CN101157444B - Use of metal supported copper catalysts for reforming alcohols - Google Patents

Abstract

This invention is directed to a process for reforming an alcohol. The process comprises contacting an alcohol with a reforming catalyst comprising copper at the surface of a metal supporting structure, preferably a metal sponge supporting structure comprising nickel. In a certain preferred embodiment, hydrogen produced by the reforming process is used as a fuel source for a hydrogen fuel cell to generate electric power, particularly for driving a vehicle.

Description

The copper catalyst of Metal Supported is used for the purposes for reforming alcohol

Invention field

Present invention relates in general to the dehydrogenation of alcohol or reformation.More particularly it relates to it is a kind of make primary alconol such as methanol or alcohol dehydrogenase with produce hydrogen, in particular for produce electric energy fuel cell hydrogen method.The method of dehydrogenating uses the Cu-contained catalyst comprising metal supporting structure.

Background of invention

Cause alcohol to decompose it is well known that primary alconol is contacted (such as more than 200 DEG C) with suitable catalyst at elevated temperatures, produce hydrogen and carbonaceous material.This method is generally known as " alcohol reforming ".For example, as shown in the equation below 1, methanol recapitalization generates hydrogen and carbon monoxide：

CH₃OH→CO+2H₂    (1)

The hydrogen formed in reforming process can be provided to fuel cell to produce electric energy.The reforming process is to absorb heat and need to transmit enough heats to catalyst, especially in needing high-peak power, particularly needing the transport applications of high-peak power on startup (such as electric automobile).Methanol recapitalization has been described, such as Gunter, J.Catal.203,133-49 (2001)；Breen etc., J.Chem.Soc.Chem.Comm., 2247-48 (1999)；European Chemical News, page 22 (on May 11st, 1998)；With Jiang etc., Appl.Cat.97A, 145-58 (1993).Methanol recapitalization and methanol recapitalization have been described as the special applications of fuel cell hydrogen source, for example, Agrell etc., Catalysis-Specialist Periodical Reports, volume 16, the 67-132 pages (J.J.Spivey is edited, Royal Society of Chemistry, Cambridge, UK, 2002).

It is important to point out that, carbon monoxide is poisonous generally to the electrode of fuel cell.For example, when the content of carbon monoxide in hydrogen charging is more than 20ppm, the performance and power of fuel cell, which are saved, will typically decline.Referring to Pettersson etc., Int ' l J.Hydrogen Energy, volume 26, page 246 (2001).It is therefore desirable for converting carbon monoxide to carbon dioxide according to the reaction of the equation below 2 by using steam：

CO+H₂O→CO₂+H₂    (2)

The conversion is referred to as water-gas shift reaction, and has widely commercially put into practice.Such as Catalyst Handbook, the 283-339 pages (second edition, M.V.Twigg is edited, Manson publishing houses, London, 1996) are found in about the catalyst of water-gas shift reaction, technique and the description of application.

To about under conditions of similar described in methanol, ethanol reformation first produces acetaldehyde, then acetaldehyde decomposable asymmetric choice net (i.e. decarbonylation) is carbon monoxide and methanol, as shown in the equation below 3 above：

CH₃CH₂OH→CH₃C(O)H+H₂→CO+CH₄+H₂    (3)

Identical with methanol recapitalization, ethanol reformation is preferably in combination with water-gas shift reaction to convert carbon monoxide to carbon dioxide and produce extra hydrogen.For example, the water-gas shift reaction combined with ethanol reformation is according to generation carbon dioxide the equation below 4 Suo Shi, methane and hydrogen：

CO+CH₄+H₂+H₂O→CO₂+CH₄+2H₂    (4)

Most common catalyst for alcohol dehydrogenase and low temperature water gas conversion reaction is included in the copper with zinc oxide on fire resisting support structures, sometimes with other co-catalysts, wherein the fire resisting support structures are usually aluminum oxide or silica.Although copper-zinc oxide catalyst shows excellent stability to methanol-fueled CLC, but have been reported it and do not have enough stability to methanol recapitalization, such as Cheng, Appl.Cat.A, 130, the 13-30 pages (1995), with Amphlett etc., Stud.Surf.Sci.Catal., 139, the 205-12 pages (2001) are described.

It is reported that the active catalyst of many other reformations for alcohol is made up of metal oxide, catalytic metal is generally comprised.Yee et al. is reported in CeO in J.Catal.186,279-95 (1999) and Sheng et al. in J.Catal.208,393-403 (2002)₂The CeO of itself or subsidiary rhodium, platinum or palladium₂The ethanol reformation of upper progress.But these articles are pointed out, ethanol can be analyzed to a variety of undesirable accessory substances, such as acetone, ketenes and butylene.

Known copper-nickel catalyst has high activity to alcohol dehydrogenase.For example, the copper-nickel catalyst being carried on aluminum oxide is active to ethanol reformation.Reformation of the ethanol on copper-nickel catalyst is via Marino et al. in Stud.Surf.Sci.Catal.130C, and 2147-52 (2000) and Freni et al. are in React.Kinet.Catal.Lett.71, described in 143-52 (2000).Although these bibliography all point out catalyst and provide good selectivity to the dehydrogenation of acetaldehyde, each bibliography encounters not exclusively conversion and the problem of water-gas shift activity is minimum at 300 DEG C.In addition, traditional ethanol reforming catalysts tend to fast deactivation because of Carbon deposition on the surface (a kind of process for being referred to as coking).At a temperature of higher than 400 DEG C, coking accelerates because catalyst surface there is acid sites, and this promotes the ethene that ethanol dehydration is formed and then polymerize.The coking problem for being related to ethanol reforming catalysts has been described, for example, Haga etc., Nippon Kagaku Kaishi, 33-6 (1997) and Freni etc., React.Kinet.Catal.Lett., 71, the 143-52 pages (2000).

Therefore, there is still a need for improved mellow wine dehydrogenating and can be carried out under medium reaction temperature alcohol reforming and have enough conversion ratios method.

Brief summary of the invention

Therefore, specific objective of the invention is to provide method novel and that the improved dehydrogenation for alcohol is to form hydrogen, especially with the method for the catalyst higher than prior art alcohol reforming catalyst density；A kind of method of improved use reforming catalyst, the catalyst provides more preferable thermal conductivity to support the endothermic reaction；A kind of method of the improved use without acid site catalyst；A kind of improved use is converted into methane and carbon monoxide to acetaldehyde at moderate temperatures has high activity and the method for the catalyst of the stability improved；A kind of method of the improved hydrogeneous product mixtures for producing the fuel cell for being applied to production electric energy；With a kind of novel and actual method for producing electric energy under reforming temperature below about 400 DEG C by ethanol, this method to need the simplification dynamical system of less expensive hydrogen fuel cell unit, and improves efficiency.

Therefore, in brief, the present invention relates to a kind of method for reforming alcohol.This method includes making alcohol contact with reforming catalyst of the metal supporting structure surface comprising copper.In preferred embodiments, the reforming catalyst includes copper in metal sponge supporting structure surface, wherein preferably comprising the metal sponge of nickel or the metal sponge comprising nickel and copper.

The invention further relates to a kind of method of reformed ethanol.This method includes making the material gas mixture comprising ethanol contact to produce the reformate mixture for including hydrogen at a temperature of below about 400 DEG C with reforming catalyst.The reforming catalyst includes copper on metal supporting structure surface.In preferred embodiments, methods described makes the material gas mixture comprising ethanol be contacted with catalyst of the nickel carrier surface comprising copper at a temperature of being included in below about 350 DEG C.

The invention further relates to a kind of method that electric energy is produced by fuel cell.This method includes making the material gas mixture comprising ethanol contact in dehydrogenation reaction zone with dehydrogenation, to produce the product mixtures for including hydrogen.The dehydrogenation includes copper on metal supporting structure surface.Hydrogen from the product mixtures and oxygen are introduced into fuel cell and flow out thing to produce electric energy and fuel cell comprising methane.The fuel cell outflow thing is introduced into combustion chamber and burnt in the presence of oxygen.

In other embodiments, the present invention relates to a kind of improved copper electroplating method for being used to prepare dehydrogenation.

The other objects and features of the invention are obvious to a certain extent and hereinafter will partly indicated.

The brief description of accompanying drawing

Fig. 1 is the dynamical system sketch according to one embodiment of this invention, wherein the hydrogeneous product mixtures produced in alcohol reforming are introduced hydrogen fuel cell to produce electric energy as fuel.

Fig. 2 is the dynamical system sketch according to another embodiment of the present invention, the hydrogeneous product mixtures wherein produced in alcohol reforming are introduced hydrogen fuel cell to produce electric energy as fuel, and the effluent wherein from the hydrogen fuel cell is sent in internal combustion engine, and the internal combustion engine is also supplied with independent raw polyol.

Preferred embodiment explanation

According to the present invention, the mixture of the mixture of copper and other metals, particularly copper and mickel is used as the catalyst of alcohol dehydrogenase (reforming).It has been found that the Cu-contained catalyst comprising metal supporting structure, such as, by the catalyst for depositing copper to nickel sponge support structures and preparing, show the activity of raising during as the catalyst for reforming primary alconol such as methanol and ethanol in the gas phase.The catalyst used in present invention practice is more stable at moderate temperatures thermally decomposing ethanol for hydrogen, methane, carbon monoxide and carbon dioxide, and is especially active to this.Produced hydrogen can be utilized, for example, by the way that hydrogen is converted into water and by methane in company with leaving any remaining combust of hydrogen one in the air-flow of fuel cell to produce energy in a fuel cell.The combustion process can or driving generator to produce extra electric energy or be utilized in internal combustion engine to produce mechanical energy.This dynamical system provides a kind of method that energy is easily obtained by ethanol, and this method also has other advantages：Undesirable discharge can be preferably minimized by the burning, while providing heat to reform catalyst bed.Broadly, the product mixtures produced in the reforming primary alcohols according to the present invention, which (can be for example carbonylated, be hydrogenated and hydroformylation) in neutralization materials processed and applied in chemical process application, is used as hydrogen and/or carbon monoxide source.In addition, alcohol reforming catalyst described herein can be used for producing the product mixtures comprising hydrogen and carbon monoxide, the mixture is referred to as the synthesis gas from raw polyol.

