Use of copper catalysts on metal carriers for reforming of alcohols

FIELD: chemistry.

SUBSTANCE: invention relates to dehydrogenation or reforming of alcohols, in particular to a method of dehydrogenation of the primary alcohol, such as methanol or ethanol, for obtaining hydrogen, in particular for use in a fuel element with the purpose of obtaining electrical energy. In the method of dehydrogenation a catalyst containing copper is used, which includes a metallic carrier. To solve the given challenge the method includes bringing to contact of the initial raw mixture of the gases containing alcohol, with the catalyst of reforming in order to obtain a mixture of products of reforming, containing hydrogen, and the catalyst for reforming the contains a metallic spongy carrier and a coating on copper, at least, partially covering surface of the given metal spongy carrier where the given metal spongy carrier is obtained by means of the method including the leaching of aluminium from an alloy, containing aluminium and the main metal.

EFFECT: increased activity in the gas-phase reforming of primary spirits and increased stability.

129 cl, 13 tbl, 13 ex

 

The technical field to which the invention relates

This invention generally relates to the dehydrogenation or reforming of alcohols. More precisely, the invention relates to a method for dehydrogenation of a primary alcohol, such as methanol or ethanol, to produce hydrogen, in particular for use in a fuel cell with the purpose of generating electrical energy. The way dehydrogenation uses a copper-containing catalyst comprising a metal carrier.

The level of technology

It is well known that contacting a primary alcohol with a suitable catalyst at elevated temperatures (for example, more than 200about(C) causes the alcohol to decompose into hydrogen gas and carbon-containing substances. This process is usually known as "alcohol reforming". For example, the reforming of methanol leads to the formation of hydrogen and carbon monoxide, as illustrated by the following equation 1:

CH3HE is> CO + 2H2(1)

The hydrogen produced in the reforming process may then be fed into a fuel cell to produce electrical energy. The reforming process is indeterminism and requires effective heat transfer to the catalyst, especially in application to vehicles (e.g. electric cars), where high peak is power, especially at startup.

Reforming of methanol is described, for example, Gunther(ω) (Gunter) with co-authors, J. Catal. 203, 133-49 (2001); Breen(Breen) with co-authors, J. Chem. Soc. Chem. Comm. 2247-48 (1999); European Chemical News, page 22, (May 11, 1998); and Zhang(ω)(Jiang) with co-workers, Appl., Cat., 97A, 145-58 (1993). Reforming of methanol and specific application reforming of methanol as a hydrogen source for fuel cells described Agrell(ω) with co-authors, Catalysis-Specialist Periodical Reports, vol 16, SS. 67-132 (J.J. Spivey, ed., Royal Society of Chemistry,Cambridge, UK, 2002).

It is important to note that carbon monoxide is usually toxic to the electrodes of the fuel cell. For example, the performance of the fuel cell and the energy savings are typically reduced when the content of carbon monoxide exceeds about 20 parts per million (by weight) in the original hydrogen. See, Peterson (Pettersson) with co-authors in the Int'1 J. Hydrogen Energy, volume 26, page 246 (2001). It is therefore desirable to convert the carbon monoxide into carbon dioxide through reaction with water vapor, as shown by the following equation 2:

CO + H2O -> CO2+ H2(2)

This transformation is known as a reaction of conversion of water vapor and is widely used in practice on an industrial scale. Description of catalysts, processes and applications of reaction conversion of water vapor, can be found, for example, in Catalyst Handbook, SS. 283-339 (2nded., M.V. Twigg ed., Manson Publishing, London, 1996.

In conditions similar to those described above relative to methanol, while reforming of ethanol first get the acetaldehyde, which then can be decomposed (i.e. decarbonylation) to carbon monoxide and methane, as shown by the following equation (3):

CH3CH2OH - CH3C(O)H + H2->CO + CH4+ H2(3)

As is the case for methanol reforming, the reforming of ethanol is preferably combined with the reaction of conversion of water vapor to convert carbon monoxide to carbon dioxide and additional hydrogen. Thus, the reaction of the conversion of water vapor in combination with the reforming of ethanol gives carbon dioxide, methane and hydrogen, as shown by the following equation 4:

CO + CH4+ H2+ H2O ->2+ CH4+ 2H2(4)

The most common catalysts for dehydrogenation of alcohol and low-temperature reactions of conversion of water vapor contain copper with zinc oxide and sometimes other promoters (accelerators catalysis) on heat-resistant structure carrier, usually aluminum oxide or silicon oxide. Catalysts (type) copper-zinc oxide, although showing excellent durability for methanol synthesis, have inadequate strength for the reforming of methanol, which was reported and described by Cheng (Cheng), Appl. Cat. A, 130, S. 13-30 (1995) and Amplicom (Amphlett) with co-authors, Sud. Surf. Sci. Catal., 139, C. 205-12 (2001).

Most of the other catalysts, which, as reported, are active for reforming alcohol, consisted of a metal oxide, usually containing catalytic metals. Yee with co-workers, J. Catal., 186, 279-95 (1999) and Sheng(Sheng) with co-authors, J. Catal., 208, 393-403 (2002) describe the reforming of ethanol (directly) over SEO2by itself or added rhodium, platinum or palladium. However, these articles have reported that ethanol can decompose to a number of undesirable side products, such as acetone, ketene and butene.

It is known that copper-Nickel catalysts have high activity for dehydrogenation of ethanol. For example, copper-Nickel catalysts deposited on aluminum, are active for reforming of ethanol. Reforming of ethanol over copper-Nickel catalysts described mariño (Marino) with co-authors in the Stud. Surf. Sci. Catal. 130c., 2147-52 (2000) and Freni Freni with co to React. Kinet. Catal. Lett. 71, 143-52 (2000). Although the references describe catalysts as providing good selectivity when carbonyliron acetaldehyde, each link suffers from disadvantages in the form of incomplete conversion and minimal activity conversion of water vapor at temperatures of about 300°C. in Addition, conventional catalysts for reforming of ethanol tend to quickly fail due to the deposition of carbon on the poverhnosti, process known as coking. Temperatures exceeding 400°coking is accelerated due to the presence of acid sites on the catalyst surface, which contribute to the dehydration of ethanol to ethylene, which is then polymerized. The problem of coking related catalysts for reforming of ethanol, as described, for example, Haga (Haga) with co-authors in Nippon Called Kaishi, 33-6 (1997) and Freni (Freni) with co to React. Kinet. Catal. Lett., 71, S. 143-52 (2000).

Therefore, continues to exist a need for improved catalysts for the dehydrogenation of the alcohol and the processes of reforming of alcohols, it is possible at moderate reaction temperatures and with sufficient conversion.

Disclosure of invention

Among the undoubted purposes of the present invention thus include: development of a new and improved method for the dehydrogenation of alcohols with hydrogen production, particularly with a method that uses a catalyst having a higher density than the catalysts for reforming of alcohol in the prior art; an improved method of using the catalyst for reforming alcohol to provide the best conductivity to maintain indeterminacy reaction; an improved method of using a catalyst without acid sites; improved the method used is the overall catalyst, having a high activity and increased strength at the conversion of acetaldehyde to methane and carbon monoxide at moderate temperatures; the improved method, which gives a mixture of products containing hydrogen suitable for use in a fuel cell to produce electrical energy; and a new and practical method of generating energy from ethanol at temperatures below about reforming 400°S, which provides a simplified energy system, requiring less expensive parts of the hydrogen fuel cell, and provides improved energy efficiency.

Briefly, therefore, the present invention relates to a method of reforming alcohol. The method comprises bringing into contact of the alcohol with a catalyst for reforming comprising copper on the surface of the metal structure of the carrier. In a preferred embodiment, the catalyst for reforming includes copper on the surface of the metal sponge carrier, preferably a metal sponge containing Nickel or iron sponge, containing Nickel and copper.

In addition, the present invention relates to a method of reforming of ethanol. The method comprises contacting at a temperature below approximately 400°With raw gas mixture containing ethane is l, with the catalyst for reforming a mixture of the products of the reforming containing hydrogen. The catalyst for reforming includes copper on the surface of the metal carrier. In a preferred embodiment, the method includes contacting at a temperature less than about 350°With raw gas mixture containing ethanol with a catalyst containing copper on the surface of the Nickel media.

In addition, the present invention relates to a method for generating electrical energy from a fuel cell. The method includes contacting the raw gas mixture containing ethanol with a catalyst for the dehydrogenation reaction zone dehydrogenation to obtain a mixture of products containing hydrogen. The dehydrogenation catalyst contains copper on the surface of the metal carrier. Hydrogen from a mixture of products and oxygen is introduced into the fuel cell to produce electrical energy and exhaust of the fuel cell stream of gases containing methane. Flowing from the fuel cell, the flow of gases injected into the combustion chamber and is burnt in the presence of oxygen. In an additional embodiment, the present invention relates to an improved method of applying a copper coating for the purpose of preparation of dehydrogenation catalyst.

Friend the e objectives and features of the present invention will be in part obvious, and partly below.

Brief description of drawings

Figure 1 is a schematic illustration of the energy system in accordance with the embodiment of the present invention, in which a mixture of hydrogen-containing product obtained by reforming alcohol, is introduced as a fuel source in a hydrogen fuel cell for generating electrical energy.

Figure 2 is a schematic illustration of the energy system in accordance with another embodiment of the present invention, in which the mixture of products containing hydrogen obtained by reforming alcohol, is introduced as a fuel source in a hydrogen fuel cell for generating electric energy, and in which the exhaust from a fuel cell, the gas stream passes to the internal combustion engine, which is also equipped with a separate raw source of alcohol.

Description of the preferred embodiments

In accordance with the present invention a mixture of copper with other metals, especially mixtures of copper and Nickel, are used as catalysts for the dehydrogenation of alcohols (for example, reforming). It was found that copper-containing catalysts containing a metal carrier, for example the catalyst was prepared by deposition of copper on the Nike is in the song data spongy media show high activity as catalysts in gas-phase reforming of primary alcohols, such as methanol and ethanol. The catalysts used in the implementation of the present invention are more stable and are particularly active for thermal decomposition of ethanol to hydrogen, methane, carbon monoxide and carbon dioxide at moderate temperatures. The resulting hydrogen can be used, for example, to generate energy by converting hydrogen into water in a fuel cell and combustion of methane together with any residual hydrogen in the gas stream exiting the fuel cell. The combustion process can result in the movement of the generator to produce additional electricity or be used in an internal combustion engine for generating mechanical energy. This power system provides a convenient way of obtaining energy from ethanol with the additional advantage that the combustion is used in order to minimize undesirable emissions, at the same time providing a warm layer of catalyst. More broadly, the mixture of products obtained by reforming primary alcohols in accordance with the present invention, can be used as a source of hydrogen and/or carbon monoxide in the applications to chemical process (for example, ka is Beylerbeyi, hydrogenation and hydroformylation) and applications to material processing.

In addition, described herein is a catalyst for reforming alcohol may be used to obtain a mixture of products containing hydrogen and carbon monoxide known as synthesis gas, from an alcohol starting material.

A. Catalyst

In one embodiment of the invention the catalyst for the dehydrogenation or reforming alcohol includes a copper-containing active phase at the surface of a metal carrier, which includes copper and/or one or more non-copper metals. The catalyst typically comprises at least about 10 wt.% copper, preferably from about 10 wt.% to about 90 wt.% copper and more preferably from about 20 wt.% to about 45 wt.% copper. The catalyst may contain essentially homogeneous structure, such as spongy copper, single-phase copper-containing alloy, or a heterogeneous structure having more than one discrete phase. Thus, the copper-containing active phase may be present on the carrier surface in the form of a discrete phase, such as a copper coating or outer layer; a surface layer or as part of a homogeneous structure of the catalyst. If mesotelioma active phase comprising discrete phase on the surface of the carrier metal is ski carrier may be fully or partially covered mesotelioma active phase. For example, in a particularly preferred embodiment, which is described below, the catalyst contains copper-containing active phase at the surface of the metal sponge media, including Nickel. Such catalysts include from about 10 wt.% to about 80 wt.% copper and more preferably from about 20 wt.% to about 45 wt.% copper. The rest of the catalyst preferably consists of Nickel and less than 10 wt.% aluminum or other metals. Additionally, in preferred embodiments, the implementation, in which the metal carrier contains Nickel, it is important to note that copper and Nickel are mixed in all proportions. Thus, the catalysts comprising copper-containing active phase at the surface of the Nickel carrier may not necessarily have a phase boundary between mesotelioma active phase and a carrier.

As usual in catalysis, the catalyst dehydrogenation increases with increasing surface area. Thus, it is generally preferable to a freshly prepared catalyst had a surface area of at least about 10 m2/g, as measured by the method of brunauer-Emmett-teller (BET). More preferably, the catalyst had a surface area according to BET of from about 10 m2/g to about 100 m2/g, even more predpochtite is) that the catalyst had a surface area according to BET of from about 25 m2/g to about 100 m2/g and even more preferably, the catalyst had a surface area according to BET of from about 30 m2/g to about 80 m2/, In a preferred embodiment, the reforming of ethanol, the surface of the catalyst preferably contains so many atoms of Nickel which promotes carbonyliron aldehydes, such as acetaldehyde. Preferably, the surface contains from about 5 to about 100 μmol/g of Nickel, which is measured by the method described in "Surfaces of Raney® Catalysts" Schmidt in "Catalysis of organic reactions" (Catalysis of Organic Reactions), SS. 45-60 (M.G. Scaros and M.L. Prunier, eds., Dekker, New York, 1995). More preferably, the surface concentration of Nickel is between about 10 mmol/g to about 80 µmol/g, most preferably from about 15 µmol/g to about 75 µmol/g

1. Structure-media

The carrier of the catalyst for the dehydrogenation of alcohol contains metal. Suitable carrier materials can include a wide range of structures and layouts. Preferably the metal carriers contain a metal having a greater tensile strength and/or yield strength than copper. Thus, in accordance with the preferred embodiment, the carrier includes different than the go metal. Other than the copper metal may contain a single metal or dissimilar metals. In this preferred embodiment, at least about 10 wt.% the metal carrier is different than the copper metal. In one particularly preferred embodiment, at least about 50 wt.% (more preferably, at least about 65 wt.%, at least about 80 wt.%, at least about 85 wt.% or even at least about 90 wt.%) metal carrier is different than the copper metal. In another particularly preferred embodiment, the medium contains at least about 10 wt.% other than the copper metal and at least about 50 wt.% (more preferably from about 60% to about 80%) of copper.

The metal or alloy from which the metal carrier preferably has a greater tensile strength and/or yield strength than the copper itself. Particularly preferred for the composition to have a yield strength of at least about 70 MPa, more preferably at least about 100 MPa, even more preferably at least about 110 MPa.

