WO1999037397A1 - Catalyst carrier carrying nickel, aluminium, lanthanum and a precious metal element - Google Patents
Catalyst carrier carrying nickel, aluminium, lanthanum and a precious metal element Download PDFInfo
- 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
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000010970 precious metal Substances 0.000 title claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 15
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 14
- 239000004411 aluminium Substances 0.000 title claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 12
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 18
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000919 ceramic Substances 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002603 lanthanum Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 238000000629 steam reforming Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- DOARWPHSJVUWFT-UHFFFAOYSA-N lanthanum nickel Chemical compound [Ni].[La] DOARWPHSJVUWFT-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- -1 nitrates Chemical class 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
A steam reforming catalyst comprises nickel, aluminium, lanthanum and a precious metal element preferably ruthenium. The catalyst is preferably presented in a porous preformed carrier. The catalyst may be made by a variety of methods.
Description
CATALYST CARRIER CARRYING NICKEL, ALUMINIUM, LANTHANUM AND A PRECIOUS METAL ELEMENT
The invention relates to catalysts containing nickel, a method of forming the catalysts and to carrier bodies containing the catalysts.
It is one object of the invention to provide a catalyst of high thermal stability and controlled carbon deposition, and which can be used for a variety of hydrocarbon feedstock ranging from natural gas, LPG and naptha and the like. It has now been discovered that incorporating a precious metal element such as ruthenium or the like in the nickel catalyst enhances the control of carbon deposition.
According to the invention in one aspect there is provided 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.
While we do not wish the scope of the monopoly to be limited in any way our investigations suggest that the formed catalyst will have a layer structure and be of the approximate chemical formula.
Ni6QAIx Lay (CO3) x + v (OH) 12 + 2 {x + y)n H2O 2 where
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.
In another aspect 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.
In another preferred aspect 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:
Ni6QAIx Lay (CO3) X ¥ (OH) 12 + 2(χ+y)n H2O 2 in which x is not less than 1 and not greater than 4; y is not less than 0.05 and not greater than 1.5, and n is approximately 4, and Q is a precious metal, following which the precursor is recovered and calcined.
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.
In another method 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. After draining the porous body may be heated to a temperature suitable for the controlled hydrolysis of the urea thus increasing the pH of the absorbed solution and bringing about the deposition of the insoluble hydroxides within the pores. 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.
In order that the invention may be well understood it will now be described with reference to the following examples.
A series of evaluations was carried out to test the effect of adding 0.2% by weight of ruthenium. In each case the control was the parallel catalyst containing nickel on a porous ceramic alpha alumina carrier free of ruthenium.
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.
5 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
0044118B.
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.
The following results were obtained (LHSV mean liquid hourly space velocity):
Test l steam carbon ratio 4.0 : 1 hydrocarbon LHSV 3.5 activity rate control 105.6 sample A 106.1 sample B 106.8
Test 3 steam : carbon 3:1 hydrocarbon LHSV 3.5 control 102.8 sample A 102.6 sample B 103.2
The results demonstrate that the catalysts containing ruthenium had better activity in steam reforming than the ruthenium-free control. The control exhibited traces of carbon at the lower steam to carbon ratios. The results also show that the method of including the ruthenium did not materially affect the activity rate, although at higher steam : carbon ratios pre-impregnation gave the best result.
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.
Claims
1. A catalyst comprising a carrier carrying as catalyst, nickel, aluminium, lanthanum and a precious metal element.
2. A catalyst according to Claim 1 , wherein the precious metal is ruthenium.
3. A catalyst according to Claim 1 or 2, comprising:
Ni6Q Alx Lay (Co3) x + v OH 12 + 2 (x + y)n H2O
2 where: Q is the precious metal element x is from about 1 to about 4 y is from about 0.05 to about 1.5 n is about 4.
4. A catalyst according to any preceding Claim, wherein the catalyst has the approximate range of:
5 to 30 wt % Ni 0.1 to 15 wt % La 0.1 to 2 wt % Ru
5. A catalyst according to Claim 4, wherein the atomic ratios of Ni:AI are 1.5 to 4:1.
9 6. A catalyst according to any preceding Claim, including magnesium in an atomic ratio of 1 to 20:1.