A. catalyst

In one embodiment of the present invention, alcohol dehydrogenase or reforming catalyst include copper-containing active phase on the surface of metal supporting structure, and the metal supporting structure includes copper and/or one or more non-copper metals.The catalyst generally comprises at least about 10 weight % copper, preferably from about 10 weight % to about 90 weight % copper, and copper of the more preferably from about 20 weight % to about 45 weight %.The catalyst can include the structure of essentially homogeneous, such as copper sponge, cupric single-phase alloy, or the heterogeneous structure with more than one discontinuous phase.For example, copper-containing active mutually can be present in the surface of support structures, such as copper coating or outer layer as discontinuous phase；It is used as a part for superficial layer or homogeneous catalyst structure.In copper-containing active in the case where supporting structure surface includes discontinuous phase, the metal supporting structure completely or partially can be coated mutually by copper-containing active.For example, in particularly preferred embodiment as described in below, catalyst includes the copper-containing active phase on the metal sponge supporting structure surface comprising nickel.This catalyst includes about 10 weight % to about 80 weight % copper, and more preferably from about 20 weight % are to about 45 weight % copper.The surplus of catalyst 10 weight % preferably by nickel and less than about aluminium or other metals is constituted.In addition, in preferred embodiment of the metal supporting structure comprising nickel, it is necessary to be pointed out that copper and nickel are all miscible under all proportions.So, the catalyst comprising the copper-containing active phase in Ni body structure surface may not necessarily have phase boundary between copper-containing active phase and support structures.

According to the routine of catalytic action, the activity of dehydrogenation can be improved by improving surface area.Therefore, for freshly prepd catalyst, it is generally preferable to at least about 10m²/ g surface area, described value is determined by Brunauer-Emmett-Teller (BET) method.It is highly preferred that the catalyst has about 10m²/ g to about 100m²/ g BET surface area, even more preferably with about 25m²/ g to about 100m²/ g BET surface area, and still more preferably from about 30m²/ g to about 80m²/ g BET surface area.

In a certain preferred embodiment for reformed ethanol, the surface of catalyst preferably comprises the nickle atom for the amount for promoting the aldehyde decarbonylation such as acetaldehyde.Preferably, nickel of the surface comprising about 5 to about 100 μm of ol/g, wherein described value are by Schmidt, " Surfaces of Raney

Catalysts, " inCatalysis of Organic Reactions, the method for the 45-60 pages description determines (M.G.Scarosand M.L.Prunier, eds., Dekker, New York, 1995).It is highly preferred that surface nickel concentration is about 10 μm of ol/g to about 80 μm of ol/g, most preferably from about 15 μm ol/g to about 75 μm of ol/g.

1. support structures

The support structures of mellow wine dehydrogenating include metal.Suitable metal supporting structure may include various structures and component.Preferably, the support structures are higher than the metal of copper comprising tensile strength and/or yield strength.Thus, according to preferred embodiment, the support structures include non-copper metal.The non-copper metal can include single metal or various metals.In this preferred embodiment, at least about 10 weight % of the metal supporting structure are non-copper metals.In a kind of particularly preferred embodiment, at least about 50 weight % (more preferably at least about 65 weight %, at least about 80 weight %, even at least at least about 85 weight % or about 90 weight %) of the metal supporting structure weight are non-copper metals.In another particularly preferred embodiment, the support structures include the copper of at least about 10 weight % non-copper metal and at least about 50 weight % (more preferably from about 60 weight % to about 80 weight %).

Preparing the metal or alloy of metal supporting structure preferably has the tensile strength and/or yield strength higher than single copper.Composition particularly preferably has at least about 70MPa yield strength, even more preferably at least about more preferably at least about 100Mpa, 110Mpa.Composition it is also particularly that with least about 221Mpa tensile strength, even more preferably at least about more preferably at least about 275Mpa, 300Mpa.For example, it was reported that the composition comprising 90 weight % copper and 10 weight % nickel has 110MPa yield strength and 303Mpa tensile strength；Composition comprising 70 weight % copper and 30 weight % nickel is it is reported that the tensile strength of yield strength and 372Mpa with 138Mpa；Composition comprising 70 weight % copper and 30 weight % zinc is it is reported that the tensile strength of yield strength and 331Mpa with 124Mpa.Referring to Krisher and Siebert, Perry ' s Chemical Engineers ' Handbook, 23-42 to 23-49 pages (the 6th edition, McGraw Hill, New York, NY1984).

Preferably, the non-copper metal of the metal supporting structure is selected from by nickel, cobalt, zinc, silver, palladium, gold, tin, iron and and its group that constitutes of mixture.It is highly preferred that the metal supporting structure includes nickel.Nickel is usually most preferred, because, for example：(1) compared with other suitable metals such as palladium, silver and cobalt, nickel is relatively cheap, (2) it is methane and carbon monoxide that nickel, which combines with copper and has been shown to promote acetaldehyde decarbonylation, and (3) copper is deposited on nickeliferous support structures it is general less than copper is deposited on into difficulty on the support structures of other suitable metals comprising significant quantity.For example, it is possible to use copper is deposited on nickeliferous support structures by simple electrochemical displacement sedimentation.But other technologies are there are, available for (such as the chemical plating and metal-organic chemical vapor deposition) being deposited on copper on the support structures comprising other suitable non-copper metals.

Often desirably, copper is deposited on to the surface of the metal supporting structure using the electrochemical displacement deposition (being also described as in the prior art " immersion plating ") being described in detail below.It that case, the metal supporting structure preferably comprises following metals：It is less than reduction potential for metallic copper for the reduction potential of the metal, i.e. relative to NHE (standard hydrogen electrode), be below about+343 millivolts for the reduction potential of the metal.Non- copper metal with this reduction potential includes such as nickel, zinc, tin, iron and cobalt.In this metal of presence close to the supporting structure surface, copper metal can be simply deposited on to the surface of the support structures by making the surface be contacted with mantoquita (being usually Cu (II) salt) solution.More specifically, in electrochemical displacement deposition process, this metal close to the supporting structure surface tends to oxidized (and entering solution as ion) when being contacted with copper ion solution.When this phenomenon occurs, the copper ion in solution close to the supporting structure surface is reduced to copper metal, and copper metal is deposited on the surface of the support structures again.For example can occur the reaction when the support structures comprising nickel are contacted with copper salt solution, the reaction is as shown in the equation below 5：

Cu²⁺+Ni⁰→Cu⁰+Ni²⁺    (5)

As it was noted above, when by using electrochemical displacement deposition by copper be deposited on the supporting structure surface so as to prepare catalyst when, particularly preferably using nickeliferous support structures because nickel have at least four it is desirable the characteristics of：(1) reduction potential to metallic copper is less than to the reduction potential of the metal, (2) relatively stablize under alcohol dehydrogenase reaction condition of the present invention, (3) there is the mechanical strength and anti-wear performance higher than copper, and (4) nickel copper catalyst promotes acetaldehyde decarbonylation generation carbon monoxide and methane.

When the support structures include more than one metal, at least about 80 weight % preferably in support structures (more preferably at least about 85 weight %, even more preferably at least about 90 weight %, even more preferably essentially all of) metal is alloy form.In a particularly preferred embodiment, the metal formation substitutional alloy (also known as " single-phase alloy "), wherein alloy has single, continuous phase.Heterogeneous alloy (alloy for including at least two discontinuous phase) is also used as support structures.In the embodiment that copper-containing active is mutually deposited on cupric multiphase load structure, the surface portion of relatively poor copper, copper tends to preferentially be covered in the copper-rich part of multiphase load body structure surface.Alloy is the component and their concentration that single-phase or multiphase depends on alloy.Usually, for example, the main metal supporting structure being made up of nickel and copper is all single-phase under any nickel concentration.But, such as when the support structures are mainly made up of copper and zinc, there are many zinc concentrations (generally higher than about 35 weight % concentration) for causing alloy for two-phase.

It should be appreciated that in addition to metallic atom, the support structures can also include non-metallic atom (such as boron, carbon, silicon, nitrogen, phosphorus).Typically it is described as " interstitial alloy " in the art containing this nonmetallic alloy.Support structures comprising this alloy may have a variety of advantages, such as enhanced mechanical strength.But, the catalyst comprising interstitial alloy typically contains at least about 70 weight % metal.

In particularly preferred embodiments, the support structures are the metal sponges comprising copper and/or one or more above-mentioned suitable non-copper metals.When for herein when, term " metal sponge " refers to at least about 10m²The porous form of the metal or metal alloy of/g BET surface areas.It is preferred that metal sponge support structures have at least about 20m²/ g BET surface area, more preferably at least about 35m²/ g, even more preferably at least about 50m²/ g, and even more preferably at least about 70m²/g.According to present invention has been found that the copper-containing active in metal sponge supporting structure surface mutually generate show mechanical strength, high surface area, high-termal conductivity and density, combine the material of the sponge supporting structure of desired copper catalysis activity.

The metal sponge support can be powder or ball shape with the catalyst formed.Moreover, the mellow wine dehydrogenating can be used with monolithic form, the monolithic form is prepared by the way that catalyst of the present invention to be mixed into the surface of suitable porous matrix (such as honeycomb).In general, in order to minimize back pressure in following reformers, the catalyst of pellet and monolithic form is preferred.Moreover, monolith catalyst may for because of vibration (such as in vehicle application) caused by chemical erosion in mechanical damage and/or reaction medium it is more stable.