Also particularly preferred for the composition to have a tensile strength of at least about 221 MPa, more preferably about 275 MPa, and even more is preferable, at least about 300 MPa. For example, a composition comprising 90 wt.% copper and 10 wt.% Nickel reportedly has a yield strength of 110 MPa and the tensile strength of 303 MPa; composition containing 70 wt.% copper by weight and 30% by weight Nickel reportedly has a yield strength of 138 MPa and the tensile strength of 372 MPa; and a composition comprising 70 wt.% copper and 30 wt.% zinc reportedly has a yield strength of 124 MPa and the tensile strength of 331 MPa. Cm. Krisher and Siebert, Perry's Chemical Engineers' Handbook, pages 23-42 in 23-49 (6th ed., McGraw Hill, New York, NY 1934).

Preferably other than copper metal metal carrier selected from the group consisting of Nickel, cobalt, zinc, silver, palladium, gold, tin, iron, and mixtures thereof. More preferably the metal carrier comprises Nickel. Nickel is usually preferred because, for example: (1) Nickel, relatively inexpensive in comparison with other suitable metals, such as palladium, silver and cobalt; (2) as shown, a combination of Nickel and copper contribute to decarbonising acetaldehyde to methane and carbon monoxide, and (3) deposition of copper on the Nickel-containing media is usually less complicated in comparison with the deposition of copper on a carrier containing a sufficient number of other suitable metals. For example, copper can is be deposited on Nickel-containing medium using a simple substitution process of electrochemical deposition. However, there are other technologies (for example, coating by the method of chemical recovery and ORGANOMETALLIC chemical vapor deposition), which can be used for the deposition of copper on the media, which includes other suitable metals, other than copper.

It is often desirable precipitate the copper on the surface of the metal carrier, using electrochemical substitution deposition (also described in the art as a metal coating by immersion, as described in more detail below. In this case, when the metal carrier preferably contains a metal, the potential recovery to the free metal is less than the reduction potential of the metal copper, i.e. the reduction potential of the metal is less than about +343 mV relative to the NHE (normal hydrogen electrode). Other than copper metals with such potential (are), for example, Nickel, zinc, tin, iron and cobalt. The presence of such metals near the surface of the carrier allows easy deposition of metallic copper on the surface of the carrier contacting the surface with a solution of salt of copper (usually salts of Cu(II)). More precisely, in the course substitution electrochemical deposition of such metal near the surface of the carrier tends to oxidation (and is arejob in solution as an ion) in contact with the solution, containing copper ion. If this happens, then the copper ions in solution near the surface of the carrier is recovered to metallic copper, which, in turn, deposited on the carrier surface. Occurring reaction, for example, when contacting the media, including Nickel, copper salt solution is illustrated in the following equation 5:

Cu2++ Ni° -> Cu° + Ni2+(5)

As suggested above, if the catalyst is prepared by deposition of copper on the surface of the carrier using substitution electrochemical deposition, it is particularly preferable to use Nickel-containing media, because Nickel has at least four desirable features: (1) reduction potential to the metal is less than the potential recovery of metallic copper, (2) the relative stability of the reaction conditions of the dehydrogenation of the alcohol according to this invention, (3) high mechanical strength and abrasion resistance than copper, and (4) catalysts Nickel/copper accelerate decarbonisation acetaldehyde to carbon monoxide and methane.

When the metal carrier comprises more than one metal, preferably at least about 80 wt.% (more preferably, at least about 85 wt.% even more preferably, IU the greater extent, about 90 wt.% and still even more preferably, essentially all of the quantity of metals in the media was in the form of alloy. In a particularly preferred embodiment, the metals forming the alloy of substitution (also known as "monophasic alloy, which alloy has a single homogeneous phase. Multiphase alloys (i.e. alloys containing at least 2 discrete phase) can also be used as carriers. In the variants of implementation, in which the copper-containing active phase precipitated on a carrier containing a multiphase alloy, copper has a tendency, it is preferable to cover the enriched copper surface multiphase media than the relatively depleted in copper surface. Whether the alloy phase or multiphase will depend on the alloy components and their concentrations. Typically, for example, metal carriers, consisting essentially of Nickel and copper, are single phase at any concentration of Nickel. But, for example, when the carrier consists essentially of copper and zinc, there are many (values) concentrations of zinc (typically, the concentration of more than about 35 wt.%), which lead to the fact that the alloy becomes mushy.

It should be understood that the carrier may also contain atoms of non-metals (i.e. boron, carbon, silicon, nitrogen, phosphorus and so on) in addition to metal atoms is A. The alloy containing such a non-metal, is generally described in the art as "an alloy of implementation". The media containing this alloy can have various advantages, such as increased mechanical strength. However, in the typical case, the catalyst comprising an alloy of implementation, contain at least about 70 wt.% metal.

In a particularly preferred embodiment, the carrier is a metal sponge containing copper and/or one or more of the above suitable metals other than copper. Used herein, the term "metal sponge" refers to porous metal or metal alloy with surface area by BET of at least about 10 m2/, Preferred metal sponge media have a surface area according to BET of at least about 20 m2/g, more preferably at least about 35 m2/g, even more preferably at least about 50 m2/g and even more preferably at least about 70 m2/Was found in accordance with the present invention, copper-containing active phase at the surface of the metal sponge media leads to a material having a mechanical strength greater surface area, high conductivity and density of si is striated media in combination with desirable catalytic activity of copper.

Metal sponge carrier and the resulting catalyst can be in the form of powder or granules. In addition, the catalyst for the dehydrogenation of the alcohol can be used in the form of a monolith obtained by the introduction of the catalyst of the invention on the surface of a suitable perforated substrate (e.g., cell structure). Typically, the catalyst in the form of pellets or monoliths is preferred to minimize back pressure in the reforming installation, as described below. In addition, the monolithic catalysts may be more resistant to mechanical damage caused by vibration (for example, when applied to a motor vehicle) and/or chemical corrosion in the reaction medium.

It is important to note that when the catalyst of the invention is used in the form of a pellet or monolith, it is assumed that only part of the pellet or monolith may include a metal sponge as a carrier mesotelioma active phase. That is, the reforming catalyst of the alcohol may include non-porous substrate to provide strength and shape of the fixed layer or monolithic catalyst, along with the presence of one or more porous areas (i.e. metal sponge) with a surface area according to BET of at least about 10 m2/g as a carrier mesotelioma active phase. On the walking non-porous materials for use as a stationary layer or monolithic substrate typically may include any material which is thermally and chemically stable under the conditions of coating and reforming. Although you can use a non-metallic substrates, usually more preferred metal substrates such as stainless steel, copper, Nickel, cobalt, zinc, silver, palladium, gold, tin, iron, and mixtures thereof.

When the metal sponge media is in the form of a powder, the preferred average particle size of the metal sponge is at least about 0.1 microns, preferably from about 0.5 to about 100 microns, more preferably from about 15 to about 100 microns, even more preferably from about 15 to about 75 μm and even more preferably from about 20 to about 65 microns. When the catalyst is in the form of granules or monolith, the size of the granules or solid substrate on which to embed the catalyst of the present invention, as well as the size of the mesh holes in any such monolithic carrier may be changed as necessary in accordance with the installation design for reforming, it is clear that the experts in this field of technology.

Metal sponge media can be prepared by means technologies generally known to experts in this field of technology. See, basically Lieber(Lieber) and Moritz(Morritz), Adv. Catal., 5, 417(1953) (basic survey on g is batim metals). Cm. also Hawley's Condensed Chemical Dictionary, 13th Ed., page 621 (Rev. by Richard J. Lewis, Sr., Van Nostrand Reinhold, New York, NY 1997) (description of the method of preparation of the iron sponge).

References describing the preparation of Nickel sponges, include, for example, Augustine, Robert L., " the Technique of catalytic dehydrogenation and application in organic synthesis" (Catalytic Hydrogenation Techniques and Applications in Organic Synthesis), pp. 147-49 (Marcel Dekker, Inc.,1965). See, also Hawley's Condensed Chemical Dictionary, 13th Ed., p. 955 (Rev, by Richard J Lewis, Sr., Van Nostrand Reinhold, New York, NY 1997) (describing generally recognized ways of making sponge Nickel by leaching aluminum from an alloy containing 50 wt.% Nickel and 50 wt.% aluminium using 25 wt.% solution of caustic soda). In the case of Nickel sponge metal carrier preferably essentially does not contain unactivated areas and washed out to the point where he essentially does not contain alumina. Unreacted aluminum will tend to react with steam in the reforming conditions with the formation of aluminum oxide, which can prevent diffusion and to provide the acid sites for ethanol dehydration.

References describing the preparation of copper-zinc sponges, include, for example, Bridgewater(a)(Bridgewater) with co-workers, Appl. Catal., 7, 369 (1983). Such references include, for example, Masonry(a)(M.S. Wainwright), "Copper Ren who I am and copper-zinc Raney" ("Raney Copper and Raney Copper-Zinc Catalysts", Chem. Ind. (Dekker), 68, 213-30 (1996).

References describing the preparation of Nickel-iron sponges, include, for example, Becker(a)(Becker) and Schmidt(a)(Schmidt), Nickel-iron catalyst Raney" ("Raney nickel-iron catalyst",Ger. Offen. DE 2713374 19780928 (1978).

References describing the preparation of Nickel-cobalt sponges, include, for example, orchard(a) with co-authors, "Preparation and properties of Nickel-cobalt catalysts of the Raney" ("Preparation and Properties of Raney Nickel-Cobalt Catalists") J. Catal., 84, 189-99 (1983).

In accordance with one preferred embodiment, the media contains Nickel-copper sponge (i.e. Nickel sponge mixed with copper or a copper sponge with a mixture of Nickel), as described in co-assigned co-assigned) U.S. patent No. 6376708.

References describing the preparation of Nickel-copper sponges, also include, for example, Jung(Young) with co-authors, J. Catal., 64, 116-23 (1980) and Wanita (Wainwright) and Anderson (Anderson), J. Catal., 64, 124-31 (1980).

Suitable metal sponges include material manufactured by W.R.Grace & Co., (Davison Division, Chattanooga, TN) under the trade mark Raney(RANEY), and also materials, usually described in this technical field as "Raney metals", regardless of the source. Raney metals can be obtained, for example, by leaching of aluminium from aluminium alloy and the base metal (for example, Nickel, cobalt, copper) with a solution of caustic soda. Various meta is symbolic sponges are also produced on an industrial scale, for example, firms Gorwara Chemical Industries (Udaipur, India); Activated Metals &Chemicals, Inc. (Sevierville, TN); Degussa-Huls Corp. (Ridgefield Park, NJ); Engelhard Corp. (Iselin, NJ) and Aldrich Chemical Co (Milwaukee, WI).

In accordance with other preferred variants of implementation, the carrier includes a Nickel sponge. Examples of suitable produced on an industrial scale Nickel sponges, for example, include RANEY 2800 (characterized by the manufacturer as having at least 89 wt.% Nickel; not more than 9.5 wt.% aluminum; not more than 0.8 wt.% iron; average particle size in the range of 20-60 μm; specific gravity is approximately 7 and a bulk density of 1.8-2.0 kg/l (15-17 lbs/Gal), based on the weight of the suspension of catalyst in water with 56 wt.% the dry residue), Raney(RANEY) 4200 (characterized by the manufacturer as having at least 93 wt.% Nickel; not more than 6.5 wt.% aluminum; not more than 0.8 wt.% iron; average particle size in the range of 20-50 μm; specific gravity is approximately 7 and a bulk density of 1.8-2.0 kg/l (15-17 lbs/Gal), based on the weight of the suspension of catalyst in water with 56 wt.% the dry residue), Raney 4310 (characterized by the manufacturer as having at least 90 wt.% Nickel; not more than 8 wt.% aluminum; 0.5 to 2.5 wt.% molybdenum; not more than 0.8 wt.% iron; average particle size in the range of 20-50 μm; specific gravity is approximately 7 and a bulk density of 1.8-2.0 kg/l (15-17 lbs/Gal), Frascati on the weight of the suspension of catalyst in water with 56 wt.% the dry residue), Renee 3110 (characterized by the manufacturer as having at least 90 wt.% Nickel; 0.5 to 1.5 wt.% molybdenum; not more than 8.0 wt.% aluminum; not more than 0.8 wt.% iron; average particle size in the range of 25-65 µm; specific gravity is approximately 7 and a bulk density of 1.8-2.0 kg/l (15-17 lbs/Gal), based on the weight of the suspension of catalyst in water with 56 wt.% the dry residue), Raney 3201 (characterized by the manufacturer as having at least 92 wt.% Nickel; not more than 6 wt.% aluminum; not more than 0.8 wt.% iron; 0.5 to 1.5 wt.% molybdenum; average particle size in the range of 25-65 µm; specific gravity is approximately 7 and a bulk density of 1.8-2.0 kg/l (15-17 lbs/Gal), based on the weight of the suspension of catalyst in water with 56 wt.% the dry residue), Raney 3300 (characterized by U.S. Patent No. 5922921 as having, 90-99,1 wt.% Nickel; not more than 8.0 wt.% aluminum; not more than 0.8 wt.% iron; 0.5 to 1.5 wt.% molybdenum; average particle size in the range of 25-65 µm; the specific gravity of approximately 7 and a bulk density of 1.8-2.0 kg/l (15-17 lbs/Gal), based on the weight of the suspension of catalyst in water with 56 wt.% the dry residue), Raney 2724 (Cr-activated), all sold by the company W R Grace & Co; the catalyst is described as "Raney Nickel", sold by the company Gorwara Chemical Industries; A-4000 and 5000 sold by Activated Metals &Chemicals Inc,; Nickel marks AVMS sold Degussa-Huls Corp, and "Raney Nickel", catalogue No. 22, 167-8, sold by Aldrich Chemical Co.

Examples of substrates in the form of a fixed layer comprising a metal carrier, include pellets of sponge Nickel, described in European patent number EP 0648534 Al and U.S. patent No. 6284703, the disclosure of which is incorporated in this description by this reference. Granules of Nickel sponge, especially for use as a stationary layer of catalysts are produced on an industrial scale, for example, a company W.R. Grace & Co., (Chattanooga, TN) and Degussa-Huls Corp. (Ridgefield Park, NJ),

2. The deposition of the active phase containing copper

Copper-containing active phase can be precipitated on the surface of a metal carrier using a variety of methods well known in the technical field of metal plating on a metal surface. These methods include, for example, liquid-phase methods, such as electrochemical substitution deposition, coating by the method of chemical recovery; methods of vapor deposition, such as physical deposition and chemical deposition. Suitable methods of deposition of copper on the surface of the metal carrier described in co-assigned U.S. patent No. 6376708 and jointly assigned simultaneously pending patent application U.S. serial No. 09/832541 and published under the nom is rum US-2002-0019564-A1. The full texts included in this description by this reference.

