• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A method for preparing a catalyst, catalyst, and process for carrying out a steam reforming reaction A method is described for preparing a catalyst suitable for use in a steam reforming process, which comprises the steps of: (i) spraying a a slurry containing a particulate catalyst compound comprising one or more catalytic metals selected from the group g which consists of ni, cu, pt, pd, rh, ru, and au on the surface of a support formed in a pan coater to form a coated shaped support material having the catalytic metal on a surface layer, (ii) drying and optionally calcining the coated shaped support material to form a catalyst precursor, and (iii) optionally reducing the metal or materials in the catalyst precursor to a lower oxidation state to form the catalyst. use of eggshell catalyst to perform a steam reforming reaction.
    公开号:BR112013020271B1
    申请号:R112013020271
    申请日:2012-02-06
    公开日:2019-11-05
    发明作者:Robert Feaviour Mark
    申请人:Johnson Matthey Plc；
    IPC主号:
    专利说明:

    "METHOD FOR PREPARING A CATALYST SUITABLE FOR USE IN A STEAM REFORM PROCESS" [0001] This invention relates to a method for preparing supported catalysts suitable for use in steam reforming processes.
    [0002] Steam reforming, whereby a hydrocarbon feed load such as natural gas or naphtha, or methanol, is reacted with steam at high temperature and pressure to generate a gas mixture containing hydrogen, known as gas of synthesis, is well established. Hydrocarbon steam reforming catalysts typically are based on nickel catalysts supported directly on formed refractory metal oxide supports such as calcium or magnesium aluminate or alpha alumina. In smaller scale steam reform processes, for example, in the production of hydrogen gas mixtures for fuel cells, or in the generation of biomass from biomass, precious metal catalysts such as Rh or Pt catalysts can be used. For steam reforming of methanol, Cu or Pd catalysts can be used.
    [0003] These catalysts are typically prepared using an impregnation / calcination technique whereby the active metal is applied to a porous support as an aqueous solution, usually from metal nitrate, followed by calcination to convert metallic nitrate to metal oxide corresponding. Before use, metal oxide is reduced, typically with a hydrogen-containing gas to generate the active catalyst. Impregnation techniques have become widely used, but there is a need to make the use of catalytically active metal more efficient, both in order to minimize the cost of production and to reduce NOx Emissions from nitrate based catalysts.
    [0004] An alternative method has been found to overcome the problems of previous preparation routes.
    Petition 870190068000, of 07/18/2019, p. 10/26 / 13 [0005] Therefore, the invention provides a method for preparing a catalyst suitable for use in a steam reforming process comprising the steps of:
    (i) spray a slurry containing a particulate catalyst compound, which comprises one or more catalytic metals selected from the group consisting of Ni, Cu, Pt, Pd, Rh, Ru and Au, on the surface of a support formed in a coating coater pan to form a coated shaped support material, (ii) drying and optionally calcining the coated shaped support material to form a catalyst precursor having the catalytic metal in a surface layer, and (iii) optionally reducing the metal or metals in the catalyst precursor to a lower oxidation state to form the catalyst. [0006] The invention also provides catalysts obtainable through the above method and the use of such catalysts to carry out a catalytic steam reforming reaction.
    [0007] The invention provides a means for producing coated catalysts particularly suitable for limited pore diffusion reactions such as steam reforming reactions.
    [0008] The particulate catalyst compound in the coating applied to the shaped support comprises one or more catalytically active metals selected from the group consisting of Ni, Cu, Pt, Pd, Rh, Ru and Au. Catalysts comprising one or more of Ni, Pt and Rh are preferred. Thus, in one embodiment, the catalytic metal in the particulate catalyst compound comprises Ni, optionally with one or more of Pt, Pd, Rh, Ru and Au. In another embodiment, the catalytic metal consists of Rh. In another embodiment, the catalytic metal in the particulate catalyst compound comprises Pt, optionally with one or more of Pd, Rh, Ru and Au, preferably comprising Pt and Rh, wherein the weight ratio of
    Petition 870190068000, of 07/18/2019, p. 11/26 / 13
    Pt: Rh is in the range of 1: 1 to 6: 1, preferably from 2: 1 to 4: 1. In yet another embodiment, the catalytic metal in the particulate catalyst compound comprises Cu, optionally with one or more of Pt, Pd, Rh, Ru and Au.
