CN100349793C - 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 load is used to the pure purposes of reforming

Invention field

Present invention relates in general to the dehydrogenation or the reformation of alcohol.More specifically, the present invention relates to a kind of make primary alconol such as methyl alcohol or alcohol dehydrogenase with produce hydrogen, in particular for the method for the hydrogen of the fuel cell that produces electric energy.Described method of dehydrogenating uses the copper containing catalyst that comprises the metal load structure.

Background of invention

As everyone knows, primary alconol (for example above 200 ℃) at elevated temperatures contacts with appropriate catalyst and causes alcohol to decompose, and produces hydrogen and carbonaceous material.This method is generally known as " alcohol is reformed ".For example, shown in following equation 1, methanol recapitalization has generated hydrogen and carbon monoxide:

CH ₃OH→CO+2H ₂ (1)

The hydrogen that forms in the reforming process can offer fuel cell then to produce electric energy.Described reforming process be heat absorption and need be to the enough heats of catalyzer transmission, especially needing high-peak power, needing when particularly starting in the transport applications of high-peak power (for example electromobile).Methanol recapitalization is existing to be described, Gunter etc. for example, J.Catal.203,133-49 (2001); Breen etc., J.Chem.Soc.Chem.Comm., 2247-48 (1999); European Chemical News, 22 pages of the mat woven of fine bamboo strips (on May 11st, 1998); With Jiang etc., Appl.Cat.97A, 145-58 (1993).Act as a fuel existing description of special applications of battery hydrogen source of methanol recapitalization and methanol recapitalization, for example, Agrell etc., Catalysis-Specialist Periodical Reports, the 16th volume, (J.J.Spivey edits the 67-132 page or leaf, Royal Society of Chemistry, Cambridge, UK, 2002).

It is important to point out that carbon monoxide is deleterious to the electrode of fuel cell usually.For example, when the content of carbon monoxide in the hydrogen charging surpassed 20ppm, fuel cell performance and power were saved and generally will be descended.Referring to, Pettersson etc., Int ' l J.Hydrogen Energy, the 26th volume, the 246th page (2001).Therefore expectation is by being converted into carbonic acid gas according to following equation 2 reactions with carbon monoxide with steam:

CO+H ₂O→CO ₂+H ₂ (2)

This conversion is called as water-gas shift reaction, and in commercial broad practice.About the description of catalyzer, technology and the application of water-gas shift reaction is found in for example Catalyst Handbook, 283-339 page or leaf (the 2nd edition, M.V.Twigg edits, Manson press, London, 1996).

Under the described similar condition of relevant methyl alcohol with preamble, ethanol is reformed and to be produced acetaldehyde earlier, and acetaldehyde can decompose (being decarbonylation) and is carbon monoxide and methyl alcohol then, shown in following equation 3:

CH ₃CH ₂OH→CH ₃C(O)H+H ₂→CO+CH ₄+H ₂ (3)

Identical with methanol recapitalization, ethanol reformation preferred combination water-gas shift reaction is to be converted into carbon monoxide carbonic acid gas and to produce extra hydrogen.For example, with ethanol reformation bonded water-gas shift reaction according to producing carbonic acid gas, methane and hydrogen shown in the following equation 4:

CO+CH ₄+H ₂+H ₂O+CO ₂+CH ₄+2H ₂ (4)

The prevailing catalyst pack that is used for alcohol dehydrogenase and low temperature water gas conversion reaction is contained in the copper that has zinc oxide on the fire-resistant support structures, has other promotors sometimes, and wherein said fire-resistant support structures generally is aluminum oxide or silicon-dioxide.Though copper-zinc oxide catalyst is to the synthetic stability that demonstrates excellence of methyl alcohol, but it does not have enough stability to methanol recapitalization existing report, as Cheng, Appl.Cat.A, 130, the 13-30 pages or leaves (1995), with Amphlett etc., Stud.Surf.Sci.Catal., 139, mat woven of fine bamboo strips 205-12 page or leaf (2001) is described.

It is reported that many other reformations for alcohol have active catalyzer and are made up of metal oxide, generally comprise catalytic metal.People such as Yee are at J.Catal.186, and people such as 279-95 (1999) and Sheng are at J.Catal.208, and 393-403 (2002) has reported at CeO ₂The CeO of itself or subsidiary rhodium, platinum or palladium ₂On the ethanol that carries out reform.But these articles point out that ethanol can be decomposed into the multiple by product of not expecting, for example acetone, ketene and butylene.

Known copper-nickel catalyst has high reactivity to alcohol dehydrogenase.For example, being carried on copper-nickel catalyst on the aluminum oxide reforms to ethanol and has activity.The reformation of ethanol on copper-nickel catalyst by people such as Marino at Stud.Surf.Sci.Catal.130C, people such as 2147-52 (2000) and Freni are at React.Kinet.Catal.Lett.71, describe among the 143-52 (2000).Provide good selectivity although these reference are all pointed out catalyzer to the dehydrogenation of acetaldehyde, each reference has all run into incomplete conversion and in the active minimum problems of 300 ℃ of following water-gas shift.In addition, traditional ethanol reforming catalyst because of carbon laydown from the teeth outwards (a kind of be called pyrogenic process) be tending towards rapid inactivation.Be higher than under 400 ℃ the temperature, coking is quickened because of there is acid sites in catalyst surface, and this impels ethanol dehydration to form polymeric ethene then.The existing description of coking problem that relates to the ethanol reforming catalyst, for example, Haga etc., Nippon Kagaku Kaishi, 33-6 (1997) and Freni etc., React.Kinet.Catal.Lett., 71, the 143-52 pages or leaves (2000).

Therefore, still need improved mellow wine dehydrogenating and can under medium temperature of reaction, carry out the alcohol reformation and have the method for enough transformation efficiencys.

Brief summary of the invention

Therefore, specific objective of the present invention provides the novel and improved dehydrogenation that is used for alcohol to form the method for hydrogen, particularly uses the method for the catalyzer higher than prior art alcohol reforming catalyst density; A kind of method of improved use reforming catalyst, described catalyzer provide better thermal conductivity to support thermo-negative reaction; A kind of improved use does not have the method for acid sites catalyzer; A kind of improved use is converted into the method for catalyzer that methane and carbon monoxide have the stability of high reactivity and raising to acetaldehyde under moderate temperature; A kind of improved generation is applicable to the method for the hydrogeneous product mixtures of the fuel cell of producing electric energy; Be lower than novelty and the practical methods that is produced electric energy under about 400 ℃ reforming temperature by ethanol with a kind of, this method makes needs the unitary simplification power system of hydrogen fuel cell of less costliness to become possibility, and has improved efficiency.

Therefore, in brief, the present invention relates to a kind of method of reforming alcohol.This method comprises to be made alcohol and contacts at the copper bearing reforming catalyst of metal load body structure surface bag.In preferred embodiments, described reforming catalyst comprises copper on metal sponge support structures surface, wherein the nickeliferous metal sponge of preferred package or comprise nickel and the metal sponge of copper.

The invention further relates to a kind of reformation alcoholic acid method.This method comprises making and comprises alcoholic acid material gas mixture and reforming catalyst and contact under about 400 ℃ temperature to produce the hydrogenous reformate mixture of bag being lower than.Described reforming catalyst comprises copper at the metal load body structure surface.In preferred embodiments, described method is included in to be lower than to make under about 350 ℃ temperature and comprises the alcoholic acid material gas mixture and contact at the copper bearing catalyzer of nickel carrier surface bag.

The invention further relates to a kind of method that produces electric energy by fuel cell.This method comprises making and comprises the alcoholic acid material gas mixture and contact at dehydrogenation reaction zone with dehydrogenation catalyst, to produce the hydrogenous product mixtures of bag.Described dehydrogenation catalyst comprises copper at the metal load body structure surface.To introduce fuel cell to produce electric energy and the fuel cell outflow thing that comprises methane from the hydrogen and the oxygen of described product mixtures.Described fuel cell outflow thing is introduced into the combustion chamber and burns in the presence of oxygen.

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

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

Brief description of drawings

Fig. 1 is the power system sketch according to one embodiment of this invention, and wherein the hydrogeneous product mixtures that produces in alcohol is reformed is used as fuel and introduces hydrogen fuel cell to produce electric energy.

Fig. 2 is the power system sketch according to another embodiment of the present invention, wherein the hydrogeneous product mixtures that produces in alcohol is reformed is used as fuel and introduces hydrogen fuel cell to produce electric energy, and wherein the effluent from described hydrogen fuel cell is sent in the oil engine, and described oil engine also is supplied with independently raw polyol.

The preferred embodiment explanation

According to the present invention, the mixture of mixture, the particularly copper and mickel of copper and other metals is as the catalyzer of alcohol dehydrogenase (promptly reforming).Have been found that the copper containing catalyst that comprises the metal load structure,, demonstrated the activity that improves during as reformation primary alconol such as methyl alcohol in gas phase and alcoholic acid catalyzer for example by depositing copper to the catalyzer that the nickel sponge support structures prepares.The catalyzer that uses in the present invention practice is for being more stable with the ethanol thermolysis as hydrogen, methane, carbon monoxide and carbonic acid gas under moderate temperature, and is activated especially to this.The hydrogen that is produced can utilize, for example, and by in fuel cell, hydrogen being converted into water and burning with generate energy together by the hydrogen of methane in company with any remnants in the air-flow that leaves fuel cell.Described combustion processes can or drive generator to produce extra electric energy or to obtain utilizing to produce mechanical energy in oil engine.This power system provides a kind of method that is obtained energy easily by ethanol, and this method also has other advantage: described burning can drop to the discharging of not expecting minimum, provides heat for the reformation catalyst bed simultaneously.More widely, the product mixtures that produces in reforming according to primary alconol of the present invention can be used in chemical process in (for example carbonylation, hydrogenation and hydroformylation) neutralization materials processed and applied and be used as hydrogen and/or carbon monoxide source.In addition, pure reforming catalyst described herein can be used for producing the product mixtures that comprises hydrogen and carbon monoxide, and this mixture is called as the synthetic gas from raw polyol.