It is important to point out that, when catalyst of the present invention with pellet or monolithic form in use, wishing only have part piller or only stone to include the metal sponge for being used for loading copper-containing active phase.That is, described alcohol reforming catalyst can be included as fixed bed or monolith catalyst and provide the non-porous matrix of intensity and shape, at the same still provide it is one or more be used to loading copper-containing active phase there is at least 10m²Porous (i.e. metal sponge) region of/g BET surface areas.Being suitable as the non-porous materials of fixed bed or only stone substrate generally may include any material thermally-stabilised and chemically stable under plating and the condition of reorganization.Although nonmetal basal body can be used, metallic matrix as stainless steel, copper, nickel, cobalt, zinc, silver, palladium, gold, tin, iron and their mixture more preferably.

When metal sponge support is powder type, the preferred average grain diameter of the metal sponge is at least about 0.1 μm, preferably from about 0.5 to about 100 μm, more preferably from about 15 to about 100 μm, even more preferably about 15 to about 75 μm, even more preferably from about 20 to about 65 μm.When the catalyst is piller or monolithic form, as understood by a person skilled in the art, catalyst of the present invention is mixed into the size of perforate in the size and any this monolithic structure of piller or only stone substrate thereon and can changed according to the need for Reformer designs.

Metal sponge support structures can be prepared by the generally known technology of those skilled in the art.It typically can be found in Lieber and Morritz, Adv.Catal., 5,417 (1953) (about the summary of metal sponge).Hawley ' s Condensed Chemical Dictionary, the 13rd edition, (the Rev.by Richard J.Lewis of page 621 can also be referred to, Sr., Van Nostrand Reinhold, New York, NY 1997) (method that description prepares iron sponge).

Bibliography prepared by description nickel sponge includes, for example, Augustine, Robert L., Catalytic Hydrogenation Techniques and Applications in OrganicSynthesis, in the 147-49 pages of annex (Marcel Dekker, Inc., 1965).Hawley ' s Condensed Chemical Dictionary can also be referred to, 13rd edition, (the Rev.byRichard J.Lewis of page 955, Sr., Van Nostrand Reinhold, New York, NY 1997) (describing the technology that the known soda lye by using 25 weight % leaches aluminium from the alloy comprising 50 weight % nickel and 50 weight % aluminium and prepares sponge nickel).In the case where preparing nickel sponge, the metal supporting structure is preferably substantially without non-activated region, and scrubbed basic alumina-free.Unreacted aluminium tends to and steam reaction under the condition of reorganization, and the aluminum oxide for spreading and being provided for ethanol dehydration acid sites can be hindered by being formed.

Bibliography prepared by description cu zn sponge includes, for example, Bridgewater etc., Appl.Catal., 7,369 (1983).This kind of bibliography also includes, for example, M.S.Wainwright,《Copper-zinc catalyst in copper and Ruan in Ruan》Chem.Ind. (Dekker), 68,213-30 (1996).

Bibliography prepared by description nickel iron sponge includes, for example, Becker and Schmidt,《Raney nickel-iron catalyst》, Ger.Offen.DE 2,713,374 19780928 (1978).

Bibliography prepared by description nickel cobalt sponge includes, for example, Orchard etc.,《The preparation of Raney nickel-Co catalysts and performance》, J.Catal., 84,189-99 (1983).

According to a kind of preferred embodiment, such as co-assigned U.S. Patent No. 6, described in 376, No. 708, support structures include nickel copper sponge (i.e. the copper sponge of the nickel sponge of Copper-cladding Aluminum Bar or nickel doping).Bibliography prepared by description nickel copper sponge also includes, such as Young, J.Catal., 64,116-23 (1980) and Wainwright and Anderson, J.Catal., 64,124-31 (1980).

Suitable metal sponge includes the material that can be obtained with trade mark RANEY from W.R.Grace＆Co. (DavisonDivision, Chattanooga, TN), and any source the material for being described as " raney metal " in this area.Raney metal for example can leach aluminium from the alloy of aluminium and base metal (such as nickel, cobalt, copper) by using soda lye and obtain.Various metal sponges can also everywhere be bought from following：For example, Gorwara Chemical Industries (Udaipur, India)；Activated Metals＆Chemicals, Inc. (Sevierville, TN)；Degussa-Huls Corp. (Ridgefield Park, NJ)；Engelhard Corp. (Iselin, NJ) and Aldrich ChemicalCo. (Milwaukee, WI).

According to another preferred embodiment of the present invention, support structures include nickel sponge.Suitable commercially available nickel sponge example includes, and (manufacturer indicates the RANEY 2800 for example sold by W.R.Grace＆Co.：With at least 89 weight % Ni；No more than 9.5 weight % Al；No more than 0.8 weight % Fe；Average grain diameter is 20-60 μm；Proportion is about 7；Bulk density based on the catalyst pulp weight containing 56% solid in water is 1.8-2.0kg/l (15-17lbs/gal)), (manufacturer indicates RANEY4200：With at least 93 weight % Ni；No more than 6.5 weight % Al；No more than 0.8 weight % Fe；Average grain diameter is 20-50 μm；Proportion is about 7；Bulk density based on the catalyst pulp weight containing 56% solid in water is 1.8-2.0kg/l (15-17lbs/gal)), (manufacturer indicates RANEY 4310：With at least 90 weight % Ni；No more than 8 weight % Al；0.5-2.5 weight % Mo；No more than 0.8 weight % Fe；Average grain diameter is 20-50 μm；Proportion is about 7；Bulk density based on the catalyst pulp weight containing 56% solid in water is 1.8-2.0kg/l (15-17lbs/gal)), (manufacturer indicates RANEY 3110：With at least 90 weight % Ni；0.5-1.5 weight % Mo；No more than 8.0 weight % Al；No more than 0.8 weight % Fe；Average grain diameter is 25-65 μm；Proportion is about 7；Bulk density based on the catalyst pulp weight containing 56% solid in water is 1.8-2.0kg/l (15-17lbs/gal)), (manufacturer indicates RANEY 3201：With at least 92 weight % Ni；No more than 6 weight % Al；No more than 0.8 weight % Fe；0.5-1.5 weight % Mo；Average grain diameter is 20-55 μm；Proportion is about 7；Bulk density based on the catalyst pulp weight containing 56% solid in water is 1.8-2.0kg/l (15-17lbs/gal)), (feature of 5,922, No. 921 descriptions of U.S. Patent No. is as follows by RANEY 3300：Ni containing 90-99.1 weight %；No more than 8.0 weight % Al；No more than 0.8 weight % Fe；0.5-1.5 weight % Mo；25-65 μm of average grain diameter；Proportion is about 7；Bulk density based on the catalyst pulp weight containing 56% solid in water is 1.8-2.0kg/l (15-17lbs/gal)), RANEY 2724 (Cr co-catalysis) and RANEY 2724 (Cr co-catalysis)；The catalyst for being described as " Raney nickel " sold by GorwaraChemical Industries；The A-4000 and A-5000 sold by ActivatedMetal＆Chemicals, Inc.；The nickel ABMC sold by Degussa-Huls Corp. and " Raney nickel " that is 22,167-8 by the Aldrich Chemical Co numberings sold.

The example of fixed bed matrix comprising metal sponge support structures includes the nickel sponge piller of 6,284, No. 703 descriptions of European Patent No. EP0648534 A1 and U.S. Patent No., and the disclosure is expressly incorporated herein by reference.Nickel sponge piller, particularly those as fixed bed catalyst, for example can buy from W.R.Grace＆Co. (Chattanooga, TN) and Degussa-Huls Corp. (Ridgefield Park, NJ).

2. the deposition of copper-containing active phase

The copper-containing active can mutually utilize well known in the art various for the technology of metal deposit to metal surface to be deposited into metal supporting structure surface.These technologies include such as liquid phase process, such as electrochemical displacement deposition and chemical plating；And CVD method, such as physical deposition and chemical deposition.For being described in co-assigned U.S. Patent No. 6,376,708 and co-assigned separately while pending U.S. Patent Application No. 09/832,541, is disclosed as US-2002-0019564-A in the suitable method of metal supporting structure copper-depositing on surface.U.S. Patent No. 6,376,708 and U. S. application US-2002-0019564-A1 full text are by reference to being fully incorporated herein.

It is important to point out that, copper and most of which supporting structure metals it is least partially miscible and with nickel complete miscibility.Thus, it has been found that copper deposition process can produce the catalyst with copper or more particularly with copper-containing active phase, in a part of the supporting structure surface as the discontinuous phase of such as outer layer or coating, it may enter the main body of support structures from the surface migration of support structures in a part of the supporting structure surface as superficial layer, or copper.It is not limited to specific theory, it is believed that the catalyst surface can be moved during the reaction of deposition and alcohol reforming process, sintered or other structural rearrangements, cause these changes of form in copper-containing active phase.However, it has been found that the copper deposition process causes copper content in catalyst to improve comprehensively, the copper of deposition is primarily present in or close to the surface of freshly prepared catalyst, the catalyst before deposition than being more rich in copper.

A. the electrochemical displacement of copper is deposited

As it was noted above, copper wherein the copper ion in the copper salt solution contacted with support structures is reduced to metallic copper, and can be oxidized by electrochemical displacement deposition method to the metal supporting structure surface close to the non-copper metal of supporting structure surface.Metallic copper is again in supporting structure surface formation coating, while non-copper ion enters solution.The general description of relevant electrochemical displacement deposition is found in, such as Krulik and Mandich, " Metallic Coatings (Survey) ", Kirk-OthmerEncyclopedia of Chemical Technology the 4th edition, volume 16, the 258-91 pages (J.I.Kroschwitz and M.Howe-Grant, eds., Wiley, New York, NY, 1995).Co-assigned U.S. Patent No. 6,376,708 is found in being more particularly described for electrochemical displacement deposition on metal sponge support structures about copper, its content is expressly incorporated herein by reference.