    [0009] The particulate catalyst compound in the coating applied to the shaped support may comprise an oxide, hydroxide or carbonate of the catalytically active metal, such as NiO, CuO or PtO. Thus, the particulate catalyst compound may comprise a mixed oxide such as CuO-ZnO-Al2O3, NiO-AhO3, NiO-MgO-SiO2, NiO-MgO-SiO2-Al2O3 or NiO-MgO-SiO2-CaO-Al2O3, which can be formed, for example, through coprecipitation. In this way, conventional reforming catalyst formulations can be prepared in powder form and applied as a coating on the shaped support. However, preferably, the particulate catalyst compound comprises one or more metals selected from the group consisting of Ni, Cu, Pt, Pd, Rh, Ru and Au dispersed on the surface of a particulate catalyst support material. In this way, the slurry can be formed from a particulate catalyst support that carries one or more of the catalytically active metals. Suitable particulate catalyst support materials are oxides such as alumina, titania, zirconia, lanthania, magnesia, ceria, preferably zirconia stabilized with lanthania, yttria or ceria; metallic aluminates such as calcium aluminate and magnesium aluminate; and mixtures thereof. Zinc oxide can also be used, especially with alumina, for copper or palladium catalysts. Particularly preferred particulate catalyst support materials comprise alumina and / or stabilized zirconia, for example, alumina materials stabilized with lanthania, ceria-zirconia-alumina, ceriatitania-alumina and ceria-magnesia-alumina. The particles of the particulate catalyst support preferably have an average particle size in the range of 1 to 80 pm, preferably 1 to 50 pm. Metals dispersed on the surface of the catalyst support material
    Petition 870190068000, of 07/18/2019, p. 12/26 / 13 particles are preferably catalytic metal crystals or catalytic metal oxide with an average crystallite particle size in the range of 5 to 50 nm as determined by XRD. The metal contents in the supported composition used to form the slurry can be in the range of 0.1 to 50% by weight. Due to their different activities, preferably precious metals such as Pt, Pd, Rh, Ru and Au are present in an amount in the range of 0.1 to 5% by weight, and Ni or Cu present in an amount in the range of 10 to 75% by weight.
    [00010] The catalytic metal or metals can be dispersed on the surface of the particulate catalyst support material through conventional impregnation of the soluble metal catalyst compounds on the particulate catalyst support followed by drying and calcination to convert the catalytic metal compound or compounds their respective oxides. Alternatively, the metal or catalytic metals can be dispersed on the surface of the particulate catalyst support material through precipitation, using metallic sols or through deposition-precipitation methods using metal amine salts that deposit insoluble metal compounds on the particulate catalyst support. of the solution on heating.
    [00011] Through the use of catalytic metals dispersed on the surface of a particulate catalyst support it is possible to produce catalysts with an improved area and surface activity on catalysts supported in conventional impregnated refractory oxide which are calcined at high temperature. To form the slurry, the particulate catalyst compound is dispersed in a liquid medium, which is desirably aqueous. The solids content of the slurry can suitably be in the range of 10 to 60% by weight. The slurry can be suitably formed using milling techniques used in the preparation of the catalyst coating layer. Binding materials such as suns
    Petition 870190068000, of 07/18/2019, p. 13/26 / 13 alumina or hydrated alumina can be included in the layer and other conventional preparation techniques can be applied, such as grinding and mixing the dispersion to obtain the desired particle size before coating the support. In a preferred embodiment, polyethylene graft polymers such as Kollicoat ® are included in the slurry. These materials, which were used in the pharmaceutical tablet coating, decrease the surface tension of the coating layer, thereby increasing the formation of moisture and droplets in the spray, and provide a degree of plasticity to the coating allowing it to resist the friction that occurs in the coating process itself.
    [00012] The shaped support is in the form of shaped units such as extrudates, pellets or granules, which can be prepared from powder support materials, which can also comprise lubricants or binders. Extrudates and pellets are preferred shaped supports. Extrudates, pellets or granules can be commercially available or are readily prepared from suitable powders using methods known to those skilled in the art.
    [00013] The shaped supports can be a variety of shapes and particle sizes, depending on the mold or matrix used in their manufacture. For example, the units can be in the form of spheres, cylinders, rings, or units with multiple holes (for example, from 2 to 10 through holes), which can be multilobulated or fluted, for example, cross section of clover leaf . So-called “wagon wheels” can also be used. The extrudates or pellets can be cylindrical, that is, circular in cross section, but are preferably lobulated or fluted to increase their geometric surface area without increasing the pressure drop through a layer formed of the units. This has the advantage that the pressure drop across the catalyst is reduced while maintaining a satisfactory geometric surface area. At
    Petition 870190068000, of 07/18/2019, p. 14/26 / 13 shaped units can be selected to provide high crushing strength combined with a high geometric surface area and low pressure drop. In this regard, 4-hole tetralobic fluted shaped units and 5-hole pentalobal units are preferred. Shapes that have a larger internal volume, such as the so-called wagon wheels, can reduce the loss of the catalyst coating by friction and thus can be particularly useful.