A. catalyzer

In one embodiment of the present invention, alcohol dehydrogenase or reforming catalyst comprise the copper-containing active phase on the surface of metal load structure, and described metal load structure comprises copper and/or one or more non-copper metals.Described catalyzer generally comprises the copper at least about 10 weight %, the preferred copper from about 10 weight % to about 90 weight %, and the more preferably copper from about 20 weight % to about 45 weight %.Described catalyzer can comprise substantially and is the structure of homogeneous, as copper sponge, cupric single-phased alloy, or has heterogeneous structure more than a kind of discontinuous phase.For example, copper-containing active can be used as the surface that discontinuous phase is present in support structures mutually, for example copper coating or skin; Part as upper layer or homogeneous catalyst structure.Comprise on the support structures surface under the situation of discontinuous phase in copper-containing active, described metal load structure can all or part ofly be coated by copper-containing active mutually.For example, as in the described particularly preferred embodiment below, catalyzer comprises and is in the lip-deep copper-containing active phase of the nickeliferous metal sponge support structures of bag.This catalyzer comprises about 10 weight % to the copper of about 80 weight %, and more preferably from about 20 weight % to about 45 weight % copper.The surplus of catalyzer preferably is made up of nickel and the aluminium or other metals that are less than about 10 weight %.In addition, in the nickeliferous preferred embodiment of metal load structure bag, it is important to point out that copper and nickel all can be miscible under all proportions.Like this, can there be phase boundary in the catalyzer that comprises the copper-containing active phase that is in the Ni body structure surface mutually and between the support structures in copper-containing active.

According to the routine of katalysis, the activity of dehydrogenation catalyst can be improved by improving surface-area.Therefore, for freshly prepd catalyzer, general preferred have at least about 10m ²The surface-area of/g, described value is measured by Brunauer-Emmett-Teller (BET) method.More preferably, described catalyzer has about 10m ²/ g is to about 100m ²The BET surface-area of/g, even more preferably have about 25m ²/ g is to about 100m ²The BET surface-area of/g, and still more preferably have about 30m ²/ g is to about 80m ²The BET surface-area of/g.

Be used for a certain preferred embodiment of alcoholic acid of reforming, the surface of catalyzer preferably comprises the nickle atom of promotion as the amount of the aldehyde decarbonylation of acetaldehyde.Preferably, described surface comprises about 5 nickel to about 100 μ mol/g, and wherein said value is passed through at Schmidt, " Surfaces of Raney ^Catalysts, " inCatalysis of Organic Reactions, the method that the 45-60 page or leaf is described is measured (M.G.Scarosand M.L.Prunier, eds., Dekker, New York, 1995).More preferably, surface nickel concentration is extremely about 80 μ mol/g of about 10 μ mol/g, and most preferably from about 15 μ mol/g are to about 75 μ mol/g.

1. support structures

The support structures of mellow wine dehydrogenating comprises metal.Suitable metal load structure can comprise various structures and component.Preferably, described support structures comprises the metal that tensile strength and/or yield strength are higher than copper.Thereby according to preferred embodiment, described support structures comprises non-copper metal.Described non-copper metal can comprise single metal or multiple metal.In this preferred embodiment, described metal load structure are non-copper metals at least about 10 weight %.In a kind of particularly preferred embodiment, described metal load structural weight be non-copper metal at least about 50 weight % (more preferably at least about 65 weight %, at least about 80 weight %, at least about 85 weight % or even at least about 90 weight %).In another particularly preferred embodiment, described support structures comprises at least about the non-copper metal of 10 weight % with at least about the copper of 50 weight % (more preferably from about 60 weight % to about 80 weight %).

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

Preferably, the non-copper metal of described metal load structure be selected from by nickel, cobalt, zinc, silver, palladium, gold, tin, iron and and composition thereof the group formed.More preferably, described metal load structure comprises nickel.Nickel generally is most preferred, because, for example: (1) is compared with other suitable metals such as palladium, silver and cobalt, nickel is relatively cheap, (2) combination of nickel and copper has shown and can promote that the acetaldehyde decarbonylation is that methane and carbon monoxide and (3) are deposited on the nickeliferous support structures copper general than difficult less on the support structures that copper is deposited on other suitable metals that comprise significant quantity.For example, can utilize simple electrochemical displacement sedimentation that copper is deposited on nickeliferous support structures.But the other technologies of existing can be used for copper is deposited on (for example electroless plating and metal-organic chemical vapor deposition) on the support structures that comprises other suitable non-copper metals.

Often desirable is to utilize the electrochemical displacement deposition of hereinafter describing in detail (also being described as " immersion plating " in the prior art) copper to be deposited on the surface of described metal load structure.Under the sort of situation, described metal load structure optimization comprises following metal: be lower than reduction potential for the reduction potential of this metal for metallic copper, that is, and with respect to NHE (standard hydrogen electrode), for the reduction potential of this metal be lower than approximately+343 millivolts.Non-copper metal with this reduction potential comprises for example nickel, zinc, tin, iron and cobalt.This metal that exists near described support structures surface can contact simply with the surface of copper metal deposition at described support structures with mantoquita (generally being Cu (II) salt) solution by making described surface.More specifically, in the electrochemical displacement deposition process, that this metal near described support structures surface is tending towards when contacting with copper ion solution is oxidized (and enter solution as ion).When this phenomenon occurred, the cupric ion near described support structures surface in the solution was reduced to the copper metal, and the copper metal is deposited on the surface of described support structures again.For example when the nickeliferous support structures of bag contacts with copper salt solution this reaction can take place, this reacts shown in following equation 5:

Cu ²⁺+Ni ⁰+Cu ⁰+Ni ²⁺ (5)

As mentioned before, when when utilizing electrochemical displacement deposition that thereby copper is deposited on described support structures surface preparation catalyzer, the nickeliferous support structures of preferred especially use, because nickel has at least four desirable characteristics: (1) is lower than reduction potential to metallic copper to the reduction potential of this metal, (2) more stable under alcohol dehydrogenase reaction conditions of the present invention, (3) have than the high physical strength of copper and wear resisting property and (4) nickel/copper catalyst and promoted the acetaldehyde decarbonylation to generate carbon monoxide and methane.

When described support structures comprises more than a kind of metal, be alloy form at least about 80 weight % (more preferably at least about 85 weight %, even more preferably at least about 90 weight %, further more preferably basic all) metal in the preferred support structures.In particularly preferred embodiment, described metal forms substitutional alloy (being called " single-phased alloy " again), single, successive phase that its interalloy has.Polyphase alloy (alloy that promptly comprises at least 2 discontinuous phases) also can be used as support structures.Be deposited on mutually in the embodiment of cupric multiphase load structure in copper-containing active, the surface portion of poor relatively copper, copper are tending towards preferentially covering the rich copper part of multiphase load body structure surface.Alloy is the single-phase or heterogeneous component of alloy and their concentration of depending on.Usually, for example, mainly the metal load structure of being made up of nickel and copper all is single-phase under any nickel concentration.But for example when described support structures mainly was made up of copper and zinc, it was the zinc concentration (general concentration greater than about 35 weight %) of two-phase that many alloys that cause are arranged.

Should be realized that except atoms metal, described support structures can also comprise non-metallic atom (for example boron, carbon, silicon, nitrogen, phosphorus etc.).Contain this nonmetallic alloy and generally be described to " gap alloy " in the art.The support structures that comprises this alloy may have multiple advantage, for example the enhanced physical strength.But the catalyzer that comprises the gap alloy generally contains the metal at least about 70 weight %.

In particularly preferred embodiments, described support structures is the metal sponge that comprises the above-mentioned suitable non-copper metal of copper and/or one or more.When being used for herein, term " metal sponge " refers to have at least about 10m ²The porous form of the metal or metal alloy of/g BET surface-area.Preferred metal sponge support structures has at least about 20m ²The BET surface-area of/g is more preferably at least about 35m ²/ g, even more preferably at least about 50m ²/ g, and further more preferably at least about 70m ²/ g.Have been found that according to the present invention the copper-containing active that is in metal sponge support structures surface has produced the material of the sponge support structures that shows copper catalytic activity physical strength, high surface area, high thermal conductivity and density, that combine expectation mutually.

The catalyzer of described metal sponge carrier and formation can be powder or ball shape.And described mellow wine dehydrogenating solely stone form uses, and this only stone form is by sneaking into catalyzer of the present invention the surface preparation of suitable porous matrix (for example honeycomb).Generally speaking, in order in following reformer back pressure to be reduced to minimum, the catalyzer of ball shape and only stone form is preferred.And monolith catalyst may be more stable for the physical abuse and/or the chemical erosion in the reaction medium that cause because of vibration (for example in vehicle is used).

It is important to point out, when catalyzer of the present invention uses with ball shape or only stone form, wish to have only part piller or only stone can comprise the metal sponge that is used for load copper-containing active phase.That is, described pure reforming catalyst can be included as the non-porous matrix that fixed bed or monolith catalyst provide intensity and shape, and one or more 10m at least that have that are used for load copper-containing active phase still are provided simultaneously ²The porous of/g BET surface-area (being the metal sponge) zone.Be suitable as fixed bed or solely the non-porous material of stone substrate can comprise usually any electroplate and the condition of reorganization under thermally-stabilised and chemically stable material.Though can use nonmetal basal body, metallic matrix as stainless steel, copper, nickel, cobalt, zinc, silver, palladium, gold, tin, iron and their mixture more preferably.

When the metal sponge carrier was powder type, the preferred median size of this metal sponge was at least about 0.1 μ m, and preferred about 0.5 to about 100 μ m, and more preferably from about 15 to about 100 μ m, even more preferably from about 15 to about 75 μ m, further more preferably from about 20 to about 65 μ m.When described catalyzer is piller or only stone form, such as understood by a person skilled in the art, catalyzer of the present invention sneak on it piller or solely in the size of stone substrate and any this monolithic structure size of perforate can change according to the needs of reformer design.

Metal sponge support structures can be by the technology preparation of those skilled in the art's common general knowledge.Generally can be referring to Lieber and Morritz, Adv.Catal., 5,417 (1953) (summaries of relevant metal sponge).Can also be with reference to Hawley ' s Condensed Chemical Dictionary, the 13rd edition, the 621st page (Rev.by Richard J.Lewis, Sr., Van Nostrand Reinhold, New York, NY 1997) (describe and prepare the method for iron sponge).

The reference of describing the nickel sponge preparation comprises, for example, and Augustine, Robert L., Catalytic Hydrogenation Techniques and Applications in OrganicSynthesis is at annex (the Marcel Dekker of 147-49 page or leaf, Inc., 1965).Can also be with reference to Hawley ' s Condensed Chemical Dictionary, the 13rd edition, the 955th page of (Rev.byRichard J.Lewis, Sr., Van Nostrand Reinhold, New York, NY 1997) (described known from the alloy that comprises 50 weight % nickel and 50 weight % aluminium, leach the technology that aluminium prepares sponge nickel) by the soda lye that uses 25 weight %.Under the situation of preparation nickel sponge, described metal load structure optimization does not have non-activated zone substantially, and has washed basic alumina-free.Unreacted aluminium is tending towards and steam reaction under the condition of reorganization, and formation can hinder diffusion and the aluminum oxide of acid sites is provided for ethanol dehydration.

The reference of describing copper/zinc sponge preparation comprises, for example, and Bridgewater etc., Appl.Catal., 7,369 (1983).This class reference also comprises, for example, and M.S.Wainwright, " in Ruan in copper and the Ruan copper-zinc catalyst) " Chem.Ind. (Dekker), 68,213-30 (1996).

