ZA200105594B - Catalyst carrier carrying nickel ruthenium and lanthanum. - Google Patents
Catalyst carrier carrying nickel ruthenium and lanthanum. Download PDFInfo
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- ZA200105594B ZA200105594B ZA200105594A ZA200105594A ZA200105594B ZA 200105594 B ZA200105594 B ZA 200105594B ZA 200105594 A ZA200105594 A ZA 200105594A ZA 200105594 A ZA200105594 A ZA 200105594A ZA 200105594 B ZA200105594 B ZA 200105594B
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- ZA
- South Africa
- Prior art keywords
- ruthenium
- nickel
- catalyst
- lanthanum
- aluminium
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 47
- 229910052746 lanthanum Inorganic materials 0.000 title claims description 18
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims description 18
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 title 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 96
- 229910052759 nickel Inorganic materials 0.000 claims description 47
- 239000004411 aluminium Substances 0.000 claims description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 32
- 229910052782 aluminium Inorganic materials 0.000 claims description 31
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 27
- 229910052707 ruthenium Inorganic materials 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 22
- 239000012018 catalyst precursor Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims description 17
- 238000000629 steam reforming Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 13
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 239000011872 intimate mixture Substances 0.000 claims description 11
- 239000008188 pellet Substances 0.000 claims description 11
- 150000003303 ruthenium Chemical class 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 9
- 150000002603 lanthanum Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- -1 ruthenium metals Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 2
- 239000002244 precipitate Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 150000002604 lanthanum compounds Chemical class 0.000 description 7
- 239000012876 carrier material Substances 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 150000001399 aluminium compounds Chemical class 0.000 description 2
- 229940077746 antacid containing aluminium compound Drugs 0.000 description 2
- 235000012245 magnesium oxide Nutrition 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 239000012266 salt solution Substances 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
Description
Coe WO 00/43121 PCT/GB99/02376
CAA re BM fveriton relates o CABBIE an th DABmIarkG Saysis for ba foro steam reforming of hydrocarbons such as methane, natural gas, LPG, and naphtha. In the steam reforming of hydrocarbons, a mixture of a hydrocarbon feedstock and steam is passed atan elevated temperature over a steam reforming catalyst. The catalyst is often disposed in externally heated tubes. The steam ratio, i.e. the number of moles of steam employed per gram atom of hydrocarbon carbon, is typically in the range 1 to 5. For economic reasons it is desirable to use low steam ratios. However when using low steam ratios, particularly where the hydrocarbon contains hydrocarbons having 2 or more carbon atoms, there is a risk that carbon will be deposited on the catalyst, resulting in a loss of activity of the catalyst.
It is known from EP 0 044 117 to'employ as catalysts for the steam reforming of hydrocarbons certain compositions obtained by reducing a precursor comprising a preformed carrier, particularly a ceramic body, carrying an intimate mixture of nickel, aluminium and lanthanum compounds. In use, the active catalyst comprises nickel metal intimately associated with the other components in oxide form, i.e. alumina and fanthana. We have found that the incorporation of ruthenium into such compositions gives-catalysts that have improved resistance to carbon deposition and which may also have increased activity.
Accordingly the present invention provides a catalyst comprising a preformed carrier carrying nickel and ruthenium metals intimately associated with alumina and lanthana.
The active catalyst may be made by subjecting to reducing conditions, a precursor comprising a preformed carrier carrying an intimate mixture of oxides of nickel, aluminium and lanthanum, and ruthenium and/or ruthenium oxide, whereby the nickel oxide and any ruthenium oxide are reduced to the elemental metals. Generally in the precursors made by the methods described hereinafter the ruthenium will be present as ruthenium metal which in some cases may have a surface coating of ruthenium oxide.
The preformed carrier is preferably a porous ceramic body adapted to hold the catalyst in the pores thereof and optionally also on the exterior of the ceramic body. The preformed carrier may be a ceramic foam. The preformed carrier may be formed from alumina, stabilised alumina, calcium aluminate cement, zirconia, spinel, aluminosilicates, silica, and the like, and is preferably in the form of cylindrical pellets, which may have one or more holes extending axially therethrough, e.g. Raschig rings. The cylindrical pellets preferably have a diameter in the range 5 to 20 mm and an aspect ratio, i.e. the ratio of the height to the diameter, in the range 0.5:1 to 2:1.