    [00014] The invention allows forms of high amount of empty space, high geometric surface area, and low pressure drop would normally be considered unsuitable for use. This is because it is possible to calcine or burn the shaped supports to very high temperatures, for example,> 900 ° C, to obtain the necessary crushing force without ruining the porosity and the surface area of the catalytic metal crystallite as would be the case with the impregnated catalysts. The required porosity and the surface area of the catalyst are provided by including the metal in the subsequently applied coating which is dried and optionally calcined at lower temperatures. In this way, the method allows both strength and catalytic activity to be maximized.
    [00015] The shaped units desirably have a smaller unit dimension, preferably in the range of 1 mm to 50 mm. The smallest dimension can be the width, for example, diameter or length, for example, height. Shaped units can be from 1 mm to 50 mm in length, preferably from 1.2 mm to 25 mm. The width or transverse diameter of the shaped units can be from 1 mm to about 25 mm, preferably from 1.2 mm to 10 mm, particularly from 1.2 mm to 5 mm. The aspect ratio, i.e., the widest dimension divided by the smallest dimension, for example, length / transverse, is preferably less than 10, more preferably less than 5, even more preferably 2.
    Petition 870190068000, of 07/18/2019, p. 15/26 / 13 [00016] The shaped support is preferably made of a refractory oxide such as alumina, magnesia, ceria, titania or zirconia, calcium aluminate or magnesium aluminate; and mixtures thereof, including layered structures in which the shaped support comprises two or more support oxides in a layered arrangement. Shaped supports of alpha alumina and calcium or magnesium aluminate are particularly preferred.
    [00017] The catalytic metal is present within a layer on the surface of the shaped support. The layer can be applied to the particulate units formed by spraying the slurry onto the heated shaped drum support units, shaped drum support units in a pot liner, which can be of the type used in the pharmaceutical or food industry for prepare coated tablet products. Such a device is commercially available. Multiple sprayers can be applied with drying between spraying. The slurry is preferably applied to the substrates at temperatures ranging from 30 to 60 ° C, preferably from 30 to 50 ° C. In this way, the support is not excessively moistened and the possibility of spray drying the slurry is avoided.
    [00018] The resulting coated shaped support material is then dried. The drying step can be carried out at 20 to 150 ° C, preferably from 20 to 120 ° C, more preferably from 95 to 110 ° C, in the air or under an inert gas such as nitrogen, or in a vacuum oven for one period as needed up to 24 hours.
    [00019] The thickness of the layer containing the catalytically active metal in the dried material is preferably in the range of 5 to 250 pm (micrometers), but is more preferably in the range of 50 to 250 micrometers, even more preferably from 10 to 200 micrometers. The thinner layers make the use of the applied metal more efficient. The layer thickness
    Petition 870190068000, of 07/18/2019, p. 16/26 / 13 containing catalytic metal can be determined using methods known to those skilled in the art, such as optical microscopy or electron probe analysis.
    [00020] In an embodiment of the invention, multiple layers are applied to the shaped support. In particular, one or more intermediate layers can be arranged between the surface catalyst layer and the shaped support. Such intermediate layers can be non-catalyzed and preferably comprise a material with an intermediate thermal expansion coefficient falling between that of the shaped support and that of the catalyst coating layer layer. In this way, the loss of the catalyst layer of the support formed by thermal shock or friction can be reduced. Alternatively, a barrier layer can be applied to the catalyst to improve chemical compatibility, particularly for high temperature applications.
    [00021] If desired, dry catalyst precursors can be calcined, that is, heated to temperatures above 250 ° C, for example, from 250 to 900 ° C in the air or in an inert gas such as nitrogen to convert any compounds non-oxide metal on the support surface conformed to its respective oxides and to burn any organic component such as Kollicoat that may be present in the slurry.
    [00022] The catalytic metal in the precursor surface layer can comprise a mixed oxide or a coating having a perovskite, pyrochlor, hydrotalcite or double layer hydroxide structure.
    [00023] The dry or calcined catalyst precursor can then be supplied to the steam reforming vessel. If reducible metals are present, the catalyst precursor is desirably reduced to generate the reduced active catalyst in situ. Alternatively, the catalyst can preferably be supplied in the “pre-reduced” form, where the precursor of dry or calcined catalyst is subjected to a reduction step so
    Petition 870190068000, of 07/18/2019, p. 17/26 / 13 that at least part of the reducible metal is transformed into the elementary “zero-valiant” state.