The reference of describing nickel/iron sponge preparation comprises, for example, and Becker and Schmidt, " (Raney nickel-iron catalyst ", Ger.Offen.DE 2,713,374 19780928 (1978).

The reference of describing nickel/cobalt sponge preparation comprises, for example, and Orchard etc., " (preparation of Raney nickel-cobalt catalyst and performance ", J.Catal., 84,189-99 (1983).

According to a kind of preferred embodiment, of No. the 6th, 376,708, co-assigned United States Patent (USP), support structures comprises nickel/copper sponge (being the adulterated copper sponge of adulterated nickel sponge of copper or nickel).The reference of describing nickel/copper sponge preparation also comprises, Young etc. for example, J.Catal., 64,116-23 (1980) and Wainwright and Anderson, J.Catal., 64,124-31 (1980).

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

According to another kind of preferred embodiment of the present invention, support structures comprises nickel sponge.The suitable nickel sponge example of buying comprises, for example by W.R.Grace ﹠amp; Co. (manufacturer indicates the RANEY 2800 of Chu Shouing: the Ni with at least 89 weight %; Be not more than the Al of 9.5 weight %; Be not more than the Fe of 0.8 weight %; Median size is 20-60 μ m; Proportion is about 7; Based on contain the heavy volume density of 56% solid catalyst pulp in water is 1.8-2.0kg/l (15-17lbs/gal)), (manufacturer indicates RANEY4200: the Ni with at least 93 weight %; Al greater than 6.5 weight %; Be not more than the Fe of 0.8 weight %; Median size is 20-50 μ m; Proportion is about 7; Based on contain the heavy volume density of 56% solid catalyst pulp in water is 1.8-2.0kg/l (15-17lbs/gal)), (manufacturer indicates RANEY 4310: the Ni with at least 90 weight %; Be not more than the Al of 8 weight %; 0.5-2.5 the Mo of weight %; Be not more than the Fe of 0.8 weight %; Median size is 20-50 μ m; Proportion is about 7; Based on contain the heavy volume density of 56% solid catalyst pulp in water is 1.8-2.0kg/l (15-17lbs/gal)), (manufacturer indicates RANEY 3110: the Ni with at least 90 weight %; 0.5-1.5 the Mo of weight %; Be not more than the Al of 8.0 weight %; Be not more than the Fe of 0.8 weight %; Median size is 25-65 μ m; Proportion is about 7; Based on contain the heavy volume density of 56% solid catalyst pulp in water is 1.8-2.0kg/l (15-17lbs/gal)), (manufacturer indicates RANEY 3201: the Ni with at least 92 weight %; Be not more than the Al of 6 weight %; Be not more than the Fe of 0.8 weight %; 0.5-1.5 the Mo of weight %; Median size is 20-55 μ m; Proportion is about 7; Based on contain the heavy volume density of 56% solid catalyst pulp in water is 1.8-2.0kg/l (15-17lbs/gal)), and RANEY 3300 (United States Patent (USP) the 5th, 922, the feature of No. 921 descriptions is as follows: the Ni that contains 90-99.1 weight %; Be not more than the Al of 8.0 weight %; Be not more than the Fe of 0.8 weight %; 0.5-1.5 the Mo of weight %; Median size 25-65 μ m; Proportion is about 7; Based on contain the heavy volume density of 56% solid catalyst pulp in water is 1.8-2.0kg/l (15-17lbs/gal)), RANEY 2724 (Cr helps catalysis) and RANEY 2724 (Cr helps catalysis); The catalyzer that is described to " Raney nickel " by GorwaraChemical Industries sale; By ActivatedMetal ﹠amp; Chemicals, A-4000 and A-5000 that Inc. sells; Be numbered 22, " Raney nickel " of 167-8 by the nickel ABMC of Degussa-Huls Corp. sale and by what Aldrich Chemical Co sold.

The example that comprises the fixed bed matrix of metal sponge support structures comprises the nickel sponge piller that European patent EP0648534A1 number and United States Patent (USP) are described for the 6th, 284, No. 703, and the disclosure of described patent is incorporated this paper into by reference.The nickel sponge piller, in particular as those of fixed bed catalyst, can be for example from W.R.Grace ﹠amp; Co. (Chattanooga, TN) (Ridgefield Park NJ) buys with Degussa-Huls Corp..

2. the deposition of copper-containing active phase

Described copper-containing active can be utilized various being used for metal deposition to the deposition techniques of metallic surface to the metal load body structure surface well known in the art mutually.These technology comprise for example liquid phase process, as electrochemical displacement deposition and electroless plating; And CVD (Chemical Vapor Deposition) method, as physical deposition and electroless plating.Be used for suitable method at metal load body structure surface deposited copper and be described in No. the 09/832nd, 541, the U.S. Patent application that No. the 6th, 376,708, co-assigned United States Patent (USP) and co-assigned separate case await the reply simultaneously, be disclosed as US-2002-0019564-A.United States Patent (USP) the 6th, 376, the full text of No. 708 and U. S. application US-2002-0019564-A1 is by with reference to all incorporating this paper into.

It is important to point out, copper and most of described support structures metal at least part miscible and with the nickel complete miscibility.Thereby, have been found that copper deposition process can produce the catalyzer that has copper or more particularly have the copper-containing active phase, be in the part of support structures surface as the discontinuous phase of for example skin or coating, be in the part of support structures surface as upper layer, perhaps copper may enter the main body of support structures from the surface transport of support structures.Be not limited to specific theory, believe that described catalyst surface can move between deposition and reaction period of pure reforming process, sintering or other structural rearrangement, cause copper-containing active mutually in these variations of form.However, have been found that described copper deposition process causes that copper content improves comprehensively in the catalyzer, sedimentary copper mainly is present in or near the surface of new preparation catalyzer, and described catalyzer more is rich in copper before than deposition.

A. the electrochemical displacement of copper deposits

As mentioned before, copper can deposit to described metal load body structure surface by the electrochemical displacement sedimentation, wherein with copper salt solution that support structures contacts in cupric ion be reduced to metallic copper, and oxidized near the non-copper metal on support structures surface.Metallic copper forms coating on the support structures surface again, and non-cupric ion enters solution simultaneously.The sedimentary general description of relevant electrochemical displacement is found in, for example Krulik and Mandich, " Metallic Coatings (Survey) ", Kirk-OthmerEncyclopedia of Chemical Technology the 4th edition, the 16th volume, mat woven of fine bamboo strips 258-91 page or leaf (J.I.Kroschwitz and M.Howe-Grant, eds., Wiley, New York, NY, 1995).The sedimentary more specifically explanation of the electrochemical displacement of relevant copper on metal sponge support structures is found in the co-assigned United States Patent (USP) the 6th, 376, No. 708, and its content is incorporated this paper into by reference.

At the special preferred method that is used for copper is deposited on the metal load structure, the electrochemical displacement deposition is carried out under alkaline condition earlier, then carries out the electrochemical displacement deposition under acidic conditions.In similar particularly preferred embodiment, in acid step, do not add copper, but the deposition again of copper can take place, because the monovalence copper dissolution that has been deposited in alkaline step on the carrier also deposits again.This step is described in following embodiment 6.Preferably, the metal load structure does not have surface oxidation substantially when copper deposits.Have in the metal load structure under the situation of oxidized surface (for example when support structures (even under water) in air exposed 6 months or be longer), especially preferably use reductive agent pre-treatment support structures.For example, described support structures can stir in sodium borohydride solution, and for every 25g metal load structure, this solution preferably comprises 1g sodium borohydride at least, and has the pH value at least about 10.Usually, support structures at room temperature contacts about 5 minutes to about support structures that just was enough to remove substantially surface oxidation in 2 hours with reductive agent.

In order to begin two steps, alkalescence/tart electrochemical displacement deposition, with metal load structure slurryization in water or alcoholic solution, preferably in water, carry out, and be 7 pH regulator.Mantoquita is added in the metal load structural paste, preferably add to comprise mantoquita and sequestrant, especially solution as the amine sequestrant of EDTA.Preferably, described copper salt solution comprises the copper of the about 10 weight % of relative metal load structure to about 30 weight %.The suitable mantoquita that is used for replacement deposition for example comprises nitrate, vitriol, hydrochloride and the acetate of (providing incomplete enumerating) copper.The salt that comprises the copper (being Cu (II)) of divalent state generally is most preferred.Also can use though comprise the salt of monovalence and means of trivalent copper, they are normally less preferred, because they are generally unstable, are difficult for buying, and/or are insoluble to alkaline mixt.

Then, lentamente alkali metal hydroxide (for example NaOH) or another kind of suitable alkali are added described slurry, preferred continuously stirring is simultaneously also used the nitrogen bubbling.The preferred described relatively mantoquita of described alkali hydroxide soln comprises the alkali metal hydroxide of at least 1 molar equivalent, more preferably with respect to described mantoquita about 1.1 alkali metal hydroxides to about 1.6 molar equivalents.Though this step comprises replacement deposition reaction, still combine closely and in next acid step, be removed with support structures from the oxidized metal of the part of support structures.In addition, the reaction of the first step alkalescence replacement deposition causes Red copper oxide (Cu ₂O) and metallic copper be deposited on the surface of support structures.

Behind alkaline replacement deposition, remove supernatant liquid by decant or additive method, and under acidic conditions, copper further is deposited on the catalyst cupport body structure surface.Behind the decant, described metal load structure slurryization once more in the alcohol or the aqueous solution.Acid buffer is added in the metal load structural paste, be lower than about 4 so that the pH value is reduced to.The temperature of damping fluid is preferably between about 40 ℃ and about 90 ℃.Described acid buffer can comprise any suitable sequestrant that can control the residual metal in the solution and reduce the pH value subsequently.More preferably, described acid buffer preferably has about 1 to about 4 pKa, so that pH value in the plating tank is maintained at about 1 to about 4.Preferably, described acid buffer is gluconic acid/gluconic acid salt buffer.For deposited copper on nickeliferous metal load body structure surface, gluconic acid is preferred, because gluconic acid is the good sequestrant of the residual aluminum ions that exists in solution.In addition, be necessary to point out, use normally less preferred based on the damping fluid of phosphoric acid because exist to form the sedimentary danger of insoluble phosphate.Can above-mentioned mantoquita (preferably as copper salt solution) added described metal load structural paste about 5 in during about 40 minutes under continuously stirring and the nitrogen bubble then.Preferably, as described in embodiment 6, add about 0.2 sulfuric acid Alloy instead of Copper salts solution to about 0.4 molar equivalent.This step has improved the activity of catalyzer to water-gas shift reaction.Then, can stop stirring and make catalyst sedimentation, thereby supernatant liquid can be removed by decant or additive method.