For copper to be deposited in the particularly preferred method of metal supporting structure, electrochemical displacement deposition is first carried out in the basic conditions, and electrochemical displacement deposition is then carried out in acid condition.In similar particularly preferred embodiment, copper is added without in acidic step, but can occur the redeposition of copper, because the monovalence copper dissolution being deposited in basic step on carrier and redeposition.The step is described in following embodiments 6.Preferably, when copper is deposited metal supporting structure substantially without surface oxidation.In the case where metal supporting structure has oxidized surface (such as when when support structures (or even under water) exposure 6 months or longer in atmosphere), particularly preferably support structures are pre-processed with reducing agent.For example, the support structures can be stirred in sodium borohydride solution, for every 25g metal supporting structures, the solution preferably comprises at least 1g sodium borohydrides, and with least about 10 pH value.Generally, support structures are contacted with reducing agent at room temperature is just enough the basic support structures for removing surface oxidation for about 5 minutes to about 2 hours.

In order to start the electrochemical displacement deposition that two-step is rapid, alkaline/acid, slurried, the progress preferably in water in water or alcoholic solution by metal supporting structure, and pH is adjusted to 7.Mantoquita is added in metal supporting structure slurry, preferably with the solution addition comprising mantoquita and chelating agent, especially such as EDTA amine chelating agent.Preferably, the copper salt solution includes the weight % of opposing metallic support structures about 10 to about 30 weight % copper.The suitable mantoquita for replacement deposition includes for example (providing incomplete enumerate) nitrate, sulfate, hydrochloride and the acetate of copper.The salt of copper (i.e. Cu (II)) comprising divalent state is usually most preferred.Although the salt comprising monovalence and means of trivalent copper can also be used, they are typically less preferred, because they are general unstable, are difficult to buy, and/or insoluble in alkaline mixt.

Then, alkali metal hydroxide (such as NaOH) or another suitable alkali are slowly added into the slurry, preferably continuously stirs simultaneously and use nitrogen bubbling.The preferably relatively described mantoquita of the alkali hydroxide soln includes the alkali metal hydroxide of at least 1 molar equivalent, the more preferably alkali metal hydroxide relative to the molar equivalent of the mantoquita about 1.1 to about 1.6.Although the step is reacted comprising replacement deposition, the oxidized metal in the part from support structures is still combined closely with support structures and is removed in subsequent acidic step.In addition, the reaction of first step basic displacement deposition causes cuprous oxide (Cu₂) and metallic copper is deposited on the surface of support structures O.

After basic displacement deposition, supernatant liquor is removed by decantation or other method, and copper is further deposited on catalyst supporting structure surface in acid condition.After decantation, the metal supporting structure is slurried again in alcohol or the aqueous solution.Acid buffer is added in metal supporting structure slurry, pH value is fallen below about 4.The temperature of buffer solution is preferably between about 40 DEG C and about 90 DEG C.The acid buffer can reduce the chelating agent of pH value comprising any residual metal that can suitably control in solution and then.It is highly preferred that the acid buffer preferably has about 1 to about 4 pKa, so as to which pH value in electroplating bath is maintained at into about 1 to about 4.Preferably, the acid buffer is gluconic acid/gluconate buffer.For depositing copper on nickeliferous metal supporting structure surface, gluconic acid is preferably as gluconic acid is the good chelating agent of the residual aluminum ions existed in solution.In addition, it is necessary to note that the use of the buffer solution based on phosphoric acid being typically less preferred, because in the presence of the danger for forming insoluble phosphate precipitation.Then it can continuously stir and above-mentioned mantoquita (preferably as copper salt solution) is added into the metal supporting structure slurry in a period of about 5 to about 40 minutes under nitrogen bubble.Preferably, as described in Example 6, the sulfuric acid for adding about 0.2 to about 0.4 molar equivalent replaces copper salt solution.The step improves activity of the catalyst to water-gas shift reaction.It is then possible to which stopping stirring making catalyst sedimentation, so that supernatant liquor can be removed by decantation or other method.

It is important to point out that, when the catalyst structure is piller or monolithic form, the copper facing may be with above-mentioned difference.For example, commercially available pellet metal sponge support is often what is not exclusively activated.The activation of commercially available pellet carrier generally include to remove it is most of to deep layer, typically up to can be of about 200 μm of aluminium, to produce metal sponge-type structure.But, the core of piller typically still includes the unactivated alloy rich in zeroth order aluminium of very big concentration.So, the aluminium at core can under the condition of reorganization with steam and ethanol synthesis, form crackle and simultaneously damage mechanical integrity.Therefore, the metal sponge activated completely is preferred.The example of complete activated material is the hollow sphere activated ni described in U.S. Patent No. 6,284,703.

In addition, diffusion can limit the plating of fixed bed carrier inside.Thus, it is preferable to the plating of a carrier be fixed at or below room temperature, because the ratio of diffusion rate and electroplating reaction speed is preferably at low temperature.To avoid copper concentration from consuming (if most copper is consumed because being deposited on outside carrier, this will occur) excessively in carrier inside, the copper concentration improved is used further preferably in electroplating bath.Embodiment 10 describes a kind of example of preferred fixed bed carrier plating step.

Preparing another preferred embodiment of the firm catalyst of mechanical performance under the condition of reorganization is, general first to be to electroplate and thermally-stabilised and chemically stable one layer of nickel-aluminum alloy of substrate deposit under the condition of reorganization by thermal spraying.Suitable matrix typically may include steel or another metal, but nonmetal basal body can also be used.The thickness of the layer is preferably between 5 to 500 μm, more preferably between 10 to 150 μm.The preparation of the metal sponge films of load is described in U.S. Patent No. 4,024,044 and Sillitto etc., Mat.Res.Soc.Sym.Proc., volume 549, the 23-29 pages (1999).The nickel-aluminum alloy-layer provides metal supporting structure and preferably in copper facing front activating.

B. electroless copper

Chemical plating can also be used for mutually depositing to copper-containing active on the surface of metal supporting structure.Similar to electrochemical displacement deposition, chemical plating is included in the solution contacted with support structures is reduced to copper metal by copper ion.But, from electrochemical displacement deposition unlike, essentially all of copper ion is reduced in itself by situ reduction agent rather than the support structures.When copper ion is reduced to copper metal in the solution, copper metal forms coating on supporting structure surface.Copper is deposited on metal supporting structure surface using chemical plating and is described in detail in co-assigned U.S. Patent No. 6,376,708, its content is expressly incorporated herein by reference.

3. the copper-containing active phase of integration

In another embodiment of the present invention, catalyst does not include the copper (mutually depositing or be covered in catalyst surface without discontinuous copper-containing active) being covered on metal supporting structure.Mixed on the contrary, copper has in the carbon monoxide-olefin polymeric of copper-containing active phase with other metals of the desirable performance of offer on surface.The carbon monoxide-olefin polymeric can be substantially homogeneous.Preferably, this catalyst is copper-containing metal form of sponge (for example, nickel copper sponge).

4. selectable assistant metal

In addition to the copper and non-copper metal of catalyst block is constituted as described above, the catalyst can be optionally comprising one or more assistant metals.Suitable assistant metal is selected from the group being made up of chromium, titanium, niobium, tantalum, zirconium, vanadium, molybdenum, manganese, tungsten, cobalt, nickel, bismuth, antimony, germanium and zinc.For example, utilize assistant metal, particularly zinc and chromium, extend the service life of copper catalyst and keep or strengthen them and be well known in the art for the activity of water-gas shift, and via Lloyd etc. in Catalyst Handbook, the 309-312 pages (second edition, M.V.Twigg is edited, Manson publishing houses, London, 1996) description.The presence of one or more this metals typically extends the life-span of catalyst, that is, extends catalyst during it can be used for alcohol reforming before its activity is reduced to unacceptable level.In above-mentioned element, vanadium, chromium, molybdenum, zinc and combinations thereof are particularly preferred, and are preferably present in the surface of catalyst in the form of an oxide.

The amount of assistant metal can change in a wide range.Preferably, the total concentration of assistant metal in the catalyst is copper at least about 10 parts by weight per million weight portions.More preferably, the total concentration of assistant metal in the catalyst is about 0.002 weight % to about 5 weight %, more preferably from about 0.002 weight % to about 2.5 weight %, even more preferably about 0.005 weight % are to about 2 weight %, even more preferably from about 0.5 weight % to about 1.5 weight %.Generally, the total concentration of assistant metal is no more than about 5 weight %.Although the assistant metal of higher concentration can be used, exceed this concentration by the way that other benefit can not be obtained, and the activity of catalyst can typically decline.

One or more assistant metals may be included in metal supporting structure and/or in the copper-containing active phase of supporting structure surface.In the case where including assistant metal in expecting alloy-metal support structures, assistant metal is preferably mixed into alloy while alloy is formed.In the case of including assistant metal in the copper-containing active phase for expecting supporting structure surface, assistant metal can be deposited simultaneously with copper in some cases.But, copper by replacement deposition or chemical plating it is (as described above) deposition in the case of, assistant metal preferably copper deposition after add catalyst because assistant metal may dissolve under the conditions of replacement deposition and suppress chemical plating.Assistant metal can typically be added to the surface of catalyst simply by making catalyst be contacted with the solution comprising assistant metal salt (such as sulfate, nitrate, hydrochloride).The method that the oxide of assistant metal is deposited on copper sponge is also suitable for the surface that metal supporting structure of the present invention is deposited to after the completion of electroplating process, and it is found in Franczyk etc. U.S. Patent No. 5,292, No. 936, the entire disclosure is expressly incorporated herein by reference.

