Steam reforming catalyst for hydrocarbons and method of producing the same

Abstract: An excellent steam reforming catalyst for hydrocarbons is provided having at least one of nickel oxide, cobalt oxide and platinum group noble metals supported on a carrier consisting essentially of aluminum oxide Aℓ₂O₃ and a metal oxide expressed by MeO, comprising about 3-35 mols of metal oxide MeO to 100 mols of aluminum oxide Aℓ₂O₃ in the carrier, Me being at least one metal selected from the group consisting of calcium Ca, barium Ba and strontium Sr. The catalyst exhibits high activity, superior mechanical strength, good heat resistant property, splendid chemical stability, and remarkable thermal shock resistant property, retains a high specific surface area at high temperatures, and does not form detrimental nickel aluminate or cobalt aluminate in steam reforming reactions of hydrocarbons. A method of producing the catalyst is also provided.

Description: The present invention relates to a steam reforming catalyst for hydrocarbons for production of hydrogen, synthetic gases or town gases, and a method of producing the catalyst. Heretofore, catalysts having as catalytically active component Ni or Co supported on alumina-based carriers have been widely used as catalysts for reforming hydrocarbons. Platinum group noble metals, such as Rh and Ru, can be used also as the active components. However, they are so expensive that they have not been used so widely as Ni and Co, though they have higher activities than Ni and Co. Carriers made of oxide of Mg, Ca, Sr, Ba, Al, Ce, Si, Ti, Zr, or combinations of at least two thereof are known. Among them, alumina is mostly used as the carrier from the view points of mechanical strength, heat resistant property and chemical stability, etc. An improved alumina carrier with an added oxide of an alkaline earth metal is also known. For example, Japanese Patent Application Publication No. 44-17, 737 discloses a reforming catalyst with 10-20 wt% of Mg, Ca, Sr or Ba added, which has less deposition of carbon thereon during the use in the reforming reaction. Further, Japanese Patent Application No. 61-264,097 (Laid-open No. 63-141,643) discloses a catalyst prepared by supporting at least one of V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ag, Cd, La, Ce, perovskite and platinum group noble metals on a carrier containing aluminum oxide and a metal oxide expressed by MeO (Me is Ca, Ba or Sr) in a mole ratio of 100: (3-25), which is mainly used for catalytic combustion processes. EP-A-0 337 730 describes catalysts based on a modified alumina structure A 1-z C z B x D u Al 12-y-u O 19-α wherein A is at least one of Ba, Ca and Sr, C is at least one of K, Rb and rare earth elements, B is at least one of Mn, Co, Fe, Ni, Cu and Cr, and D is at least one of Au, Ag, and platinum group noble metals, z lies in the range of 0 - 0.4, x lies in the range of 0 - 4, y lies in the range of x - 2x, u has a value of not less than 0.01, x + u is no greater than about 4, and α is determined by the valences X, Y, Z and U of the elements A, B, C and D, the values x, y, z and u according to the formula α = 1 2 {X-z(X-Y) + xZ + uU 3y-3u)} providing catalysts of good heat resistance and high activity. The active catalytic components B and/or D are incorporated or fixed in the crystal lattice. GB-A-997 523 proposes a nickel oxide catalyst supported on an anhydrous alumina and clay carrier bonded with calcium aluminate which is fired only at about 827°C whereby the alumina/clay character of the carrier is unchanged. Catalysts using conventional alumina series carriers have the following drawbacks; (1) If Ni or Co supported on alumina is exposed to a high temperature oxidising atmosphere, nickel aluminate or cobalt aluminate which is a compound of Ni or Co and alumina is formed to decrease the catalyst activity. (2) During the reforming reaction, the surface of the catalyst is covered by carbon formed by