It is important to point out that when described catalyst structure was piller or only stone form, described copper facing may be with above-mentioned different.For example, commercially available ball shape metal sponge carrier often is incomplete activatory.The activation of commercially available ball shape carrier generally include remove great majority to deep layer, generally reach as high as the aluminium of about 200 μ m, to produce the metal sponge-type structure.But the core of piller generally still comprises the not activation alloy that is rich in zeroth order aluminium of very big concentration.Like this, can be under the condition of reorganization and steam and ethanol synthesis at the aluminium at core place, form crackle and also damage mechanical integrity.Therefore, activatory metal sponge is preferred fully.Fully the example of activated material is at United States Patent (USP) the 6th, 284, the hollow sphere activated ni of describing in No. 703.

In addition, diffusion can limit the plating of fixed bed carrier inside.Thereby, preferably in room temperature or be lower than the plating of carrying out the fixed bed carrier under the room temperature, because the ratio of rate of diffusion and electroplating reaction speed is preferably at low temperatures.For avoiding consume (if most copper because of be deposited on carrier outside consume, this will take place) of copper concentration, also preferably in plating tank, use the copper concentration that improves in carrier inside.Embodiment 10 has described a kind of example of preferred fixed bed carrier plating step.

Another preferred embodiment of the catalyzer that preparation mechanical property under the condition of reorganization is firm is at first generally to be to deposit on the thermally-stabilised and chemically stable matrix under plating and the condition of reorganization one deck nickel-aluminium alloy by thermospray.Suitable matrix generally can comprise steel or another kind of metal, but nonmetal basal body also can use.The thickness of described layer is preferably between 5 to 500 μ m, more preferably between 10 to 150 μ m.The preparation of the metal sponge film of load is described in United States Patent (USP) the 4th, 024, No. 044 and Sillitto etc., Mat.Res.Soc.Sym.Proc., the 549th volume, 23-29 page or leaf (1999).Described nickel-aluminium alloy layer provides the metal load structure and preferably at the copper facing front activating.

B. electroless copper

Electroless plating also can be used for copper-containing active is deposited on the surface of metal load structure mutually.With the electrochemical displacement sediment-filled phase seemingly, in the solution that electroless plating is included in support structures contacts cupric ion is reduced to the copper metal.But different with the electrochemical displacement deposition is that all basically cupric ions are all by outside reductive agent rather than described support structures reduction itself.When cupric ion was reduced to the copper metal in solution, the copper metal formed coating on the support structures surface.Use electroless plating that copper is deposited on the metal load body structure surface and be described in detail in the co-assigned United States Patent (USP) the 6th, 376, No. 708, its content is incorporated this paper into by reference.

3. incorporate copper-containing active phase

In another embodiment of the present invention, catalyzer does not comprise and covers the structural copper of metal load (promptly do not have discontinuous copper-containing active to deposit mutually or cover catalyst surface).On the contrary, copper has in the copper-containing active catalyst composition mutually on the surface with other metals that desirable performance is provided and mixes.Described catalyst composition can be uniform substantially.Preferably, this catalyzer is copper-containing metal form of sponge (for example, nickel/copper sponge).

4. selectable assistant metal

Except that copper that constitutes the catalyzer block as mentioned above and non-copper metal, described catalyzer can optionally comprise one or more assistant metals.Suitable assistant metal is selected from the group of 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, prolong the work-ing life of copper catalyst and keep or strengthen them being known in the art for the activity of water-gas shift, and by Lloyd etc. at Catalyst Handbook, 309-312 page or leaf (the 2nd edition, M.V.Twigg edits, Manson press, London, 1996) describe.The existence of one or more this metals has generally prolonged life of catalyst, prolonged promptly that catalyzer can be used for before its activity is reduced to unacceptable level that alcohol reforms during.In above-mentioned element, vanadium, chromium, molybdenum, zinc and their combination are particularly preferred, and preferably are present in the surface of catalyzer with oxide form.

The amount of assistant metal can change in wide region.Preferably, the total concn of assistant metal in catalyzer is that the copper of per 1,000,000 weight parts is at least about 10 weight parts.More preferably, the total concn of assistant metal in catalyzer is that about 0.002 weight % is to about 5 weight %, more preferably from about 0.002 weight % is to about 2.5 weight %, in addition more preferably from about 0.005 weight % to about 2 weight %, further more preferably from about 0.5 weight % to about 1.5 weight %.Usually, the total concn of assistant metal is no more than about 5 weight %.Though can use the assistant metal of greater concn, surpass this concentration by can not obtaining other benefit, and activity of such catalysts can descend generally.

One or more assistant metals can be contained in the metal load structure and/or the copper-containing active on support structures surface mutually in.Comprise under the situation of assistant metal in expectation alloy-metal load structure, assistant metal is preferably sneaked into alloy when forming alloy.Comprise under the situation of assistant metal in mutually in the copper-containing active on expectation support structures surface, assistant metal can deposit with copper in some cases simultaneously.But, passing through under replacement deposition or the sedimentary situation of electroless plating (as mentioned above) at copper, assistant metal preferably adds catalyzer after the copper deposition, because assistant metal may dissolve and suppress electroless plating under the replacement deposition condition.Generally can be simply by making catalyzer contact the surface that assistant metal is added catalyzer with the solution that comprises assistant metal salt (for example vitriol, nitrate, hydrochloride etc.).The oxidate of assistant metal also is suitable for depositing to the surface of metal load structure of the present invention after electroplating process is finished to the method on the copper sponge, and be found in the United States Patent (USP) the 5th of Franczyk etc., 292, No. 936, its whole disclosures are incorporated this paper into by reference.

B. preferred pure reforming reaction condition and power system

The present invention's alcohol reforming method generally comprises the material gas mixture that comprises alcohol reactant is contacted at dehydrogenation reaction zone with the above-mentioned catalyst bed that comprises copper containing catalyst.

Described dehydrogenation reaction zone preferably comprises continuous-flow system, and the configuration of this system can be guaranteed low back pressure and initiation, keep the heat passage fully of thermo-negative reaction.Realize that fully heat passage reformer design is known, and be described in the United States Patent (USP) the 5th, 935, No. 277 and the 5th, 928, No. 614 of No. the 3rd, 522,019, the United States Patent (USP) of Buswell for example etc. and Autenrieth etc.Thereby each patent has all been described by heat conductive wall and thermal source and has been carried out the catalytic reforming alcohol reactor that heat exchange provides heat.Preferably be used to heat the most normal waste gas that comprises the pure incomplete oxidation of being reformed of thermal source of dehydrogenation reaction zone from part, or from the independent burning reaction of using alcohol or another fuel source.As described below, particularly preferred embodiment of the present invention is to use from the combustion chamber, and the waste gas of combustion chamber that preferably is in the dehydrogenation reaction zone downstream is as the thermal source of dehydrogenation reaction zone.

The alcohol reforming reaction is a strong endothermic reaction, and is necessary to the net heat transmission of dehydrogenation reaction zone for good transformation efficiency.Importantly be, compare that the copper containing catalyst that comprises the metal load structure described herein shows better thermal conductivity with traditional reforming catalyst that comprises ceramic monolith.For example, as Gersten etc. at " The Physics and Chemistry of Materials, " Wiley, New York, 2001, the 144 pages describe, the thermal conductivity of copper and mickel is respectively 401W/m.K and 91W/mK under 300K.By comparison, the thermal conductivity of traditional reforming catalyst material such as Alpha-alumina is 36W/mK under the 300K, and silicon-dioxide is 1.4W/mK, and magnesium oxide is 36W/mK.The thermal conductivity of copper containing catalyst under 300K that comprises metal load structure of the present invention is preferably at least about 50W/mK, more preferably at least about 70W/mK, especially at least about 90W/mK.

Described pure reforming reaction is generally carried out in gas phase being higher than under about 100 ℃ temperature.But, according to the present invention, the preferred alcohol in the reformer feed gas mixture under being lower than about 400 ℃ temperature.More preferably, reforming reaction is carried out under about 150 ℃ to about 400 ℃, and more preferably from about 200 ℃ to about 375 ℃ temperature, and most preferably from about 250 ℃ to about 325 ℃ temperature.For example, have been found that and to use copper facing metal sponge catalysts in the methods of the invention that when particularly comprising nickel or mixing the copper facing metal sponge of nickel of copper, ethanol is reformed and can be carried out with sufficiently high transformation efficiency at about 250 ℃ to about 300 ℃ temperature.

Because reforming reaction is thermo-negative reaction, therefore must the temperature of other heat supplied needing to keep at dehydrogenation zone.Usually, during pure reforming reaction, reforming reaction can be by any way control well known in the art in the temperature of catalyst bed.Preferably, the temperature of catalyst bed is controlled as on its length isothermal or has positive thermograde (being temperature improves to outlet gradually from the inlet of bed).For example, pure reactant gases can introduced catalyst bed for low about 10 ℃ than required catalyst bed temperature out to about 50 ℃ temperature, provide the additional heat of necessity to keep the desired temperatures state in catalyst bed to dehydrogenation reaction zone simultaneously.

When reformation ethanol, it is important to point out, in the narrow temperature scope operation and avoid too high temperature to reduce the formation of too much methane byproduct.The formation of methane (i.e. " methanation ") is not expected, because should react the hydrogen production that needs the speed consume expensive of 3 moles of hydrogen with every production 1 mole of methane.Operation under low pressure also can be avoided the over-drastic methanation.Therefore, the pressure of catalyst bed ingress preferably is lower than about 30psig, more preferably less than about 10psig.

Described dehydrogenation reaction has produced wraps the hydrogenous hydrogen fuel cell of can introducing to produce the gaseous product mixture of electric energy.Therefore, particularly preferred embodiment of the present invention is the hydrogen that primary alconol such as methyl alcohol, ethanol or their mixture dehydrogenation is used for producing at fuel cell electric energy with generation.For example, the suitable applications of the hydrogen in product mixtures of the present invention of generation comprises that it is used as hydrogen fuel source in polymer dielectric fuel cell, alkaline fuel cell, phosphoric acid fuel cell, molten carbonate fuel cell and Solid Oxide Fuel Cell.For polymer dielectric fuel cell, particularly proton exchange membrane (PEM) fuel cell, the hydrogen source that acts as a fuel is normally most preferred.The PEM fuel cell generally moves under about 80 ℃ or lower temperature.Thereby the present invention can carry out alcohol at low temperatures and reform, and its advantage is to simplify the design of power system, and improves efficiency.

When the present invention's alcohol reformate mixture is used as the hydrogen source of fuel cell, preferably dehydrogenation reaction is combined with above-mentioned water-gas shift and carry out, to drop to the CO content in the product mixtures minimum.Therefore, often preferably in sending into the material gas mixture of dehydrogenation reaction zone, alcohol is mixed with water, to promote the removal of carbon monoxide from the product logistics by water-gas shift.For example, alcohol preferably before introducing dehydrogenation reaction zone with the water of at least 1 molar equivalent, most preferably mix with about 1.05 water to about 1.2 molar equivalents.