B. preferred alcohol reforming reaction condition and dynamical system

Alcohol reforming method of the present invention, which is generally comprised, makes the material gas mixture comprising alcohol reactant be contacted with the above-mentioned catalyst bed comprising Cu-contained catalyst in dehydrogenation reaction zone.

The dehydrogenation reaction zone preferably comprises continuous-flow system, and the configuration of the system can ensure that low back pressure and initiation, the sufficient heat transfer for maintaining the endothermic reaction.The Reformer designs for realizing abundant heat transfer are known, and are described in U.S. Patent No. 3,522,019 and Autenrieth such as Buswell etc. U.S. Patent No. 5,935, No. 277 and the 5th, 928, No. 614.Each patent is all described to be carried out heat exchange to provide the catalytic reforming alcohol reactor of heat by heat conductive wall and thermal source.Being preferably used in the thermal source of Heating Dehydrogenation reaction zone most often includes the waste gas from the alcohol incomplete oxidation being partly reformed, or from the independent burning reaction using alcohol or another fuels sources.As described below, especially preferred embodiment of present invention be use come from combustion chamber, be preferably in dehydrogenation reaction zone downstream combustion chamber waste gas as dehydrogenation reaction zone thermal source.

Alcohol reforming reaction be strong endothermic reaction, and to the effective heat transfer of dehydrogenation reaction zone be necessary for good conversion ratio.It is important to, compared with traditional reforming catalyst comprising ceramic monolith, the Cu-contained catalyst described herein comprising metal supporting structure shows more preferable thermal conductivity.For example, such as Gersten exists, " The Physics and Chemistry of Materials, " Wiley, New York, described by page 2001,144, the thermal conductivity of copper and mickel is respectively 401W/mK and 91W/mK at 300k.By comparison, the thermal conductivity of traditional reforming catalyst material such as Alpha-alumina is 36W/mK under 300K, and silica is 1.4W/mK, and magnesia is 36W/mK.The thermal conductivity of Cu-contained catalyst comprising metal supporting structure of the present invention at 300k preferably at least about 50W/mK, more preferably at least about 70W/mK, about especially at least 90W/mK.

The alcohol reforming reaction is general to be carried out at a temperature of greater than about 100 DEG C in gas phase.But, according to the present invention, the alcohol preferably at a temperature of below about 400 DEG C in reformer feed gas mixture.It is highly preferred that reforming reaction is carried out at about 150 DEG C to about 400 DEG C, more preferably from about 200 DEG C to about 375 DEG C of temperature, most preferably from about 250 DEG C to about 325 DEG C of temperature.For example, it was found that copper-plated metal sponge catalyst ought be used in the methods of the invention, during copper-plated metal sponge particularly comprising nickel or the nickel for mixing copper, ethanol reformation can be carried out with sufficiently high conversion ratio at a temperature of about 250 DEG C to about 300 DEG C.

Because reforming reaction is the endothermic reaction, it is therefore necessary to the temperature for supplying heat in addition to keep needing in dehydrogenation zone.Generally, during alcohol reforming is reacted, reforming reaction can be controlled in the temperature of catalyst bed by any mode well known in the art.Preferably, the temperature of catalyst bed is controlled as isothermal over its length or with positive thermograde (i.e. temperature is gradually stepped up from the entrance of bed to outlet).For example, alcohol reacting gas can introduce catalyst bed at a temperature of about 10 DEG C to about 50 DEG C lower than required catalyst bed exit temperature, while providing necessary additional heat to keep desired state of temperature in catalyst bed to dehydrogenation reaction zone.

When reformed ethanol, it is necessary to, it is noted that in narrow temperature range of operation and avoiding too high temperature from reducing the formation of excessive methane byproduct.The formation (i.e. " methanation ") of methane is undesirable, because the reaction needs the speed of 3 moles of hydrogen to consume expensive hydrogen production with 1 mole of methane of every production.Operation can also avoid excessive methanation under low pressure.Therefore, the preferably less than about 30psig of the pressure at catalyst bed inlet, more preferably less than about 10psig.

The dehydrogenation reaction is generated can introduce hydrogen fuel cell to produce the gaseous product mixture of electric energy comprising hydrogen.Therefore, especially preferred embodiment of present invention is to produce the hydrogen for producing electric energy in a fuel cell by primary alconol such as methanol, ethanol or their mixture dehydrogenation.For example, the suitable applications of the hydrogen in product mixtures of the present invention produced are used as hydrogen fuel source including it in polymer electrolyte fuel battery, alkaline fuel cell, phosphoric acid fuel cell, molten carbonate fuel cell and SOFC.For polymer electrolyte fuel battery, particularly PEM (PEM) fuel cell, hydrogen is typically most preferred as fuels sources.PEM fuel cell is general to be run under about 80 DEG C or lower temperature.Thus, the present invention can carry out alcohol reforming at low temperature, and its advantage is can to simplify the design of dynamical system, and improve efficiency.

When alcohol reforming product mixtures of the present invention are used as the hydrogen source of fuel cell, dehydrogenation reaction is preferably combined into progress with above-mentioned water-gas shift, the CO content in product mixtures is preferably minimized.Therefore, often preferably alcohol is mixed with water in the material gas mixture of feeding dehydrogenation reaction zone, to promote carbon monoxide from the removal in product stream by water-gas shift.For example, alcohol is preferably mixed before dehydrogenation reaction zone is introduced with least water of 1 molar equivalent, the water most preferably with about 1.05 to about 1.2 molar equivalents.

In general, the invention described above catalyst has certain activity for water-gas shift.But, in certain embodiments, preferably using additional water-gas shift catalyst, to reach lower carbonomonoxide concentration in the product mixture.When changing catalyst using additional water-gas, the water-gas transformation catalyst can be mixed in reforming catalyst bed with reforming catalyst, or be placed on reforming catalyst downstream, in identical or independent catalyst bed.

For the embodiment of the present invention using independent water-gas transfer catalyst, it is necessary to run, it is noted that the reaction of most of conventional water-gas shifts is general at about 200 DEG C, the typical operating temperature than reforming catalyst of the present invention is low.Therefore, cooling reformate mixture is probably necessary or desirable before being contacted with water-gas transformation catalyst.Generally, any device well known in the art for cooled product can be used, including heat exchanger.In one embodiment, it can be introduced the water between reformer and water-gas shift reactor in reformate gas.In this embodiment, water is introduced into after reformer can reduce or remove the water in the alcohol-water material gas mixture for sending into the reformer.

Although to the present invention it is not necessary to or it is crucial, but the carbon monoxide during the reformate stream for leaving dehydrogenation reaction zone, water-gas transformation catalyst bed and/or fuel cell is reduced using one or more addition theretos, or other controls are carried out to it, it is probably desired in certain embodiments of the invention.The example of the appropriate action of control or reduction carbon monoxide is described extensively, such as Pettersson, Int ' l J.Hydrogen Energy, volume 26, the 243-64 pages (2001), and including optionally oxidizing carbon monoxide, methanation of carbon monoxide and implement anode gas leakage.

The hydrogen produced in dehydrogenation zone is admitted in preferred embodiment of the fuel cell to produce electric energy, and dehydrogenation reaction is carried out preferably in the fixed bed reactors comprising above-mentioned Cu-contained catalyst packed bed.It is preferred that take measures to make back pressure minimum, such as by the way that inert solid diluent is added into the catalyst bed with separating catalyst particles and spacing is kept between them.The diluent is preferably the acid sites without the reaction for being capable of catalysis ethanol dehydration generation ethene and under the reaction conditions heat-staple material.The activated carbon of carborundum and not yet acid activation is the example of preferred diluent.

Alternatively, it can also minimize back pressure by using the Cu-contained catalyst comprising pellet rather than the metal sponge support structures of powder.The support structures of this shaping are included in the nickel sponge ball described in the A1 of European patent EP 0648534 and U.S. Patent No. 6,284,703, and the disclosure of which is expressly incorporated herein by reference.Nickel sponge ball, especially as fixed bed catalyst, can buy from such as W.R.Grace ＆ Co. (Chattanooga, TN) and Degussa-Huls Corp. (Ridgefield Park, NJ).In the preferred embodiment of other replacements, the catalyst can be used with monolithic form, so as to which the back pressure in reforming reactor is preferably minimized, the monolith catalyst is prepared by the way that catalyst of the present invention to be mixed into the surface of suitable porous matrix (such as honeycomb).

A kind of embodiment by producing the system of electric energy according to the ethanol reformation of the present invention is described with reference to Fig. 1.Although description below is disclosed particularly as using above-mentioned Cu-contained catalyst progress alcohol dehydrogenase, but it is to be understood that the principle is generally applicable to include the dehydrogenation of other primary alconols of methanol or ethanol and carbinol mixture.

The alcohol of mixture comprising ethanol and water/water raw material is introduced into dehydrogenation reaction zone, the reaction zone includes the packed bed 101 of the cupric dehydrogenation containing metal supporting structure.The raw material comprising ethanol/water mixture is preferably in the form of gaseous feed mixture, for example, after being evaporated as known in alcohol reforming technology in evaporator (not shown), introducing dehydrogenation reaction zone.With the heatable catalyst of heating jacket 102 bed 101, to keep desired temperature in dehydrogenation zone.Reformation of the ethanol/water mixture in catalyst bed 101 generates the product mixtures for including hydrogen, carbon monoxide, carbon dioxide, water and methane.Then the product mixtures are passed through to the additional catalyst bed 103 for changing catalyst comprising suitable water-gas, using optionally by Oxidation of Carbon Monoxide as carbon dioxide.Compact water-gas shift component has been developed, and can be bought from such as Hydrogen Source (South Windsor, CT).The product mixtures for leaving catalyst bed 103 are then cooled to suitable temperature (generally 80 DEG C or lower), and are introduced into together with oxygen source (such as air) in hydrogen fuel cell 105 (such as Proton Exchange Membrane Fuel Cells) to produce electric energy.The reaction that electric energy generates water in a fuel cell by hydrogen and oxygen is produced.It should be understood that identical with the convention of fuel cells applications, the fuel cell can include multiple fuel cells (i.e. fuel cell pack).

