the fuel feed position that is arranged in according to one or more embodiments of the present invention.
43., also comprise the mixture chemical treatment of metal oxide and promotor to activate ceramic composite powder according to the method for claim 40.
44. according to the method for claim 40, wherein reactions steps is carried out via spraying drying, directly mixing, common dipping or its combination.
45. according to the method for claim 40, wherein via extrude, granulation, efflorescence (pelietization) and its combination carry out the conversion of ceramic composite powder.
46. pass through the particle of the method preparation of claim 40.
47. according to the particle of claim 46, wherein this metal oxide comprises the metal that is selected from Fe, Cu, Ni, Sn, Co, Mn and its combination.
48. according to the particle of claim 46, wherein this ceramic composite comprises this metal oxide of 40wt% at least.
49. according to the particle of claim 46, 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.
50. according to the particle of claim 46, wherein ceramic composite comprises 5wt% solid support material at least.
51. particle according to claim 46, wherein this particle comprises the promotor that contains pure metal, metal oxide, 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.
52. according to the particle of claim 51, wherein ceramic composite comprises 40wt% promoter material at the most.
53. according to the method for claim 40, 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, wherein this particle can operate be used for 10 or more times reprocessing cycle after keep active.
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