Accordingly the present invention also provides a catalyst precursor comprising cylindrical pellets, which may have one or more holes extending axially therethrough, of a carrier material carrying an intimate mixture of oxides of nickel, aluminium and lanthanum, and ruthenium and/or ruthenium oxide. ‘The catalyst precursor preferably contains 5 to 30% by weight of nickel as nickel oxide,
NiO, 0.1 to 15% by weight of lanthanum as lanthanum oxide La,0;, and 0.1 to 2.5% by weight
SUBSTITUTE SHEET (RULE 26)
of ruthenium as metal and/or ruthenium oxide, based on the total weight of the precursor. As indicated above, the carrier material of the support may be, or contain, alumina. In the catalysts and precursors of the invention, alumina is present in intimate admixture with the nickel (or nickel oxide), ruthenium (and/or ruthenium oxide), and lanthana in addition to any alumina in the carrier material, Preferably the precursor contains 0.5 to 10% by weight of aluminium, as alumina Al,O,, based on the total weight of the precursor, in intimate admixture with the nickel oxide, ruthenium oxide and lanthanum oxide, in addition to any alumina present in the carrier material.
Correspondingly the reduced catalysts preferably contain, based upon the total weight ofthe reduced catalyst, about 5 to about 33% by weight of nickel metal, about 0.1 to about 2.5% by weight of ruthenium metal, about 0.1 to about 20% by weight of lanthana and about 1 to 20% by weight of alumina (in addition to any alumina present in the carrier material).
The nickel to lanthanum atomic ratio is preferably in the range 4:1 to 12:1 and the nickel to aluminium (in addition to any aluminium present in the carrier material) atomic ratio is preferably in the range 1.5:1 to 6:1, particularly 1.5:1 to 4:1. The ruthenium to nickel atomic ratio is preferably in the range 0.002:1 to 0.15:1, particularly 0.01:1 to 0.1:1.
The precursor may be formed impregnation of a preformed carrier, e.g. porous ceramic body, especially cylindrical pellets as aforesaid, with a solution containing heat-decomposable nickel, aluminium and lanthanum salts, e.g. nitrates, followed by calcination to effect decomposition of said salts. To incorporate the ruthenium component, the carrier is impregnated with a solution of a decomposable ruthenium salt, e.g. ruthenium chloride, before, ‘simultaneously with, or after impregnation with the nickel, aluminium and lanthanum salts. indeed, the ruthenium salt may be included in the solution containing the nickel, aluminium and lanthanum salts. Altematively, a precursor comprising the preformed carrier carrying an intimate mixture of nickel, aluminium and lanthanum oxides, for example as obtained by calcination of a porous ceramic body impregnated with heat-decomposable nickel, aluminium and lanthanum salts, may be impregnated with a solution of a ruthenium salt and then calcined to decompose the ruthenium salt. The calcination step or steps are preferably effected by heating the impregnated carrier in air at a temperature in the range 250°C to 600°C, particularly at about 450°C.
In another preferred method of forming the precursor, a porous carrier is impregnated with a solution containing nickel, aluminium and lanthanum salts and a hydrolysable precipitation agent such as urea, and then, after draining any excess of the solution from the carrier, heating the impregnated carrier to effect controlled hydrolysis of the precipitation agent so as to increase the pH of the absorbed solution to effect precipitation of heat-decomposable nicket, aluminium and lanthanum compounds, e.g. hydroxides, within the pores of the carrier.
The precursor is then calcined to convert the precipitated nickel, aluminium and lanthanum compounds to the corresponding oxides. The ruthenium may be incorporated by impregnation of the camer with a heat-decomposable ruthenium salt solution before impregnation with the
SUBSTITUTE SHEET (RULE 26)
ow WO 00/43121 3 PCT/GB99/02376 nickel, aluminium and lanthanum salts. Alternatively a ruthenium salt may be included in the solution of nickel, aluminium and lanthanum salts and precipitation agent, so that ruthenium or a compound thereof is precipitated with the nickel, aluminium and lanthanum compounds.
Altematively, and preferably, a precursor comprising a preformed porous carrier carrying nickel,
S$ aluminium and lanthanum compounds precipitated as aforesaid may be impregnated with a solution of a heat-decomposable ruthenium salt before or, preferably after, the calcination step.
Where a calcined precursor comprising the porous carrier carrying precipitated nickel, aluminium and lanthanum compounds is impregnated with a solution of a heat-decomposable ruthenium salt, the resultant product should be subjected to a further calcination step to decompose the ruthenium salt.