Generally speaking, the invention described above catalyzer has certain activity for water-gas shift.But, in certain embodiments, can preferably use additional water-gas shift catalyzer, so that in product mixtures, reach lower carbon monoxide concentration.When using additional water-gas to change catalyzer, described water-gas changes catalyzer can be mixed with reforming catalyst in the reforming catalyst bed, perhaps is placed on the reforming catalyst downstream, in identical or independent catalyst bed.

Embodiment of the present invention for using independent water-gas transfer catalyst it is important to point out, most of traditional water-gas shift are generally in about 200 ℃ of operations down, and are lower than the typical operating temperature of the present invention reforming catalyst.Therefore, may be necessity or desirable with cool reformate mixture before water-gas changes catalyzer and contact.Usually, any device that is used for cooled product well known in the art can use, and comprises heat exchanger.In one embodiment, can between reformer and water-gas shift reactor, water be introduced in the reformate gas.In this embodiment, after reformer, introduce water and can reduce or remove the water yield in alcohol-water material gas mixture of sending into this reformer.

Though to the present invention is not necessary or crucial, but the carbon monoxide during the reformate that is to use one or more addition thereto minimizings to leave dehydrogenation reaction zone, water-gas transformation catalyst bed and/or fuel cell flows, or it is carried out other control, may expect in certain embodiments of the invention.Control or existing extensive description of example of reducing the appropriate action of carbon monoxide, Pettersson etc. for example, Int ' l J.Hydrogen Energy, the 26th volume, 243-64 page or leaf (2001), and comprise optionally oxidizing carbon monoxide, methanation carbon monoxide and the gas leakage of enforcement anode.

Be admitted in the preferred embodiment of fuel cell with the generation electric energy at the hydrogen that dehydrogenation zone produces, dehydrogenation reaction is preferably carried out in the fixed-bed reactor that comprise above-mentioned copper containing catalyst bed of packings.Preferably take measures to make the back pressure minimum, for example keep spacing with separating catalyst particles and between them by inert solid diluent being added described catalyst bed.Described thinner preferably do not contain can catalysis ethanol dehydration generate ethene reaction acid sites and under this reaction conditions heat-staple material.The silicon carbide Buddhist monk not activated carbon of acid activation is the example of preferred diluent.

As selection, can also back pressure be minimized by the copper containing catalyst that use comprises the metal sponge support structures of ball shape rather than powder.The support structures of this moulding is included in the nickel sponge ball of describing in No. the 6th, 284,703, European patent EP 0648534Al and the United States Patent (USP), and its disclosure is by with reference to incorporating this paper into.The nickel sponge ball, especially as fixed bed catalyst, can be from for example W.R.Grace ﹠amp; Co. (Chattanooga, TN) (Ridgefield Park NJ) buys with Degussa-Huls Corp..In other alternate preferred embodiments, described catalyzer solely stone form uses, so that the back pressure in the reforming reactor is dropped to minimum, described monolith catalyst prepares by the surface of catalyzer of the present invention being sneaked into suitable porous matrix (for example honeycomb).

With reference to figure 1 a kind of embodiment that is produced the system of electric energy by ethanol reformation according to the present invention is described.Though narration is hereinafter specifically just used above-mentioned copper containing catalyst to carry out alcohol dehydrogenase and disclosed, should be realized that described principle generally is applicable to the dehydrogenation of other primary alconols that comprise methyl alcohol or ethanol and carbinol mixture.

Alcohol/water the raw material that will comprise the mixture of ethanol and water is introduced dehydrogenation reaction zone, and this reaction zone comprises the bed of packings 101 of the cupric dehydrogenation catalyst that contains the metal load structure.The described raw material that comprises ethanol/water mixture for example, after evaporating, is introduced dehydrogenation reaction zone preferably with the form of gaseous feed mixture in the vaporizer (not shown) known in the alcohol reformation technology.With heating jacket 102 heatable catalyst beds 101, to keep desired temperatures at dehydrogenation zone.The reformation of ethanol/water mixture in catalyst bed 101 produced the product mixtures that comprises hydrogen, carbon monoxide, carbonic acid gas, water and methane.Then this product mixtures is fed the additional catalyst bed 103 that suitable water-gas changes catalyzer that comprises, optionally carbon monoxide is oxidized to carbonic acid gas.Compact type water-gas changes assembly and develops, and can (South Windsor CT) buys from Hydrogen Source for example.The product mixtures that leaves catalyst bed 103 is cooled to suitable temperature (being generally 80 ℃ or lower) then, and is introduced in the hydrogen fuel cell 105 (for example Proton Exchange Membrane Fuel Cells) to produce electric energy with oxygen source (as air).Electric energy produces by hydrogen and oxygen generate water in fuel cell reaction.It should be understood that identically with the convention of fuel cells applications, described fuel cell can comprise a plurality of fuel cells (being fuel cell pack).

Then, the fuel cell that comprises water vapor, methane and carbonic acid gas flows out thing and burns with air in for the combustion chamber 107 that oxygen source (for example air) arranged.Suitable combustion chamber can comprise that internal combustion turbine, hot machine, oil engine or other are used to drive the equipment of the generator 109 that produces additional electrical energy.The heat burning effluent that comes from generator 109 can be recycled to the thermal source of heating jacket 102 as heating dehydrogenation zone reforming catalyst bed 101.

The burning that described fuel cell flows out thing also provides a kind of facilitated method of handling the power system discharging.Described fuel cell flows out does not expect component in the thing, and for example acetaldehyde, carbon monoxide, remaining alcohol and/or methane will be converted into carbonic acid gas in large quantities by burning in combustion chamber 107.Remaining hydrogen will be oxidized to water.There is report to think that the hydrogen discharge of overflowing may be a threat to ozonosphere in the recent period.(referring to Tromp etc., Science, 300,1740-2, (2003)).In addition, the waste gas (different with the waste gas of conventional P EM fuel cell power system) that comes from oil engine is enough warm, and catalyst is effectively played a role, and has further reduced noxious emission.

In vehicle power is used, preferably will mainly be that the fuel cell of hydrogen, water vapor and the carbon monoxide of carbonic acid gas, methane and trace flows out the firing system that thing is introduced can provide electric energy and/or mechanical energy.In this application, firing system can comprise the oil engine of the moment of torsion that produce to drive vehicle, or with the generator bonded oil engine that produces additional electrical energy.

In particularly preferred embodiments, use the power system combustion fuel battery effluent of the variable fuel combustion that has comprised the alcohol that to burn, methane or their mixture, and provide mechanical power source to drive vehicle.For there being the galvanic one or more electric motor that produced by fuel cell that additional energy is provided, this is to be similar to the configuration that is used for hybrid vehicle.This preferred power system is shown in Figure 2 as what use ethanol to act as a fuel.

With reference to Fig. 2, water-ethanol raw mix (molar weight of water is excessive slightly) is introduced hydrogenation reaction zone and pass through heating jacket 202 heating, wherein hydrogenation reaction zone comprises bed of packings 201 and the water-gas transformation catalyzer 201B that contains nickel plated copper sponge reforming catalyst.As previously mentioned, alcohol is reformed in bed of packings, has generated the reformate that comprises hydrogen, carbonic acid gas and methane.Reformate from dehydrogenation zone is sent into hydrogen fuel cell 205 to produce direct current energy with oxygen source (for example air) under suitable temperature.Methane and carbonic acid gas do not reduce the PEM fuel cell performance.The effluent of fuel cell 205 mainly is methane and carbonic acid gas, and they and oxygen source (for example air) burn in oil engine 207.Then, the hot waste gas that comes from oil engine was used as the thermal source of heating jacket 202 before leaving this system as waste gas, preferably by the catalyst (not shown).Like this, will be used, the heat that needs is provided for the ethanol reforming reaction of absorbing heat from the used heat of oil engine.Can be known in the art in the design of independently carrying out the reformer of heat exchange between hot gas flow and the reforming catalyst bed.

Because the endothermic character of pure reforming reaction, the remarkable shortcoming of fuel cell operation in vehicle transport is used appears at when starting.Particularly, fuel cell can not make vehicle " cold start-up " (promptly before generation is enough to drive the energy of vehicle, lifetime postpones when starting, and reaches their design and operation temperature up to reformer and fuel cell).Thereby, in particularly preferred embodiment of the present invention, the oil engine 207 of the combustion-driven power system of describing with reference to Fig. 2 is a kind of variable fuel combustion, and it can use raw polyol or another kind ofly flow out the isolating cold start fuel of thing source 211 with fuel cell and move.The raw polyol of described oil engine is preferably anhydrous, therefore separates with the alcohol-water raw material of reforming reactor.When starting, oil engine uses from the operation that acts as a fuel of the alcohol in cold start fuel source 211 independently, to provide and to use the similar cold starting performance of traditional combustion engine generation vehicle powered.Normally in service, after reformer and fuel cell reached their design and operation temperature, vehicle can mainly produce power by electric motor, and wherein electric motor is for the direct current that produces by hydrogen fuel cell is arranged.The part basis power that oil engine continues to play a role and needs with the compensation vehicle, but oil engine has been a fuel from the methane of fuel battery effluent since main, rather than from the alcohol in cold start fuel source 211 independently.If drive condition needs other instantaneous power, vehicle can utilize oil engine to produce additional torque so.In addition, the methane that flows out in the thing at the fuel cell that enters oil engine can be by replenishing to produce this additional torque from the alcohol in cold start fuel source 211 independently.Additional additional power also can be provided by battery.

Except cold start-up preferably and instantaneous dynamic performance were provided, this preferred disposition can make up power system with very low cost.Hydrogen fuel cell is normally based on the most expensive assembly in the automotive power of fuel cell.The fuel cell capacity that power system described herein needs significantly is lower than traditional design, because peak value power is replenished by oil engine.This design only needs to be enough to provide the fuel cell capacity of part basis power, and other parts are provided by the oil engine that uses the operation of alcohol and/or methane.

Embodiment

Assign embodiment and only be intended to further specify and explain the present invention.Therefore, the present invention should not be limited to any details of these embodiment.

Other the preparation embodiment that is used to prepare the copper facing metal catalyst is described in co-assigned United States Patent (USP) the 6th, 376, No. 708 and co-assigned separate case be U.S. Patent Application Serial 09 ' 832,541, the publication number US-2002-0019564-A1 of pending trial simultaneously.United States Patent (USP) the 6th, 376, the full text of No. 708 and US publication US-2002-0019564-A1 is by with reference to incorporating this paper into.