    [00024] In this way, a reduction step can be carried out by passing a gas containing hydrogen such as hydrogen, synthesis gas or a mixture of hydrogen with nitrogen or other inert gas over the dry or calcined catalyst precursor at elevated temperature, for example , passing the gas containing hydrogen over the composition at temperatures in the range of 200 to 600 ° C, preferably for between 1 and 24 hours at atmospheric or higher pressures of up to about 25 bar.
    [00025] Catalysts having metals in elementary or zerovalent state can be difficult to handle while they can react spontaneously with oxygen in the air, which can lead to undesirable self-heating and loss of activity. Consequently, the reduced nickel and copper catalysts suitable for steam reforming processes are preferably protected by passivating the surface of the reduced metal with a thin layer of oxide. These can be produced by treating the reduced catalyst with a gas mixture of diluted air / nitrogen, diluted oxygen / nitrogen or CO2 using known techniques.
    [00026] The catalysts prepared according to the invention can be used in reform processes such as primary steam reform, secondary reform of a primary reformed gas mixture, autothermal reform and pre-reform. Catalysts can also be used to reform through partial catalytic oxidation, either alone or in combination with steam reforming. Catalysts can also be used for methanation reactions and hydrogenation reactions.
    [00027] In reform, a hydrocarbon, typically a gas containing methane such as natural gas, or naphtha, or a liquid fuel such as methanol, diesel ethanol, gasoline or liquefied petroleum gas (LPG), is reacted with steam and / or , where appropriate, carbon dioxide, on a material
    Petition 870190068000, of 07/18/2019, p. 18/26 / 13 catalytically active to produce a gas containing hydrogen and carbon oxides. The reactions that produce hydrogen are:
    CH4 + H2O θ CO + 3H2 “CH2” + H2O CO + 2H2 (“CH2” represents hydrocarbons larger than methane, for example, normally gaseous hydrocarbons and normally liquid hydrocarbons boiling up to 200 ° C). Analogous reactions with carbon dioxide can be carried out separately or with the reaction with steam.
    CH4 + CO2 2CO + 2H2 "Cl 12" + CO2 2CO + H2 [00028] Methanol reacts with steam according to the following equation.
    CH3OH + H2O CO2 + 3H2 [00029] The steam reform reactions are strongly endothermic and the process is especially suitable when they are carried out with external heating as in the tubular steam reform. Alternatively, heat can be provided by heating the reactants and passing steam over the catalyst in an adiabatic bed or in a process in which oxygen is also a reagent, so that the heat involved in oxidation is absorbed through reform reactions endothermic steam. The hybrid process can be applied to the product of the tubular or adiabatic process, that is, in the “secondary reform”, or to the fresh feed load (“partial catalytic oxidation” or “autothermal reform”). In the autothermal reform, oxygen and steam can be reacted simultaneously with the hydrocarbon on the reform catalyst or the reform catalyst can be disposed downstream of a non-catalytic partial combustion step.
    [00030] Catalysts can also be used in the reforming of gasification effluents from coal or biomass to reform methane and higher hydrocarbons, including tars in the gas streams that
    Petition 870190068000, of 07/18/2019, p. 19/26 / 13 comprise hydrogen and carbon oxides.
    [00031] For the production of hydrogen containing synthesis gas from natural gas or naphtha using nickel or precious metal catalysts, the outlet temperature is preferably at least 500 ° C. While the temperature with Ni catalysts is generally in the range of 750 to 900 ° C to manufacture synthesis gas for the production of ammonia or methanol, this can be as high as 1100 ° C for the production of metallurgical reduction gas, or as low as 700 ° C for the production of lighting gas. For the hybrid process using oxygen, the temperature can be as high as 1300 ° C in the hottest part of the catalyst bed. The reform of methanol on copper or palladium catalysts is preferably carried out at lower temperatures, in the range of 200 to 250 ° C.