It is important to note that copper is at least partially miscible with most metals of interest media and fully mixed with Nickel. Thus, it was found that the deposition process of copper results in a catalyst having copper or, more specifically copper-containing active phase at the surface of the substrate as part of a discrete phase, such as an outer layer or coating on the surface of the carrier as part of the surface layer, or copper may migrate from the surface of the medium in a volume of media. Without going into a detailed theory, suppose that the surface of the catalyst can be moved to specalise or otherwise modify the structure under the reaction conditions of deposition and processes of reforming of alcohol that leads to such changes mesotelioma active phase. However, it was found that the deposition process of copper leads to an overall increase in the copper content in the catalyst, and the precipitated copper is mainly present on or near the surface of the freshly prepared catalyst, which is richer in copper than before deposition.

A. Electrochemical substitution deposition of copper

The above-mentioned copper can be precipitated on the surface of a metal carrier by electrochemical C is mistitling deposition, in which copper ions in the copper salt solution in contact with the carrier is recovered to metallic copper, while other than copper metals near the surface of the substrate are oxidized. Copper metal (metal containing copper), in turn, forms a coating on the surface of the substrate, while BizMedia ions into solution. The main discussion related to electrochemical substitution deposition, can be found, for example, in the work of Crulic (Krulik) and Mandich "Metallic coating" ("Metallic Coatings (Survey)"), Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., volume 16, page 258-91 (J.I. Kroschwitz and M. Howe-Grant, eds., Wiley, New York, NY, 1995). For a more detailed discussion of electrochemical substitution deposition of copper on the metal porous media can be found in belonging to the same applicant's U.S. patent No. 6376708, which is incorporated into this description by this reference.

In a particularly preferred method of deposition of copper on the metal carrier electrochemical substitution deposition is carried out in basic conditions, with subsequent electrochemical substitution deposition in acidic conditions. In a similar, particularly preferred embodiment, copper is not added in the acid stage, but is pereosazhdeniya copper in the form of monovalent copper, already besieged by the media during the main stage of restorani and resultant deposition rates. This procedure is described in example 6 below. Preferably the metal carrier is essentially free from surface oxidation during the deposition of copper. In those cases, when the metal carrier is oxidized surface (i.e., when the medium is exposed to air (even in water) for 6 months or more), particularly preferably pre-treat the media with a reducing agent. For example, the medium may be stirred in a solution of sodium borohydride, which preferably contains at least about 1 gram of sodium borohydride in 25 grams of a metal carrier and has a pH of at least 10. Usually contacting the substrate with a reducing agent for from about 5 minutes to about 2 hours at room temperature is sufficient to remove the carrier surface oxidation. In order to start the two-stage main-acid electrochemical substitution deposition, the metal carrier is suspended in water or alcohol solution, preferably in water, and the pH is adjusted (set) 7. To a suspension of a metal carrier salt of copper, preferably in the form of a solution containing a salt of copper and helatoobrazovatel, especially helatoobrazovatel in the form of an amine, such as add (ethylenediaminetetraacetic acid). Preferably actor copper salt contains from about 10 wt.% to about 30 wt.% copper relative to the weight of the metal substrate. Taking into account the incompleteness of the list of suitable salts of copper substitution for deposition include, for example, nitrate, sulfate, chloride salts of copper and copper acetates. Salt containing copper in the divalent state (i.e., Cu(II), is usually preferred. Although there may be used salts containing monovalent and trivalent copper, but they are generally less preferred because they tend to be unstable, less manufactured on an industrial scale and/or insoluble in an alkaline mixture.

Then a solution of alkali metal hydroxide (such as NaOH or other suitable base is added slowly to the suspension, preferably with continuous stirring and bubbling nitrogen. A solution of the hydroxide of an alkali metal preferably contains at least one molar equivalent of alkali metal hydroxide relative to the salt of copper, and more preferably from about 1.1 to about 1.6 molar equivalents of alkali metal hydroxide relative to the salts of copper. Although this stage involves the substitution reaction of the deposition, part of the oxidized metal from the carrier remains closely associated with the carrier and acid is removed in a later stage. However, the main substitution reaction deposition leads to the deposition of copper oxide (Cu2O), and the metal is some of the copper on the surface of the carrier.

After the main substitution precipitation of the supernatant liquid removed by decantation or other means and advanced copper precipitated on the surface of the catalyst carrier in acidic conditions. After decanting, the metal carrier is again suspended in alcohol or aqueous solution. Acid buffer solution was added to a suspension of a metal carrier to reduce a pH of less than about 4. The temperature of the buffer is preferably from about 40°s and 90°C. Acid buffer may include any suitable helatoobrazovatel, subsequently allowing the control of residual metals in solution during the reduction of pH. More precisely, the acid buffer preferably have RK (a measure of acidity) from about 1 to about 4, in order to maintain the pH in the electrolytic bath from about 1 to about 4. Preferably the acidic buffer solution is a buffer gluconic acid/gluconate. Gluconic acid is preferred for the deposition of copper on the surface of the metal carriers, including Nickel, because gluconic acid is a good helatoobrazouatelem for residual aluminum ions present in the solution. In addition, it is important to note that the use of buffers, based on phosphoric acid, usually less preferred than the C of the risk of formation of insoluble deposits of phosphates. Salt of copper, described above, can then be added to the suspension of a metal carrier, preferably in the form of a copper salt solution, under continuous stirring and bubbling nitrogen for from about 5 to about 40 minutes.

Preferably, as described in example 6, add about 0.2 to about 0.4 molar equivalents of sulfuric acid instead of the solution of salt of copper. This operation leads to the improvement of the activity of the reaction of conversion of water vapor. Subsequently, the stirring may be suspended, in order that the catalyst could be deposited, allowing to remove the supernatant liquid by decantation or other means.

It is important to note that the deposition of copper coatings can different from those already described above, if the carrier of the catalyst is in the form of a pellet or monolith. For example, produced on an industrial scale metal sponge media in the form of granules often not fully activated. Typically, the activation produced in industrial scale granular media includes the removal of much of the aluminum is typically at a depth of about 200 μm to obtain a metal subcategorises patterns. However, the core of the granules will typically still contain significant concentrations of non-activated alloy enriched with aluminum zero valence. Thus, the Alu is ini in the core of the granules may react with steam and ethanol reforming conditions, which leads to the formation of cracks and leads to loss of mechanical integrity. Accordingly, the preferred metal sponge media, which are fully activated.

An example of a fully activated material are hollow balls of activated Nickel, described in U.S. patent No. 6284703.

In addition, diffusion may limit the coating inside the fixed layer media. Thus, it is preferable to carry out the coating on the stationary layer of the device at room temperature or below, because the ratio of the rate of diffusion to the speed of the coating is more favorable at lower temperatures. Preferably also, the use of higher concentrations of copper in the electrolytic bath in order to avoid excessive reduction of the concentration of copper within the media, which may occur if a large part of the copper used for the deposition on the outer sections of the media. An example of a preferred coating for the fixed layer of the media described in Example 10.

An alternative preferred embodiment of the preparation of catalysts having mechanical strength in terms of reforming is to first apply, usually by thermal spraying, a layer of Nickel-aluminum alloy on the substrate, which those who mikeski and mechanically stable in the coating and the conditions of the reformer. Suitable substrates may typically include steel or other metal, although it can be used and non-metallic substrates. Preferably the thickness of the layer is from 5 to 500 μm and more preferably from 10 to 150 μm. Preparation of spongy metal films media described in U.S. patent No. 4024044, and Sillito (Sillitto) with co-authors, Mat. Res. Soc. Sym. Proc., Tom. 549, pages 23-29 (1999). A layer of Nickel-aluminum alloy provides a metal carrier and is preferably activated before applying the copper coating.

B. The coating method of chemical recovery

The coating method of chemical recovery alternative can be used for deposition mesotelioma of the active phase on the surface of the metal carrier. Like electrochemical substitution deposition, coating by the method of chemical recovery includes recovery of copper ions to metallic copper in the solution in contact with the carrier. However, unlike electrochemical substitution deposition, essentially all of the copper ions are restored by an external reductant, and not by the media. Because copper ions are restored to metallic copper in the solution, the metallic copper forms a coating on the surface of the carrier. Using application pok is itia by the method of chemical recovery for the deposition of copper on the surface of the metal carrier is described in detail belonging to the same applicant's U.S. patent No. 6376708, which is incorporated into this description by this reference.

3. United copper-containing active phase

In another embodiment of the present invention the catalyst comprises copper, covering the metal substrate (i.e. there are no discrete mesotelioma active phase deposited on the surface or covering the surface of the catalyst). Instead, the copper is mixed with other metals, which provide desirable properties in the composition of the catalyst having a copper-containing active phase at the surface. The composition of the catalyst may be essentially homogeneous. Preferably, this catalyst is in the form mesotelioma metal sponge (i.e. Nickel-copper sponge).

4. Optional metal

The catalyst may optionally contain one or more additional metals in addition to copper and other than copper metals that make up the volume of the catalyst, as described above. Suitable additional metals selected from the group consisting of chromium, titanium, niobium, tantalum, zirconium, vanadium, molybdenum, manganese, tungsten, cobalt, Nickel, bismuth, antimony, lead, germanium and zinc. For example, the use of additional metals, especially zinc and chromium, to extend the service life of copper catalysts and save Il who increase their activity in the reaction of conversion of water vapor is well known in the technical field described by Lloyd (Lloyd) with co-authors, Catalyst Handbook, pages 309 to 312, (2nded., M.V. Twigg ed., Manson Publishing, London, 1996). The presence of one or more of these metals help extend the service life of the catalyst, thus increasing the period of time during which the catalyst may be used in the reforming of alcohol before his activity will decrease to an unacceptable level. Of the above elements vanadium, chromium, molybdenum, zinc and combinations thereof, are especially preferred and are preferably present on the catalyst surface in the form of oxides.

The number of additional metal may vary within wide limits. Preferably the total concentration of the additional metal is at least about 10 parts per million parts of copper in the catalyst inventory. More preferably the total concentration of additional metal in the catalyst is from about 0.002 wt.% to about 5 wt.%, more preferably from about 0.002 wt.% up to about 2.5 wt.%, even more preferably from about 0.005 wt.% to about 2 wt.% and even more preferably from about 0.5 wt.% up to about 1.5 wt.%. Typically, the total concentration of the additional metal does not exceed about 5 wt.%. Although it can be used by large concentrations of additional metals, but no additional benefits when exceeding this concentration is usual not get and the catalyst is usually reduced.

One or more additional metals may be contained in a metal carrier and/or mesotelioma active phase on the surface of the carrier. If it is desirable to include additional metal in the medium of the metal alloy, the additional metal is preferably introduced into the alloy during the formation of the alloy. If it is desirable to include additional metal in the copper-containing active phase at the surface of the carrier, in some cases, additional metal may be deposited simultaneously with the copper. However, where the copper is precipitated by substitution deposition or coating by the method of chemical recovery (discussed above), additional metal is added to the catalyst preferably after deposition of the copper, because of the additional metal can be dissolved in terms of substitution deposition and to prevent the coating by the method of chemical recovery. Additional metal can usually be added to the catalyst surface by simple contact of the catalyst with an aqueous solution containing a salt of the additional metal (e.g., sulfate, nitrate, chloride and so on). Methods of deposition of oxides of additional metals on copper sponge, which is also suitable for deposition on a surface is of a metal carrier of the present invention after completion of the coating by the method of chemical recovery can be found at Francica (Franczyk) with co, U.S. patent No. 5292936, a full description of which is incorporated into this description by this reference.

B. the Preferred reaction conditions of reforming of alcohol and energy systems

Method of reforming spirit of the present invention typically includes contacting the raw gas mixture containing an alcohol reagent, with a layer of a catalyst containing the copper containing catalyst described above, in the reaction zone dehydrogenation.

The reaction zone dehydrogenation preferably includes a continuous flow system, which combine to guarantee low backpressure and efficient transfer of heat to start and maintain indeterminacy reaction. The design of facilities for reforming, ensuring efficient heat transfer, are well known and described, for example, Boswella (Buswell) with co-authors in U.S. patent No. 3522019 and Autenrieth al. in U.S. patent No. 5935277 and No. 5928614. Each of these patents describes a reactor for catalytic reforming of alcohol, in which heat is supplied by heat exchange with a source of heat through a thermally conducting wall. Preferred heat sources for heating the reaction zone dehydrogenation most often include exhaust gases from the partial oxidation of a part of the JV the mouth, subjected to reforming, or from a separate combustion reaction using alcohol or other fuel source. As described below, a particularly preferred implementation of the present invention uses the exhaust gas from the combustion chamber, preferably downstream flows of the reaction zone dehydrogenation of the combustion chamber.

The reforming reaction of the alcohol is strongly indeterminacy, and efficient transfer of heat to the reaction zone of dehydrogenation required for good conversion. It is important that the copper-containing catalysts comprising a metal carrier, described in the present description, show better thermal conductivity compared to conventional catalysts for reforming, including ceramic substrates. For example, as described by Herstrom (Gersten) with co-authors in " Physics and chemistry of materials" ("The Physics and Chemistry of Materials), Wiley, New York, 2001, on page 144, thermal conductivity at 300K Nickel and copper is 401 W/m·and 91 W/m·respectively. In comparison, thermal conductivity at 300K conventional materials of catalysts for reforming, such as α-aluminum oxide, is 36 W/m·To, silicon dioxide 1.4 W/m·and magnesium oxide 36 W/m·K. Copper-containing catalysts comprising a metal carrier in accordance with the present invention preferably show teploprovodnosti 300K, at least about 50 W/m·K, more preferably at least about 70 W/m·and particularly preferably, at least about 90 W/m·K.

The reforming reaction of the alcohol is usually carried out in the gas phase at temperatures above about 100°C. However, in accordance with the present invention, it is preferable to reform the alcohol in the raw gas mixture at a temperature less than approximately 400°C. More preferably the reforming reaction carried out at a temperature of from about 150°With up to approximately 400°S, more preferably at a temperature of from about 200°C to about 375°and most preferably from about 250°up to about 325°C. for Example, it was found that when the method of the present invention use copper-plated metal sponge catalysts, particularly copper-plated metal sponge comprising or Nickel or Nickel alloyed with copper, the reforming of ethanol can be produced with high conversion at a temperature of from about 250°up to about 300°C.

While the reforming reaction is indeterminacy, then there must be additional heat to maintain the desired temperature in the reaction zone dehydrogenation. Usually the temperature of the reforming reaction in the catalyst bed during the reaction the AI reforming of alcohol can be controlled in any way, known in the art. Preferably the temperature of the catalyst layer is controlled, so that was izotonicnosti throughout its length or had a positive temperature gradient (i.e. increasing temperature between input and output layer). For example, the alcohol reactant in the form of a gas can be introduced into the catalyst bed at a temperature below the desired temperature at the outlet of the catalyst layer on the order of about 10°With up to about 50°With, while additional heat input to the reaction zone dehydrogenation is necessary to ensure the desired temperature profile in the catalyst bed.

