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WO1999037397A1 - Support de catalyseur renfermant du nickel, de l'aluminium, du lanthane et un element des metaux precieux - Google Patents

Support de catalyseur renfermant du nickel, de l'aluminium, du lanthane et un element des metaux precieux Download PDF

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Publication number
WO1999037397A1
WO1999037397A1 PCT/GB1999/000207 GB9900207W WO9937397A1 WO 1999037397 A1 WO1999037397 A1 WO 1999037397A1 GB 9900207 W GB9900207 W GB 9900207W WO 9937397 A1 WO9937397 A1 WO 9937397A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
precious metal
lanthanum
aluminium
nickel
Prior art date
Application number
PCT/GB1999/000207
Other languages
English (en)
Inventor
Rodney Martin Sambrook
John Kevin Dunleavy
Original Assignee
Dytech Corporation Ltd.
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 Dytech Corporation Ltd. filed Critical Dytech Corporation Ltd.
Priority to AU21769/99A priority Critical patent/AU2176999A/en
Priority to JP2000594571A priority patent/JP2002535119A/ja
Priority to BR9916931-2A priority patent/BR9916931A/pt
Priority to AU50549/99A priority patent/AU5054999A/en
Priority to NZ512781A priority patent/NZ512781A/xx
Priority to EP99934927A priority patent/EP1169126A1/fr
Priority to PCT/GB1999/002376 priority patent/WO2000043121A1/fr
Priority to KR1020017009132A priority patent/KR20010101612A/ko
Priority to CA002359940A priority patent/CA2359940A1/fr
Publication of WO1999037397A1 publication Critical patent/WO1999037397A1/fr
Priority to NO20013570A priority patent/NO20013570D0/no
Priority to US09/909,983 priority patent/US20020042340A1/en

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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/007—Mixed salts
    • 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
    • B01J23/83—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 rare earths or actinides
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates

Definitions

  • the invention relates to catalysts containing nickel, a method of forming the catalysts and to carrier bodies containing the catalysts.
  • a preformed carrier carrying as a catalyst nickel, aluminium, lanthanum and a precious metal element.
  • the precious metal element may be Pt, Pd, Ru, Rh; preferably it is ruthenium.
  • Q is the precious metal element x is from about 1 to about 4 2 y is from about 0.05 to about 1.5 n is about 4
  • the preformed carrier is preferably a preformed porous ceramic body adapted to hold the catalyst in the pores and optionally on the exterior too.
  • the preformed porous ceramic body may be alumina, stabilised alumina, zirconia, spinel, aluminosilicates, silica, and the like.
  • the invention provides a method of forming a catalyst by impregnation of a preformed porous ceramic body with a decomposable nickel salt and lanthanum salt with the addition of a precious metal component either during the initial impregnation stage or following impregnation and calcining.
  • the precious metal component will be provided by a decomposable salt of one of the following precious metals: Pt, Pd, Ru, Rh.
  • the preferred precious metal component is a thermally decomposable salt of ruthenium.
  • the invention provides a method which comprises first forming a catalyst precursor by co-precipitating nickel, aluminium, lanthanum and the precious metal from a solution of their salts, e.g. nitrates, the pH and temperature of the solution being kept substantially constant throughout the reaction so that the precursor formed comprises a layer structure and the approximate chemical composition:
  • the catalyst composition may be utilised either in a form in which it is held within a porous ceramic matrix or as an apparently homogenous material, the form being chosen according to need.
  • the preformed porous ceramic body is impregnated, preferably under vacuum, with a solution containing salts of nickel, lanthanum, aluminium and the precious metal, e.g. the nitrates, with a precipitation agent such as urea.
  • a solution containing salts of nickel, lanthanum, aluminium and the precious metal e.g. the nitrates
  • a precipitation agent such as urea.
  • the catalyst is then dried by heating to a suitably elevated temperature.
  • the precious metal component may also be added by post impregnation).
  • the metal loading of the catalyst may be increased by repetition of the process steps. Prior to re-impregnation of the catalyst the pores must be opened. The process the pores may be opened by thermal decomposition of material within the pores. Alternatively the catalyst is washed with water or weak alkaline solution and then dried at a suitable elevated temperature. The catalyst of the required metal loading is subjected to a final calcination temperature of about 450°C.
  • the final composition in the ceramic pores has the preferable approximate range of about 5-30 wt. %, Ni, about 0.1 - about 15 wt. % La and about 0.1 - about 2% Ru. It is preferred that the atomic ratios of Ni:AI in the active material are about 1.5 to about 4:1. 4 Promoters/spacers such as zirconium may be added, preferably as the nitrate, to further increase the stability and/or improve the selectivity of the catalyst. If magnesium is present in the nickel-aluminium phase, which is an optional variation, it is preferred that the atomic ratios of Ni:Mg in the active material are about 1 to about 20:1.
  • the catalyst composition of the invention will have enhanced thermal stability and carbon gasification activity.
  • the nickel catalyst composition may be used for example in the high temperature steam reforming of hydrocarbons.
  • Other possible applications include the methanation of gases containing high concentration of carbon oxide particularly arising from coal gasification processes.
  • Sample A was prepared by impregnating the alpha alumina carrier with 0.2% by weight of ruthenium, following which the carrier was impregnated with nickel, aluminium and lanthanum by urea deposition in the manner of our EP 0044118B.
  • Sample B was prepared by adding 0.2% ruthenium to the nickel, lanthanum and aluminium coprecipitated in the alpha alumina carrier in the manner of our EP 0044117B.
  • Sample C was prepared by post-impregnating the alpha alumina carrier with 0.2% ruthenium, already impregnated with nickel lanthanum aluminium in the manner of our EP
  • a control was prepared by coprecipating nickel aluminum and lanthanum by urea hydrolysis in an alpha alumina carrier to provide a standard reforming catalyst (known as DYCAT 890 - DYCAT is a registered trade mark).
  • the samples were tested for activity by flowing hexane gas over a fixed catalyst bed.
  • the pressure was atmospheric and the exit temperature was 750°C.
  • test 2 steam carbon 3.5 : 1 hydrocarbon LHSV 3.5 control 105.2 sample A 105.1 sample B 105.4 sample C 108.3
  • Test 3 steam carbon 3:1 hydrocarbon LHSV 3.5 control 102.8 sample A 102.6 sample B 103.2
  • the invention is not limited to the examples.
  • the ruthenium may be replaced in whole or in part by another precious metal, e.g. palladium or platinum.
  • the ruthenium containing catalysts were completely free of carbon deposits indicating a superior performance at lower steam to carbon ratios.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