The preparation of embodiment 1 nickel plated copper sponge catalysts

This embodiment has illustrated and has utilized the replacement deposition legal system to be equipped with the nickel plated copper sponge catalysts.

In glass beaker, with the nickel sponge support structures (68.7g, RANEY 4200, from W.R.Grace, Chattanooga TN) is suspended in the water of nitrogen bubbling (400ml).Under agitation add the NaBH that is dissolved in 12% among the 14M NaOH ₄(50g) solution.Observe strong foaming 1 minute.After stirring 10 minutes, make catalyst sedimentation and decant supernatant liquid.The water (400ml) and the of short duration stirring that add the nitrogen bubbling of extention.Before the decant clear liquid, make the sedimentation once more of this catalyzer.

The water (250ml) of third part nitrogen bubbling is added in this catalyzer.Add glacial acetic acid (about 8ml) pH is reduced to 5.Make the CuSO of described catalyst suspension and nitrogen bubbling then ₄5H ₂O (54.0g, copper is 20 weight % with respect to the content of catalyzer) contacts with the solution of ethylenediamine tetraacetic acid (EDTA) (EDTA) four sodium dihydrates (108.0g) in water (300ml).Under the condition of continuously stirring and nitrogen bubbling, in 103 minutes, add NaOH (2.5N, 73.0ml).The pH value of suspension is raised to 11.3 by 6.8.Make catalyst sedimentation, twine beaker with heat tape, and the supernatant liquid of decant blueness.

With CuSO ₄5H ₂O (67.5g, copper is 25 weight % with respect to the content of catalyzer) is dissolved in the water (200ml) of nitrogen bubbling to form copper solutions.Add the suspension that described catalyzer forms catalyzer by hot mixt (74 ℃) with the water (250ml) of 50% gluconic acid (159.0g), 2.5NNaOH (54ml) and nitrogen bubbling.Then, under agitation in 95 minutes, described copper solutions is added in this catalyst suspension, apply heat (72 ℃ of outlet temperatures) with heat tape for this beaker simultaneously.The pH value drops to 3.1 by 3.8.Make the supernatant liquid of catalyst sedimentation and decant green.

Catalyzer cleans with the water (700ml) of nitrogen bubbling.The decant scavenging solution reclaims 75.6g obscure-aeneous catalyzer and storage under water.The composition of this catalyzer is 66.1%Ni, 30.4%Cu and 3.5%Al.

When with the small sample (about 1g) of this catalyzer when suspending in water, find that this catalyzer is made up of two portions.These two portions are made up of coppery lower floor and grey upper strata.After being 130 ℃ of following hydrogen dryings, adopt Schmidt, " Surfaces of Raney ^Catalysts ", the method for describing among the Catalysis of organicReactions, mat woven of fine bamboo strips 45-60 page or leaf (M.G.Scaros and M.L.Prunier, eds., Dekker, NewYork, 1995) is measured BET surface-area and surface nickel concentration.Analytical results is listed in table 1.The data that provided RANEY 4200 matrix simultaneously are for comparing.

Table 1

Sample	The BET surface-area	Surface nickel
			RANEY 4200	70m 2/g	700-800μmole/g
Top section	36.8m 2/g	54.8μmole/g
			Underclad portion	40.1m 2/g	32.1μmole/g

Embodiment 2 utilizes nickel plated copper sponge catalysts reformation ethanol

This embodiment has illustrated the nickel plated copper sponge catalysts alcoholic acid purposes that is used to reform.

This experiment is comprising stainless steel 304 pipe (long 457.2mm, internal diameter 12.7mm), is being wound with in the stainless steel reactor of spiral cable well heater and carries out.Be used for the top of the pipe coupling of preheating ethanol raw material at this reactor.Described catalyst distribution at glass fibre beyond the Great Wall, glass wool plug is held in place on the hollow inset of tubular reactor bottom.Thermopair is placed on the bottom of described catalyst bed and utilizes the spiral cable well heater to monitor and control reaction temperature.Effluent utilizes thermal conductivity detector by gas chromatographic analysis.The outlet of described reactor is under the barometric point.

Described reactor such as following filling.After inserting fresh glass wool plug, make the aqueous slurry of 325 purpose silicon carbide (1.0g) (from Alfa Aesar, Ward Hill, MA acquisition) pass reactor, be positioned at the basis of the catalytic bed at glass fibre top with formation.Make the slurry of the catalyzer (2.02g) of silicon carbide (1.5g) and embodiment 1 pass reactor then.Do not observe and run through phenomenon, illustrate that all catalyzer that loaded all are retained in the reactor.Before use, catalyzer is spent the night in the reactor inner drying under 120 ℃ in nitrogen.

Table 2 has provided the result that ethanol is reformed when adopting water concentration in different temperature, flow velocity and the raw material.Before acquisition tables 2 data, described catalyzer is used for the ethanol reformation and amounts to about 30 hours.Note, because the methanation of analytical error and the CO shown in equation 6, methane production and can surpass 100% based on the mass balance of methane:

CO+3H ₂→CH ₄+H ₂O (6)

Be also noted that table 2 and the following examples have been omitted the productive rate of hydrogen.Though hydrogen is directly measured in gas-chromatography, to compare with carbon-containing molecules, thermal conductivity detector is lower to the sensitivity of hydrogen, has therefore caused the more polydispersion of data.Therefore, the productive rate of hydrogen can be calculated more accurately by the productive rate of carbon compound such as carbon monoxide, carbonic acid gas and methane.

Table 2

Ethanol product under the different condition distributes, with the molar yield report with respect to the ethanol raw material amount

H in the raw material 2O 1 (wt.％)	Temperature (℃)	Raw material (ml/min)	CH 3CH 2OH％	CH 3C(O)H％	CH 4％	CO 2％
							50％	250	0.15	Trace	4.3	95.1	6.5
	0.30	21.7	26.7	52.2	4.5
								0.40	42.3	29.6	25.7	1.5
	0.80	62.8	27.9	9.2	0.2
								1.20	74.7	20.9	4.5	Trace
50％	280	0.20	0	0	101.0								24.5
							0.40	14.2	19.6	66.8	6.0
		0.80	50.4	26.2	22.9							2.1
								64.2	21.9	14.0	1.1
	30％	250	0.30	44.2	14.8							40.8	1.5
280						0.30	12.9	9.6	76.9	3.7
		300	0.30	0	2.9						97.5	6.7
300						0.20	0	0	102.0	15.1
		320	0.20	0	0						104.6	42.0
10％						250	0.20	22.2	8.3	69.5			1.3
	250	0.30	47.1	12.1	40.8						0.5
						280	0.20	6.2	3.9	90.5		2.1
	0％	250	0.20	0	0						104.4		3.5
						0.25	9.9	3.9	87.5	0.8
			0.40	33.3	9.0						58.3	0.3
						0.60	50.9	11.1	38.3	0.1
			0.90	78.3	9.0						11.8	Trace

¹The rest part of raw material is an ethanol.

Embodiment 3 utilizes nickel plated copper sponge catalysts reforming methanol

This embodiment explanation utilizes nickel plated copper sponge catalysts reforming methanol.

This experiment is carried out according to the foregoing description 2, but is to use the raw material of being made up of 70 weight % methyl alcohol and 30 weight % water.The results are shown in following table 3.

The methanol recapitalization products distribution that table 3 is obtained by 70% methyl alcohol of reforming

Temperature	Raw material flow rate (ml/min)	Methyl alcohol	Methane	CO	CO 2
						300℃	0.40	13.3％	3.2％	81.2％	2.3％
300℃	0.20	2.4％	3.7％	86.9％	7.0％
						320℃	0.20	1.7％	5.5％	75.5％	17.9％

The ethanol that embodiment 4 prolonged in the cycle of operation is reformed

This embodiment illustrates the ability of catalyzer of the present invention support high conversion in the ethanol reformation cycle that prolongs.

This experiment is carried out under condition substantially the same manner as Example 2, but reactor is earlier by depositing silicon carbide (1.0g), the slurry with catalyzer (2.50g) that comprises embodiment 1 and silicon carbide (5.0g) loads then.Temperature monitors by thermopair, and described thermopair is inserted to position than the high about 10.2cm in catalyst bed bottom downwards along the inner chamber of reactor.

This reactor remains on 280 ℃ mode with the temperature of the product mixtures that leaves catalyst bed and moves.The temperature of last thermopair is maintained at about 430 ℃ relatively consistently.Ethanol/water raw mix (ethanol/water weight ratio 70: 30) is introduced dehydrogenation zone with the speed of 0.3ml/min with the nitrogen of 100sccm.This reactor operation 44 hours, the pressure of reactor is elevated to 80psig by 28psig during this period.During this period, do not detect ethanol or acetaldehyde in the product mixtures, and methane conversion is 100% in the analytical error scope.Following table 4 has provided in experimentation CO and CO ₂Selectivity.

Table 4

At 280 ℃ of ethanol reformate yields that use 70% ethanol raw material down

Time (hour)	CO％	CO 2％
			2	34	66
5	60	40
			12	81	19
20	85	15

25	85	15
			31	88	12
35	88	12
			40	88	12
44	87	13

The reformation of embodiment 5 ethanol in having the bed of packings of thermal gradient

This embodiment explanation is by being that 300 ℃ or lower and temperature in are lower than under the thermal gradient of temperature out reformation ethanol and have realized high conversion and low methanation with the nickel plated copper sponge catalysts in low pressure, temperature out.

Use vertically arranged stainless steel tubular type reactor (the long 457.2mm that is tied with the spiral cable well 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.Thermopair is placed on the upstream and downstream of catalyst bed.The catalyzer (2.50g) that use prepares in embodiment 1.Speed with 0.1ml/min is sent the mixture of weight ratio 70% ethanol/30% water into reactor, and with the controllable rate reactor heating, so that the temperature out of catalyst bed effluent is 275 ℃.During Therapy lasted, the catalyst bed upstream temperature is stabilized in 245 ℃.The pressure of reactor upstream is no more than 5psig.

Table 5 has shown the high conversion that reaches between 200 hours continuous operating period surpassing.After producing 286 hours, temperature out is elevated to 300 ℃.The data of gathering under this temperature are listed in table 6.In product mixtures, do not detect acetaldehyde or ethanol.Temperature is elevated to 300 ℃ of transformation efficiencys and also brings up to 100%.Not finding in the whole experiment can detected methanation.