reactions, such as disproportionation of CO and decomposition of CH₄, to decrease the strength and the activity of the catalyst. For obviating the drawback (2), an attempt has been made to add a basic component to the alumina to neutralize the acid point of the alumina. However, if K is added as the basic component to the alumina, K is dissipated from the catalyst during the reforming reaction. While, if MgO is added as the basic component to the alumina, hydroxide of Mg is formed in the presence of steam, so that the formed catalyst assumes a powdery state during the reforming reaction. An object of the present invention is to obviate the above drawbacks. Another object of the present invention is to provide a steam reforming catalyst which has a high specific surface area and does not form nickel aluminate or cobalt aluminate even in a high temperature oxidizing atmosphere, and which substantially does not suffer from decrease of activity and strength caused by deposition of carbon, etc., during the reforming reaction. The present invention, as set forth in the claims, is a steam reforming catalyst for hydrocarbons having at least one of Ni oxide, Co oxide and a platinum group metal supported on a carrier consisting essentially of aluminum oxide Al2O3 and a metal oxide MeO wherein Me is selected from Ca, Ba and Sr, the metal oxide MeO and the aluminum oxide Al2O3 being present in a mole ratio MeO/(MeO + Al2O3) of 10/100-15/100 and being essentially in the form of a complexed oxide expressed mainly as MeO.6Al2O3, at least a part of said metal Me being added in the form of calcium aluminate cement as a moulding binder in an amount of from 10-40 wt% relative to the essential components of the carrier. The catalyst of the present invention can contain from 3-50 parts by weight of at least one of nickel oxide and cobalt oxide supported on the carrier, relative to 100 parts by weight of the carrier. The catalyst of the present invention can contain from 0.03-3 parts by weight of at least one platinum group noble metal supported on the carrier, relative to 100 parts by weight of the carrier. The catalyst of the present invention can contain from 3-50 parts by weight of at least one of nickel oxide and cobalt oxide, and from 0.03-3 parts by weight of at least one platinum group noble metal, supported on the carrier relative to 100 parts by weight of the carrier. Preferably, the aluminum oxide and the metal oxide expressed as MeO which are the essential components of the carrier are in the form of complexed oxides expressed mainly as MeO.6Al₂O₃ in the carrier (as may be verified by X-ray diffraction analysis). Also, the present invention provides a method of producing a reforming catalyst for hydrocarbons, comprising mixing carrier components consisting essentially of Al₂O₃ and/or aluminium hydroxide Al₂O₃.nH₂O and a metal oxide compound MeO wherein Me is selected from Ca, Ba and Sr to make a mixture, the metal oxide MeO and the aluminium oxide Al₂O₃ being present in a mole ratio MeO/(MeO + Al₂O₃) of 10/100 - 15/100, adding calcium aluminate cement as a moulding binder in an amount of from 10-40 wt% relative to the essential components of the carrier and moulding the mixture, calcining the mixture to provide a catalyst carrier at a temperature of not less than 900°C essentially in the form of a complexed metal oxide expressed mainly as MeO.6Al₂O₃ wherein Me is provided at least partly in said cement, impregnating the catalyst carrier with an aqueous solution of at least one of a nickel compound, a cobalt compound, and a platinum group noble metal compound, and calcining the impregnated catalyst carrier. The addition of calcium aluminate cement improves not only the mechanical strength and spalling-proof property of the steam reforming catalyst of the present invention, but also exhibits a quite unexpected and remarkable increase in the activity. In a preferred embodiment of the present invention, the mixture of aluminum