It is important to note that when reforming of ethanol process within a narrow temperature interval and avoid extremes in temperature reduces the formation of methane by-products. The formation of methane (i.e. "mahanirvana") is undesirable because the reaction consumes useful hydrogen product at the rate of three moles of hydrogen per mole of methane produced. Excessive mahanirvana can also be avoided by working at low pressure. Accordingly, the pressure at the inlet to the catalyst bed is preferably less than about 30 lbs/inch2(206,8 kPa), more preferably less than about 10 pounds-force/inch2(for 68.9 kPa).

Rea is of dehydrogenation produces a mixture of gaseous products, containing hydrogen, which can be introduced in a hydrogen fuel cell to produce electrical energy. Accordingly, particularly preferred embodiment of the present invention is the dehydrogenation of a primary alcohol, such as methanol, ethanol, or mixtures thereof, with the aim of producing hydrogen for use in electric power generation in a fuel cell. For example, the appropriate use of hydrogen in the mixture of the products of the present invention include its use as a source of hydrogen fuel in fuel cells with polymer electrolyte, alkaline fuel cells, phosphoric acid fuel cell, fuel cells with molten carbonate, tverdooksidnyh fuel cells. The use of hydrogen as a fuel source for a fuel cell with a polymer electrolyte, particularly a fuel cell with a proton exchange membrane (POM), is usually the most preferred. Fuel cells with POM typically operate at temperatures of approximately 80aboutWith or less. Thus, the possibility of reforming spirit of the present invention at a low temperature is advantageous because it can be simplified design of the energy system and increased energy the I effectiveness. When the mixture of products of the reforming spirit of the present invention is used as a hydrogen source for a fuel cell, it is preferable to carry out the dehydrogenation reaction in combination with the reaction of the conversion of water vapor, as described above, to minimize the amount of carbon monoxide in a mixture of products. Accordingly, it is often preferable to mix the alcohol with water in the raw gas mixture fed to the dehydrogenation zone, facilitating the removal of carbon monoxide from the product stream through the reaction of conversion of water vapor. For example, the alcohol is preferably mixed with at least one molar equivalent of water, most preferably about from 1.05 to about 1.2 molar equivalents of water before introduction into the reaction zone dehydrogenation.

Usually the above catalysts of the present invention have some activity in the reaction of conversion of water vapor. However, in some embodiments, the implementation may be preferable to use an additional catalyst for the reaction of conversion of water vapor to obtain even lower concentrations of carbon monoxide in a mixture of products. When using the catalyst of the reaction of conversion of water vapor to the catalyst reaction of the conversion of water vapor can be either mixed with the catalysts of the om for reforming the catalyst bed in the reformer or is located in the lower part of the catalyst for reforming in the same layer or a separate layer of the catalyst.

For embodiments of the present invention using a specific catalyst for the reaction of conversion of water vapor is important to note that the most appropriate reaction conversion of water vapor is usually carried out at about 200°that is colder than the typical operating temperature of the reforming catalysts of the present invention. Accordingly, it may be necessary or desirable to cool the mixture of products of reforming before contacting with the catalyst of the reaction of conversion of water vapor. Usually you can use any of the known methods in this field of technology for cooling a gaseous product, including the heat exchanger. In one embodiment, it is possible to enter into a gaseous product of the reforming water between plant for reforming and reactor for the conversion of water vapor. In this embodiment, the introduction of water after installation for reforming makes it possible to reduce or remove the amount of water in spirtovodnogo source gas mixture that is fed in to the reformer.

Although it is not essential or critical to the present invention, it may be desirable in certain embodiments of the implementation of the present invention to provide one or more additional recovery options or other regulated the I residual carbon monoxide in the product stream reforming, emerging from the reaction zone dehydrogenation, the catalyst bed of the reaction of conversion of water vapor or fuel cell. Examples of suitable methods for adjustment or recovery of carbon monoxide generally described, for example, Peterson (Pettersson) with co-authors, Int'1 J. Hydrogen Energy, volume 26, pp. 243-64 (2001), and include selective oxidation of carbon monoxide, mahanirvana of carbon monoxide and implementation of the anode exhaust gas.

In a preferred embodiment, in which the hydrogen produced in the dehydrogenation zone, enters the fuel cell to produce electrical energy, the dehydrogenation reaction is preferably carried out in a fixed bed reactor containing a compacted layer described above, a copper-containing catalyst. Preferably take measures to minimize back pressure, for example, by adding an inert solid diluent to the catalyst layer to separate the catalyst particles and to keep a clear space between them. The diluent is usually the preferred material, free from acid sites, which can catalyze the dehydration of ethanol to ethylene and thermally stable under the reaction conditions. Silicon carbide and activated carbon, which was not kislotoustoichivam, are examples of predpochtitel what's thinners.

Alternatively, the pressure can be minimized through the use of a copper-containing catalyst comprising a metal sponge media, but rather in the form of granules, not powders. Examples of such shaped carriers include pellets of sponge Nickel, described in European patent number EP 0648534 Al and U.S. patent No. 6284703, the disclosure of which is incorporated into this description by this reference. Pellets of sponge Nickel, especially for use as a stationary layer of catalysts are produced on an industrial scale, for example, firms W.R.Grace & Co., (Chattanooga, TN) and Degussa-Huls Corp. (Ridgefield Park, NJ). In an additional alternative preferred embodiment, the catalyst can be used in the form of a monolith obtained by introducing a catalyst according to the invention on the surface of a suitable perforated substrate (e.g., cellular) to minimize back pressure inside the reactor for reforming.

Referring to figure 1, will be described one way of implementing the generation of energy based on the conversion of ethanol in accordance with the present invention. Although the following description will disclose in detail the use of the above copper-based catalyst for dehydrogenation of ethanol, it should be understood that the General principles in General, p is iminime for dehydrogenation of primary alcohols, comprising methanol or a mixture of ethanol with methanol.

Source sportowego feed mixture comprising a mixture of ethanol with water, is introduced into the reaction zone dehydrogenation, comprising a fixed layer 101 copper-containing dehydrogenation catalyst comprising a metal carrier. The original reaction mixture, comprising a mixture of ethanol with water is preferably introduced into the reaction zone dehydrogenation in the form of a gaseous source of a mixture of, for example, after evaporation in the evaporator (not shown)that are generally well known in the technical field of reforming alcohol. The catalyst layer 101 is heated by a heating jacket 102 to maintain the desired temperature in the dehydrogenation zone. Reforming of ethanol with water inside the catalyst layer 101 gives a mixture of products comprising hydrogen, carbon monoxide, carbon dioxide, water and methane. The mixture of products then passes through the bed of catalyst 103 containing a suitable catalyst for the conversion of water vapor selectively oxidizing carbon monoxide to carbon dioxide. Developed compact modules for the conversion of water vapor produced in industrial scale, for example, Hydrogen Source (South Windsor, CT). The mixture of products emerging from the catalyst layer 103, and then cooled to an acceptable temperature (usually 80°or lower) and injected into Ogorodny fuel cell 105 (for example, fuel cell with proton exchange membrane) with a source of oxygen (e.g. air) to generate electrical energy. Electrical energy is generated by the reaction of hydrogen with oxygen in a fuel cell to produce water. It should be understood that the fuel cell may include multiple fuel cells ( i.e. "battery" fuel cells)that traditionally in applications of the fuel element.

Exhaust gases flow from the fuel element, which contains water vapor, methane, and carbon dioxide, then burned with air in the combustion chamber 107, provided with a source of oxygen (e.g. air). Suitable combustion chamber may include a gas turbine, a heat engine, the internal combustion engine or other device for the propulsion generator 109, which generates additional electricity. Exhaust the hot stream of gases of combustion from the generator 109 may be returned in the heating jacket 102 as the source of the heating layer 101 of the reforming catalyst in the dehydrogenation zone.

The combustion exhaust from the fuel cell gases also provides a suitable way to handle emissions from the energy system. Undesirable components of the exhaust gases of the fuel cell, such as acetaldehyde, carbon monoxide, OS is enough alcohol and/or methane will be converted to carbon dioxide by combustion in the combustion chamber 107. The residual hydrogen is oxidized to water. It was recently reported that volatile hydrogen emissions can pose a threat to the ozone layer. (See Tromp(Tromp) with co-authors, Science, 300, 1740-2, 2003). In addition, the exhaust gases of the internal combustion engine (as opposed to emissions from conventional energy systems with POM-fuel cell) is quite hot, which allows for effective functioning catalytic converters of exhaust gases, making it possible to further reduce harmful emissions.

Preferably in transport energy applications outgoing gases from the fuel cell, mainly carbon dioxide and methane with traces of hydrogen, water vapor and carbon monoxide, is introduced into the combustion system, which can provide or electrical and/or mechanical energy. In such applications, the combustion system may include an internal combustion engine, to obtain the torque for the propulsion of motor vehicles or internal combustion engine in combination with the generator to produce additional electric power.

In a particularly preferred embodiment, the energy system includes an internal combustion engine with a "universal fuel"that allows the combustion of alcohols, methane or mixtures thereof, using the second combustion exhaust from the fuel cell gases, that provides a source of mechanical energy for the propulsion of motor vehicles. One or more electric motors direct current produced by the fuel cell, provide additional energy in the design, similar to those used for hybrid vehicles (vehicles with a combined power plant). Such preferred energy system that uses ethanol as fuel, shown in figure 2.

With reference to figure 2, water-ethanol the initial mixture with a slight molar excess of water is introduced into the reaction zone dehydrogenation comprising a compacted layer 201 containing copper-plated Nickel sponge catalyst reforming A and catalyst B conversion of water vapor, and is heated by a heating jacket 202. The alcohol is converted to the product of reforming containing hydrogen, carbon dioxide and methane in the compacted layer, as described above. The exhaust stream reforming product from the dehydrogenation zone is served in a hydrogen fuel cell 205 at a suitable temperature with a source of oxygen (e.g. air) to generate electrical energy in the form of a constant electric current. Methane and carbon dioxide do not impair the performance of fuel elements IND. Exhaust gases flow from the fuel element 205, mainly methane and carbon dioxide, burn with a source of oxygen (e.g. air) in the internal combustion engine 207. Hot exhaust gases from the internal combustion engine will then use as a heat source for heating shirts 202 before their exit from the system in the form of exhaust gases, preferably through a catalytic afterburner exhaust gases (not shown). In this way the waste heat of the internal combustion engine are implementing, maintaining the desired temperature for indeterminacy reforming reaction of ethanol. Design of installation for reforming, which enable heat exchange between separate hot gas stream and the catalyst layer, for reforming, well known in this technical field.

Because indeterminado nature of the reforming reaction has a significant impediment to the operation of the fuel element in its application to the propulsion of the vehicle at launch. In particular, fuel cells do not provide for a "cold start" of the vehicle (i.e. there is a time delay at startup before the installation for the reformer and the fuel cell will not reach their design operating temperature before Generalova the ü energy sufficient for driving the vehicle). Thus, in a particularly preferred embodiment of the present invention, the internal combustion engine 207 energy subsystem driven by the combustion, as described above with reference to figure 2, an internal combustion engine on a "universal" fuel, which can operate using alcohol raw material or other source of fuel for cold start 211, separate from the waste stream (gas) from the fuel element. Alcohol raw materials for the internal combustion engine is preferably anhydrous and therefore separated from the ethanol-water raw materials of the reactor for reforming. When starting the internal combustion engine works, using alcohol from a separate source of fuel for cold start 211 as fuel to ensure cold start like in vehicles driven in the usual internal combustion engines. During normal operation, after setting the reformer and the fuel cell have reached their design operating temperature, the vehicle may be first set in motion by an electric motor fed by a constant current generated by a hydrogen fuel cell. Engine internal sorayarodrigue to function offsetting some of the basic energy (power)required motor vehicle, but the internal combustion engine in the first place is supplied with fuel in the form of methane from the waste stream (gas) fuel cell than alcohol from a separate fuel source cold start 211. If the launch condition require additional short single pulse of energy, the vehicle can then move around due to the additional torque from the internal combustion engine. In addition, the methane in the exhaust from a fuel cell flow to the internal combustion engine can be added alcohol raw materials from a separate fuel source cold start 211 to generate an additional torque. Extra added energy may also be provided with a rechargeable battery.

In addition to providing better cold start and provide a short pulse of energy such preferred arrangement enables the design of a power system with significantly less cost. Hydrogen fuel cells are typically the most expensive components of energy systems based on fuel cells for vehicles. Described here is the energy the system requires significantly less capacity of the fuel element, than the traditional layout, because the maximum power is complemented by the internal combustion engine. Layout only requires sufficient capacity of the fuel element to provide part of the basic energy consumption, the other part is provided by the internal combustion engine running on alcohol and/or methane.

EXAMPLES

The following examples are intended merely to further illustrate and explain the present invention. The invention, therefore, is not limited by any details in these examples.

Furthermore, existing examples of preparation of copper-plated metal catalysts described in belonging to the same applicant's U.S. patent No. 6376708 and owned by the same applicant jointly filed and simultaneously considering the patent application U.S. serial No. 09/832541, published under number US-2002-0019564-A1. The full text of U.S. patent No. 6376708 and from the publication № US-2002-0019564-Al is incorporated into this description by this reference.

Example 1

Preparation of copper-plated Nickel sponge catalyst

This example shows the preparation of copper-plated Nickel sponge catalyst using substitution deposition.

Nickel sponge media (68,7 g alloy Raney (RANEY) 4200, manufactured by W.R.Grace, Chattanooga, TN) suspended in barotraumas nitrogen water (400 ml) in a glass beaker. With stirring was added a 12%solution of NaBH4(50 g) in 14 M NaOH. Intensive foaming was observed within 1 minute. After 10 minutes of stirring, the catalyst was allowed to settle and decantation of the supernatant liquid. Added additional portion barotraumas nitrogen water (400 ml) and thoroughly mixed. The catalyst was again given the opportunity to settle before decanting the wash liquid.

The catalyst was added to the third portion barotraumas nitrogen water (250 ml). Added glacial acetic acid (about 8 ml) to reduce the pH to 5. Then the suspension of the catalyst is brought into contact with barotrauma nitrogen with a solution of CuSO4·5H2O (54,0 g, 20 wt.% copper relative to the catalyst) and dihydrate chetyrehmetrovoy salt ethylenediaminetetraacetic acid (tetrasodium EDTA) (108,0 g) in water (300 ml). NaOH (sodium hydroxide)(2,5 N. 73,0 ml) was added over 103 minutes with continuous stirring and sparging with nitrogen, the pH of the suspension was raised from 6.8 to 11.3. The catalyst was allowed to settle, chemical glass was wrapped in tape heater, and the blue supernatant decantation.

CuSO4·5H2O (67,5 g, 25 wt.% copper relative to the catalyst) was dissolved in barotraumas and the Otomi water (200 ml) with formation of a solution of copper. The suspension of catalyst was formed by adding to the catalyst hot (74° (C) a mixture of 50%gluconic acid (159,0 g), 2,5 N. NaOH (54 ml) and barotraumas nitrogen water (250 ml). Then, to the suspension of catalyst solution was added copper with stirring for 95 minutes, while chemical beaker was heated tape heater (final temperature 72°). the pH fell from 3.8 to 3.1. The catalyst was allowed to settle and decantation green supernatant.