Table 5

Embodiment 5 is at 275 ℃ of following product yields

Time (hour)	CO％	CO 2％	CH 4％	CH 3C(O)H％	Ethanol %
						10	96.1	2.0	101.9	ND	ND
20	97.1	1.8	101.1	ND	ND
						40	96.3	2.5	101.2	ND	ND
60	96.5	2.5	101.0	ND	ND
						80	96.3	2.7	101.0	ND	ND
100	95.4	3.4	101.1	ND	ND
						120	96.5	2.6	100.9	ND	ND
140	96.6	2.4	100.8	0.05	ND
						160	96.8	2.2	100.9	ND	ND
180	97.1	2.1	100.8	ND	ND
						201	96.6	2.2	101.1	ND	ND
220	95.8	2.2	100.8	0.57	ND
						265	96.1	2.4	99.5	0.71	0.31％
285	95.3	2.1	99.3	1.03	0.62％

ND=does not detect

Table 6

Embodiment 5 brings up to product yield after 300 ℃ in temperature out

Time (hour)	CO％	CO 2％	CH 4％	CH 3C(O)H％	Ethanol %
						290	91.4	8.2	100.4	ND	ND
295	91.2	8.2	100.6	ND	ND
						300	91.9	7.7	100.3	ND	ND
306	91.5	8.2	100.3	ND	ND
						310	91.5	7.7	100.5	ND	ND

The preparation of embodiment 6 nickel plated copper sponge catalysts

This embodiment illustrates a kind of method for plating that is used for metal sponge matrix, with Morgenstern etc. people's's (United States Patent (USP) the 6th, 376, No. 708) or embodiment 1 in method compare, this method provides similar transformation efficiency and better carbon dioxide level, and needs less copper sulfate.This method is also used high solid concentration, therefore makes refuse volume minimum.In this embodiment, matrix and catalyst quality are determined by the water method of replacing, are supposed that bulkfactor is 1.16.

With the nickel sponge support structures (48.3g, RANEY 4200, from Grace Davison, Chattanooga TN) transfer in the 1L beaker of the water with nitrogen bubbling, and decant is removed excessive water.With CuSO ₄5H ₂O (47.45g) and Na ₄EDTA2H ₂The solution of the nitrogen bubbling of O (94.92g) in water (400ml) adds this catalyzer and stirs this slurry, adds 2.5NNaOH (91ml) simultaneously in 48 minutes.PH is elevated to 11.4 by 8.4.The blue clear liquid of decant also twines this beaker with heat tape.

The hot mixt of 50% gluconic acid (11g) and water (400ml) is added described catalyzer.Apply heat and in 43 minutes, add the vitriol oil (5.70g) and the mixture of water (50ml).Temperature-stable between 59 ℃ to 60 ℃ and pH drop to 2.2 by 5.2.This mixture of restir 45 minutes.Final pH is 2.8.

The blue clear liquid of decant also adds the water (500ml) of nitrogen bubbling, with sodium hydroxide pH is adjusted to 7.This step helps to remove remaining nickel and EDTA.Make catalyst sedimentation and remove supernatant liquid by decant.Reclaimed the catalyzer that 51.3g has following composition: 76.8%Ni, 19.9%Cu, 3.2%Al and 0.2%Fe.

Embodiment 7 uses nickel plated copper sponge catalysts reformation ethanol

The ethanol of this embodiment explanation in the presence of the copper bearing catalyzer of nickel sponge support structures surface bag is reformed.

To put into the reactor that has with the foregoing description 2 identical configurations according to the catalyzer (2.50g) of embodiment 6 preparations.The raw polyol that will comprise 70 weight % ethanol and 30 weight % water is introduced this reactor with the speed of 0.1ml/min.In first 24 hours of experiment, temperature out is brought up to 300 ℃ gradually.Notice that transformation efficiency is a little less than embodiment 5, but CO is to CO ₂Conversion (water-gas shift) proceed to much bigger degree.The methanation degree is also higher, but as in next embodiment, seeing that it reduced along with the time.

Table 7

Embodiment 7 effluents are formed

Time (hour)	Temperature out	CO％	CO 2％	CH 4％	CH 3C(O)H％	Ethanol %
							7	270℃	81.7	14.3	103.5	0.2	ND
15	270℃	80.7	15.2	101.8	0.6	0.5％
							20	270℃	68.5	26.8	104.0	0.3	ND
31	300℃	44.1	49.8	106.1	ND	ND
							35	300℃	47.2	46.9	105.9	ND	ND
40	300℃	43.7	51.0	105.1	ND	ND
							45	300℃	47.2	48.6	104.2	ND	ND

The ethanol that embodiment 8 prolonged in the cycle of operation is reformed

This embodiment explanation alcoholic acid isothermal in the time cycle that prolongs is reformed.This embodiment further specifies and uses embodiment 6 catalyst methaneization progressively to descend, and keeps high CO simultaneously ₂Transformation efficiency.

Identical with the foregoing description 7, with the described identical reactor facilities of embodiment 2 in pack into according to the catalyzer (2.50g) of embodiment 6 preparations, and use the flow velocity operation of the raw material that comprises 70 weight % ethanol/30 weight % water with 0.1ml/min.The temperature out of catalyst bed remains on 300 ℃.Run duration does not detect acetaldehyde or ethanol in product mixtures.As shown in table 8, the experimental session methanation is stable to descend.

Table 8

Embodiment 8 effluents are formed

Time (hour)	CO％	CO 2％	CH 4％
				10	57.6	37.5	104.8
20	64.0	31.9	104.1
				32	64.1	32.5	103.3
41	66.4	30.8	102.8
				50	70.9	27.1	102.0
61	76.9	21.8	101.3
				70	77.8	20.8	101.3
85	60.3	37.2	102.5
				91	69.6	28.9	101.5
100	68.6	30.5	100.9
				110	77.9	21.8	100.3

Embodiment 9 uses nickel plated copper sponge catalysts reforming methanol

This embodiment illustrates that catalyzer of the present invention is at gentle, active and stable near reforming methanol under the isothermal condition.

The catalyzer (2.52g) that will in embodiment 1, prepare and polymer globules thinner (1.0g, Tenax TA, 80-100 order, from Alltech Associates, Deerfield IL) mixes and packs into as in the embodiment 2 described reactors, and reactor in this experiment in horizontal direction.Add the mixture (0.1ml/min, water: the mol ratio of methyl alcohol is 1.19: 1) of 60% methyl alcohol/40% water to reactor with the speed of 0.1ml/min, temperature out remains on 320 ℃.Pressure remains below 5psig in the whole service process.The temperature of catalyst bed upstream is about 335 ℃, and is changed to 369 ℃ at experimental session by 309 ℃.

Table 9 has shown the result.The temperature that acquisition is higher than 90% methanol conversion needs is higher than the temperature of ethanol needs.The methane yield is general about 1%, and is similar to the alcoholic acid value.

Table 9

Embodiment 9 effluents

Time (hour)	CO％	CO 2％	CH 4％	Methyl alcohol %
					10	70.5	25.6	2.9	1.0
20	79.5	17.1	1.8	1.6
					30	83.4	13.3	1.8	1.5
40	84.7	11.5	1.7	2.2
					50	85.5	9.7	1.4	3.3
60	84.1	5.8	0.4	9.7
					70	83.1	4.7	0.5	11.8
80	84.7	6.4	0.6	8.3
					90	83.3	5.0	0.6	11.1
100	80.3	9.1	1.0	9.6
					110	79.5	8.1	0.9	11.5

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

This embodiment has described by copper being plated to the fixed bed carried structure of nickel sponge and has prepared fixed bed catalyst.

(45 balls, it comprises 6.79g Metalyst will to be distributed in the piller matrix ^α-1401-X018 can be from German Degussa AG, and Hanau buys) the nickel sponge support structures under vacuum in 120 ℃ of dried overnight, use nitrogen purging.Described piller is packed into along plastics tubing (internal diameter 9.525) length direction in nitrogen atmosphere, between glass wool plug, and makes and comprises CuSO ₄5H ₂O (10.67g) and Na ₄EDTA2H ₂The coating bath liquid of the solution of O (21.34g) in water (300ml) dripped the mixture of 2.5N NaOH (26ml) and water (50ml) simultaneously at room temperature in the catalyzer cocycle in 124 minutes.During plating, coating bath solution is kept in the agitated pool that is in the nitrogen atmosphere, and utilizes peristaltic pump to circulate between catalyzer and pond.PH is elevated to 12.0 by 10.0.Water cleaning catalyst then.

Then, with CuSO ₄5H ₂The mixture of O (6.67g), gluconic acid (5.2g), 2.5N NaOH (2.7g) and water (300ml) adds in the described pond, and at room temperature in catalyzer cocycle 2 hours.The water cleaning catalyst in a vacuum in 120 ℃ of dried overnight, is used nitrogen purging then.Reclaim 6.65g (98%) catalyzer.

Ethanol under embodiment 11 isothermal conditions is reformed

This embodiment explanation is used for reformation alcoholic acid catalyst performance under approaching isothermal condition (comparing with the ethanol reformation that has thermograde in the embodiment 7 described reactors).

This experiment comprises the catalyzer reformation ethanol that uses embodiment 6 preparations, and catalyst bed keeps near isothermal down at 280 ℃.In order to eliminate thermograde, use improved reactor.Material gas mixture (70 weight % ethanol/30 weight % water) pumps into preheater with 0.10ml/min speed by stainless steel tube (external diameter 1.58mm), this preheater is by being filled with Stainless Steel Ball (diameter 3mm and 4mm) and being tied with vertical stainless steel tube (the long 457.2mm of cable well heater, internal diameter 9.525mm, external diameter 12.7mm) constitute.Feed-pipe is wrapped on the cable well heater in a spiral manner, and links to each other with preheater in the bottom.

The top of described preheater (outlet) connects with the stainless steel tube (long 177.8mm, internal diameter 9.525mm, external diameter 12.7mm) that is included in the catalyzer (2.49g) of preparation among the embodiment 6, and catalyzer is filled between the glass wool plug of two passivation.Last pipe (reactor) is tied with independent cable well heater.The thermopair that is in preheater and reactor tube junction is used to control this preheater and keeps the catalyst bed upstream temperature constant, and is in the thermopair umbilical cable well heater that just is higher than catalyst bed (downstream of catalyst bed) and catalyst bed downstream (outlet) temperature is remained on 280 ℃.These two temperature were stablized in two hours and are kept constant, and fluctuation is within 1 ℃.The all heat insulation processing of all components, and the down-stream system that is used for gas chromatographic analysis is with identical described in the embodiment 2.

Table 10 shows is realizing high conversion and stability near operation under the isothermal condition.The preheater upstream pressure keeps below 15psi in the whole experiment.Notice that under isothermal condition, too much methane forms and fails to about 2% steady state value after 8 hours.Find the ethanol of trace, but be lower than quantitative restriction.Acetaldehyde has only reached gageable level when end of run.In the whole experiment, the both is lower than 1%.