oxide Al₂O₃ and/or aluminum hydroxide Al₂O₃.nH₂O and Me compound is a coprecipitate or a hydrolysis product or a heat decomposition product obtained from a mixed solution of a water soluble or alcohol soluble aluminum compound and water soluble or alcohol compound of Me. In another preferred example of the method of the present invention, a portion or the whole of the mixture of aluminum oxide Al₂O₃ and/or aluminum hydroxide Al₂O₃.nH₂O and Me compound is a hydrolysis product or a heat decomposition product of a mixed or complexed alkoxide of aluminum and the metal Me. Preferably, a portion of the whole of the aluminum oxide Al₂O₃ and/or aluminum hydroxide Al₂O₃.nH₂O contained in the mixture before calcination is a hydrolysis or a heat decomposition product of at least one aluminum alkoxide. In a preferred embodiment of the above described method of the present invention, the catalyst carrier is produced by mixing and/or kneading powdery aluminum oxide Al₂O₃ and/or powdery aluminum hydroxide Al₂O₃.nH₂O and a powdery Me compound or a solution of Me compound, and calcining. The catalyst carrier used in the present invention consists essentially of CaO·6Al₂O₃, BaO·6Al₂O₃ or SrO·6Al₂O₃, and shows an excellent heat resistant property even at high temperatures at which the steam reforming reactions are effected. Crystal structure of CaO·6Al₂O₃, BaO·6AlO₃ and SrO·6Al₂O₃, is layered alumina structure, which is considered to be a cause of the high heat resistant property of the catalyst carrier. Existence of the layered alumina structure in the carrier can be ascertained by an X-ray diffraction analysis. The existence of CaO·6Al₂O₃, BaO·6Al₂O₃ or SrO·6Al₂O₃ is considered to prevent the formation of nickel aluminate and cobalt aluminate so as to provide a steam reforming catalyst having a stable activity. The catalyst carriers of the present invention can be produced according to a method described in Japanese Patent Application Laid-open No 62-153,158. A catalyst carrier for use in making the steam reforming catalyst of the present invention is preferably produced by mixing a water soluble aluminum salt and a water soluble barium salt in water in the required molar ratio (as described above) to form an aqueous solution, adding a coprecipitant to the aqueous solution to produce a mixed composition in a form of coprecipitate, removing the solvent from the coprecipitate by washing and filtering the coprecipitate or evaporating to dryness, precalcining the coprecipitate at from 200-500°C, and calcining the precalcined coprecipitate at a temperature of not less than about 900°C for from 5-30 hours. In this case, as the water soluble aluminum compound, aluminum nitrate, aluminum sulphate, aluminum chloride, etc., can be used. As the water soluble barium compound, barium nitrate, barium chloride, barium acetate, etc., can be used. As the coprecipitating agent or coprecipitant, sodium hydroxide, sodium carbonate, caustic potash and aqueous ammonia, etc., can be used. As the water soluble starting materials, basic salt such as sodium aluminate and barium hydroxide, etc., can be used. In this case, an acidic coprecipitant such as nitric acid or carbonic acid should be used. The precalcination step may be omitted, as the case may be. In a more preferable production method for the catalyst carrier of the steam reforming catalyst described herein, an alkoxide method may be used which uses mixed or complexed alkoxides of aluminum and barium as starting raw material to provide the essential components of the eventual carrier. Formation of the oxide of aluminum and barium from their alkoxides is preferably effected through their hydrolysis reactions, though other processes such as thermal decomposition, etc., can be used. It is not necessary that all of these oxides are prepared from the corresponding alkoxides. For example, alumina, barium carbonate, etc., can be added to the hydrolysis product or the heat decomposition product of