    [00032] The pressure in steam reforming processes is typically in the range of 1 to 50 bar abs., But pressures up to 120 bar abs. are proposed. An excess of steam and / or carbon dioxide is normally used, especially in the range of 1.5 to 6, for example 2.5 to 5 mol of steam or carbon dioxide per gram of carbon atom in the starting hydrocarbon. [00033] In the catalytic reform of a gasifying effluent containing methane and higher hydrocarbons, including tars, the gasifying effluent containing steam can be treated in one or more steps using the catalysts of the present invention. For example, a supported Rh catalyst or a supported Pt / Rh catalyst can be used alone or downstream of a supported Ni reform catalyst to reform both tars and methane in the gasification effluent. Preferably, the solids containing powder and / or carbon are separated from the gas before the reform step, for example, by physical methods such as cyclones, filters, scrubbers or deflectors. Since catalysts are stable at high temperatures, they can be used directly after gasification without cooling the gasification effluent, but because it has a high activity,
    Petition 870190068000, of 07/18/2019, p. 20/26 / 13 this can also be used after some cooling of the effluent has occurred. The reforming of the gasification effluent is preferably carried out at temperatures in the range of 500 to 1,000 ° C in the pressure of the gasification effluent. [00034] The invention will now be described with reference to the following examples and Figures 1 and 2. Figure 1 is an optical micrograph of a catalyst precursor prepared according to the method of Example 1. Figure 2 is a diagram of the conversion of the methane vs temperature for the catalyst of Example 1 and a comparative method catalyst.
    [00035] Pellet coating was performed using a Profile Automation Pilot XT bench top ventilated pan coater. The coating was applied with a spray nozzle feed through a peristaltic pump (Watson Marlow 101U / R) which provides the coating layer to the pan coater through silicone tubes (5 mm id). [00036] The slurries were pre-ground using an Eiger Torrence minimotor 250 mill using 1 mm YSZ beads as the grinding medium. The particle size distribution was measured using a Malvern Mastersizer laser diffraction particle size analyzer.
    [00037] The pH of the slurry was measured using a Jenway 370 pH meter and the solids content of the slurry was measured using a Sartorius MA45 + solid content balance Example 1: Catalyst preparation [00038] A 2% powder Rh / 30% Ce ^, 75Zr at 25O2-70% AhO 3 (470 g) was dispersed in demineralized water to make a 45% solids slurry. This was ground for 8 minutes at 350 rpm and a resulting D50 of 2.2 microns was obtained. The pH of 478 g of coating layer was adjusted from 6.7 (natural) to 4.0 by adding acetic acid and Dipseral P3 alumina (Sasol) was added (21.5 g) followed by mixing with a top of high shear in a Silverson (20 minutes at about 3000 rpm). Kollicoat IR (17.6 g (8% by weight of catalyst)
    Petition 870190068000, of 07/18/2019, p. 21/26 / 13 previously dissolved in demineralized water (150 ml) was added and the final weight of the covering layer was 7 05 g. 388 g of this coating layer were applied to 1 l (1180 g) of alpha-alumina tablets in the form of a clover leaf in a pan coater. The coating parameters were as follows, inlet T (50 ° C), pan speed (20 rpm), pump speed (18 rpm), pan depression (-30 Pa). The coating took 29 minutes. The product was calcined at 500 ° C for 2 hours. The resulting catalyst layer was 100 to 150 microns thick.
    [00039] Figure 1 represents the catalyst precursor, having a catalyst containing an outer catalyst layer in a shaped alpha alumina core.
    Example 2: Test [00040] The coated pellets of Example 1 were tested for steam methane reforming activity. 24 pellets plus 24 uncoated pellets were placed in a large 1 ”x 2.2” (2.54 x 5.58 cm) diameter reactor tube. The steam methane reform was carried out in a vapor: carbon ratio of 3.25 at a pressure of 1 atm.
    [00041] Figure 2 compares a 0.2% Rh / CaAl2O4 catalyst prepared by conventional incipient moisture impregnation using a Rh Nitrate solution with the above-coated catalyst (indicated as 2Rh / CZA). The incipient moisture catalyst has Rh dispersed across the surface of the support at a depth of up to 500 micrometers, considering that the coated catalysts prepared in the pan coater have an outer layer containing Rh. The pan-coated catalyst, with a 0.15% Rh load, surpassed the comparative impregnated catalyst in terms of methane conversion across the investigated total temperature range, despite having a significantly lower Rh content.
    权利要求:
    Claims (14)
    [1]
    1. Method for preparing a catalyst suitable for use in a steam reforming process, characterized by the fact that it comprises the steps of:
    (i) spray a slurry containing a particulate catalyst compound, which comprises one or more catalytic metals selected from the group consisting of Ni, Pt, Pd, Rh, Ru and Au, on the surface of a support shaped in a pan coater for form a shaped shaped support material having the catalytic metal in a surface layer, wherein the particulate catalyst compound comprises one or more metals selected from the group consisting of Ni, Pt, Pd, Rh, Ru and Au dispersed on the surface of a particulate catalyst support material and the solids content of the slurry is in the range of 1 to 60% by weight; and (ii) drying and optionally calcining the coated shaped support material to form a catalyst precursor; and (iii) optionally reducing the metal or metals in the catalyst precursor to a lower oxidation state to form the catalyst.