The catalyst was washed barotraumas nitrogen water (700 ml). The wash liquid decantation and 75.6 g of a slightly coloured catalyst copper color, were isolated and kept under water. The composition of the catalyst was as follows: 66,1 wt.% Ni, a 30.4 wt.% Cu and 3.5 wt.% Al.

It was found that the catalyst consists of two fractions, where a small sample (approximately 1 g) was suspended in water. Faction consisted of painted a copper color of the lower layer and the gray of the upper layer. Surface area by BET surface and the Nickel concentration were determined after hydrogen drying at 130aboutWith the method described in Schmidt (Schmidt) in the surface of the catalysts of the Raney" ("Surfaces of Raney® Catalysts"),"Catalysis of organic reactions" (Catalysis of OrganicReactions, SS. 45-60 (M.G. Scaros and M.L. Prunier, eds. Dekker, New York, 1995). The results of the analysis are presented in table 1.

Table 1
SampleSurface area by BETSurface Nickel
The Raney(RANEY) 420070 m2/g700-800 µmol/g
The top fraction36,8 m2/g54,8 µmol/g
The bottom fraction40,1 m2/g32.1 mmol/g

Example 2

Reforming of ethanol using Nickel sponge catalyst, copper-plated

This example demonstrates the use of Nickel sponge catalyst, copper-plated for reforming of ethanol.

The experiment was carried out in a reactor made of stainless steel containing tube 304 stainless steel (457,2 mm length, 12.7 mm inner diameter)wrapped spiral heater. To pre-heat the ethanol feedstock tube was connected to the upper part of the reactor. Catalytic mass was placed on a strip of glass wool, which is located on the floor of the liner at the bottom of the tubular reactor. thermocouple was placed at the bottom of the catalytic layer and used for control and regulation of the reaction temperature using a spiral heater. The waste stream was analyzed by gas chromatography using detec the ora thermal conductivity. The output of the reactor was kept at atmospheric pressure.

The reactor was loaded, as described below. After insertion of a fresh pad of glass wool aqueous suspension (particles) (size) 325 mesh silicon carbide (1.0 g)(manufactured by Alfa Aesar, Ward Hill, MA) was passed through the reactor for the formation of the foundations of the catalytic layer on top of glass wool. Then was passed through the reactor, the suspension of silicon carbide (1.5 g) and catalyst (2,02 g) from example 1. Penetrations were observed, which showed that the entire load of the catalyst remained in the reactor. Before use, the catalyst was dried in the reactor during the night at 120° (atmosphere) nitrogen.

Table 2 gives the results of reforming of ethanol using different temperatures, flow rates and concentrations of water in raw materials. The catalyst was in operation in the process of reforming of ethanol is only about 30 hours to obtain the data in table 2. It should be noted that the outputs of methane and the balance by weight, based on the methane that may exceed 100% due to analytical error and mahanirvana WITH that illustrated by equation 6:

CO + 3H2-> CH4+ H2About (6)

Also note that the yield of hydrogen removed from the table and the following examples. Although hydrogen was measured directly in the gas chromatograph, thermal conductivity detector has a low sensitivity in the Dorado compared with carbon-based molecules which leads to a greater spread in the data. Accordingly, the yield of hydrogen can be calculated more carefully from the output of carbon-containing compounds, such as carbon monoxide, carbon dioxide and methane.

250
Table 2
The distribution of the products of reforming of ethanol under various conditions are given as molar outputs relative to the original amount of ethanol
H2O raw materials1(wt.%)Pace,

°
Source

raw material

(ml/min)
CH3CH2OH

%
CH3C(O)H

%
CH4< / br>
%
CO2< / br>
%
50%2500,15traces4,395,16,5
0,3021,726,752,24,5
0,4042,329,625,71,5
0,8062,827,99,20,2
1,2074,720,94,5traces
50%2800,2000101,024,5
0,4014,219,666,86,0
0,8050,426,222,92,1
64,2of 21.914,01,1
30%2500,3044,214,840,81,5
2800,3012,99,676,93,7
3000,3002,997,56,7
3000,2000102,015,1
3200,2000104,642,0
10%2500,2022,28,369,51,3
2500,3047,112,140,80,5
2800,206,2a 3.990,52,1
0%0,2000104,43,5
0,259,9a 3.987,50,8
0,4033,39,058,30,3
0,6050,911,1to 38.30,1
0,90to 78.39,011,8traces

1The rest of the raw materials contained ethanol.

Example 3

Reforming of methanol using a Nickel sponge catalyst, copper-plated

This example demonstrates the reforming of methanol using a Nickel sponge catalyst is copper-plated.

The experiment was carried out in accordance with the above example 2, except that the used raw materials, consisting of 70 wt.% methanol and 30 wt.% water. The results are shown below in table 3.

Table 3
The distribution of products for methanol reforming in the reforming raw material with 70% methanol
TemperatureThe flow of the feedstock (ml/min)MethanolMethane COCO2
300°0,4013,3%3,2%81,22,3%
300°0,202,4%3,7%86,97,0%
320°0,201,7%5,5%75,517,9%

Example 4

Reforming of ethanol for long period

This example demonstrates the ability of the catalyst of the present invention to provide a high conversion rate for an extended period of time reforming of ethanol.

The experiment was performed under conditions essentially similar to example 2, except that in the initial stage of the reactor was loaded, depositing the first silicon carbide (1.0 g), and then the suspension containing the catalyst of example 1 (2.5 g) and silicon carbide (5.0 g). The temperature was monitored by a thermocouple inserted from below into the opening of the reactor, located approximately 10.2 cm above the bottom of the catalytic layer.

The reactor is operated so that the temperature of the mixture of products leaving the catalytic layer supported (equal) 280°C. the upper Temperature thermocouple remained relatively constant at approximately 430°C. the Ethanol-water source raw mixture (the ratio is the development of ethanol and water by weight of 70:30) was introduced into the dehydrogenation zone with a speed of 0.3 ml/min with nitrogen at 100 sccm. The reactor worked 44 hours, after which the pressure in the reactor rose from 28 pounds/inch2up to 80 pounds/inch2. During this period, we were not ethanol or acetaldehyde in a mixture of products, and conversion to methane was 100% (including) the analytical error. Table 4 below shows the selectivity for co and CO2in the course of the experiment.

Table 4
The output products of the reforming of ethanol using 70%ethanol feedstock at 280°
Time(hours)COCO2
23466
56040
128119
208515
258515
318812
358812
408812
448713

Example 5

Reforming of ethanol in a fixed bed having a temperature gradient

This example demonstrates that high conversion and low mahanirvana achieved when rifor the Inge ethanol with copper-plated Nickel sponge catalyst in a fixed bed, current at low pressure, the outlet temperature of 300°s or less and a temperature gradient, for which the temperature at the inlet is lower than the outlet temperature.

Used vertically mounted tubular reactor made of stainless steel (457,2 mm length, 12.7 mm inner diameter)wrapped spiral heater, just as in example 2, except that the flow of raw ethanol was injected at the bottom of the reactor and the catalyst bed was located in the upper part of the reactor between two strips of glass wool.

Thermocouples were located at the beginning and at the end of the catalytic layer on the traffic flow. Used catalyst (2.50 g), prepared in example 1. A mixture consisting of 70 wt.% ethanol and 30 wt.%, were loaded into the reactor with a speed of 0.1 ml/min and the reactor was heated with a controlled rate to ensure that the temperature of the exhaust gas flow 275°at the outlet of the catalytic layer. During the whole experiment the temperature at the beginning of the catalyst layer in the course of the stream was the same - 245°C. the pressure at the beginning of the reactor in the course of the stream did not exceed 5 pounds/inch2.

Table 5 shows high conversion achieved during a period of more than 200 hours of continuous operation. After 286 hours of continuous operation at the temperature increased to 300°C. the Data obtained is ri this temperature, shown in table 6. In the mixture of products was not detected acetaldehyde or ethanol. During the experiment was not detected detected of mahanirvana.

Table 5
Outputs products of example 5 with 275°
Time

(watch)
CO%CO2%CH4%CH3C(O)H%Ethanol%
1096,12,0101,9ButBut
20to 97.11,8101,1ButBut
4096,32,5101,2ButBut
6096,52,5101,0ButBut
8096,32,7101,0ButBut
10095,43,4101,1ButBut
12096,52,6100,9ButBut
14096,62,4100,80,05But
160/td> 96,82,2100,9ButBut
180to 97.12,1100,8ButBut
20196,62,2101,1ButBut
22095,82,2100,80,57But
26596,12,499,50,710,31
285for 95.32,199,31,030,62

But - Not found

Table 6
The output products of example 5 after raising the outlet temperature to 300°
Time

(watch)
CO%CO2%CH4%CH3C(O)H%Ethanol%
29091,48,2to 100.4ButBut
29591,28,2100,6ButBut
30091,97,7100,3ButBut
306 91,58,2100,3ButBut
31091,57,9100,5ButBut

Example 6

Preparation of Nickel sponge catalyst, copper-plated

This example illustrates the method of applying a coating to a metal foam substrate, which provides a similar conversion and higher levels of carbon dioxide and which requires less copper sulfate than the way Morgenstern (Morgenstern)with co (U.S. patent No. 6376708) or the method according to example 1.

The experiment also used a high concentration of dry substances, thus minimizing excessive amount of. In the example, the mass of the substrate and the catalyst was determined by the method of water displacement, provided that the density ratio is 1.16.

Nickel sponge media (48,3 g alloy Raney (RANEY) 4200, manufactured by Grace Davison, Chattanooga, TN) was placed in chemical beaker with a capacity of 1 l with barotraumas nitrogen with water and excess water was removed by decantation. Barberey nitrogen a solution of CuSO4·5H2O (47,45 g) and Na4EDTA·2H2On (94,92 g) in water (400 ml) was added to the catalyst and the suspension was stirred, and after 48 minutes was added 2.5 N. NaOH (91 ml). the pH increased from 8.4 to 11.4. Blue supernatant Dec who was niraval and the glass was wrapped in tape heater.

The hot mixture of 50%gluconic acid (11 g) and water (400 ml) was added to the catalyst. Was heated and after 43 minutes was added a mixture of concentrated sulfuric acid (5,70 g) and water (50 ml). The temperature was fixed between 59°s and 60°and pH fell from 5.2 to 2.2. The mixture was stirred for 45 minutes. The final pH was 2,8.

Blue supernatant decantation, was added Bartiromo nitrogen water (500 ml) and the pH was brought to 7 with sodium hydroxide. This stage helps to remove the residual Nickel and EDTA. The catalyst was allowed to settle and the supernatant liquid was removed by decantation. Was allocated to 51.3 g of a catalyst having the composition of 76.8% Ni, 19,9% Cu, 3.2% of Al and 0.2% Fe.

Example 7

Reforming of ethanol using Nickel sponge catalyst, copper-plated

This example illustrates the reforming of ethanol in the presence of a catalyst comprising copper on the surface of the Nickel sponge media.

The catalyst, prepared as in example 6 (2.50 g)was placed in a reactor having a configuration identical to that described above in example 2. Alcohol feedstock containing 70 wt.% ethanol and 30 wt.% water was injected into the reactor with a speed of 0.1 ml/min. and the Temperature was gradually increased to 300°within the first 24 hours of the experiment. It should be noted that the conversion is slightly lower than in example 5, but the conversion of CO in the CO2(reaction conversion of water vapor) flows in a substantially greater extent. Mahanirvana also more, but, as can be seen from the following example, decreases with time.

Table 7
Example 7. The composition of the exhaust gases flow
Time

(watch)
The pace. on

output
CO

%
C02< / br>
%
CH4< / br>
%
CH3C(O)H

%
Ethanol

%
7270°C81,714,3103,50,2But
15270°C80,715,2101,80,60,5%
20270°C68,526,8104,00,3But
31300°C44,149,8106,1ButBut
35300°Cto 47.246,9105,9ButBut
40300°C43,751,0105,1ButN the
45300°Cto 47.248,6104,2ButBut

Example 8

Reforming of ethanol for long period

This example shows isothermal reforming of ethanol for a long period. The example additionally illustrates the gradual decrease of mahanirvana with the use of the catalyst of example 6 while maintaining high conversion of CO2.

As in the above example 7, in a reactor identical design, which is described in example 2, downloaded the catalyst (2.50 g), prepared as in example 6, and worked at a flow rate of 0.1 ml/min, using a feedstock comprising 70 wt.% ethanol/30 wt.% water. Maintained a temperature of 300°at the outlet of the catalyst. In a mixture of products during the run was not detected acetaldehyde and ethanol. Mahanirvana decreased continuously during the experiment, as shown in table 8.

Table 8
Example 8. The composition of the exhaust gases flow
Time(hour)CO%CO2%CH4%
1057,637,5104,8
204,0 31,9104,1
3264,132,5103,3
4166,430,8102,8
5070,927,1102,0
6176,921,8101,3
7077,820,8101,3
8560,337,2102,5
9169,628,9of 101.5
10068,630,5100,9
11077,921,8100,3

Example 9

Reforming of methanol using a spongy Nickel catalysts, copper-plated

This example demonstrates the activity and durability of the catalyst of this invention for reforming of methanol in soft and close to isothermal conditions.

The catalyst prepared in example 2 (2,52 g), was mixed with beads of polymeric diluent (1.0 g brand Tenax TA, 80-100 mesh, manufactured by Alltech Associates, Deerfield, IL) and were loaded into the reactor as described in example 2, located horizontally for this experiment. Into the reactor was fed a mixture of 60% methanol/40% water (0.1 ml/min, the molar ratio of water:methanol - 1,19:1) and the wide temperature 320° With the output. The pressure remained below 5 pounds/inch2during the run. The temperature along the catalytic layer was approximately 335°and changed from 309°to 369°in the course of the experiment.

Table shows the results. To maintain the conversion of methanol over 90% require higher temperatures than are required for ethanol. Methane yield is usually about 1%, and similarly for ethanol.

Table 9
Example 9. Exhaust gases flow from the reactor
Time

(watch)
WITH%CO2%CH4%Methanol%
1070,525,62,91,0
2079,517,11,81,6
30of 83.413,31,81,5
4084,711,51,72,2
5085,5the 9.71,43,3
6084,15,80,4the 9.7
7083,1the 4.70,511,8
8084,76,40,68,3
9083,35,00,611,1
10080,39,11,09,6
11079,58,10,911,5

Example 10

Preparation of Nickel sponge catalyst, copper-plated, for use with fixed bed

This example describes the preparation of a fixed catalyst layer by coating of copper on the stationary layer of Nickel sponge media.