the alkoxides. The hydrolysis reaction is preferably effected at from 50-110°C rather than to effect same at room temperature. Influence of pH of water added for hydrolysis reaction is not noticeable. However, influence of aging time after the addition of water on the specific surface area of the heat resistant carrier is quite large. The longer the aging time is, the larger the specific surface area is. Thus, the aging time is preferably at least one hour, and more preferably as long as possible, such as 5-10 hours, within an economically permissible extent. The inventors have found out that specific surface area of the heat resistant carrier is influenced by the amount of water used in the hydrolysis, and that an unexpected large specific surface area can be obtained, even when the amount of water used in the hydrolysis is less than the amount of water necessary for hydrolyzing all the amount of existing complexed or mixed alkoxides into hydroxides and alcohols (hereinafter, abbreviated as "equivalent amount of water"). Thus, the amount of water can be less than the equivalent amount of water. However, less than about 0.5 equivalent amount of water is not desirable because the specific surface area of the produced heat resistant catalyst carrier decreases rapidly. On the other hand, use of an unnecessarily large amount of water in the hydrolysis is also not desirable, because it incurs an excessive investment cost and energy consumption, so that water amount is preferably equal to or less than about 10 equivalents of water from an economical viewpoint. Therefore, the amount of water to be used is generally from 0.5-10 equivalents of water. However, the amount of water is not exclusively limited to this range, and water amounts beyond this range can be used, if some loss in economy is tolerable. In a preferred embodiment of production, the essential components of the catalyst carrier for steam reforming catalysts of the present invention are produced by dissolving aluminum alkoxide and barium alkoxide in an a mole ratio of MeO/(MeO + Al₂O₃) of 10/100 - 15/100 in alcohol to form an alcoholic solution, adding from 0.5-10 equivalents of water to the alcoholic solution to hydrolyze the alkoxides at a temperature of 50-100°C, aging the hydrolyzed solution for 5-10 hours, removing the solvent by e.g. filtering, evaporation to dryness to obtain a mixture of decomposed products, precalcining the mixture of decomposed products at a temperature of from 200-500°C, and precalcining the mixture at a temperature of not less than about 900°C for from 5-30 hours. Sometimes, the precalcination step may be omitted, as the case may be. The produced catalyst carrier is used for the production of the steam reforming catalyst of the present invention. In this case, any usual method of producing a steam reforming catalyst can be used for production. As the raw material for the active ingredient Ni, use is made of nickel acetate, nickel sulfate, nickel chloride, nickel carbonate, nickel citrate, nickel hydroxide, nickel nitrate, nickel bromide, nickel iodide, and the like nickel compounds. As the raw material for the active ingredient Co, use is made of cobalt acetate, cobalt sulfate, cobalt chloride, cobalt carbonate, cobalt citrate, cobalt hydroxide, cobalt nitrate, and the like cobalt compounds. As the raw material for the active ingredient platinum group noble metal, use can be made of inorganic salts such as nitrate, organic salts such as acetate, halides such as chloride, halogeno complexes, ammono complexes, cyano complexes and any other compounds generally used as raw materials in the production of catalysts. In producing the catalyst using nickel as an active ingredient, use can be made of an impregnation method wherein a previously formed carrier is impregnated with a solution of a nickel compound, dried and calcined to support nickel of a desired amount on the carrier, a coprecipitation method of coprecipitating a