[go: up one dir, main page]

WO2009016177A1 - Catalyseurs pour production de gaz de synthèse par reformage d'alcools comprenant un support zno et leur utilisation - Google Patents

Catalyseurs pour production de gaz de synthèse par reformage d'alcools comprenant un support zno et leur utilisation Download PDF

Info

Publication number
WO2009016177A1
WO2009016177A1 PCT/EP2008/059937 EP2008059937W WO2009016177A1 WO 2009016177 A1 WO2009016177 A1 WO 2009016177A1 EP 2008059937 W EP2008059937 W EP 2008059937W WO 2009016177 A1 WO2009016177 A1 WO 2009016177A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalysts
zno
group
catalysts according
support
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2008/059937
Other languages
English (en)
Inventor
Paolo Bert
Claudio Bianchini
Stefano Catanorchi
Paolo Fornasiero
Mauro Graziani
Barbara Lorenzut
Hamish Andrew Miller
Tiziano Montini
Marina Ragnoli
Adriana Scaffidi
Alessandro Tampucci
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
UNVERSITA' DEGLI STUDI DI TRIESTE
Acta SpA
Original Assignee
UNVERSITA' DEGLI STUDI DI TRIESTE
Acta SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by UNVERSITA' DEGLI STUDI DI TRIESTE, Acta SpA filed Critical UNVERSITA' DEGLI STUDI DI TRIESTE
Publication of WO2009016177A1 publication Critical patent/WO2009016177A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C01B2203/1229—Ethanol
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • This invention refers to catalysts for syn-gas production, in particular hydrogen, by alcohols reforming, in particular ethanol.
  • catalysts for syn-gas production in particular hydrogen
  • alcohols reforming in particular ethanol
  • the actual world hydrogen production is mainly used for the ammonia synthesis (fertilizers) and in the oil-refining.
  • the growing hydrogen demand in the processes involved in the oil purification processes for the removal of sulphur - HDS and nitrogen - HDN
  • the use of hydrogen fuel cells for electric power production presents enormous potentiality both for the increased energy efficiency and for the possibility to reduce the emissions of pollutant produced by the traditional combustion engines, especially from cars.
  • SR catalytic steam reforming reaction
  • POX Partial OXidation
  • ATR AutoThermal Reforming
  • DR Dry Reforming
  • metal based catalysts such as Fe, Co, Ni, Cu, Zn, Ru, Pt o Pd
  • various oxides such as AI 2 O 3 , ZnO, SiO 2 , TiO 2 , V 2 O 5 , La 2 O 3 , CeO 2 and Sm 2 O 3
  • AI 2 O 3 , ZnO, SiO 2 , TiO 2 , V 2 O 5 , La 2 O 3 , CeO 2 and Sm 2 O 3 have been widely studied and used in ethanol steam reforming (e.g. A. Haryanto et al., Energy and Fuels, 19 (2005) 2098; PCT/ EP2005/054619).
  • catalysts based on Ni supported on AI 2 O 3 , MgO, La 2 O 3 , SiO 2 , Y 2 O 3 and YSZ doped with Cu, Cr, Zn, Na or K have been widely investigated for ethanol steam reforming (e.g. A.N. Fatsikostas et al. Catal. Today, 75 (2002) 145).
  • the positive effect due to the formation of alloys plays a relevant role mainly on the selectivity (i.e. reforming product distribution) and stability of the active phase; moreover, on Ni-based catalysts can be observed that the formation of alloys inhibits secondary reactions that lead to coke deposition on the active phase and therefore prevents catalyst deactivation (e.g. F. Besenbacher, et al., Science, 279 (1998) 1913).
  • the preparation of reforming catalysts is usually performed through two methodologies:
  • the metal precursors are impregnated on the preformed support and subsequently the sample is then calcinated to decompose the precursor of the active phase and eventually also reduced.
  • the second case involves the deposition of the precursors of the active phase onto the support by coprecipitation, followed by calcination and eventually by reduction; this methodology is often presented also as " Solid Phase Crystallization " (e.g. K. Takehira et al., J. Catal., 207 (2002) 307); the main advantage of this technique is the possibility to obtain a nanostructured catalyst, that produces hydrogen rich mixtures and mainly inhibits the secondary reactions.
  • Fig. 2 shows the conversion of ethyl alcohol and the H 2 yield in the presence of nanostructured metal catalysts supported on ZnO.
  • Fig. 3 shows the conversion of ethyl alcohol and the H 2 yield in the presence of the templating polymer, without metallic particles, supported on ZnO.