7. A catalyst according to any preceding Claim, wherein the carrier is porous and the catalyst is present in the pores.
8. A catalyst according to any preceding Claim, wherein the carrier is porous and the catalyst is present on the exterior surface.
9. A catalyst according to any preceding Claim, including a promoter or spacer.
10. A catalyst according to Claim 9, wherein the promoter or spacer is zirconium.
11. A method of forming a catalyst comprising impregnating a porous carrier with a solution containing the salts of nickel, lanthanum, aluminium and a precious metal element, adding a hydrolysable precipitation agent, heating to increase the pH and so precipitate the elements, and then calcining.
12. A method of forming a catalyst, the method comprising impregnating a preformed porous ceramic body with a solution of decomposable nickel salt and aluminium salt and lanthanum salt and adding the decomposable salt of a precious metal element either during or following impregnation and then calcining.
13. A method of forming a catalyst comprising first forming a catalyst precursor by coprecipitating nickel, aluminium, lanthanum and a precious metal from a salt thereof, the pH and the temperature of the solution being kept substantially 10 constant through the reaction so that the precursor formed comprises a layer structure and has the approximate chemical composition defined in Claim 3, following which the precursor is recovered and calcined.
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 (en) | 1999-01-21 | 1999-07-21 | Catalyst carrier carrying nickel ruthenium and lanthanum |
| BR9916931-2A BR9916931A (en) | 1999-01-21 | 1999-07-21 | Catalyst, catalyst precursor, vapor improvement process, vapor enhancer tubes, and catalyst precursor formation process |
| 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 (en) | 1999-01-21 | 1999-07-21 | Catalyst carrier supporting nickel, ruthenium and lanthanum |
| PCT/GB1999/002376 WO2000043121A1 (en) | 1999-01-21 | 1999-07-21 | Catalyst carrier carrying nickel ruthenium and lanthanum |
| KR1020017009132A KR20010101612A (en) | 1999-01-21 | 1999-07-21 | Catalyst Carrier Carrying Nickel Ruthenium and Lanthanum |
| CA002359940A CA2359940A1 (en) | 1999-01-21 | 1999-07-21 | Catalyst carrier carrying nickel ruthenium and lanthanum |
| NO20013570A NO20013570D0 (en) | 1999-01-21 | 2001-07-19 | Catalyst comprising nickel, ruthenium and lanthanum |
| 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 (en) | 1999-07-29 |
Family
ID=10825675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB1999/000207 WO1999037397A1 (en) | 1998-01-21 | 1999-01-21 | Catalyst carrier carrying nickel, aluminium, lanthanum and a precious metal element |
Country Status (4)
| Country | Link |
|---|---|
| AU (1) | AU2176999A (en) |
| GB (1) | GB9801321D0 (en) |
| WO (1) | WO1999037397A1 (en) |
| ZA (1) | ZA200105594B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008110331A1 (en) * | 2007-03-13 | 2008-09-18 | Umicore Ag & Co. Kg | Metal-doped nickel oxides as catalysts for the methanation of carbon monoxide |
| 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)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2298367A1 (en) * | 1975-01-24 | 1976-08-20 | Grace W R Ltd | Dual-purpose catalysts for exhaust gas purifcn - by simultaneous oxidn and reduction in a single-bed process |
| US4152299A (en) * | 1974-09-11 | 1979-05-01 | Ford Motor Company | Ruthenium catalyst system and method of stabilizing a ruthenium catalyst system |
| EP0044117A2 (en) * | 1980-07-16 | 1982-01-20 | Dyson Refractories Limited | Catalyst |
| DE3809226A1 (en) * | 1987-03-20 | 1988-09-29 | Toshiba Kawasaki Kk | HIGH TEMPERATURE COMBUSTION CATALYST AND METHOD FOR PRODUCING THE SAME |
| 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 (en) * | 1995-02-03 | 1996-08-07 | SNAMPROGETTI S.p.A. | Material having layered structure of hydrotalcite type, and uses thereof |
-
1998
- 1998-01-21 GB GBGB9801321.2A patent/GB9801321D0/en not_active Ceased
-
1999
- 1999-01-21 AU AU21769/99A patent/AU2176999A/en not_active Abandoned