catalyst component and a carrier component, a precipitation method wherein nickel is precipitated by addition of a precipitant to an aqueous solution of a nickel compound in the presence of a powdery carrier, and a kneading method wherein a nickel compound and a carrier material is mixed in a slurry or paste state, then molded, dried and calcined, and the like methods. The catalyst of the present invention contains 3-50 wt% of nickel, calculated as NiO. If the NiO content is less than 3 wt%, the catalyst has low activity in a steam reforming reaction, and if the content exceeds 50 wt%, the superior properties of the carrier are not reflected in the properties of the catalyst. A more preferable NiO content is in the range of 5-25 wt%. The same as described about the production method using Ni as an active ingredient can be applied to the production method of catalyst using cobalt as the active ingredient and the production method of the catalyst using both nickel and cobalt as the active ingredients. Production methods of the catalyst using a platinum group noble metal alone or together with nickel oxide and/or cobalt oxide as active ingredients, can be practised in a similar manner as the production method of the catalyst using nickel as the active ingredient. However, the content of the noble metals is preferably in a range of 0.03-3 wt%. If the noble metal content is less than 0.03 wt%, the activity of the catalyst in the steam reforming reaction is insufficient, while the content exceeding 3 wt% is not advisable economically. Steam reforming catalyst of the present invention can be used in powder or granular form, but, in general it is used as tablet, ring, sphere, or extruded form. For this invention, the forming by use of calcium aluminate cement is especially desirable because it exhibits also a subsidiary effect of remarkably improving the catalyst activity. Catalyst of the present invention is used in steam reforming reactions of hydrocarbons. As the hydrocarbons in the reaction, methane, ethane, propane, butane, or mixtures thereof, or naphtha, etc., can be used. A reaction temperature in a range of 400-1,200°C is used, and a reaction pressure in a range of atmospheric to 40 kg/cm² is used. Mol ratio of steam to carbon in the raw material hydrocarbon used in the reaction is usually, in a range of 2-5. Space velocity SV can be selected within a range of 100-50,000, depending on the process conditions. For a better understanding of the present invention, reference is made to the accompanying drawings, in which: Fig. 1 is a graph showing a relation between the value x of a carrier (BaO) x ·(Aℓ₂O₃) l-x obtained by calcining at 1,450°C for 5 hrs and the specific surface area thereof; Fig. 2 is a graph of X-ray diffractions of (BaO) x · (Aℓ₂O₃) l-x ; Fig. 3 is a graph showing a relation between the calcining temperature and the specific surface area of obtained carriers (BaO) 0.143 ·(Aℓ₂O₃) 0.857 and Aℓ₂O₃; Fig. 4 is a graph of X-ray diffractions of the carrier (BaO) 0.143 ·(Aℓ₂O₃) 0.857 and Aℓ₂O₃; and Fig. 5 is a graph of X-ray diffractions of a catalyst carrier (BaO) 0.14 ·(Aℓ₂O₃) 0.86 obtained by solids mixing method and alkoxide method and calcined at 1,000°C, 1,200°C, 1,450°C or 1,600°C. Hereinafter, the present invention will be explained in more detail by way of reference examples. Comparative Examples 1-5 and Referential Examples 1-2 As starting raw materials, aluminum oxide and barium carbonate are fed to a ball mill, and pulverized and mixed for 24 hours. These mixed materials are then calcined at 1,450°C for 5 hours to obtain catalyst carriers. Mol ratio of barium oxide to the sum of barium oxide and aluminum oxide were set respectively to 0% (Referential Example 1), 5% (Example 1), 10% (Example 2), 14.3% (Example 3), 15% (Example 4), 20% (Example 5) and 50% (Referential Example 2). Compositions and BET specific surface areas of the carriers thus obtained are shown in the following Table 1 and