The metal loading of the catalyst may be increased by repetition of the process steps.
Prior to re-impregnation of the carrier, it is preferably to re-open any pores therein for example by thermal decomposition of material within the pores, e.g. by calcination as aforesaid.
Alternatively the impregnated carrier is washed with water or weak alkaline solution and then dried at a suitable elevated temperature prior to re-impregnation.
Promoters such as zirconium or magnesium oxides may be added to further increase the stability and/or improve the selectivity of the catalyst. Such promoters may be incorporated i” by including a suitable salt, e.g. nitrate, in the solution employed to introduce the nickel. If _ magnesium oxide is present in the intimate mixture, it is preferred that the nickel to magneskim atomic ratio is in the range 1:1 to 20:1.
The catalysts of the invention are primarily of utility for the steam reforming of “hydrocarbons. As indicated above, in such a process, a mixture of the hydrocarbon feedstock and steam is passed over the reduced catalyst at an elevated temperature. Generally the process is operated such that the temperature of the reformed gas mixture leaving the catalyst ~.25 hasa temperature in the range 450°C to 850°C. The catalysts are of particular utility for the so- . called “high-temperature” steam reforming process wherein the catalyst is disposed tubes and a preheated mixture of the hydrocarbon feedstock and steam is passed through the tubes, which are typically several metres long, e.g. 3 to 15, particularly at least 10, m long, and have an inside diameter in the range 6 to 20 cm and which are externally heated so that the temperature of the reformed gas leaving the tubes is in the range from about 600°C to about 850°C. Often the process is operated at an elevated pressure, for example in the range 10 to
S0 bar abs. Prior to reforming, the hydrocarbon feedstock should be desulphurised since sulphur compounds tend to de-activate nickel-containing steam reforming catalysts. Since the tendency to form carbon deposits is most prevalent in the inlet portion of the reforming tubes, in a preferred steam reforming process, the catalyst or precursor of the invention is charged to the inlet portion of the tubes, for example the first 5 to 40% of the length of the tubes, and a ruthenium-free steam reforming catalyst, or a precursor thereto, e.g. nickel (optionally in : intimate admixture with {anthana and alumina) on a suitable preformed carrier, is charged to the remainder of the length of the tubes.
SUBSTITUTE SHEET (RULE 26)
The catalysts, particularly those containing a relatively high nickel content, eg. above 20% by weight, are also of utility for the so-called “low-temperature” steam reforming process, otherwise termed “pre-reforming”, where a preheated mixture of steam and hydrocarbon feedstock is passed adiabatically through a bed of the catalyst. In such a process, the § temperature of the reformed gas mixture leaving the catalyst is typically in the range 450°C to 600°C.
Other possible applications of the catalysts include the methanation of gases containing high concentration of carbon oxide particularly arising from coal gasification processes. : :
In the aforementioned steam reforming and methanation processes, the vessel, e.g. tubes, in which the reaction is to take place, may be charged with the precursor which is then reduced in situ by passing hydrogen diluted with an inert gas such as nitrogen through the precursor at an elevated temperature. ]
The invention is illustrated by the following examples.
Example 1 (comparative)
A catalyst precursor A was prepared by co-precipitating an intimate mixture of nickel, lanthanum and aluminium compounds from a solution containing nickel, lanthanum and } aluminium nitrates and urea in the pores of an alpha-alumina carrier by the procedure of
EP 0044 118 B, and then calcining the product at 450°C. | Example 2
A catalyst precursor B was prepared by the procedure of Example 1 except that the alpha-alumina carrier was impregnated with a solution of ruthenium chloride, followed by calcination, prior to co-precipitating the intimate mixture of nickel, ruthenium, lanthanum and aluminium compounds. : : Example 3 : A catalyst precursor C was prepared by the procedure of Example 1 except that the solution containing nickel, lanthanum and aluminium nitrates and urea also contained ruthenium chloride.
Example 4
A catalyst precursor D was prepared by the procedure of Example 1 and then, after calcination, was impregnated with a solution of ruthenium chloride, followed by a further step of calcination at 450°C.
The precursors all contained about 10% by weight of nickel as nickel oxide, 2.5% by weight of lanthanum as lanthana, and about 1.5% by weight aluminium as alumina (in addition to the alpha-alumina present as the carrier). The precursors B, C and D each also contained about 0.2% by weight of ruthenium.