    [2]
    2. Method according to claim 1, characterized in that the catalytic metal in the composite particulate catalyst compound comprises Ni, optionally with one or more of Pt, Pd, Rh, Ru and Au.
    [3]
    Method according to claim 1, characterized in that the catalytic metal in the particulate catalyst compound comprises Pt, optionally with one or more of Pd, Rh, Ru and Au, preferably Pt with Rh.
    [4]
    Method according to claim 1, characterized in that the catalytic metal in the particulate catalyst compound consists of Rh.
    [5]
    Method according to any one of claims 1 to
    Petition 870190068000, of 07/18/2019, p. 23/26
    2/3
    4, characterized by the fact that the particulate catalyst compound comprises a catalytically active metal oxide, hydroxide or carbonate.
    [6]
    A method according to any one of claims 1 to
    5, characterized by the fact that the particulate catalyst support material is selected from the group consisting of alumina, titania or zirconia, zinc oxide, lanthania, magnesia, ceria, metallic aluminates and mixtures thereof.
    [7]
    Method according to any one of claims 1 to
    6, characterized by the fact that the particulate catalyst support material comprises stabilized alumina and / or zirconia.
    [8]
    Method according to any one of claims 1 to
    7, characterized by the fact that one or more intermediate layers are applied between the shaped support and the catalytic surface layer.
    [9]
    Method according to any one of claims 1 to
    8, characterized by the fact that the shaped support comprises extrudates, pellets or granules.
    [10]
    Method according to any one of claims 1 to 9, characterized in that the shaped support has a length of 1 mm to 50 mm, and a width or transverse diameter of 1 mm to 25 mm.
    [11]
    Method according to any one of claims 1 to 10, characterized in that the shaped support is a refractory oxide comprising a support oxide selected from the group consisting of alumina, ceria, magnesia, titania or zirconia, aluminum calcium or magnesium aluminate; and mixtures thereof.
    [12]
    Method according to any one of claims 1 to 11, characterized in that the shaped support is calcium or magnesium aluminate or alpha alumina.
    [13]
    13. Method according to any one of claims 1
    Petition 870190068000, of 07/18/2019, p. 24/26
    3/3 to 12, characterized by the fact that the support is coated at a temperature in the range of 30 to 60 ° C.
    [14]
    Method according to any one of claims 1 to 13, characterized in that the thickness of the layer containing the catalytically active metal in the dry material is in the range of 5 to 250 pm.
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    同族专利:
    公开号 | 公开日
    JP2014507274A|2014-03-27|
    EP2675561A1|2013-12-25|
    WO2012110781A1|2012-08-23|
    CN103442803A|2013-12-11|
    JP2017013049A|2017-01-19|
    JP5955868B2|2016-07-20|
    BR112013020271B8|2019-12-10|
    JP6247344B2|2017-12-13|
    CN106362735B|2019-07-02|
    US20140005042A1|2014-01-02|
    US9511351B2|2016-12-06|
    RU2580548C2|2016-04-10|
    RU2013142164A|2015-03-27|
    EP2675561B1|2019-10-02|
    BR112013020271A2|2016-10-18|
    GB201102502D0|2011-03-30|
    CN106362735A|2017-02-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS5355492A|1976-10-29|1978-05-19|Kobe Steel Ltd|Pellet-like catalyst|
    DE2805801C2|1978-02-11|1989-09-07|Driam Metallprodukt Gmbh & Co Kg, 7991 Eriskirch, De|
    DE3125062C2|1981-06-26|1984-11-22|Degussa Ag, 6000 Frankfurt|Process for the production of abrasion-resistant coated catalysts and the use of a catalyst obtained in this way|
    JP3307976B2|1992-02-07|2002-07-29|ズードケミー触媒株式会社|Hydrocarbon steam reforming catalyst|
    US5532199A|1992-06-19|1996-07-02|Mitsubishi Rayon Co., Ltd.|Carrier-supported catalyst for the synthesis of unsaturated aldehydes and unsaturated carboxylic acids and process for preparing the same|
    JP3276984B2|1992-06-19|2002-04-22|三菱レイヨン株式会社|Supported catalyst for synthesis of unsaturated aldehyde and unsaturated carboxylic acid and method for producing the same|