Nickel sponge media, posted on the granular substrate (45 granules containing 6,79 g (product) brand Metalyst® alpha-1401-X018 produced in industrial scale by the firm Degussa AG, Hanau(Hanau, Germany) was dried overnight in vacuum at 120aboutWith compressed nitrogen. The pellets were placed along the plastic tube (9,525 mm inner diameter) between the strips of glass wool in a nitrogen atmosphere, and the solution of the electroplating baths containing CuSO4·5H2O (10,67 g) and Na4EDTA·2H2O (21,34 g) in water (300 ml), circulated over the catalyst at room temperature over 124 minutes was added dropwise a mixture of 2.5 N. NaOH (26 ml) and water (50 ml). During the coating solution from the galvanic is practical baths for coating kept in a container with a stirrer in a nitrogen atmosphere and was carried out by circulation between the catalyst and capacity using a peristaltic pump. the pH was increased from 10.0 to 12.0. Then the catalyst was rinsed with water.

The mixture CuSO4·5H2O in (6.67 g), gluconic acid (5.2 g), 2,5 N. NaOH (2.7 g) and water (300 ml) was added into the vessel and carried circulation over the catalyst for two hours at room temperature. The catalyst was rinsed with water and then dried overnight at 120aboutWith the vacuum with nitrogen purge. Allocated of 6.65 g (98%) of the catalyst.

Example 11

Reforming of ethanol in isothermal conditions

This example demonstrates the effect of a catalyst reforming of ethanol in a nearly isothermal conditions (compared with reforming of ethanol in the presence of a temperature gradient along the reactor as described in example 7). The experiment included reforming of ethanol using a catalyst prepared in example 6, while maintaining the catalyst bed almost izotermiczne condition, at a temperature of 280°C. to eliminate the temperature gradient, used the modified reactor. The source gas mixture (70 wt.% ethanol/30 wt.% water) was pumped with a speed of 0.1 ml/min through a stainless steel tube (1,58 mm outer diameter) in the heater, consisting of a vertical stainless steel tube (457,2 mm length, 9,525 mm inner diameter, 12.7 mm outer diameter), filled with balls of stainless steel (diameter 3 mm diameter 4 mm), the wrapped heater. The original tube was collapsed spiral on top of the heater and then attached to the heater at the bottom.

The upper part of the heater (output) was attached to the stainless steel tube (177.8 mm length, 9,525 mm inner diameter, 12.7 mm outer diameter), containing the catalyst prepared in example 6 (2,49 g), Packed between two deactivated strips of glass wool. Top tube (reactor) was wrapped around a separate heater. thermocouple located at the junction between the heater and the tube reactor used for controlling the heater and keep the temperature constant at the beginning of the catalytic layer (along the stream), while thermocouple located directly above the catalyst layer (at the end of the layer along the flow controlled electric heater and maintained the temperature at the end of the catalytic layer in the course of the stream (output) 280°C. Both temperature was set for two hours and remained constant within 1°C. the Design is completely insulated, and the system output for gas chromatographic analysis was the same as described in example 2.

Table 10 shows a high conversion and stability achieved when working in nearly isothermal conditions. D. the pressure of the input stream in the heater remained below 15 pounds/inch 2during the entire experiment. It is noted that under isothermal conditions excessive methane formation was decreased to values unchanged state variable about 2% after eight hours. Were seen traces of ethanol, but they were below the limit of quantitation. Acetaldehyde has reached the level of the contents, quantifiable, only at the end of the run. Both were less than 1% during the entire experiment.

Table 10
The yields of products in the reformer at 280°in isothermal conditions in example 11
Time

(watch)
H2COCH4CO2Acetaldehyde
0,6149,6%10,3%111,7%78,0%0,0%
1,2103,9%81,6%103,7%14,7%0,0%
2,097,2%90,2%102,4%7,4%0,0%
4,094,9%90.1%of103,0%6,9%0,0%
5,996,8%90,3%102,8%6,9%0,%
8,296,3%91,4%102,0%6,9%0,0%
10,395,2%of 92.9%101,9%5,2%0,0%
15,397,3%91.3%of102,0%6,7%0,0%
19,898,7%90,7%101,8%7,5%0,0%
25,899,6%of 91.6%101,5%6,8%0,0%
30,3to 96.9%92,5%101,7%5,8%0,0%
40,8the 98.9%91.3%of101,5%to 7.2%0,0%
60,399,0%92,2%101,5%6,3%0,0%
79,5101,5%86,4%101,9%11,6%0,0%
100,599,5%90,6%101,4%8,0%0,0%
120,1104,6%88,9%101,0%10,0%0,0%
141,197,7%94,1%101,3%4,5%0,0%
149,1 97,5%95,4%100,5%2,9%0,6%

Example 12

Reforming of ethanol with a porous layer of Nickel sponge catalyst, copper-plated

This example demonstrates the use of Nickel sponge catalyst-coated copper, in a still layer when reforming of ethanol. The experiment involves reforming of ethanol in isothermal conditions at 300°using the catalyst prepared in example 10 (of 1.46 g, 10 pellets) in the same design as described in example 11. Raw gas mixture containing 70 wt.% ethanol and 30 wt.% water was injected with a speed of 0.06 ml/min to ensure that the ratio of the flow velocity and catalyst, equivalent to that provided in the previous examples using 2.50 g of catalyst and 0.10 ml/min raw mixture of gases.

As illustrated by data in table below, the fixed layer of material provides a high (>85%) conversion at 300°C. the Fixed catalyst bed is also different from the powder catalysts that reduce mahanirvana occurs more slowly and continuously, requiring about 20 hours at 300°C.

Table 11
The results of the example is 12
Time

(watch)
H2COCH4CO2AcetaldehydeEthanol
0,927,0%0,7%147,3%52,0%0,0%0,0%
1,843,6%1,1%140,4%58,5%0,0%0,0%
the 3.853,0%7,5%134,6%58,0%0,0%0,0%
6,166,9%27,0%124,5%48,5%0,0%0,0%
8,178,2%49,6%116,4%34,0%0,0%0,0%
the 10.185,4%61,3%111,9%26,6%0,1%0,0%
14,892,6%74,6%105,8%17,7%1,0%0,0%
20,296,4%79,2%98,4%12,6%2,4%2,5%
30,2 98,6%78,0%89,3%10,0%4,7%6,6%
of 40.398,4%78,5%85,1%7,8%5,1%9,2%
60,7107,0%86,0%of 92.7%9,4%2,6%3,3%
an 80.2102,4%76,3%76,9%6,3%6,5%13,8%
99,899,9%70,6%70,5%5,8%7,9%18,7%
120,095,5%67,0%67,4%5,9%8,1%21,7%

Example 13

Reforming of ethanol at various temperatures with a fixed catalyst bed

This example describes the use of a fixed catalyst for reforming of ethanol at various temperatures.

The experiment was a continuation of the experiment described in the foregoing example 12, when varied the flow rate and temperature. Maintained isothermal conditions. Table summarizes the performance of the catalyst at 300°and 320°at some values of the velocities of flows.

Table 12
Reforming of ethanol, which is described in example 12, with variations of temperature and flow velocity
Pace,

°
The flow rate

(ml/min))
H2COCH4CO2CH3C(O)HCH3CH2HE
3000,01100,5%64,1%106,1%29,5%0,2%0,0%
3000,02119,9%83.4%of90,9%16,9%1,7%2,7%
3000,03111,3%82,1%86,0%11,5%3,3%6,9%
3200,02104,0%64,8%105,5%29,7%0,0%0,0%
3200,03109,3%78,2%100,3%20,7%0,2%0,2%
3200,045118,2%87,9%93,5%15,3%0,7%1,0%
3200,0 126,1%92,2%89,1%13,3%1,4%1,3%

The result of the experiment made the discovery that most of the catalysts were turned into powder. This loss of structural integrity due to neaktivirovannye aluminum in the inner part (core) of the substrate, which reacts with water vapor to form aluminum oxide under the reaction conditions.

The present invention is not limited to the above-mentioned variants of the implementation and can be variously modified. The above description of preferred embodiments is intended only to acquaint others skilled professionals in this area of technology with the invention, its principles and their practical application so that others skilled professionals in this area of technology could adapt and apply the invention in its numerous variants, which may best be suited to the requirements of a particular application.

Regarding the use of the word (s) "contain", or "contains"or "containing" throughout the present description (including the following claims) it should be noted that, unless the context requires otherwise, those words are used on the basis and unambiguous Pont is mania, they should be interpreted inclusively rather than exclusively, and that implies that each of these words must be interpreted in the interpretation of this complete description.

1. Method of reforming alcohol including

bringing into contact the source of the raw material mixture gas containing alcohol, with a reforming catalyst to obtain a mixture of products of reforming, with hydrogen, the reforming catalyst contains a metal sponge carrier and a coating of copper, at least partially covering the surface of this metal sponge media, where this metal sponge media produced by the process comprising leaching aluminum from an alloy containing aluminum and the base metal.

2. The method according to claim 1, in which the raw gas mixture contains a primary alcohol selected from the group consisting of methanol, ethanol and mixtures thereof.

3. The method according to claim 2, in which the method further includes the introduction of hydrogen from a mixture of the products of reforming and oxygen in a fuel cell to generate electricity.

4. The method according to claim 1, in which the reforming catalyst has a surface area from about 10 m2/g to about 100 m2/g, as measured by the method of brunauer-Emmett-teller.

5. The method according to claim 4, in which the catalyst p is forminga has a surface area from about 25 m 2/g to about 100 m2/g, as measured by the method of brunauer-Emmett-teller.

6. The method according to claim 5, in which the reforming catalyst has a surface area from about 30 m2/g to about 80 m2/g, as measured by the method of brunauer-Emmett-teller.

7. The method according to claim 1, in which the reforming catalyst contains at least about 10 wt.% copper.

8. The method according to claim 1, in which the reforming catalyst contains from about 10% to about 90 wt.% copper.

9. The method according to claim 1, wherein the metal sponge carrier of the reforming catalyst has a surface area of at least about 10 m2/g, as measured by the method of brunauer-Emmett-teller.

10. The method according to claim 9, in which the metal sponge carrier of the reforming catalyst has a surface area of at least about 50 m2/g, as measured by the method of brunauer-Emmett-teller.

11. The method according to claim 10, in which the metal sponge carrier of the reforming catalyst has a surface area of at least about 70 m2/g, as measured by the method of brunauer-Emmett-teller.

12. The method according to claim 9, in which the metallic porous media may contain Nickel.

13. The method according to item 12, in which a metallic porous medium contains at least about 50 wt.% Nickel.

14. The method according to item 13, in which the metal sponge wear the fir contains, at least about 85 wt.% Nickel.

15. The method according to item 12, in which the reforming catalyst contains from about 10 wt.% to about 80 wt.% copper.

16. The method according to item 15, in which the reforming catalyst contains from about 20 wt.% to about 45 wt.% copper.

17. The method according to item 12, in which the reforming catalyst contains from about 5 to about 100 μmol/g of Nickel on the surface of the above-mentioned catalyst.

18. The method according to 17, in which the reforming catalyst contains from about 10 to about 80 µmol/g of Nickel on the surface of the above-mentioned catalyst.

19. The method according to p, in which reforming catalyst contains from about 15 to about 75 µmol/g of Nickel on the surface of the above-mentioned catalyst.

20. The method according to item 12, in which the mixture of gases contains a primary alcohol selected from the group consisting of methanol, ethanol, and mixtures thereof.

21. The method according to item 12, additionally including the introduction of hydrogen from a mixture of the products of reforming and oxygen in a fuel cell to generate electricity.

22. The method according to claim 1, in which the mentioned source raw gas mixture is brought into contact with the said catalyst for reforming at a temperature below approximately 400°C.

23. The method according to claim 1, in which the mentioned source raw gas mixture is brought into contact with said catalyst for a reformer when the temperature is ur from about 200° With up to about 375°C.

24. The method according to item 23, in which the mentioned source raw gas mixture is brought into contact with the said catalyst for reforming at a temperature of from about 250°up to about 325°C.

25. The method according to claim 1, in which the reforming catalyst introduced to the surface of granular or monolithic substrate.

26. The method according A.25, in which reforming catalyst comprises Nickel sponge media.

27. Method of reforming of ethanol, comprising bringing into contact the source of the raw material mixture gas containing ethanol, with a reforming catalyst at a temperature below approximately 400°obtaining a mixture of products of reforming, with hydrogen, and mentioned reforming catalyst contains copper on the surface of the metal carrier.

28. The method according to item 27, which referred to the original feed mixture of gases is in contact with the said reforming catalyst at a temperature of from about 250°up to about 300°C.

29. The method according to item 27, in which the reforming catalyst has a thermal conductivity at 300 K of at least about 50 W/m·K.

30. The method according to clause 29, in which the reforming catalyst has a thermal conductivity at 300 K of at least about 70 W/m·K.

31. The method according to item 30, in which the reforming catalyst has a thermal conductivity at 300 K, Myung is our least about 90 W/m·K.

32. The method according to item 27, in which the method further includes introducing fuel cell hydrogen from a mixture of the products of reforming and oxygen to generate electricity.

33. The method according to item 27, in which the reforming catalyst has a surface area from about 10 m2/g to about 100 m2/g, as measured by the method of brunauer-Emmett-teller.

34. The method according to p, in which the reforming catalyst has a surface area from about 25 m2/g to about 100 m2/g, as measured by the method of brunauer-Emmett-teller.

35. The method according to clause 34, in which the reforming catalyst has a surface area from about 30 m2/g to about 80 m2/g, as measured by the method of brunauer-Emmett-teller.

36. The method according to item 27, in which the reforming catalyst contains at least about 10 wt.% copper.

37. The method according to p, in which reforming catalyst contains from about 10 wt.% to about 90 wt.% copper.

38. The method according to item 27, in which the metal carrier comprises a metal sponge.

39. The method according to § 38, in which the metal sponge carrier of the catalyst for reforming has a surface area of at least about 10 m2/g, as measured by the method of brunauer-Emmett-teller.

40. The method according to § 39, in which the metal sponge media catalysis is the Torah for the reformer has a surface area, at least about 50 m2/g, as measured by the method of brunauer-Emmett-teller.

41. The method according to p, in which the metal sponge carrier of the catalyst for reforming has a surface area of at least about 70 m2/g, as measured by the method of brunauer-Emmett-teller.

42. The method according to § 38, in which the metal sponge media includes Nickel.

43. The method according to § 42, in which a metallic porous medium contains at least about 50 wt.% Nickel.

44. The method according to item 43, in which a metallic porous medium contains at least about 85 wt.% Nickel.

45. The method according to § 42, in which the reforming catalyst contains from about 10 wt.% to about 80 wt.% copper.

46. The method according to item 45, in which the reforming catalyst contains from about 20 wt.% to about 45 wt.% copper.

47. The method according to § 42, in which the reforming catalyst contains from about 5 to about 100 μmol/g of Nickel on the surface of the above-mentioned catalyst.