  • Fig. 4 shows the conversion of ethyl alcohol and the H 2 yield in the presence of the catalyst supported on ZnO, which was obtained by impregnation of the corresponding metal salts in the absence of polymer and not nanostructured.
  • Fig. 5 shows the conversion of ethyl alcohol and the H 2 yield in the presence of nanostructured metal catalysts supported on ZnO dispersed in boron nitride.
  • Fig. 6 shows the amount of H 2 produced using this process of reforming of ethyl alcohol / H 2 O mixtures, at the constant temperature of 620 °C, in the presence of nanostructured metal catalysts supported on ZnO.
  • the present invention allows to solve the above mentioned problems through the use of catalysts including a ZnO support with known nanostructured metal catalysts deposited on it.
  • nanostructured metal catalysts used for the preparation of the catalysts according to the invention are known and are obtained treating with a reducing agent of hydrogen and/or pyrolysis of metal complexes formed between salts of Fe, Co, and Ni and their alloys and templating polymers (already described in the above mentioned PT WO 2004/036674) obtained by condensation of a 4- ⁇ 1 - [(phenyl-2,4-disubstituted)-hydrazono]-alkyl ⁇ -benzene-1 ,3-diol with a 3,5- disbustituted phenol and formaldehyde or para-formaldehyde in presence of an acid or basic catalyst in water/alcohol mixtures at temperatures between 20 and 150 °C and having a molecular weight between 1000 and 50000.
  • the templating procedure allows the achievement of metal clusters with highly reduced dimensions, elevated surface area and enhanced catalytic activity (PTWO 2004/036674).
  • PTWO 2004/036674 enhanced catalytic activity
  • the 4- ⁇ 1 -[(phenyl-2,4- disubstituted)-hydrazono]-alkyl ⁇ -benzene-1 ,3-diol is preferably a compound with the following general formula (A):
  • R 1 is chosen among the group which comprises H and hydrocarbon radicals containing from 1 to 10 carbon atoms, eventually bearing halogen atoms;
  • R 2 and R 3 are H or a with-drawing group chosen among the group which comprises halide, nitro, acyl, ester, carboxylic acid, formyl, nitrile, sulfonic acid, aryl group or linear alkyls or branched alkyls containing from 1 to 15 carbon atoms, eventually functionalized with halogen atoms or condensed with each other so as to form one or more cycles with the phenyl ring.
  • a with-drawing group chosen among the group which comprises halide, nitro, acyl, ester, carboxylic acid, formyl, nitrile, sulfonic acid, aryl group or linear alkyls or branched alkyls containing from 1 to 15 carbon atoms, eventually functionalized with halogen atoms or condensed with each other so as to form one or more cycles with the phenyl ring.
  • the 3,5 disubstituted phenol is a compound with the following general formula
  • R 4 and R 5 are H or a with-drawing group chosen among the among the group which comprises OH, ether, amine, aryl groups and linear or branched alkyls containing from 1 to 15 carbon atoms.
  • Said polymers of the invention can be represented by the following repeating unit with formula (C):
  • R 1 , R 2 , R3, R4 and R 5 are defined above.
  • the metal salts of iron, cobalt and nickel or their alloys are salts chosen among the group which comprises carboxylates, halides, acetates, alcoholates, acetyl aceto nates, formats, oxalates, malonates and analogous organic salts and their mixtures or carbonates, oxides, bicarbonates or their mixtures.
  • Zinc oxide is a well known support and the particle's diameter is lower than 5 ⁇ m.
  • the nanostructured metal catalysts are supported on ZnO by their solubilization in acetone, addition to the solution of the oxide and its dispersion and finally evaporation of the solvent.
  • the obtained supported catalyst is used for the production of syn gas or mixtures rich in hydrogen starting from reforming reactions (partial oxidation, steam reforming or autothermal reforming) of ethanol.
  • the catalysts prepared following the present invention present the following advantages:
  • the catalysts reported in the present patent are active for both the reforming and the water gas shift reactions, leading to very high H 2 yields (very closed to the theoretical yield) with simultaneous elimination of carbon monoxide.
  • a catalyst To test the activity of a catalyst, it is placed in a U-shaped quartz reactor inside an electric furnace and the gaseous mixture is flowing through the catalytic bed; the real temperature of the catalyst is controlled by a thermocouple inserted inside the catalytic bed; all the transport lines until the reactor are maintained at a temperature of 120 °C to avoid the condensation of the liquid reagents.