    JP3347767B2|1992-07-10|2002-11-20|フロイント産業株式会社|Bread coating equipment|
    JPH0631173A|1992-07-10|1994-02-08|N E Chemcat Corp|Catalyst for purification of exhaust gas and method for purifying exhaust gas|
    US6274113B1|1994-01-04|2001-08-14|Chevron Phillips Chemical Company Lp|Increasing production in hydrocarbon conversion processes|
    WO1999028027A1|1996-11-28|1999-06-10|Idemitsu Kosan Co., Ltd.|Alumina-supported ruthenium catalyst|
    US6177381B1|1998-11-03|2001-01-23|Uop Llc|Layered catalyst composition and processes for preparing and using the composition|
    JP3743995B2|1999-12-15|2006-02-08|日産自動車株式会社|Methanol reforming catalyst|
    US7176159B1|2001-08-15|2007-02-13|Iowa State University Research Foundation, Inc.|Catalyst and sorbent material for the production of hydrogen|
    JP2004344752A|2003-05-21|2004-12-09|Nissan Motor Co Ltd|Foam-carried catalyst|
    RU2329100C2|2003-06-13|2008-07-20|Яра Интернэшнл Аса|Method of obtaining oxide catalysts on a substrate|
    JP4332724B2|2004-02-13|2009-09-16|戸田工業株式会社|Autothermal reforming catalyst and method for producing the same, and method for producing hydrogen using the autothermal reforming catalyst|
    GB0420245D0|2004-09-13|2004-10-13|Johnson Matthey Plc|Improvements in catalyst coatings|
    JP4684639B2|2004-12-09|2011-05-18|日揮ユニバーサル株式会社|Hydrocarbon reforming catalyst, method for producing the catalyst, and reforming method using the catalyst|
    US20060204614A1|2005-03-09|2006-09-14|Rapp Knut M|Pan coating process|
    US7862848B2|2005-08-03|2011-01-04|The University Of Western Ontario|Direct coating solid dosage forms using powdered materials|
    US20090018366A1|2005-09-08|2009-01-15|Monika Berweiler|Production and use of supported activated base metal catalysts for organic transformation|
    US7297830B2|2005-09-14|2007-11-20|Uop Llc|Process for isomerizing non-equilibrium xylene-containing feed streams|
    US7453016B1|2005-12-20|2008-11-18|Uop Llc|Selective hydrogenation process using layered catalyst composition and preparation of said catalyst|
    US7541309B2|2006-05-16|2009-06-02|Headwaters Technology Innovation, Llc|Reforming nanocatalysts and methods of making and using such catalysts|
    EP2076331A4|2006-10-23|2012-02-08|Bp Plc|Process and catalyst for hydrocarbon conversion|
    WO2009011133A1|2007-07-19|2009-01-22|Toda Kogyo Corporation|Catalyst for decomposing hydrocarbon|
    JP2009165904A|2008-01-10|2009-07-30|Honda Motor Co Ltd|Exhaust gas purifier|
    US9090465B2|2008-09-24|2015-07-28|Nippon Steel & Sumitomo Metal Corporation|Method for producing catalyst reforming tar-containing gas, method for reforming tar and method for regenerating catalyst for reforming tar-containing gas|
    GB0907539D0|2009-05-01|2009-06-10|Johnson Matthey Plc|Catalyst preparation method|
    JP2010279911A|2009-06-05|2010-12-16|Nippon Shokubai Co Ltd|Catalyst for manufacturing hydrogen, manufacturing method of the catalyst, and manufacturing method of hydrogen using the catalyst|
    GB0914272D0|2009-08-17|2009-09-30|Johnson Matthey Plc|Sorbent|
    JP5537960B2|2010-01-15|2014-07-02|日揮ユニバーサル株式会社|Hydrocarbon reforming catalyst, method for producing the catalyst, and reforming method using the catalyst|
    JP5355492B2|2010-05-14|2013-11-27|リンナイ株式会社|Grill burner equipment|WO2014184685A2|2013-05-09|2014-11-20|Sabic Global Technologies B.V.|Alkaline earth metal/metal oxide supported catalysts|
    IN2014DE00087A|2014-01-13|2015-07-17|Council Scient Ind Res|
    DK3129142T3|2014-04-07|2021-01-25|Topsoe Haldor As|SCALE IMPREGNATED CATALYST AND METHOD FOR PREPARING A SCALE IMPREGNATED CATALYST BODY|
    JP6541339B2|2014-12-01|2019-07-10|クラリアント・プロドゥクテ・（ドイチュラント）・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング|Steam reforming catalyst for hydrocarbon-containing gas, hydrogen production apparatus, and hydrogen production method|
    JP6462448B2|2015-03-25|2019-01-30|株式会社大貴|Water absorption treatment material and method for producing the same|