- 1999-01-21 WO PCT/GB1999/000207 patent/WO1999037397A1/en active Application Filing
-
2001
- 2001-07-06 ZA ZA200105594A patent/ZA200105594B/en unknown
Patent Citations (6)
| 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 (en) * | 1975-01-24 | 1976-08-20 | Grace W R Ltd | Dual-purpose catalysts for exhaust gas purifcn - by simultaneous oxidn and reduction in a single-bed process |
| EP0044117A2 (en) * | 1980-07-16 | 1982-01-20 | Dyson Refractories Limited | Catalyst |
| DE3809226A1 (en) * | 1987-03-20 | 1988-09-29 | Toshiba Kawasaki Kk | HIGH TEMPERATURE COMBUSTION CATALYST AND METHOD FOR PRODUCING THE SAME |
| 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 (en) * | 1995-02-03 | 1996-08-07 | SNAMPROGETTI S.p.A. | Material having layered structure of hydrotalcite type, and uses thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008110331A1 (en) * | 2007-03-13 | 2008-09-18 | Umicore Ag & Co. Kg | Metal-doped nickel oxides as catalysts for the methanation of carbon monoxide |
| CN101631613B (en) * | 2007-03-13 | 2013-01-30 | 乌米科雷股份两合公司 | Metal-doped nickel oxides as catalysts for the methanation of carbon monoxide |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0266875B1 (en) | Method of catalytic combustion using heat-resistant catalyst | |
| JP4812993B2 (en) | Method and catalyst structure for steam reforming hydrocarbons | |
| Le et al. | The impact of Ce‐Zr addition on nickel dispersion and catalytic behavior for CO2 methanation of Ni/AC catalyst at low temperature | |
| US4469815A (en) | Catalyst and method of preparation | |
| CA2483942A1 (en) | Catalyst for partial oxidation of hydrocarbon, process for producing the catalyst, process for producing hydrogen-containing gas with a use of the catalyst, and method of using hydrogen-containing gas produced with the use of the catalyst | |
| US11213805B2 (en) | Catalyst for the conversion of natural or associated gas into synthesis gas in an autothermal reforming process and method for preparing the same | |
| JPS6313729B2 (en) | ||
| EP0044117B1 (en) | Catalyst | |
| JP2005529824A (en) | Suppression of methanation activity of platinum group metal catalysts for water-gas conversion | |
| KR100858924B1 (en) | Supported catalyst for producing hydrogen gas by steam reforming of liquefied natural gas, method for producing same and method for producing hydrogen gas using said supported catalyst | |
| US20020042340A1 (en) | Catalyst carrier carrying nickel ruthenium and lanthanum | |
| RU2292237C1 (en) | Catalyst, method for preparation thereof, and synthetic gas production process | |
| JPS63190644A (en) | Heat-resistant combustion catalyst and catalytic combustion method using the same | |
| US4451580A (en) | Method of preparing a supported catalyst | |
| JP2003519011A (en) | Enhanced hydrocarbon synthesis catalysts with hydrogen and ammonia | |
| WO1999037397A1 (en) | Catalyst carrier carrying nickel, aluminium, lanthanum and a precious metal element | |
| US20070254805A1 (en) | Reforming Catalyst | |
| Shishido et al. | Steam reforming of CH4 over Ni/Mg-Al catalyst prepared by spc-method from hydrotalcite | |
| JPS6012132A (en) | Heat-resistant catalyst and its usage | |
| Marconi et al. | Rare Earth Modified Ni-γAlumina Catalysts for CO 2 Recycling into Life Support Consumables and Fuel | |
| JPS6082136A (en) | Reforming catalyst of methanol | |
| CN1061320C (en) | Nickel based catalyst for prepn. of synthetic gas by methane direct oxidation | |
| RU2552639C1 (en) | Method of preparing oxide-polymetallic catalysts based on heat-resistant alloys for partial oxidation of hydrocarbons into synthesis-gas | |
| CN119701975A (en) | Catalyst for reforming methane mixed with other low-carbon alkane and foaming method and application thereof | |
| RU2336947C1 (en) | Catalist of purification of hidrogen-containing gas mixture from co and method of its preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
| 122 | Ep: pct application non-entry in european phase | ||
| WWE | Wipo information: entry into national phase |
Ref document number: 09909983 Country of ref document: US |