Table 10

The product yield that the embodiment 11 that carries out under 280 ℃ of isothermal conditions reforms

Time (hour)	H 2	CO	CH 4	CO 2	Acetaldehyde
						0.6	149.6％	10.3％	111.7％	78.0％	0.0％
1.2	103.9％	81.6％	103.7％	14.7％	0.0％
						2.0	97.2％	90.2％	102.4％	7.4％	0.0％
4.0	94.9％	90.1％	103.0％	6.9％	0.0％
						5.9	96.8％	90.3％	102.8％	6.9％	0.0％
8.2	96.3％	91.4％	102.0％	6.6％	0.0％
						10.3	95.2％	92.9％	101.9％	5.2％	0.0％
15.3	97.3％	91.3％	102.0％	6.7％	0.0％
						19.8	98.7％	90.7％	101.8％	7.5％	0.0％
25.8	99.6％	91.6％	101.5％	6.8％	0.0％
						30.3	96.9％	92.5％	101.7％	5.8％	0.0％
40.8	98.9％	91.3％	101.5％	7.2％	0.0％
						60.3	99.0％	92.2％	101.5％	6.3％	0.0％
79.5	101.5％	86.4％	101.9％	11.6％	0.0％
						100.5	99.5％	90.6％	101.4％	8.0％	0.0％
120.1	104.6％	88.9％	101.0％	10.0％	0.0％
						141.1	97.7％	94.1％	101.3％	4.5％	0.0％
149.1	97.5％	95.4％	100.5％	2.9％	0.6％

Embodiment 12 ethanol of on nickel plated copper sponge fixed bed catalyst, reforming

This embodiment illustrates the performance of nickel plated copper sponge fixed bed catalyst in reformation ethanol.

This experiment comprise catalyzer (1.46g, 10 balls) that use prepares in embodiment 10 under 300 ℃ of isothermal conditions with embodiment 11 described identical facilities in the ethanol of reforming.The material gas mixture that comprises 70 weight % ethanol and 30 weight % water is introduced with the flow velocity of 0.06ml/min, so that flow velocity suitable with the embodiment of aforementioned use 2.50g catalyzer and 0.10ml/min material gas mixture and the ratio between the catalyzer to be provided.

Shown in the data in the following table 12, described fixed bed material has reached high conversion (＞85%) at 300 ℃.This fixed bed catalyst is also different with fine catalyst, and wherein the decline of methanation occurs more slowly and continuous, needs about 20 hours under 300 ℃.

Table 12

The result of embodiment 12

Time (hour)	H 2	CO	CH 4	CO 2	Acetaldehyde	Ethanol
							0.9	27.0％	0.7％	147.3％	52.0％	0.0％	0.0％
1.8	43.6％	1.1％	140.4％	58.5％	0.0％	0.0％
							3.8	53.0％	7.5％	134.6％	58.0％	0.0％	0.0％
6.1	66.9％	27.0％	124.5％	48.5％	0.0％	0.0％
							8.1	78.2％	49.6％	116.4％	34.0％	0.0％	0.0％
10.1	85.4％	61.3％	111.9％	26.6％	0.1％	0.0％
							14.8	92.6％	74.6％	105.8％	17.7％	1.0％	0.0％
20.2	96.4％	79.2％	98.4％	12.6％	2.4％	2.5％
							30.2	98.6％	78.0％	89.3％	10.0％	4.7％	6.6％
40.3	98.4％	78.5％	85.1％	7.8％	5.1％	9.2％
							60.7	107.0％	86.0％	92.7％	9.4％	2.6％	3.3％
80.2	102.4％	76.3％	76.9％	6.3％	6.5％	13.8％
							99.8	99.9％	70.6％	70.5％	5.8％	7.9％	18.7％
120.0	95.5％	67.0％	67.4％	5.9％	8.1％	21.7％

Embodiment 13 ethanol of under differing temps, on fixed bed catalyst, reforming

This embodiment describes fixed bed catalyst reformation alcoholic acid purposes under differing temps.

This experiment is the continuation of the foregoing description 12 described experiments, changes flow velocity and temperature simultaneously.Keep isothermal condition.Table 13 has been summed up this catalyzer performance under 300 ℃ and 320 ℃ under different in flow rate.

Table 13

Reform as the ethanol that has temperature and change in flow as described in the embodiment 12

Temperature (℃)	Flow velocity (ml/min)	H 2	CO	CH 4	CO 2	CH 3C(O)H	CH 3CH 2OH
								300	0.01	100.5％	64.1％	106.1％	29.5％	0.2％	0.0％
300	0.02	118.9％	83.4％	90.9％	16.9％	1.7％	2.7％
								300	0.03	111.3％	82.1％	86.0％	11.5％	3.3％	6.9％
320	0.02	104.0％	64.8％	105.5％	29.7％	0.0％	0.0％
								320	0.03	109.3％	78.2％	100.3％	20.7％	0.2％	0.2％
320	0.045	118.2％	87.9％	93.5％	15.3％	0.7％	1.0％
								320	0.06	126.1％	92.2％	89.1％	13.3％	1.4％	1.3％

Experiment finishes the back and finds that many catalyzer all are reduced to powder.This loss of structural integrity is to form aluminum oxide with steam reaction because be in the not activation aluminium at matrix center under reaction conditions.

The present invention is not limited to above-mentioned embodiment and multiple variation can be arranged.The description of above-mentioned preferred embodiment only is intended to make those skilled in the art to understand the present invention, its principle and its practical application, so that those skilled in the art can revise and use the present invention in many ways, to adapt to requirement of actual application better.

About of the application of words (" comprise ", " comprises ", " comprising " in the English) such as " comprising ", " comprising ", " containing " at this specification (claims below comprising), should be noted that, unless otherwise indicated herein, these words all are based on following basis and clearly understand and used: they should be interpreted as " comprising " listed content, rather than " eliminating " row content not, and wish that each speech all should explain like this analyzing on the basis in full.

Claims (37)

1. One kind reform alcohol method, this method comprises: the material gas mixture that comprises alcohol is contacted with reforming catalyst to make the hydrogenous reformate mixture of bag, described reforming catalyst comprises the copper-containing active phase on the surface of metal sponge support structures, and wherein said metal sponge support structures is by comprising that the method that leaches aluminium from the alloy that contains aluminium and base metal obtains.
2. 2. the method for claim 1, the copper content of wherein said reforming catalyst is higher than the copper content in the described metal sponge support structures.
3. 3. the method for claim 1, wherein said Preparation of catalysts comprise copper are deposited on the metal sponge support structures.
4. 4. the method for claim 1, wherein material gas mixture comprises the primary alconol that is selected from methyl alcohol, ethanol and their mixture.
5. 5. method as claimed in claim 4, this method also comprise introduces fuel cell to produce electric energy with hydrogen and oxygen from the reformation product mixtures.
6. 6. the method for claim 1, wherein said reforming catalyst has 10m according to the measurement of Brunauer-Emmett-Teller method ²/ g to 100m ²The surface-area of/g.
7. 7. method as claimed in claim 6, wherein said reforming catalyst has 25m according to the measurement of Brunauer-Emmett-Teller method ²/ g to 100m ²The surface-area of/g.
8. 8. method as claimed in claim 7, wherein said reforming catalyst has 30m according to the measurement of Brunauer-Emmett-Teller method ²/ g to 80m ²The surface-area of/g.
9. 9. the method for claim 1, wherein said reforming catalyst comprises the copper of at least 10 weight %.
10. 10. the method for claim 1, wherein said reforming catalyst comprises the copper of 10 weight % to 90 weight %.
11. 11. the method for claim 1, the metal sponge support structures of wherein said reforming catalyst has 10m at least according to the measurement of Brunauer-Emmett-Teller method ²The surface-area of/g.
12. 12. method as claimed in claim 11, the metal sponge support structures of wherein said reforming catalyst has 50m at least according to the measurement of Brunauer-Emmett-Teller method ²The surface-area of/g.
13. 13. method as claimed in claim 12, the metal sponge support structures of wherein said reforming catalyst has 70m at least according to the measurement of Brunauer-Emmett-Teller method ²The surface-area of/g.
14. 14. method as claimed in claim 11, wherein said metal sponge support structures comprises nickel.
15. 15. method as claimed in claim 14, wherein said metal sponge support structures comprises the nickel of at least 50 weight %.
16. 16. method as claimed in claim 15, wherein said metal sponge support structures comprises the nickel of at least 85 weight %.
17. 17. method as claimed in claim 14, wherein said reforming catalyst comprise the copper of 10 weight % to 80 weight %.
18. 18. method as claimed in claim 17, wherein said reforming catalyst comprise the copper of 20 weight % to 45 weight %.
19. 19. method as claimed in claim 14, wherein reforming catalyst comprises the nickel of 5 to 100 μ mol/g on the surface of described catalyzer.
20. 20. method as claimed in claim 19, wherein reforming catalyst comprises the nickel of 10 to 80 μ mol/g on the surface of described catalyzer.
21. 21. method as claimed in claim 20, wherein reforming catalyst comprises the nickel of 15 to 75 μ mol/g on the surface of described catalyzer.
22. 22. method as claimed in claim 14, wherein material gas mixture comprises the primary alconol that is selected from methyl alcohol, ethanol and their mixture.
23. 23. method as claimed in claim 14, this method further comprise hydrogen and oxygen from the reformation product mixtures are introduced fuel cell to produce electric energy.
24. 24. the method for claim 1, wherein said copper-containing active comprise the copper applicator that covers described metal sponge support structures to small part mutually.
25. 25. method as claimed in claim 22, wherein said material gas mixture comprises ethanol.
26. 26. method as claimed in claim 25, wherein said material gas mixture contact with described reforming catalyst being lower than under 400 ℃ the temperature.
27. 27. method as claimed in claim 25, wherein said material gas mixture contact with described reforming catalyst under 200 ℃ to 375 ℃ temperature.
28. 28. method as claimed in claim 27, wherein said material gas mixture contact with described reforming catalyst under 250 ℃ to 325 ℃ temperature.
29. 29. the method for claim 1, wherein reforming catalyst is sneaked into the surface of ball shape or only stone substrate.
30. 30. method as claimed in claim 28, wherein reforming catalyst comprises the nickel sponge support structures.
31. 31. the method for claim 1, wherein said base metal comprise copper and/or are selected from the non-copper metal of nickel, cobalt, zinc, silver, palladium, gold, tin, iron and composition thereof.
32. 32. method as claimed in claim 31, wherein said base metal comprises nickel, cobalt or copper.
33. 33. method as claimed in claim 32, wherein said base metal comprises nickel.
34. 34. the method for claim 1, it comprises makes described material gas mixture by comprising the catalyst bed of described reforming catalyst, and described reforming catalyst is powder or ball shape.
35. 35. as method as described in the claim 26, wherein the reformate mixture also contains methane.
36. 36. method as claimed in claim 35, it further comprises sends into the methane that obtains in the oil engine in the reformate mixture.
37. 37. method as claimed in claim 35, it further comprises sends into the hydrogen that obtains in the oil engine in the reformate mixture.

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