To test the catalytic activity, each precursor was charged to an exemally heated tube and reduced to the active catalyst by passing a mixture of hydrogen and nitrogen containing about 2% by volume of hydrogen through the precursor at atmospheric pressure while heating
SUBSTITUTE SHEET (RULE 26)
RN WO 00/43121 5 PCT/GB99/02376 to about 600°C. Liquid hexane was vaporised at a rate of 3.5 mi per hour per ml of catalyst precursor charged to the tube and mixed with such an amount of steam to give the desired steam to hydrocarbon carbon ratio then the resultant mixture was passed through the reduced catalyst at atmospheric pressure while heating the tube to give an exit temperature of 750°C. § The test was repeated for various steam to hydrocarbon carbon ratios. The activity was assessed by comparing the extent of reforming to that given by a standard catalyst. The results are shown in the following table.
Relative activity at steam ratio 1032 105.4 106.8
At steam ratios of 3:1 and 3.5:1, the catalyst A exhibited traces of carbon. The tests on the ruthenium-containing materials, catalysts B, C and D, were completely free of carbon deposits indicating a superior performance at lower steam to carbon ratios. The results also _demonstrate that the catalysts containing ruthenium incorporated at the same time as, or particularly after, the nickel, aluminium and lanthanum compounds had better activity in steam reforming than the ruthenium-free catalyst A_
SUBSTITUTE SHEET (RULE 26)
Claims (23)
1. A catalyst comprising a preformed carrier carrying nickel and ruthenium metals intimately associated with alumina and lanthana.
2. A catalyst according to claim 1 containing about 5 to about 33% by weight of nickel metal, about 0.1 to about 2.5% by weight of ruthenium metal, about 0.1 to about 20% by weight of lanthana, and about 1 to 20% by weight of alumina (in addition to any alumina present as the carrier), said percentages being based upon the total weight of the catalyst.
3. A catalyst according to any one of claims 1 to 3 obtainable by subjecting to reducing conditions a precursor comprising a preformed carrier carrying an intimate mixture of oxides of nickel, aluminium and lanthanum, and ruthenium and/or ruthenium oxide, whereby the nickel oxide and any ruthenium oxide are reduced to the elemental i metals.
4, A catalyst precursor comprising cylindrical pellets of a carrier carrying an intimate mixture of oxides of nickel, aluminium and lanthanum, and ruthenium and/or ruthenium oxide. '
5, A catalyst precursor according to claim 4 wherein the cylindrical pellets have one or more holes extending axially therethrough.
6. A catalyst precursor according to claim 4 or claim 5 wherein the cylindrical pellets have a diameter in the range 5 to 20 mm and an aspect ratio in the range 0.5:1 to 2:1.
7. A catalyst precursor according to any one of claims 4 to 6 containing 5 to 30% by weight of nickel as nickel oxide, NiO, 0.1 to 15% by weight of lanthanum as lanthanum oxide, La,0;, and 0.1 to 2.5% by weight of ruthenium, based on the total weight of the precursor.
8. A catalyst precursor according to claim 7 containing 0.5 to 10% by weight of aluminium, as alumina Al,O,, based on the total weight of the precursor, in intimate admixture with : the nickel oxide, lanthanum oxide and ruthenium and/or ruthenium oxide, in addition to any alumina present in the carrier.
9. *A catalyst according to any one of claims 110 3 or a precursor according to any one of claims 4 to 8 wherein the nickel to lanthanum atomic ratio is in the range 4:1 to 12:1 SUBSTITUTE SHEET (RULE 26)
and the nickel to aluminium (in addition to any aluminium present in the carrier) atomic ratio is in the range 1.5:1 to 6:1.
10. A catalyst according to any one of claims 1 to 3 or 9 or a precursor according to any one of claims 4 to 9 wherein the ruthenium to nickel atomic ratio is in the range 0.002:1 t0 0.15:1.
11. A process for the steam reforming of a hydrocarbon feedstock comprising passing a mixture of the hydrocarbon feedstock and steam over a catalyst according to any one of claims 1 to 3 or 9 to 10, or the product of reducing a precursor according to any one of claims 4 to 10, disposed in tubes extemally heated such that the temperature of the reformed gas mixture leaving the catalyst has a temperature in the range 600°C to 850°C.
12. Steam reformer tubes charged with a catalyst precursor comprising a preformed carrier carrying an intimate mixture of oxides of nickel, aluminium and lanthanum, and ruthenium and/or ruthenium oxide.