attached Figure 1. X-ray diffraction patterns of the carriers containing 0, 10, 14.3, 15 and 50 mol% of barium oxide are measured to examine crystal structures of these carriers. The results are shown in attached Fig. 2. In the Fig. 2, the symbols ○ means α-Aℓ₂O₃,  means BaO·6Aℓ₂O₃, and the symbol ▿ means BaO·Aℓ₂O₃. The carrier containing 14.3 mol% of BaO exhibiting the maximum specific surface area shows the structure of BaO·6Aℓ₂O₃ by X-ray diffraction, so that it is considered that the small reduction of the specific surface area of the carrier at high temperature is brought from the formation of the stable BaO·6Aℓ₂O₃ phase. Carrier BaO (mol%) Aℓ₂O₃ (mol%) Specific surface area (m²/g) Referential Example 1 0 100 1.4 Example 1 5 95 2.5 Example 2 10 90 4.5 Example 3 14.3 85.7 5.4 Example 4 15 85 3.7 Example 5 20 80 1.3 Referential Example 2 50 50 0.7 Comparative Examples 6-11 and Referential Examples 3-7 The same starting raw materials of Aℓ₂O₃ and BaO as in Example 1 are pulverized and mixed as in Example 1 to produce uncalcined mixtures of (Aℓ₂O₃) 0.857 (BaO) 0.143 . The uncalcined mixtures and referential γ-alumina not containing BaO are respectively calcined at 1,000°C, 1,100°C, 1,200°C, 1,300°C, 1,400°C and 1,450°C for 5 hours to obtain carriers of Comparative Examples 6-11 and Referential Examples 3-7. BET specific surface area of the carriers are shown in the following Table 2 and attached Fig. 3. Calcining temperature (°C) Specific surface area (m²/g) Comparative Example 6 1,000 125 Comparative Example 7 1,100 89 Comparative Example 8 1,200 24 Comparative Example 9 1,300 6 Comparative Example 10 1,400 5.3 Comparative Example 11 1,450 5.4 Referential Example 3 1,000 126 Referential Example 4 1,100 102 Referential Example 5 1,200 5.5 Referential Example 6 1,300 1.7 Referential Example 7 1,450 1.3 Crystal structures of the (Aℓ₂O₃) 0.857 (BaO) 0.143 carriers of Comparative Examples 7, 8, 10 and 11 respectively calcined at 1,100°C, 1,200°C, 1,400°C and 1,450°C are analyzed by X-ray diffraction. The results are shown in attached Fig. 4. In Fig. 4, the symbols · and ▿ means BaO·6Aℓ₂O₃ and BaO·Aℓ₂O₃, respectively. As seen from Fig. 4, it is considered that the calcination of the uncalcined mixtures at a temperature of not less than 1,200°C has produced high temperature heat resistant carriers comprising the formed BaO·6Aℓ₂O₃, so that sintering of the carriers has been suppressed or decreased to the minimum. Comparative Example 12 Aluminum nitrate and barium nitrate are dissolved in water in an Aℓ₂O₃:BaO mol ratio of 85.7:14.3 to prepare an aqueous solution, and sodium carbonate is added to the solution to adjust pH thereof to 8 to form coprecipitates. Thus obtained coprecipitates are washed, filtered, dried at 200°C for 2 hours, precalcined at 500°C for 2 hours, and thereafter calcined at 1,450°C for 5 hours to obtain a carrier of Comparative Example 12. BET specific surface area of the carrier was 5.5 m²/g. Comparative Examples 13-15 Aluminum nitrate and nitrate of Me (Me is Ba, Ca or Sr) are dissolved in water in a mol ratio of Aℓ₂O₃:MeO of 85.7:14.3 to prepare an aqueous solution thereof. The solutions have aqueous ammonia added dropwise to pH 8, and evaporated to dryness to form coprecipitation products. The formed products are dried at 200°C for 2 hours, precalcined at 500°C for 2 hours, and then calcined at 1,450°C for 5 hours to obtain carriers of Comparative Examples 13, 14 and 15. BET specific surface area of these carriers are shown in Table 3. Composition Specific surface area (m²/g) Comparative Example 13 (BaO) 14.3 (Aℓ₂O₃) 85.7 5.2 Comparative Example 14 (CaO) 14.3 (Aℓ₂O₃) 85.7 5.0 Comparative Example 15 (SrO) 14.3 (Aℓ₂O₃) 85.7 4.2 As seen from above Table 3, the addition of calcium oxide or strontium oxide to alumina also brought about retention of high specific surface area of the carriers at high temperatures. Comparative Examples 16-17 and Referential Example 8 Barium isopropoxide and aluminum