Cette invention se rapporte à un catalyseur de reformage à la vapeur, qui comprend du nickel, de l'aluminium, du lanthane et un élément des métaux précieux, tel que de préférence le ruthénium. Ce catalyseur est de préférence présenté sur un support préformé poreux. Ce catalyseur peut être fabriqué par une grande variété de procédés.
PCT/GB1999/000207 1998-01-21 1999-01-21 Support de catalyseur renfermant du nickel, de l'aluminium, du lanthane et un element des metaux precieux WO1999037397A1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
AU21769/99A AU2176999A (en) 1998-01-21 1999-01-21 Catalyst carrier carrying nickel, aluminium, lanthanum and precious metal element
EP99934927A EP1169126A1 (fr) 1999-01-21 1999-07-21 Support d'un catalyseur a base de nickel, ruthenium et lanthane
BR9916931-2A BR9916931A (pt) 1999-01-21 1999-07-21 Catalisador, precursor de catalisador, processopara melhoria de vapor, tubos melhoradores devapor, e processo de formação de um precursorde catalisador
AU50549/99A AU5054999A (en) 1999-01-21 1999-07-21 Catalyst carrier carrying nickel ruthenium and lanthanum
NZ512781A NZ512781A (en) 1999-01-21 1999-07-21 Catalyst carrier carrying nickel ruthenium and lanthanum
JP2000594571A JP2002535119A (ja) 1999-01-21 1999-07-21 ニッケル、ルテニウム及びランタンを担持する触媒担体
PCT/GB1999/002376 WO2000043121A1 (fr) 1999-01-21 1999-07-21 Support d'un catalyseur a base de nickel, ruthenium et lanthane
KR1020017009132A KR20010101612A (ko) 1999-01-21 1999-07-21 니켈, 루테늄 및 란타늄을 담지한 촉매 담체
CA002359940A CA2359940A1 (fr) 1999-01-21 1999-07-21 Support d'un catalyseur a base de nickel, ruthenium et lanthane
NO20013570A NO20013570D0 (no) 1999-01-21 2001-07-19 Katalysator omfattende nikkel, rutenium og lantanum
US09/909,983 US20020042340A1 (en) 1999-01-21 2001-07-23 Catalyst carrier carrying nickel ruthenium and lanthanum