    CN107921427B|2015-07-01|2021-08-03|沙特基础工业全球技术公司|Methane dry reforming reaction, catalyst containing nickel and cerium and with core-shell structure for methane dry reforming reaction and preparation method of catalyst|
    KR101799384B1|2015-09-21|2017-11-21|서울과학기술대학교 산학협력단|Method for manufacturing catalyst for reforming hydrocarbon fuel using electro-spray|
    EP3409361A4|2016-01-26|2019-07-17|Toda Kogyo Corp.|Heterogeneous-system catalyst structure and manufacturing method therefor|
    TWI611839B|2016-09-07|2018-01-21|國立清華大學|Catalyst applied in hydrogen production by low temperature partial oxidation of light hydrocarbon|
    US9987612B1|2017-04-13|2018-06-05|Caterpillar Inc.|Reactor assembly|
    RU2650495C1|2017-05-22|2018-04-16|Акционерное общество "Ангарский завод катализаторов и органического синтеза" |Catalyst for vapor hydrocarbon conversion|
    WO2018231961A1|2017-06-13|2018-12-20|Gas Technology Institute|Nano-engineered catalysts for dry reforming of methane|
    SG11202000676UA|2017-07-28|2020-02-27|Rohm & Haas|Heterogeneous catalyst|
    KR20200032130A|2017-07-28|2020-03-25|다우 글로벌 테크놀로지스 엘엘씨|Method for preparing methyl methacrylate by oxidative esterification using a heterogeneous catalyst|
    WO2019022889A1|2017-07-28|2019-01-31|Dow Global Technologies Llc|A method for production of methyl methacrylate by oxidative esterification using a heterogeneous catalyst|
    KR20200033277A|2017-07-28|2020-03-27|다우 글로벌 테크놀로지스 엘엘씨|Method for preparing methyl methacrylate by oxidative esterification using a heterogeneous catalyst|
    BR112020001740A2|2017-07-28|2020-07-21|Rohm And Haas Company|method for preparing methacrolein methyl methacrylate and methanol.|
    EP3658531A1|2017-07-28|2020-06-03|Rohm and Haas Company|A method for production of methyl methacrylate by oxidative esterification using a heterogeneous catalyst|
    EP3658532A1|2017-07-28|2020-06-03|Rohm and Haas Company|A method for production of methyl methacrylate by oxidative esterification using a heterogeneous catalyst|
    CN110997617A|2017-07-28|2020-04-10|罗门哈斯公司|Method for producing methyl methacrylate by oxidative esterification using heterogeneous catalysts|
    CA3071437A1|2017-07-28|2019-01-31|Rohm And Haas Company|A method for production of methyl methacrylate by oxidative esterification using a heterogeneous catalyst|
    US20200223692A1|2017-08-30|2020-07-16|Polyvalor, Limited Partnership|Microwave-assisted catalytic reactions using modified bed particles|
    CN111417617A|2017-09-19|2020-07-14|陶氏环球技术有限责任公司|Method for producing methyl methacrylate by oxidative esterification using heterogeneous catalysts|
    US11123711B2|2017-12-28|2021-09-21|University Of Kentucky Research Foundation|System and method for alcohol oxidation reaction of lignins|
    CN108134102B|2018-01-04|2020-10-09|西南化工研究设计院有限公司|Catalyst for methane steam reforming in fuel cell|
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    RU2707880C1|2018-12-03|2019-12-02|Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" |Catalyst and method of producing hydrogen-enriched gaseous mixture from dimethoxymethane and air|
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    CN111450840B|2020-01-15|2020-11-20|成都理工大学|Cobalt-cerium-manganese composite oxide catalyst for autothermal reforming of acetic acid to produce hydrogen|
    法律状态:
    2019-04-24| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-10-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-11-05| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/02/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    2019-12-10| B16C| Correction of notification of the grant [chapter 16.3 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/02/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) REF. RPI 2548 DE 05/11/2019 QUANTO A DATA DA PRIORIDADE UNIONISTA. |
    优先权:
    申请号 | 申请日 | 专利标题
    GBGB1102502.0A|GB201102502D0|2011-02-14|2011-02-14|Catalysts for use in reforming processes|
    PCT/GB2012/050250|WO2012110781A1|2011-02-14|2012-02-06|Catalysts for use in steam reforming processes|
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