  • Ar is used as carrier gas.
  • the catalysts are reduced using H 2 (5%) in Ar (40 ml/min) at 360 °C for 30 minutes.
  • the reaction mixture is injected inside the reactivity line in an inert gas flow using a syringe moved by an automatic pump.
  • the mass of catalyst and the flow of the gaseous mixture are chosen in order to achieve the proper Gas Hourly Space Velocity (GHSV).
  • GHSV Gas Hourly Space Velocity
  • the reaction mixture is introduced in the reactor maintaining the furnace at 150 °C. After 1 hour, the furnace temperature is increased up to 800 °C (heating ramp 1 °C/min).
  • the composition of the gaseous mixture exiting from the reactor is analyzed through gaschromatography.
  • the amounts of the carbonaceous compounds are determined using a column system Select Permanent Gases/CO 2 (PoraPLOT Q 50 m x 0.53 mm ID column in parallel with a Molsieve 5A 10 m x 0.32 mm ID column) using He as carrier and connected to a methanator and a Flame Ionization Detector (FID).
  • the amount of produced H 2 is determined using a Molsieve 5A (25 m x 0.52 mm ID) using Ar as carrier and connected to a Thermoconductivity Detector (TCD).
  • TCD Thermoconductivity Detector
  • the efficiency of the catalyst containing metalized polymer is confirmed by the comparative study held in the same operative conditions using the support without metal as catalyst, based on the zinc oxide alone, or using the support ZnO impregnated with solutions containing Fe(II), Co(II) and Ni(II) ions without the complexing polymer, reduced at 360 °C by gaseous hydrogen.
  • the thermal stability of these catalysts is evaluated at 620 °C with a space velocity GHSV of 31000 ml_ g "1 h “1 .
  • the amount of H 2 produced remains constant for the entire test, demonstrating the ability of these catalysts to operate continuously during long time periods, without sensitive changes of their activity.
  • the metal content was evaluated by ICP-AES analysis.
  • Zinc oxide (Aldrich) was mixed at the 33.30 wt% with inert Ci-AI 2 O 3 (SASOL) and formed into pellets of 250-300 ⁇ m.
  • SASOL inert Ci-AI 2 O 3
  • EXAMPLE 7 This example shows the ability by the catalyst based on the nanostructured metal catalyst supported on ZnO, prepared following the Example 3, to promote the ethanol reforming reaction leading to syn gas rich in hydrogen.
  • 0,046 mg of the sample prepared following the Example 3 are loaded in the reactor and treated as reported in the Example 6.
  • the obtained results are reported in Fig. 2: it is evident that the use of this catalyst leads to an optimal H 2 yield.
  • acetaldehyde formed above 450 °C is completely consumed at higher temperatures (above 600 °C) leading to a further increment of the H 2 production (maximum obtained value: 5.5 mol[H 2 ]/mol[initial EtOH], maximum theoretical value: 6 mol[H 2 ]/mol[initial EtOH]).
  • This catalyst can be attributed to the preparation method and, in particular, to the use of the templating polymer that, imparting a particular structure to the metal active phase, improves its activity; not less important is the use of ZnO as support/promoter.
  • This example shows the ability of the catalyst, prepared accordingly to the example 5, to promote the ethanol reforming reaction leading to hydrogen rich syn gas.
  • This example shows the possibility to dilute the A109 catalyst supported on ZnO with boron nitride.
  • EXAMPLE 11 This Example shows the stability of the catalyst A109 supported on ZnO under operative conditions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne des catalyseurs pour la préparation de gaz de synthèse par reformage d'alcools, comprenant un support ZnO sur lequel des catalyseurs métalliques nanostructurés sont déposés. Les catalyseurs métalliques nanostructurés sont obtenus par traitement au moyen d'un agent de réduction, ou d'hydrogène et/ou par pyrolyse de complexes métalliques formés par des sels de Fe, Co et Ni et leurs alliages et des polymères structurants.
PCT/EP2008/059937 2007-07-31 2008-07-29 Catalyseurs pour production de gaz de synthèse par reformage d'alcools comprenant un support zno et leur utilisation Ceased WO2009016177A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITFI2007A000179 2007-07-31
IT000179A ITFI20070179A1 (it) 2007-07-31 2007-07-31 Catalizzatori per la produzione di gas di sintesi da reforming di alcoli comprendenti un supporto in zno e loro uso.