Then, fuel cell comprising water vapour, methane and carbon dioxide flow out thing in the combustion chamber 107 for being provided with oxygen source (such as air) with the combust of air one.Suitable combustion chamber can include gas turbine, heat engine, internal combustion engine or other be used for the equipment that drives the generator 109 for producing additional electrical energy.Heating jacket 102 can be recycled to as the thermal source of Heating Dehydrogenation area reforming catalyst bed 101 by going out the hot combustion effluent of self generator 109.

The burning of the fuel cell outflow thing additionally provides a kind of facilitated method for handling dynamical system discharge.Undesirable component in the fuel cell outflow thing, such as acetaldehyde, carbon monoxide, remaining alcohol and/or methane will be converted into carbon dioxide in large quantities by being burnt in combustion chamber 107.Remaining hydrogen will be oxidized to water.It may be a threat to ozone layer to have been reported that the hydrogen emission for thinking effusion in the recent period.(referring to Tromp etc., Science, 300,1740-2, (2003)).In addition, coming from waste gas (different from the waste gas of the conventional PEM fuel cell dynamical system) heat enough of internal combustion engine, catalyst can be made effectively to play a role, further reduce noxious emission.

In vehicle power application, the combustion system of electric energy and/or mechanical energy can be provided by preferably introducing the fuel cell outflow thing of the hydrogen, water vapour and carbon monoxide of mainly carbon dioxide, methane and trace.In this applications, combustion system may include the internal combustion engine for producing the moment of torsion of driving vehicle, or with producing the internal combustion engine that the generator of additional electrical energy is combined.

In particularly preferred embodiments, using the dynamical system burning fuel cell effluent for the variable fuel internal combustion engine for including can burn alcohol, methane or their mixture, and provide mechanical power source to drive vehicle.The one or more motor for being provided with the direct current produced by fuel cell provide additional energy, and this is analogous to the configuration for hybrid vehicle.This preferred dynamical system as use ethanol as Fig. 2 of fuel shown in.

Reference picture 2, water-ethanol raw mixture (mole of water is slightly excessive) is introduced into hydrogenation reaction zone and heated by heating jacket 202, wherein hydrogenation reaction zone includes the packed bed 201 containing copper-plated nickel sponge reforming catalyst and water-gas transformation catalyst 201B.As it was previously stated, alcohol is reformed in packed bed, the reformate for including hydrogen, carbon dioxide and methane is generated.Reformate from dehydrogenation zone sends into hydrogen fuel cell 205 to produce direct current energy together with oxygen source (such as air) at a suitable temperature.Methane and carbon dioxide does not reduce the performance of PEM fuel cell.The effluent of fuel cell 205 is mainly methane and carbon dioxide, and they and oxygen source (such as air) burn in internal combustion engine 207.Then, the hot waste gas for coming from internal combustion engine is used as the thermal source of heating jacket 202 before the system is left as waste gas, preferably passes through catalyst (not shown).So, the used heat from internal combustion engine is used, the heat needed is provided for the ethanol reformation reaction of heat absorption.The design for the reformer that heat exchange can be carried out between independent thermal current and reforming catalyst bed is well known in the art.

Due to the endothermic character that alcohol reforming is reacted, the significant drawback that fuel cell is run in vehicle transport application occurs on startup.Particularly, fuel cell can not make vehicle " cold start-up " (i.e. before producing and being enough to drive the energy of vehicle, existence time postpones on startup, until reformer and fuel cell reach their design and operation temperature).Thus, in particularly preferred embodiment of the invention, the internal combustion engine 207 for the burning driving power system that reference picture 2 is described is a kind of variable fuel internal combustion engine, and it can use raw polyol or another cold start fuel source 211 separated with fuel cell outflow thing to run.The raw polyol of the internal combustion engine is preferably anhydrous, therefore is separated with the alcohol-water raw material of reforming reactor.On startup, internal combustion engine uses the alcohol from independent cold start fuel source 211 as operating fuel, with the similar cold starting performance of the vehicle for providing with power being produced using traditional combustion engine.In normal operation, after the design and operation temperature that reformer and fuel cell reach them, vehicle mainly can produce power by motor, and wherein motor is provided with the direct current produced by hydrogen fuel cell.Internal combustion engine continues to play a role to compensate the part basis power of vehicle needs, but has been fuel from the methane of fuel cell effluent since internal combustion engine is main, rather than from the alcohol in independent cold start fuel source 211.If drive condition needs other transient dynamics, then vehicle can produce additional torque using internal combustion engine.In addition, the methane in the fuel cell outflow thing of internal combustion engine is entered can be supplemented to produce this additional torque with origin from the alcohol in independent cold start fuel source 211.Additional supplement power can also be provided by battery.

In addition to providing preferable cold start-up and transient dynamics performance, the preferred disposition can be with very low cost construction force system.Hydrogen fuel cell is normally based on the component of most expensive in the automotive power of fuel cell.The fuel cell capacity that dynamical system described herein needs is substantially less than traditional design, because peak power is supplemented by internal combustion engine.The design only needs the fuel cell capacity for being enough to provide part basis power, and other parts are provided by the internal combustion engine run using alcohol and/or methane.

Embodiment

Following embodiments are only intended to further illustrate and explain the present invention.Therefore, the present invention should not necessarily be limited by any details of these embodiments.

The preparation embodiment that others are used to prepare copper-plated metal catalyst is described in co-assigned U.S. Patent No. 6,376,708 and the co-pending U.S. Patent Application Serial 09/832,541 of co-assigned separate cases, publication number US-2002-0019564-A1.U.S. Patent No. 6,376,708 and US publication US-2002-0019564-A1 full text are expressly incorporated herein by reference.

The preparation of the copper-plated nickel sponge catalyst of embodiment 1

This embodiment illustrates prepare copper-plated nickel sponge catalyst using replacement deposition method.

In glass beaker, nickel sponge support structures (68.7g, RANEY 4200, from W.R.Grace, Chattanooga, TN) are suspended in the water of nitrogen bubbling (400ml).12% NaBH being dissolved in 14M NaOH is added under agitation₄(50g) solution.It was observed that foaming 1 minute strongly.After stirring 10 minutes, make catalyst sedimentation and supernatant liquor is decanted.Add the water (400ml) of the nitrogen bubbling of extention and of short duration stirring.The catalyst is set to settle again before decantation clear liquid.

The water (250ml) of Part III nitrogen bubbling is added in the catalyst.Add glacial acetic acid (about 8ml) and pH is reduced to 5.Then the CuSO of the catalyst suspension and nitrogen bubbling is made₄·5H₂O (54.0g, copper is 20 weight % relative to the content of catalyst) and solution of the sodium dihydrate (108.0g) of ethylenediamine tetra-acetic acid (EDTA) four in water (300ml) are contacted.Continuously stirring and adding NaOH (2.5N, 73.0ml) under conditions of nitrogen bubbling in 103 minutes.The pH value of suspension is raised to 11.3 by 6.8.Make catalyst sedimentation, wind beaker with heat tape, and the supernatant liquor of blueness is decanted.

By CuSO₄·5H₂O (67.5g, copper is 25 weight % relative to the content of catalyst) is dissolved in the water of nitrogen bubbling (200ml) to form copper solution.By the suspension that (74 DEG C) of the hot mixt of the water (250ml) of 50% gluconic acid (159.0g), 2.5NNaOH (54ml) and nitrogen bubbling is added to the catalyst formation catalyst.Then, under agitation in adding the copper solution in the catalyst suspension in 95 minutes, while being that the beaker applies heat (72 DEG C of final temperature) with heat tape.PH value drops to 3.1 by 3.8.Make catalyst sedimentation and the supernatant liquor of green is decanted.

Catalyst is cleaned with the water (700ml) of nitrogen bubbling.Cleaning fluid is decanted, reclaims 75.6g obscure-aeneouses catalyst and stores under water.The composition of the catalyst is 66.1%Ni, 30.4%Cu and 3.5%Al.

When a small amount of sample (about 1g) of the catalyst is suspended in water, it is found that the catalyst is made up of two parts.This two parts is made up of copper-colored lower layer and gray upper layer.After being that hydrogen is dried at 130 DEG C, using Schmidt, " Surfaces of Raney

Catalysts ", Catalysis of organicReactions, the method described in the 45-60 pages (M.G.Scaros and M.L.Prunier, eds., Dekker, NewYork, 1995) determine BET surface area and surface nickel concentration.Analysis result is listed in table 1.Give the data of the matrix of RANEY 4200 to compare simultaneously.

Embodiment 2 utilizes copper-plated nickel sponge catalyst reformed ethanol

This embodiment illustrates the purposes that copper-plated nickel sponge catalyst is used for reformed ethanol.

The experiment comprising stainless steel 304 pipe (long 457.2mm, internal diameter 12.7mm), be wound with the stainless steel reactor of coiled cable heater and carry out.The top of the reactor is connected to for preheating the pipe of ethanol raw material.In glass fibre beyond the Great Wall, glass wool plug is placed on the hollow insert of tubular reactor bottom the catalyst distribution.Thermocouple is placed on the bottom of the catalyst bed and utilizes coiled cable heater monitoring and controlling reaction temperature.Effluent passes through gas chromatographic analysis using thermal conductivity detector.The outlet of the reactor is under atmospheric pressure.