isopropoxide are dissolved in isopropyl alcohol in a mole ratio of 1:12 to prepare an alcoholic solutions to which dropwise addition of water is carried out to effect hydrolysis thereof. The hydrolysis of the isopropoxides are carried out at a temperature of 80°C, in nitrogen atmosphere. Thus obtained suspension liquids are aged for 12 hours under agitation and then dried under reduced pressure to obtain uncalcined powders of Example 16. Meanwhile, barium carbonate BaCO₃ and γ-alumina in a mol ratio of 1:6 are pulverized and mixed in a ball mill for 24 hours to obtain uncalcined powders of Comparative Example 17. Thus obtained two types of powders and γ-alumina powder (Referential Example 8) are calcined at 1,000, 1,100, 1,200, 1,300, 1,450 and 1,600°C, respectively for 5 hours. BET specific surface area of these calcined powders are measured, and the results are shown in Table 4 below. Specific surface area (m²/g) 1,000°C 1,100°C 1,200°C 1,300°C 1,450°C 1,600°C Comparative Example 16 79 60 38 18 12 11 Comparative Example 17 125 90 23 6 5 4 Referential Example 8 126 100 5 1.7 1.2 1.0 As seen from above Table 4, specific surface area of γ-alumina (Referential Example 8) decreased noticeably at around 1,200°C, and became about 1 m²/g at the temperatures above 1,400°C. The decrease of the specific surface area is caused by the phase transition of γ-alumina to α-alumina. In the case of the powders of Comparative Example 17 obtained by the solids mixing method, specific surface area of the powders started to decrease much at 1,200°C, but the specific surface area of 5 m²/g was kept even at 1,400°C, and this is about 4 times higher than that of Referential Example 8. In the case of the powders of Comparative Example 16 obtained by the alkoxide method, retention of the specific surface area is further improved, and is always about 2-3 times higher than that of Comparative Example 17. It kept high specific surface area of more than 10 m²/g even after it was calcined at 1,600°C. Thus, adoption of the alkoxide method undoubtedly brings about marked improvement of the specific surface area of the catalyst carrier or catalyst. X-ray diffraction patterns of the calcined powders of Comparative Example 16 are measured, and the results are shown in Fig. 5. In Fig. 5, the symbol  means BaO·6Aℓ₂O₃. The alkoxide method enables direct formation of the target BaO·6Aℓ₂O₃ at temperatures of 1,200°C or higher without forming the intermediate BaO·Aℓ₂O₃. The directly formed BaO·6Aℓ₂O₃ appears to function to suppress the decrease of the specific surface area at 1,200°C or temperatures higher than 1,200°C. In addition, the alkoxide method allows treatment of complexed oxides at low temperatures, and this is considered as a reason of affording the more stabilized high specific surface area of the products obtained from alkoxides. Comparative Examples 18-20 By using aluminum isopropoxide and barium isopropoxide, calcium isopropoxide or strontium isopropoxide, various calcined powders of Comparative Examples 18, 19 and 20 of an Aℓ₂O₃:MeO mol ratio of 85.7:14.3 are produced in the same manner as in Comparative Example 16. BET specific surface area of these samples are measured. The results are shown in the following Table 5. Composition Specific surface area (m²/g) Comparative Example 18 BaO·6Aℓ₂O₃ 13.8 Comparative Example 19 CaO·6Aℓ₂O₃ 12.5 Comparative Example 20 SrO·6Aℓ₂O₃ 12.3 Comparative Example 21 Barium carbonate and aluminum hydroxide are fed to a ball mill, and pulverized and mixed for 24 hours to obtain a mixture of a Ba:Aℓ mol ratio of 1:12. The mixture thus obtained is dried at 400°C for 4 hours, then moulded into cylinders of 3/16 inch (0.48 cm) diameter by a tablet machine. Thus obtained tablets are calcined at 1,300°C for 5 hours to obtain catalyst carriers. According to X-ray diffraction measurement, the catalyst carriers are essentially composed of BaO·6Aℓ₂O₃. The catalyst carriers are impregnated with an aqueous solution