48. The method according to claim,47, in which the reforming catalyst contains from about 10 to about 80 µmol/g of Nickel on the surface of the above-mentioned catalyst.

49. The method according to p, in which reforming catalyst contains from about 15 to about 75 µmol/g of Nickel on the surface of the above-mentioned catalyst.

50. The method according to § 42, in which the method further what about includes the introduction of hydrogen from a mixture of the products of reforming and oxygen in a fuel cell to generate electricity.

51. The method according to item 27, in which the reforming catalyst introduced to the surface of granular or monolithic substrate.

52. The method according to § 51, in which the reforming catalyst comprises Nickel sponge media.

53. The way to generate electricity from a fuel cell, including

bringing into contact the source of the raw material mixture gas containing ethanol, with a dehydrogenation catalyst at a temperature below approximately 400°in the reaction zone dehydrogenation, to obtain a mixture of products containing hydrogen, where the said dehydrogenation catalyst comprises copper on the surface of the metal carrier; the introduction of hydrogen from a mixture of food and oxygen in a fuel cell to produce electricity and exhaust of the fuel cell stream of gases containing methane; the introduction of exhaust from a fuel cell flow of flue gas and oxygen into the combustion chamber; the combustion exhaust from the fuel cell the flow of gases in the combustion chamber.

54. The method according to item 53, in which the raw gas mixture further comprises water.

55. The method according to item 54, in which the reaction zone dehydrogenation further comprises a catalyst for the conversion of water vapor, effective for catalysis of the reaction of conversion of water vapor between the carbon monoxide produced by degidio the project of ethanol, and water to form carbon dioxide and hydrogen.

56. The method according to § 55, in which the catalyst conversion of water vapor is separated from the catalyst dehydrogenation.

57. The method according to item 53, further comprising transferring heat of combustion generated in the combustion chamber to the reaction zone dehydrogenation.

58. The method according to item 53, further including the absorption of the energy of combustion for the generation of mechanical and/or additional electrical energy.

59. The method according to § 58, in which the energy of combustion from the said combustion chamber is used to drive a generator to generate additional electrical energy.

60. The method according to § 58, in which the dehydrogenation zone and the combustion chamber are part of the energy system of the vehicle, and/or the mechanical energy is used to propel the vehicle.

61. The method according to item 53, additionally comprising introducing into the combustion chamber separate source of fuel for the cold start burning source of fuel for cold starts in the presence of oxygen.

62. The method according to p, in which the exhaust from the fuel cell, the flow of gases and a source of fuel for cold start is injected into the combustion chamber of the internal combustion engine with the universal source of fuel, able is about to carry out the combustion of methane and/or a separate source of fuel for cold start.

63. The method according to item 62, in which the dehydrogenation zone and the source of the universal fuel of the internal combustion engine are part of the energy system of the vehicle, and the method further includes the absorption of the energy of combustion for the generation of mechanical and/or additional electrical energy and the use of the above mechanical energy and/or the electric energy for the propulsion of the vehicle.

64. The method according to item 53, in which the mentioned source of raw mixture of gases is in contact with the said dehydrogenation catalyst at a temperature of from about 250°up to about 300°C.

65. The method according to item 53, in which the dehydrogenation catalyst has a thermal conductivity at 300 K of at least about 50 W/m·K.

66. The method according to p, in which the dehydrogenation catalyst has a thermal conductivity at 300 K of at least about 70 W/m·K.

67. The method according to p, in which the dehydrogenation catalyst has a thermal conductivity at 300 K of at least about 90 W/m·K.

68. The method according to item 53, in which the dehydrogenation catalyst has a surface area from about 10 m2/g to about 100 m2/g, as measured by the method of brunauer-Emmett-teller.

69. The method according to p, in which the dehydrogenation catalyst has a surface area the tee from about 25 m 2/g to about 100 m2/g, as measured by the method of brunauer-Emmett-teller.

70. The method according to p, in which the dehydrogenation catalyst has a surface area from about 30 m2/g to about 80 m2/g, as measured by the method of brunauer-Emmett-teller.

71. The method according to item 53, in which the dehydrogenation catalyst contains at least about 10 wt.% copper.

72. The method according to p, in which the dehydrogenation catalyst contains from about 10 wt.% to about 90 wt.% copper.

73. The method according to item 53, in which a metal catalyst carrier for dehydrogenation contains a metal sponge.

74. The method according to p, in which the metal sponge media dehydrogenation catalyst has a surface area of at least about 10 m2/g, as measured by the method of brunauer-Emmett-teller.

75. The method according to p in which spongy metal carrier catalyst for dehydrogenation has a surface area of at least about 50 m2/g, as measured by the method of brunauer-Emmett-teller.

76. The method according to item 75, in which the metal sponge carrier of the catalyst for dehydrogenation has a surface area of at least about 70 m2/g, as measured by the method of brunauer-Emmett-teller.

77. The method according to p, in which a metallic porous media may contain Nickel.

78. SPO is about on p, in which a metallic porous medium contains at least about 50 wt.% Nickel.

79. The method according to p, in which a metallic porous medium contains at least about 85 wt.% Nickel.

80. The method according to p, in which the dehydrogenation catalyst contains from about 10 wt.% to about 80 wt.% copper.

81. The method according to item 80, in which the dehydrogenation catalyst contains from about 20 wt.% to about 45 wt.% copper.

82. The method according to item 80, in which the dehydrogenation catalyst contains from about 5 to about 100 μmol/g of Nickel on the surface of the above-mentioned catalyst.

83. The method according to p, in which the dehydrogenation catalyst contains from about 10 to about 80 µmol/g of Nickel on the surface of the above-mentioned catalyst.

84. The method according to p, in which the dehydrogenation catalyst contains from about 15 to about 75 µmol/g of Nickel on the surface of the above-mentioned catalyst.

85. The method according to item 53, in which the catalyst for the dehydrogenation imbedded on the surface of granular or monolithic substrate.

86. The method according to p, in which the catalyst for the dehydrogenation includes Nickel sponge media.

87. The method according to claim 1, wherein the obtaining of the reforming catalyst includes copper deposition on the metal sponge media.

88. The method according to p, in which copper is precipitated with the aid of the method, includes the electrochemical reaction of substitution between metal metal sponge carrier and copper ions.

89. The method according to p, in which copper is precipitated by using a method, which includes the deposition of metallic copper on the metal sponge media by the method of chemical recovery.

90. The method according to claim 1, wherein the base metal comprises copper and/or a metal other than copper selected from the group consisting of Nickel, cobalt, zinc, silver, palladium, gold, tin, iron, and mixtures thereof.

91. The method according to p, in which the base metal comprises copper and/or a metal other than copper selected from the group consisting of Nickel, cobalt and mixtures thereof.

92. The method according to p, in which the base metal includes Nickel.

93. The method according to claim 20, in which the original raw material mixture gas contains ethanol.

94. The method according to claim 1, in which the mixture of products of the reforming unit contains methane.

95. The method according to p, which includes the supply of methane obtained in a mixture of products of reforming, in the internal combustion engine.

96. The method according to p, which includes the supply of hydrogen in the mixture of products of reforming, in the internal combustion engine.

97. The method according to item 27, in which the mixture of products of the reforming unit contains methane.

98. The method according to p, which includes the supply of hydrogen in the mixture is of Reducto reforming, in the internal combustion engine.

99. The method according to p, which includes the supply of methane obtained in a mixture of products of reforming, in the internal combustion engine.

100. The method according to p, in which a metallic porous media are using the method, which includes the leaching of aluminum from an alloy containing aluminum and the base metal.

101. The method according to item 100, in which the base metal comprises copper and/or a metal other than copper selected from the group consisting of Nickel, cobalt, zinc, silver, palladium, gold, tin, iron, and mixtures thereof.

102. The method according to p, in which the base metal comprises copper and/or a metal other than copper selected from the group consisting of Nickel, cobalt, and mixtures thereof.

103. The method according to 102, in which the base metal includes Nickel.

Cab in § 38, in which the reforming catalyst contains copper coating at least partially covering the surface of the metal sponge media.

105. The method according to p, in which the obtaining of the reforming catalyst includes copper deposition on the metal sponge media.

106. The method according to p, in which copper is precipitated using a method comprising the electrochemical reaction of substitution between metal metal sponge carrier and copper ions.

107. The method according to p, what oterom copper precipitated by using method, includes the deposition of metallic copper on the metal sponge media by the method of chemical recovery.

108. The method according to p, in which a metallic porous media are using the method, which includes the leaching of aluminum from an alloy containing aluminum and the base metal.

109. The method according to p, in which the base metal comprises copper and/or a metal other than copper selected from the group consisting of Nickel, cobalt, zinc, silver, palladium, gold, tin, iron, and mixtures thereof.

110. The method according to p, in which the base metal comprises copper and/or a metal other than copper selected from the group consisting of Nickel, cobalt, and mixtures thereof.

111. The method according to p, in which the base metal includes Nickel.

112. The method according to p, in which the said dehydrogenation catalyst comprises a copper coating at least partially covering the surface of the metal sponge media.

113. The method according to p, in which the receiving catalyst includes copper deposition on the metal sponge media.

114. The method according to p, in which copper is precipitated using a method comprising the electrochemical reaction of substitution between metal metal sponge carrier and copper ions.

115. The method according to p, in which copper is precipitated with the aid of the method, includes the deposition of metallic copper on the metal sponge media using the method of chemical recovery.

116. Method of reforming alcohol, comprising bringing into contact the source of the raw material mixture gas containing alcohol, with a reforming catalyst, to obtain a mixture of products of reforming, with hydrogen, where the reforming catalyst produced using the method, which includes the deposition of copper on the metal sponge media.

117. The method according to p, in which copper is precipitated using a method comprising the electrochemical reaction of substitution between metal metal sponge carrier and copper ions.

118. The method according to p, in which copper is precipitated by using a method, which includes the deposition of metallic copper on the metal sponge media using the method of chemical recovery.

119. The method according to p, in which a metallic porous media may contain Nickel.

120. The method according to p, in which the raw gas mixture contains a primary alcohol selected from the group consisting of methanol, ethanol, and mixtures thereof.

121. The method according to p in which outgoing raw material mixture gas contains ethanol.

122. The method according to p, which referred to the original raw gas mixture is brought into contact with the said reforming catalyst in temp is the temperature below approximately 400° C.

123. The method according to p, in which the mixture of products of the reforming unit contains methane.

124. The method according to p, which includes the supply of methane obtained in a mixture of products of reforming, in the internal combustion engine.

125. The method according to p, which includes the supply of hydrogen in the mixture of products of reforming, in the internal combustion engine.

126. The method according to p, in which the structure of the metal sponge media was produced using the method, comprising leaching aluminum from an alloy containing aluminum and the base metal.

127. The method according to p, in which the base metal comprises copper and/or a metal other than copper selected from the group consisting of Nickel, cobalt, zinc, silver, palladium, gold, tin, iron, and mixtures thereof.

128. The method according to p, in which the base metal comprises copper and/or a metal other than copper selected from the group consisting of Nickel, cobalt, and mixtures thereof.

129. The method according to p, in which the base metal includes Nickel.

Priority items:

18.10.2002 - according to claim 1 and dependent claim 2 is 26, 87-96; p and dependent PP-129;

25.07.2003 - item 27 and dependent p-52; item 53 and dependent PP-86; 108-115.



 

Same patents:

Fuel cell system // 2326471

FIELD: heating.

SUBSTANCE: invention relates to fuel cell system, which is able to improve efficiency of fuel cells due to reaction acceleration. Enhancement of specific characteristics due to supply of ozone to the cathode of fuel cell stack is a technical result of the invention. According to the invention, fuel cell system consists of a fuel cell stack, including anode, cathode and electrolytic membrane, installed in between them, a fuel tank for supply of hydrogen-containing fuel to anode of the fuel cell stack, and an oxidiser supply unit aimed to add ozone to oxygen-containing air and, thus, providing delivery to the cathode of fuel cell stack. Respectively, ozone is supplied to the cathode of the fuel cell stack to speed up the reaction in the fuel cell stack and, thus, to obtain a comparatively high flow density.

EFFECT: enhancement of specific characteristics of fuel cells.

5 cl, 5 dwg

FIELD: chemistry.

SUBSTANCE: according to invention as fuel sources spray cans under pressure or without pressure can be used. Spray cans are applied with any fuel elements including fuel element directly on methanol or fuel element on reforming product. From one aspect fuel source can contain reaction chamber for fuel transformation to hydrogen. Besides fuel sources can include pump. Fuel source and be equipped with valve connecting fuel source to fuel element and hole for gas outlet from fuel element. Methods of various fuel sources formation are disclosed.

EFFECT: easy replacement and refuelling of fuel source.

38 cl, 20 dwg

FIELD: fuel elements.

SUBSTANCE: system of fuel elements consists of heat exchange unit, the sad unit controls temperature of fuel and/or air, supplied into the batteries unit. According to one variant of implementation, the fuel elements system includes reforming unit to generate a free hydrogen gas; the said unit supplies free hydrogen gas via a fuel supply pipeline. The reforming unit includes burner. The fuel elements system also includes batteries unit to generate electrical power as a result of electrochemical reaction between air and free hydrogen gas. The fuel elements system also includes the heat exchange unit. The heat exchange unit consists of case with a leak proof interior portion into which the exhaust gas, generated in a burner is supplied. A portion of the fuel supply pipeline runs through an interior portion of the case.

EFFECT: increase of service life.

10 cl, 6 dwg

FIELD: power installations incorporating electrochemical generator.

SUBSTANCE: proposed power installation has electrochemical generator incorporating oxygen supply line communicating with oxygen storage and treatment unit, water drain line communicating with water accumulation tank, hydrogen supply line communicating with hydrogen outlet line of water-activated chemical current supply with gas cushion incorporating soluble metal anode and inert catalytic cathode both installed in sealed tank filled with aqueous solution of electrolyte which is provided with electrolyte level sensor and communicates with water supply line and with solid-phase reaction product accumulation line, voltage converter whose inputs are connected to electric outputs of electrochemical generator and chemical current supply, outputs being connected to users. Newly introduced in power installation are at least two groups of reversible hydrogen storages with hydrogen filling and draining lines for alternate connection through controlled valves to line for hydrogen outlet from sealed-bowl gas cushion of water-activated chemical current supply and with hydrogen supply lines of electrochemical generator. Hydrogen storages are provided with heat-transfer surfaces connected via lines to coolant heating and cooling systems and accommodating valves affording alternate heat supply to one of hydrogen storage groups and heat transfer from other group; hydrogen storage filling line communicates with water admixture accumulating system through periodically opened valve. Hydrogen filling capacity of each group of hydrogen storages is not over 20% of that required to ensure desired rated capacity of power installation.

EFFECT: enhanced safety and functional efficiency of electrochemical generator.

2 cl, 2 dwg

FIELD: high-temperature fuel cells.