For example following fillings of the reactor.After insertion fresh glass wool plug, the aqueous slurry of the carborundum (1.0g) (from Alfa Aesar, Ward Hill, MA acquisition) of 325 mesh is set to pass through reactor, to form the basis for the catalytic bed being located at the top of glass fibre.Then the slurry of carborundum (1.5g) and the catalyst (2.02g) of embodiment 1 is made to pass through reactor.It is not observed through phenomenon, illustrates that all catalyst loaded are remained in reactor.Before use, by catalyst in nitrogen at 120 DEG C in being dried overnight in reactor.

Table 2 give using in different temperature, flow velocity and raw material during water concentration ethanol reformation result.Before the data of acquisition tables 2, the catalyst amounts to about 30 hours for ethanol reformation.Note, because analytical error and the CO as shown in equation 6 methanation, methane production and mass balance based on methane can be more than 100%：

CO+3H₂→CH₄+H₂O    (6)

It is furthermore noted that table 2 and the following examples eliminate the yield of hydrogen.Although hydrogen is directly measured in gas-chromatography, compared with carbon-containing molecules, sensitivity of the thermal conductivity detector to hydrogen is relatively low, therefore result in the more polydispersion of data.Therefore, the yield of hydrogen can be more precisely computed by the yield of carbon compound such as carbon monoxide, carbon dioxide and methane.

Table 2

Ethanol product distribution under different condition, to be reported relative to the molar yield of ethanol raw material amount

¹The remainder of raw material is ethanol.

Embodiment 3 utilizes copper-plated nickel sponge catalyst reforming methanol

Embodiment explanation utilizes copper-plated nickel sponge catalyst reforming methanol.

The experiment is carried out according to above-described embodiment 2, but uses the raw material being made up of 70 weight % methanol and 30 weight % water.As a result 3 are listed in the table below.

Table 3 is distributed by reforming the methanol reformate that 70% methanol is obtained

Ethanol reformation in the extension cycle of operation of embodiment 4

The embodiment illustrates the ability that catalyst of the present invention supports high conversion within the ethanol reformation cycle of extension.

The experiment is carried out under conditions of substantially the same manner as Example 2, but reactor first passes through depositing silicon silicon (1.0g) and then loaded with the slurry of the catalyst (2.50g) comprising embodiment 1 and carborundum (5.0g).Temperature is by thermocouples monitors, and inner chamber of the thermocouple along reactor is inserted to downwards about 10.2cm higher than catalyst bed bottom position.

The temperature of product mixtures of the reactor to leave catalyst bed is run in the way of being maintained at 280 DEG C.The temperature of upper thermocouple remains relatively constant at about 430 DEG C.Ethanol/water raw mixture (ethanol/water weight is than 70: 30) is concomitantly introduced into dehydrogenation zone with the nitrogen of 0.3ml/min speed and 100sccm.The reactor run 44 hours, during this period the pressure of reactor 80psig is increased to by 28psig.During this period, ethanol or acetaldehyde are not detected in product mixtures, and methane conversion is 100% in the range of analytical error.Table 4 below is given in experimentation to CO and CO₂Selectivity.

Table 4

The ethanol reformation product yield of 70% ethanol raw material is used at 280 DEG C

Reformation of the ethanol of embodiment 5 in the packed bed with thermal gradient

The embodiment illustrates that reformed ethanol realizes high conversion and low methanation in the case where low pressure, outlet temperature are 300 DEG C or thermal gradient of the lower and inlet temperature less than outlet temperature by using copper-plated nickel sponge catalyst.

Use vertically arranged stainless steel tubular reactor (the long 457.2mm for being tied with coiled cable heater similar to Example 2, internal diameter 12.7mm), but ethanol raw material stream is introduced in the bottom of reactor, and catalyst bed is placed on reactor head and is between two glass wool plugs.Thermocouple is placed on the upstream and downstream of catalyst bed.Use the catalyst (2.50g) prepared in embodiment 1.Weight is sent into by reactor than the mixture of the water of 70% ethanol/30% with 0.1ml/min speed, and with controllable rate heating response device, so that the outlet temperature of catalyst bed effluent is 275 DEG C.During Therapy lasted, catalyst bed upstream temperature is stable at 245 DEG C.The pressure of reactor upstream is no more than 5psig.

Table 5 shows the high conversion reached between the continuous operating period more than 200 hours.After production 286 hours, outlet temperature is increased to 300 DEG C.The data gathered at this temperature are listed in table 6.Acetaldehyde or ethanol are not detected in the product mixture.Temperature is increased to 300 DEG C of conversion ratios and also brings up to 100%.Do not have to find detectable methanation in whole experiment.

Table 5

The product yield at 275 DEG C of embodiment 5

ND=is not detected

Table 6

The product yield that embodiment 5 is brought up to after 300 DEG C in outlet temperature

The preparation of the copper-plated nickel sponge catalyst of embodiment 6

The embodiment illustrates a kind of method for plating for metal sponge matrix, with Morgenstern et al. (U.S. Patent No. 6,376, No. 708) or the method in embodiment 1 compare, similar conversion ratio and more preferable carbon dioxide level is this method provide, and needs less copper sulphate.This method also uses high solid concentration, therefore makes Waste volume minimum.In this embodiment, matrix and catalyst quality are determined by water method of replacing, it is assumed that bulkfactor is 1.16.

Nickel sponge support structures (48.3g, RANEY 4200, from Grace Davison, Chattanooga, TN) are transferred in the 1L beakers of the water with nitrogen bubbling, and the water for removing excess is decanted.By CuSO₄·5H₂O (47.45g) and Na₄EDTA·2H₂The solution of nitrogen bubblings of the O (94.92g) in water (400ml) adds the catalyst and stirs the slurry, while adding 2.5NNaOH (91ml) in 48 minutes.PH is increased to 11.4 by 8.4.Decantation blue supernatant simultaneously winds the beaker with heat tape.

The hot mixt of 50% gluconic acid (11g) and water (400ml) is added into the catalyst.Apply heat and the mixture of the concentrated sulfuric acid (5.70g) and water (50ml) was added in 43 minutes.Temperature stabilization is between 59 DEG C to 60 DEG C and pH drops to 2.2 by 5.2.It is stirred for the mixture 45 minutes.Final pH is 2.8.

Decantation blue supernatant and the water (500ml) for adding nitrogen bubbling, 7 are adjusted to sodium hydroxide by pH.The step helps to remove remaining nickel and EDTA.Make catalyst sedimentation and remove supernatant liquor by being decanted.Having reclaimed 51.3g has the catalyst of following compositions：76.8%Ni, 19.9%Cu, 3.2%Al and 0.2%Fe.

Embodiment 7 uses copper-plated nickel sponge catalyst reformed ethanol

The embodiment illustrates the ethanol reformation in the presence of catalyst of the nickel sponge supporting structure surface comprising copper.

The catalyst (2.50g) prepared according to embodiment 6 is put into in the reactor similarly configured with above-described embodiment 2.Raw polyol comprising 70 weight % ethanol and 30 weight % water is introduced into the reactor with 0.1ml/min speed.Outlet temperature was gradually increased to 300 DEG C in 24 hours by first in experiment.Note, conversion ratio is slightly below embodiment 5, but CO is to CO₂Conversion (water-gas shift) proceed to much bigger degree.Methanation is also higher, but as seen in next embodiment, it is reduced over time.

Table 7

The effluent of embodiment 7 is constituted

Ethanol reformation in the extension cycle of operation of embodiment 8

The embodiment illustrates that the isothermal of the ethanol within the time cycle of extension is reformed.The embodiment is further illustrated progressively to be declined using the catalyst methaneization of embodiment 6, while keeping high CO₂Conversion ratio.

It is identical with above-described embodiment 7, with loading the catalyst (2.50g) prepared according to embodiment 6 in identical reactor facility described in embodiment 2, and using comprising 70 weight % ethanol/30 the raw material of weight % water run with 0.1ml/min flow velocity.The outlet temperature of catalyst bed is maintained at 300 DEG C.Acetaldehyde or ethanol are not detected during operation in the product mixture.As shown in table 8, methanation is stable during experiment declines.

Table 8

The effluent of embodiment 8 is constituted

Embodiment 9 uses copper-plated nickel sponge catalyst reforming methanol

The embodiment illustrates catalyst of the present invention in gentle, the reforming methanol close under conditions of isothermal activity and stability.

By the catalyst prepared in embodiment 1 (2.52g) and polymer bead diluent (1.0g, Tenax TA, 80-100 mesh, from Alltech Associates, Deerfield, IL) mix and be fitted into reactor as described in Example 2, reactor is in this experiment in horizontal direction.With 0.1ml/min speed adding the mixture of the water of 60% methanol/40% to reactor, (mol ratio of 0.1ml/min, water: methanol is 1.19: 1), outlet temperature is maintained at 320 DEG C.Pressure is maintained at less than 5psig during whole service.The temperature of catalyst bed upstream is about 335 DEG C, and turns to 369 DEG C by 309 DEG C of changes during testing.

Table 9 shows result.The temperature that obtaining the methanol conversion higher than 90% needs is higher than the temperature that ethanol needs.Methane yield general about 1%, it is similar to the value of ethanol.

Table 9

The effluent of embodiment 9

Embodiment 10 is used for the preparation for fixing the copper-plated nickel sponge catalyst of bed operating

This embodiment describes prepare fixed bed catalyst by the way that copper is plated into the fixed bed carried structure of nickel sponge.

Will be distributed over piller matrix, (45 balls, it includes 6.79g Metalystα -1401-X018, can buy from German Degussa AG, Hanau) nickel sponge support structures be dried overnight under vacuo in 120 DEG C, purged with nitrogen.The piller loads in blanket of nitrogen along plastic tube (internal diameter 9.525) length direction, between glass wool plug, and makes to include CuSO₄·5H₂O (10.67g) and Na₄EDTA·2H₂The plating tank liquor of solution of the O (21.34g) in water (300ml) on catalyst at room temperature in circulating, while the mixture of 2.5N NaOH (26ml) and water (50ml) was added dropwise in 124 minutes.During plating, coating bath solution is stored in the stirring pool in blanket of nitrogen, and is circulated using peristaltic pump between catalyst and pond.PH is increased to 12.0 by 10.0.Then water cleaning catalyst is used.