Publications (1)

Publication Number Publication Date
WO2009016177A1 true WO2009016177A1 (fr) 2009-02-05

Family

ID=40076585

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/059937 Ceased WO2009016177A1 (fr) 2007-07-31 2008-07-29 Catalyseurs pour production de gaz de synthèse par reformage d'alcools comprenant un support zno et leur utilisation

Country Status (2)

Country Link
IT (1) ITFI20070179A1 (fr)
WO (1) WO2009016177A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010060736A1 (fr) * 2008-11-03 2010-06-03 Acta S.P.A. Catalyseurs à base de métaux non nobles pour la décomposition de l'ammoniac et leur préparation
CN112876235A (zh) * 2021-01-28 2021-06-01 苏州金宏气体股份有限公司 ZnO/NiO异质结压电陶瓷、其制法与自供能高效制氢中的应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113531539A (zh) * 2021-07-20 2021-10-22 浙江红狮环保股份有限公司 一种氯化钠废盐资源化利用的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006045673A1 (fr) * 2004-10-27 2006-05-04 Acta S.P.A. Utilisation de catalyseurs metalliques a nanostructures pour la production de gaz de synthese et de melanges gazeux riches en hydrogene

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006045673A1 (fr) * 2004-10-27 2006-05-04 Acta S.P.A. Utilisation de catalyseurs metalliques a nanostructures pour la production de gaz de synthese et de melanges gazeux riches en hydrogene

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HOMS ET AL: "Low-temperature steam-reforming of ethanol over ZnO-supported Ni and Cu catalysts", CATALYSIS TODAY, ELSEVIER, vol. 116, no. 3, 15 August 2006 (2006-08-15), pages 361 - 366, XP005590593, ISSN: 0920-5861 *
JORDI LLORCA ET AL: "Direct production of hydrogen from ethanolic aquoues solutions over oxide catalysts", CHEMICAL COMMUNICATIONS - CHEMCOM, ROYAL SOCIETY OF CHEMISTRY, GB, 1 January 2001 (2001-01-01), pages 641 - 642, XP002438327, ISSN: 1359-7345 *
LLORCA J ET AL: "Efficient Production of Hydrogen over Supported Cobalt Catalysts from Ethanol Steam Reforming", JOURNAL OF CATALYSIS, ACADEMIC PRESS, DULUTH, MN, US, vol. 209, no. 2, 25 July 2002 (2002-07-25), pages 306 - 317, XP004468876, ISSN: 0021-9517 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010060736A1 (fr) * 2008-11-03 2010-06-03 Acta S.P.A. Catalyseurs à base de métaux non nobles pour la décomposition de l'ammoniac et leur préparation
CN112876235A (zh) * 2021-01-28 2021-06-01 苏州金宏气体股份有限公司 ZnO/NiO异质结压电陶瓷、其制法与自供能高效制氢中的应用