SUBSTANCE: proposed system of solid-state oxide fuel cells has set of solid-state oxide fuel cells and gas-turbine engine. Set of solid-state oxide fuel cells has plurality of solid-state oxide fuel cells, each incorporating electrolyte, anode, and cathode. Gas-turbine engine has compressor and turbine. Compressor is designed to feed oxidant to cathode. There are means for feeding fuel to anode and means for feeding part of unused oxidant from solid-state oxide fuel cells to cathodes. Facility for feeding at least oxidant has combustion chamber and ejector. Combustion chamber is designed to burn at least part of unused fuel coming from solid-state oxide fuel cells and to feed its products of combustion to oxidant supplied by compressor to cathodes for heating compressor-fed oxidant.

EFFECT: enhanced effectiveness of fuel cell system.

22 cl, 4 dwg

FIELD: power installations designed for electrical energy storage.

SUBSTANCE: proposed power installation built around fuel cells of hydrogen-oxygen energy storage has electrochemical generator and electrolysis unit disposed in common housing and pneumatically interconnected by means of oxygen and hydrogen lines with compressed oxygen and hydrogen cylinders connected to these lines, respectively, as well as reaction water container hydraulically coupled with electrochemical generator and electrolysis tank. Reaction water container is made in the form of hollow water-filled barrier dividing power installation housing into two parts of which one accommodates compressed hydrogen cylinder and other, compressed oxygen cylinder.

EFFECT: enhanced fire and explosion safety of power installation.

2 cl, 1 dwg

FIELD: power engineering.

SUBSTANCE: invention can be used in stationary power plants and in transport. Proposed power plant on fuel elements contains methane partial oxidation reformer, alkaline electrochemical generator with unit to clean air from carbon dioxide and fuel gas afterburner includes additionally series-connect unit to clean methane from carbon dioxide, drying unit, proportioner and gas mixer connected to unit for cleaning air from carbon dioxide whose output communicates with input of methane partial oxidation reformed whose outputs is connected with input of alkaline electrochemical generator through unit for cleaning gases from carbon dioxide, fuel gas afterburner being connected to output of electrochemical generator along fuel line. Natural gas is cleaned from carbon dioxide before reforming.

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3 cl, 1 dwg

FIELD: petrochemical industry; other industries; methods of production of the hydrogen for the fuel composition.

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EFFECT: the invention ensures the increased efficiency of the production process.

10 cl, 3 tbl, 3 ex

FIELD: power engineering; stationary and mobile power installations using electrochemical hydrogen-oxygen generators.

SUBSTANCE: proposed power installation built around electrochemical generators has oxygen storage and supply unit pneumatically communicating with electrochemical generator oxygen inlet, hydrogen receiver pneumatically communicating with electrochemical generator hydrogen inlet, hydrogen producer depending for its operation on exothermal hydrolysis reaction and provided with chemical agent feed system and drain valve, as well as water accumulation tank whose water line communicates with electrochemical generator and hydrogen producer; the latter is heat-insulated and its steam-hydrogen mixture outlet pneumatically communicates with inlet of steam-gas turbine unit introduced in power installation, its outlet being in communication with hydrogen receiver; the latter, in its turn, hydraulically communicates with water accumulation tank.

EFFECT: enhanced efficiency of power installation.

1 cl, 1 dwg

FIELD: fuel cells and batteries.

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3 cl, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention pertains to the method of obtaining porous substances on a substrate for catalytic applications, to the method of obtaining porous catalysts for decomposition of N2O and their use in decomposing N2O, oxidising ammonia and reforming methane with water vapour. Description is given of the method of obtaining porous substances on a substrate for catalytic applications, in which one or more soluble precursor(s) metal of the active phase is added to a suspension, consisting of an insoluble phase of a substrate in water or an organic solvent. The suspension undergoes wet grinding so as to reduce the size of the particles of the substrate phase to less than 50 mcm. The additive is added, which promotes treatment before or after grinding. A pore-forming substance is added and the suspension, viscosity of which is maintained at 100-5000 cP, undergoes spray drying, is pressed and undergoes thermal treatment so as to remove the pore-forming substance, and is then baked. Description is also given of the method of obtaining porous catalysts on a substrate for decomposing N2O, in which a soluble cobalt precursor is added to a suspension of cerium oxide and an additive, promoting treatment, in water. The suspension is ground to particle size of less than 10 mcm. A pore-forming substance, viscosity of which is regulated to approximately 1000 cP, is added before the suspension undergoes spray drying with subsequent pressing. The pore-forming substance is removed and the product is baked. Description is given of the use of the substances obtained above as catalysts for decomposition of N2O, oxidation of ammonia and reforming of methane with water vapour.

EFFECT: obtaining catalysts with homogenous distribution of active phases and uniform and regulated porosity for optimisation of characteristics in catalytic applications.

FIELD: chemistry.

SUBSTANCE: converter includes housing and devices for input oxygen enriched air, fed of vapour-hydrocarbon mix and bleeding of converted gas. The housing is provided with inner fikking designed as two cylindrical tubes installed one inside the other and forming with the converter housing two radial clearances: the outer clearance for input vapour-hydrocarbon mix and inner one for output of converted gas. At that the packing made of channeled plates is provided for inner fikking, this packing forms the channels of square section; the upper part (1/20-1/25) of channels is provided with perforation track, the middle part (1/5-1/6) of channels height located lower than perforation track is filled with catalyst used for primary and secondary hydrocarbon conversions; and the lowest part (1/6-1/8) of channels height is filled with catalyst used for preliminary hydrocarbon conversion. The device for input oxygen enriched air is positioned in the upper part of channels. The method is implemented in converter. Hydrocarbon material heating and converted gas cooling are carried out by the way of its passing through heat exchanger and mixing of hydrocarbon material with water vapour, then vapour-hydrocarbon mix is fed downstream through outer radial clearance and further it is delivered up the channels through catalyst bed for implementing of preliminary and primary conversions. Then through perforation track it is fed down the channels for converted gas oxidizing and secondary vapour conversion with subsequent converted gas upflow takeoff through inner radial clearance.

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2 cl, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to two methods (two variants) of reforming process using oxidizing gas at temperature 980-1000°C. The recirculation of the flow part outgoing from the autothermic reformer to the flowrate vapour-hydrocarbon is described at that the said recirculation is implemented throught the instrumentality of thermocompressor ejector using heated beforehand supplied mix as operative fluid. For the optimization of general configuration the mole ratio of recirculating synthesis gas and operative fluid was chosen in the range 0.2-1.0. In order to prevent the carbon black formation in the reforming process recirculated hydrogen and vapour are fed to the input flow and the temperature of feeding is increased. Since there is a certain pressure drop between initial mixture of vapour and natural gas and the mix fed to reformer it is necessary to increase the pressure of initial mixture but it is compensated with the lower pressure drop in the heater and other equipment laid out upstream and downstream because of decreasing of vapour capacity.

EFFECT: reforming process is carried out without carbon black formation.

27 cl, 2 dwg, 1 tbl

FIELD: chemistry; processing of hydrocarbon material to synthesis gas.

SUBSTANCE: porous ceramic catalytical module represents the product of exothermic finely dispersed nickel-aluminium mixture exposed to vibration compaction and to sintering. The said product contains: nickel 55.93-96.31 Wt%; aluminium 3.69-44.07 Wt%. Porous ceramic catalytical module may contain up to 20 Wt% (based on the module weight) of titanium carbide as well as catalytic coating including following groups: La and MgO, or Ce and MgO, or La, Ce and MgO, or ZrO2, Y2O3 and MgO, or Pt and MgO, or W2O5 and MgO in quantity 0,002-6 Wt% based on the module weight synthesis gas is produced by conversion of methane and carbon dioxide mixture on porous ceramic catalytical module in filtration mode The process conditions are as follows: temperature 450-700°C, pressure 1-10 atm, rate of CH4-CO2 mixture delivery to catalytical module 500-5000 l/dm3*hr.

EFFECT: inventions permit to carry out the process at lower temperatures.

5 cl, 37 dwg

FIELD: hydrogen production processes.

SUBSTANCE: invention relates to catalysts for hydrolysis of hydride compounds to produce pure hydrogen for being supplied to power installations, including fuel cells. Invention provides catalyst for production of hydrogen from aqueous or water-alkali solutions of hydride compounds containing platinum group metal deposited on complex lithium-cobalt oxide and, additionally, modifying agent selected from series: titanium dioxide, carbon material, oxide of metal belonging to aluminum, magnesium, titanium, silicon, and vanadium subgroups. According to second variant, catalyst contains no platinum group metal. Described are also catalyst preparation method (variants) and hydrogen generation process, which is conducted at temperature no higher than 60°C both in continuous and in periodic mode. As hydrogen source, sodium borohydride, potassium borohydride, and ammine-borane can be used.

EFFECT: increased catalyst activity at environmental temperatures (from -20 to 60°C), prolonged time of stable operation of catalytic system, and reduced or suppressed platinum metals in composition of catalyst.

14 cl, 1 tbl, 20 ex

FIELD: method and torch for producing synthesis gas at decomposition of liquid hydrocarbons such as oil and natural gas at elevated temperatures without usage of catalyst by CO and hydrogen.

SUBSTANCE: method is realized by partial oxidation of liquid and solid combustible materials at presence of oxygen and oxygen containing gases. Fuel, oxygen-containing gas and atomizing fluid are fed to torch separately. Atomizing fluid is expanded just in front of inlet opening for fuel by means of one or several nozzles providing speed of atomizing fluid in range 20 - 300 m/s. Relation of diameter of outlet opening of nozzle for liquid fuel to diameter of opening of nozzle for atomizing fluid is in range 1/1.1 - 1/5.

EFFECT: possibility for simplifying process.

2 dwg, 2 ex

FIELD: method for producing synthetic gas, which may be used in oil chemistry for producing motor fuels.

SUBSTANCE: method includes processing of biogas under temperature of 1420-1800°C and following cooling of resulting synthetic gas. Thermal processing of biogas is performed in liquid heat carrier with ratio of volume of liquid heat carrier to volume of barbotaged gas, equal to 10-100 during 0,3-2 seconds, or in boiling layer of solid particles, where the speed of biogas is selected to be greater than minimal speed of fluidization.

EFFECT: increased purity of produced synthetic gas.

8 cl, 6 ex

FIELD: alternative fuels.

SUBSTANCE: invention relates to catalysts and process of steam conversion of hydrocarbons to produce synthesis gas. Proposed catalyst for steam conversion of hydrocarbons contains nickel oxide (4.0-9.2%) and magnesium oxide (4.0-6.5%) supported by porous metallic nickel (balancing amount). Carrier has specific surface area 0.10-0.20 m2/g, total pore volume 0.07-0.12 cm3/g, predominant pore radius 1-30 μm, and porosity at least 40%. Described are also catalyst preparation method and generation of synthesis gas via steam conversion of hydrocarbons.

EFFECT: increased heat conductivity of catalyst resulting in stable activity in synthesis gas generation process.

8 cl, 1 tbl, 5 ex

FIELD: production of synthesis-gas.

SUBSTANCE: proposed method is carried out at temperature of 750-900 C due to external heating of tubular furnace reaction tubes filled with catalyst; mixture of natural gas and superheated steam is fed to reaction tubes. External heating of reaction tubes filled with catalyst is first performed by burning the natural gas in air; after attaining the required mode of operation, external heating is carried out by burning the synthesis-gas fed from tubular furnace outlet to reaction tube external heating chamber. Device proposed for realization of this method includes tubular furnace with reaction tubes filled with catalyst, chamber for mixing the natural gas with superheated steam and external heating chamber for heating the reaction tubes filled with catalyst for maintenance of conversion process; heating chamber is provided with air inlet. Device is also provided with gas change-over point whose one inlet is used for delivery of natural gas fed to chamber of external heating tubular furnace reaction tubes during starting the mode of steam conversion process; other inlet of gas change-over point is used for delivery of synthesis-gas from tubular furnace outlet through distributing synthesis-gas delivery point. Device is also provided with regulator for control of delivery of synthesis-gas to reaction tube external heating chamber required for combustion.

EFFECT: enhanced economical efficiency of process.

3 cl, 1 dwg

FIELD: steam catalytic conversion of natural gas into synthesis-gas with the use of thermal and kinetic energy of synthesis-gas.

SUBSTANCE: proposed method includes external heating of reaction tubes of tubular furnace filled with nickel catalyst on aluminum oxide substrate by passing mixture of natural gas and superheated steam through them. External heating of reaction tubes filled with catalyst is performed by burning the natural gas in air at exhaust of flue gases from heating zone. After tubular furnace, the synthesis-gas is directed to gas turbine for utilization of thermal and kinetic energy; gas turbine rotates electric generator; then, synthesis-gas is directed to synthesis-gas burner of electric power and heat supply system; flue gases from external heating zone are directed to heat exchangers for preheating the natural gas and steam before supplying them to reaction tubes of tubular furnace. Device proposed for realization of this method includes sulfur cleaning unit, tubular furnace with reaction tubes filled with nickel catalyst on aluminum oxide substrate with inlet for gas mixture of natural gas and superheated steam; device also includes external heating zone for reaction tubes with flue gas outlet and gas burner for external heating of reaction tubes of tubular furnace with inlet for natural gas and air. For utilization of thermal and kinetic energy of synthesis-gas, device is provided with gas turbine and electric generator at tubular furnace outlet and synthesis-gas burner of electric power and heat supply system; device is also provided with heat exchangers for preheating the natural gas and steam before supplying them to tubular furnace.

EFFECT: improved ecological parameters; enhanced power efficiency of process.

3 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention pertains to the method of obtaining porous substances on a substrate for catalytic applications, to the method of obtaining porous catalysts for decomposition of N2O and their use in decomposing N2O, oxidising ammonia and reforming methane with water vapour. Description is given of the method of obtaining porous substances on a substrate for catalytic applications, in which one or more soluble precursor(s) metal of the active phase is added to a suspension, consisting of an insoluble phase of a substrate in water or an organic solvent. The suspension undergoes wet grinding so as to reduce the size of the particles of the substrate phase to less than 50 mcm. The additive is added, which promotes treatment before or after grinding. A pore-forming substance is added and the suspension, viscosity of which is maintained at 100-5000 cP, undergoes spray drying, is pressed and undergoes thermal treatment so as to remove the pore-forming substance, and is then baked. Description is also given of the method of obtaining porous catalysts on a substrate for decomposing N2O, in which a soluble cobalt precursor is added to a suspension of cerium oxide and an additive, promoting treatment, in water. The suspension is ground to particle size of less than 10 mcm. A pore-forming substance, viscosity of which is regulated to approximately 1000 cP, is added before the suspension undergoes spray drying with subsequent pressing. The pore-forming substance is removed and the product is baked. Description is given of the use of the substances obtained above as catalysts for decomposition of N2O, oxidation of ammonia and reforming of methane with water vapour.

EFFECT: obtaining catalysts with homogenous distribution of active phases and uniform and regulated porosity for optimisation of characteristics in catalytic applications.

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