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9801321.2A GB9801321D0 (en) 1998-01-21 1998-01-21 Catalysis
GB9801321.2 1998-01-21

Publications (1)

Publication Number Publication Date
WO1999037397A1 true WO1999037397A1 (fr) 1999-07-29

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1999/000207 WO1999037397A1 (fr) 1998-01-21 1999-01-21 Support de catalyseur renfermant du nickel, de l'aluminium, du lanthane et un element des metaux precieux

Country Status (4)

Country Link
AU (1) AU2176999A (fr)
GB (1) GB9801321D0 (fr)
WO (1) WO1999037397A1 (fr)
ZA (1) ZA200105594B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008110331A1 (fr) * 2007-03-13 2008-09-18 Umicore Ag & Co. Kg Oxydes de nickel dopés par un métal comme catalyseurs pour la méthanation du monoxyde de carbone
GB2607380A (en) * 2021-02-08 2022-12-07 Petroleo Brasileiro Sa Petrobras Catalysts, process for obtaining and steam pre-reforming process of hydrocarbons

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2298367A1 (fr) * 1975-01-24 1976-08-20 Grace W R Ltd Catalyseur a double usage pour gaz d'echappement
US4152299A (en) * 1974-09-11 1979-05-01 Ford Motor Company Ruthenium catalyst system and method of stabilizing a ruthenium catalyst system
EP0044117A2 (fr) * 1980-07-16 1982-01-20 Dyson Refractories Limited Catalyseur
DE3809226A1 (de) * 1987-03-20 1988-09-29 Toshiba Kawasaki Kk Hochtemperatur-verbrennungskatalysator und verfahren zur herstellung desselben
US5492878A (en) * 1992-03-31 1996-02-20 Mitsui Mining & Smelting Co., Ltd. Catalyst for cleaning exhaust gas with alumina, ceria, zirconia, nickel oxide, alkaline earth oxide, and noble metal catalyst, and method for preparing
EP0725038A1 (fr) * 1995-02-03 1996-08-07 SNAMPROGETTI S.p.A. Matériau de type hydrotalcite ayant une structure en couches et son utilisation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4152299A (en) * 1974-09-11 1979-05-01 Ford Motor Company Ruthenium catalyst system and method of stabilizing a ruthenium catalyst system
FR2298367A1 (fr) * 1975-01-24 1976-08-20 Grace W R Ltd Catalyseur a double usage pour gaz d'echappement
EP0044117A2 (fr) * 1980-07-16 1982-01-20 Dyson Refractories Limited Catalyseur
DE3809226A1 (de) * 1987-03-20 1988-09-29 Toshiba Kawasaki Kk Hochtemperatur-verbrennungskatalysator und verfahren zur herstellung desselben
US5492878A (en) * 1992-03-31 1996-02-20 Mitsui Mining & Smelting Co., Ltd. Catalyst for cleaning exhaust gas with alumina, ceria, zirconia, nickel oxide, alkaline earth oxide, and noble metal catalyst, and method for preparing
EP0725038A1 (fr) * 1995-02-03 1996-08-07 SNAMPROGETTI S.p.A. Matériau de type hydrotalcite ayant une structure en couches et son utilisation

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008110331A1 (fr) * 2007-03-13 2008-09-18 Umicore Ag & Co. Kg Oxydes de nickel dopés par un métal comme catalyseurs pour la méthanation du monoxyde de carbone
CN101631613B (zh) * 2007-03-13 2013-01-30 乌米科雷股份两合公司 作为一氧化碳甲烷化的催化剂的掺杂金属的氧化镍
GB2607380A (en) * 2021-02-08 2022-12-07 Petroleo Brasileiro Sa Petrobras Catalysts, process for obtaining and steam pre-reforming process of hydrocarbons
GB2607380B (en) * 2021-02-08 2025-05-07 Petroleo Brasileiro Sa Petrobras Catalysts, process for obtaining and steam pre-reforming process of hydrocarbons

Also Published As

Publication number Publication date
GB9801321D0 (en) 1998-03-18
AU2176999A (en) 1999-08-09
ZA200105594B (en) 2002-10-07

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