Then, by CuSO₄·5H₂O (6.67g), gluconic acid (5.2g), the mixture of 2.5N NaOH (2.7g) and water (300ml) are added in the pond, and at room temperature in being circulated 2 hours on catalyst.Water cleaning catalyst is used, is then dried overnight, is purged with nitrogen in 120 DEG C in a vacuum.Reclaim 6.65g (98%) catalyst.

Ethanol reformation under the isothermy of embodiment 11

The embodiment illustrates for the catalyst performance in the reformed ethanol close under conditions of isothermal (compared with the ethanol reformation with thermograde in the reactor described in embodiment 7).

The catalyst reformed ethanol that the experiment is prepared including the use of embodiment 6, and catalyst bed keeps at 280 DEG C close to isothermal.In order to eliminate thermograde, improved reactor is used.Material gas mixture (70 weight % ethanol/30 weight % water) is pumped into preheater with 0.10ml/min speed by stainless steel tube (external diameter 1.58mm), the preheater is by filled with stainless steel ball (diameter 3mm and 4mm) and being tied with vertical stainless steel tube (the long 457.2mm of cable heater, internal diameter 9.525mm, external diameter 12.7mm) constitute.Feed pipe is helically wound on cable heater, and is connected in bottom with preheater.

The top (outlet) of the preheater and stainless steel tube (the long 177.8mm of the catalyst (2.49g) prepared included in embodiment 6, internal diameter 9.525mm, external diameter 12.7mm) connect, catalyst is filled between the glass wool plugs of two passivation.Upper pipe (reactor) is tied with single cable heater.Thermocouple in preheater Yu reactor tube junction is used to control the preheater and keeps catalyst bed constant temperature upstream, and the thermocouple in just above catalyst bed (downstream of catalyst bed) controls cable heater and catalyst bed downstream (outlet) temperature is maintained at into 280 DEG C.The two temperature are stable in two hours and keep constant, fluctuate within 1 DEG C.The all heat-insulated processing of all components, and it is identical with described in embodiment 2 for the down-stream system of gas chromatographic analysis.

Table 10 show close under conditions of isothermal operation realize high conversion and stability.Preheater upstream pressure keeps below 15 psi in whole experiment process.Note, under isothermal conditions, about 2% steady state value is arrived in the decline of excessive methanogenesis after 8 hours.The ethanol of trace is found that, quantitative limitation but is below.Acetaldehyde has only reached measurable level in end of run.In whole experiment process, both less than 1%.

Table 10

The product yield that the embodiment 11 carried out under 280 DEG C of isothermys is reformed

The reformed ethanol on copper-plated nickel sponge fixed bed catalyst of embodiment 12

The embodiment illustrates performance of the copper-plated nickel sponge fixed bed catalyst in reformed ethanol.

The experiment including the use of the catalyst (1.46g, 10 balls) prepared in embodiment 10 under 300 DEG C of isothermys with reformed ethanol in identical facility described in embodiment 11.Material gas mixture comprising 70 weight % ethanol and 30 weight % water is introduced with 0.06ml/min flow velocity, with the ratio between the offer flow velocity suitable with the embodiment of foregoing use 2.50g catalyst and 0.10ml/min material gas mixtures and catalyst.

As shown in the data in table 12 below, the fixed bed material has reached high conversion (＞ 85%) at 300 DEG C.The fixed bed catalyst is also different from fine catalyst, and the decline of wherein methanation occurs more slow and continuous, and about 20 hours are needed at 300 DEG C.

Table 12

The result of embodiment 12

Embodiment 13 is at different temperatures in reformed ethanol on fixed bed catalyst

The embodiment describes the purposes of fixed bed catalyst reformed ethanol at different temperatures.

The experiment is the continuation tested described in above-described embodiment 12, while changing flow velocity and temperature.Keep isothermy.Table 13 summarizes the catalyst under different in flow rate in the performance at 300 DEG C and 320 DEG C.

Table 13

There is the ethanol reformation of temperature and change in flow as described in Example 12

Experiment finds that many catalyst are all reduced to powder after terminating.This loss of structural intergrity is because the unactivated aluminium in matrix center forms aluminum oxide with steam reaction at reaction conditions.

The invention is not limited in the embodiment above and there can be a variety of changes.The description of above-mentioned preferred embodiment is only intended to make skilled in the art realises that the present invention, its principle and its practical application, so that those skilled in the art can change and using the present invention in many ways, to better adapt to the requirement of practical application.

On the word such as " comprising ", "comprising", " containing " (" comprise ", " comprises ", " comprising " in English) in the application of this specification (including following claims), it should be noted that, unless otherwise indicated herein, these words are all based on following basis and are clearly understood from what is used：They should be interpreted that content listed by "comprising", rather than " exclusion " non-row content, and it is desirable that each word should so be explained on the basis of analysis full text.

Claims (37)

1. a kind of method of reformed ethanol, this method includes making the material gas mixture comprising ethanol contact at a temperature of less than 400 DEG C with powder reforming catalyst to manufacture the reformate mixture for including hydrogen, and the reforming catalyst includes the copper coating at least partly surface of covering metal supporting structure.

2. the method as described in claim 1, wherein the material gas mixture is contacted at a temperature of 250 DEG C to 300 DEG C with the reforming catalyst.

3. method as claimed in claim 2, wherein reforming catalyst have at least 50W/mK thermal conductivity at 300k.

4. method as claimed in claim 3, wherein reforming catalyst have at least 70W/mK thermal conductivity at 300k.

5. method as claimed in claim 4, wherein reforming catalyst have at least 90W/mK thermal conductivity at 300k.

6. the method as described in claim 1, wherein methods described further comprise introducing fuel cell to produce electric energy by the hydrogen from reformate mixture and oxygen.

7. the method as described in claim 1, wherein the reforming catalyst has 10m according to the measurement of Brunauer-Emmett-Teller methods²/ g to 100m²/ g surface area.

8. method as claimed in claim 7, wherein the reforming catalyst has 25m according to the measurement of Brunauer-Emmett-Teller methods²/ g to 100m²/ g surface area.

9. method as claimed in claim 8, wherein the reforming catalyst has 30m according to the measurement of Brunauer-Emmett-Teller methods²/ g to 80m²/ g surface area.

10. the method as described in claim 1, wherein the reforming catalyst includes at least 10 weight % copper.

11. method as claimed in claim 10, wherein the reforming catalyst includes 10 weight % to 90 weight % copper.

12. the method as described in claim 1, wherein the metal supporting structure includes metal sponge.

13. method as claimed in claim 12, wherein the metal sponge support structures of the reforming catalyst have at least 10m according to the measurement of Brunauer-Emmett-Teller methods²/ g surface area.

14. method as claimed in claim 13, wherein the metal sponge support structures of the reforming catalyst have at least 50m according to the measurement of Brunauer-Emmett-Teller methods²/ g surface area.

15. method as claimed in claim 14, wherein the metal sponge support structures of the reforming catalyst have at least 70m according to the measurement of Brunauer-Emmett-Teller methods²/ g surface area.

16. method as claimed in claim 12, wherein metal sponge support structures include nickel.

17. method as claimed in claim 16, wherein the metal sponge support structures include at least 50 weight % nickel.

18. method as claimed in claim 17, wherein the metal sponge support structures include at least 85 weight % nickel.

19. method as claimed in claim 16, wherein the reforming catalyst includes 10 weight % to 80 weight % copper.

20. method as claimed in claim 19, wherein the reforming catalyst includes 20 weight % to 45 weight % copper.

21. method as claimed in claim 16, wherein reforming catalyst include 5 to 100 μm of ol/g nickel on the surface of the catalyst.

22. method as claimed in claim 21, wherein reforming catalyst include 10 to 80 μm of ol/g nickel on the surface of the catalyst.

23. method as claimed in claim 22, wherein reforming catalyst include 15 to 75 μm of ol/g nickel on the surface of the catalyst.

24. method as claimed in claim 16, this method further comprises introducing fuel cell to produce electric energy by the hydrogen from reformate mixture and oxygen.

25. the method as described in claim 1, wherein the reforming catalyst is mixed into the surface of pellet or only stone substrate.

26. method as claimed in claim 25, wherein the reforming catalyst includes nickel sponge support structures.

27. method as claimed in claim 13, wherein the reforming catalyst includes nickel sponge support structures.

28. the method as described in claim 1, wherein the reformate mixture includes methane.

29. method as claimed in claim 28, including the methane obtained in reformate mixture is sent into internal combustion engine.

30. method as claimed in claim 28, including the hydrogen obtained in reformate mixture is sent into internal combustion engine.

31. method as claimed in claim 12, wherein the metal sponge support structures are prepared by following methods：This method includes leaching aluminium from the alloy comprising aluminium and base metal.

32. method as claimed in claim 31, wherein the base metal includes copper and/or the non-copper metal selected from the group being made up of nickel, cobalt, zinc, silver, palladium, gold, tin, iron and its mixture.

33. method as claimed in claim 32, wherein the base metal includes copper and/or the non-copper metal selected from the group being made up of nickel, cobalt and its mixture.

34. method as claimed in claim 33, wherein the base metal includes nickel.

35. the preparation of the method as described in claim 1, wherein reforming catalyst includes copper being deposited on metal sponge support structures.

36. method as claimed in claim 35, wherein depositing copper by following methods：The electrochemical displacement that this method is included between the metal and copper ion of metal sponge support structures reacts.

37. method as claimed in claim 35, wherein depositing copper by following methods：This method includes copper metal chemistry being plated on metal sponge support structures.