Also Published As

Publication number Publication date
ITFI20070179A1 (it) 2009-02-01

Similar Documents

Publication Publication Date Title
EP1819634A1 (fr) Utilisation de catalyseurs metalliques a nanostructures pour la production de gaz de synthese et de melanges gazeux riches en hydrogene
KR101437072B1 (ko) 효율적인 이산화탄소 전환 촉매 및 이의 제조 방법
AU2010254196B2 (en) Methanol steam reforming catalysts
US20040166056A1 (en) Sulfur-tolerant catalysts and related precursors and processes
CN107042111B (zh) 一种乙酸自热重整制氢的层状钙钛矿型催化剂及制备方法
Garbarino et al. Steam reforming of phenol–ethanol mixture over 5% Ni/Al2O3
Sollier et al. Synthesis and characterization of electrospun nanofibers of Sr-La-Ce oxides as catalysts for the oxidative coupling of methane
Wyrwalski et al. Synergistic coupling of the redox properties of supports and cobalt oxide Co3O4 for the complete oxidation of volatile organic compounds
Chen et al. Improved catalytic activity and stability of Cu/ZnO catalyst by boron oxide modification for low-temperature methanol synthesis
US11724936B2 (en) Catalyst for low temperature ethanol steam reforming and related process
Jiao et al. Hydrogen-rich syngas production by toluene reforming in a microchannel reactor coated with Ni/MgO–Al2O3 multifunctional catalysts
KR102186058B1 (ko) 산화마그네슘-알루미나 복합 지지체를 이용한 알코올의 이산화탄소 개질 반응용 촉매 및 이를 이용한 합성가스의 제조방법
WO2009016177A1 (fr) Catalyseurs pour production de gaz de synthèse par reformage d'alcools comprenant un support zno et leur utilisation
Umar et al. Perovskite modified catalysts with improved coke resistance for steam reforming of glycerol to renewable hydrogen fuel
US20190330059A1 (en) Boron-containing catalysts for dry reforming of methane to synthesis gas
Kapran et al. Decomposition of methanol on ZnO (CeO2, La2O3)-CuO-NiO-based monoliths
JPS58193738A (ja) 水素富化ガス製造用触媒
KR101400889B1 (ko) 탄화수소 개질촉매 및 이의 제조방법
CN118634828A (zh) 一种耐积碳的高稳定性乙醇蒸汽重整制包覆型镍基催化剂及其制备方法和应用
KR101969554B1 (ko) 고열량 합성천연가스 생산용 철-코발트계 복합 촉매 및 이의 용도
CN112916018B (zh) 一种乙酸自热重整制氢的镨锆复合氧化物钴基催化剂
JP2010184202A (ja) 水素生成触媒及びその製造方法
JP4860226B2 (ja) 部分酸化改質触媒および部分酸化改質方法
KR102186052B1 (ko) 산화마그네슘-알루미나 복합 지지체를 이용한 아세톤의 이산화탄소 개질 반응용 촉매 및 이를 이용한 합성가스의 제조방법
WO2017094030A2 (fr) Catalyseur métallique de support actif et son procédé de préparation

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08786574

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08786574

Country of ref document: EP

Kind code of ref document: A1