13. Steam reformer tubes according to claim 12 wherein the inlet portion of the tubes is charged with a catalyst precursor comprising a preformed carrier carrying an intimate mixture of oxides of nickel, aluminium and lanthanum, and ruthenium and/or ruthenium oxide, and a ruthenium-free steam reforming catalyst precursor is charged to the remainder of the length of the tubes.
14. A steam reforming process comprising passing a mixture of steam and a hydrocarbon feedstock adiabatically through a bed of a catalyst according to any one of claims 1 to 3 or 9 to 10 containing at least 20% by weight of nicke!, the mixture being preheated such that the temperature of the reformed gas mixture leaving the catalyst is in the range 450°C to 600°C.
15. A method of forming a catalyst precursor comprising impregnating cylindrical pellets of a porous carrier with a solution containing salts of nickel, lanthanum, aluminium and ruthenium, and a hydrolysable precipitation agent, heating the impregnated pellets to increase the pH and so precipitate heat-decomposable compounds of nickel, aluminium and tanthanum and ruthenium or a heat-decomposable compound of ruthenium, and then calcining the product to decompose the heat-decomposable compounds to the comresponding oxides. SUBSTITUTE SHEET (RULE 26)
8 PCT/GB99/02376
16. A method of forming a catalyst precursor comprising impregnating cylindrical pellets of a porous carrier with a solution containing heat-decomposable nickel, aluminium and lanthanum salts, impregnating the cylindrical pellets with a solution of a heat-decomposable ruthenium salt before or after impregnation with the solution containing the heat-decomposable salts of nickel, aluminium and lanthanum, and then calcining.
17. A catalyst according to claim 1, substantially as herein described and illustrated.
18. A catalyst precursor according to claim 4, substantially as herein described and illustrated.
19. A process according to claim 11, substantially as herein described and illustrated.
20. Steam reformer tubes according to claim 12, substantially as herein described and illustrated.
21. A process according to claim 14, substantially as herein described and illustrated.
22. A method according to claim 15, or claim 16, substantially as herein described and illustrated.
23. A new catalyst, a new catalyst precursor, a new steam reforming process, a new method of forming a catalyst precursor, or new steam reformer tubes, substantially as herein described. AMENDED SHEET
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9801321.2A GB9801321D0 (en) | 1998-01-21 | 1998-01-21 | Catalysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ZA200105594B true ZA200105594B (en) | 2002-10-07 |
Family
ID=10825675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ZA200105594A ZA200105594B (en) | 1998-01-21 | 2001-07-06 | Catalyst carrier carrying nickel ruthenium and lanthanum. |
Country Status (4)
| Country | Link |
|---|---|
| AU (1) | AU2176999A (en) |
| GB (1) | GB9801321D0 (en) |
| WO (1) | WO1999037397A1 (en) |
| ZA (1) | ZA200105594B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100168257A1 (en) * | 2007-03-13 | 2010-07-01 | Matthias Duisberg | Metal-doped nickel oxides as catalysts for the methanation of carbon monoxide |
| BR102021002346A2 (en) * | 2021-02-08 | 2022-08-23 | Petróleo Brasileiro S.A. - Petrobras | CATALYSTS, PROCUREMENT PROCESSES AND HYDROCARBON STEAM PRE-REFORMATION PROCESS |
Family Cites Families (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 |
| JPS5187490A (en) * | 1975-01-24 | 1976-07-31 | Grace W R & Co | |
| GB2080136B (en) * | 1980-07-16 | 1984-05-16 | Dyson Refractories | Coprecipitated modified nickel catalysts |
| US4857499A (en) * | 1987-03-20 | 1989-08-15 | Kabushiki Kaisha Toshiba | High temperature combustion catalyst and method for producing the same |
| JP3145175B2 (en) * | 1992-03-31 | 2001-03-12 | 三井金属鉱業株式会社 | Exhaust gas purification catalyst and method for producing the same |
| IT1273491B (en) * | 1995-02-03 | 1997-07-08 | Snam Progetti | MATERIAL WITH A LAYER STRUCTURE OF THE HYDROTHALCITE TYPE AND RELATED USES |
-
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
Also Published As
| Publication number | Publication date |
|---|---|
| WO1999037397A1 (en) | 1999-07-29 |
| GB9801321D0 (en) | 1998-03-18 |
| AU2176999A (en) | 1999-08-09 |
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