of nickel nitrate, and calcined at 600°C for 5 hours to obtain steam reforming catalysts for hydrocarbons. Nickel content of the catalysts is 5 wt% calculated as nickel oxide NiO. The catalysts thus produced are calcined at a temperature of 900°C, 1,100°C, 1,300°C or 1,400°C, respectively for 5 hours in air to examine formation of nickel aluminate. Formation of nickel aluminate is judged by appearance of nickel aluminate peak (2ϑ=45.1°) and disappearance of NiO peak (2ϑ=43.51°) in X-ray diffraction measurement by Cu-Kα ray. As a result of X-ray diffraction measurement, it is found out that nickel aluminate is not produced up to the temperature of 1,300°C. Referential Example 9 Commercial aluminum hydroxide is dried at 400°C for 4 hours, moulded into cylinders of 3/16 inch (0.48 cm) diameter by using a tablet machine, and then calcined at 1,300°C for 5 hours in an electric furnace to obtain a catalyst carrier. As a result of X-ray diffraction measurement, the main component of the catalyst carrier is found to be α-Aℓ₂O₃. The catalyst carrier is impregnated with an aqueous solution of nickel nitrate, and calcined at 600°C for 5 hours to obtain a steam reforming catalyst for hydrocarbons. Nickel content of this catalyst is 5 wt% calculated as nickel oxide NiO. The catalyst is used in a nickel aluminate formation test in the similar manner as in Example 21. As the result of the test, it is found that nickel aluminate is formed even at 900°C by using the Ni/Aℓ₂O₃ catalyst. Comparative Example 22 A catalyst consisting of 5 wt% of nickel oxide NiO supported on a carrier essentially composed of CaO·6Aℓ₂O₃ is prepared, in the similar manner as in Comparative Example 21 except that aluminum hydroxide and calcium carbonate are used as raw materials. The catalyst is used in a nickel aluminate formation test in the same manner as in Comparative Example 21 to find that nickel aluminate is not formed up to the temperature of 1,100°C. Comparative Example 23 A catalyst consisting of 5 wt% of NiO supported on a carrier essentially composed of SrO·6Aℓ₂O₃ is prepared, in the similar manner as in Comparative Example 21 except that aluminum hydroxide and strontium carbonate are used as raw materials. The catalyst is used in a nickel aluminate formation test in the same manner as in Comparative Example 21 to find that nickel aluminate is not formed up to the temperature of 1,200°C. Comparative Examples 24-26 Using the same catalyst as used in Comparative Examples 21-23, steam reforming tests of butane are performed. Prior to the tests, 200 cc of cylinder type catalysts of 3/16 inch (0.48 cm) diameter and 3/13 inch (0.59 cm) height are charged into a reactor of 30 mm diameter, then reduced by passing hydrogen at a rate of 200 Nℓ/hr for 5 hours under atmospheric pressure at 500°C. The steam reforming reactions are performed by passing butane of 100 g/hr, water of 385 g/hr and hydrogen of 4.4 Nℓ/hr to the reactor containing the reduced catalyst. At about 2 hours after the settling of the reaction conditions (reaction temperature of 850°C and reaction pressure of 16 kg/cm²G), the outlet gas is analyzed by TCD gaschromatograph. The result of this analysis is shown in Table 7. Referential Example 10 Using the same NiO (5 wt%)/α-Aℓ₂O₃ catalyst as that produced in Referential Example 8, a steam reforming test is performed in the same manner as in Comparative Examples 24-26. Test result is shown in the following Table 7. Comparative Example 24 Comparative Example 25 Comparative Example 26 Referential Example 10 Composition of carrier BaO·6Aℓ₂O₃ CaO·6Aℓ₂O₃ SrO·6Aℓ₂O₃ α-Aℓ₂O₃ Composition of outlet gas CH₄ 4.9 5.1 5.0 6.6 CO 15.1 15.0 15.0 14.3 CO₂ 11.5 11.6 11.6 12.0 H₂ 68.5 68.3 68.4 67.1 Comparative Example 27 A catalyst is prepared in the similar manner as in Comparative Example 21 except that a mixture of raw materials for the carrier is shaped into rings of 5/8 inch (1.59 cm) outer diameter, 1/4 inch (0.64 cm) inner diameter and 5/8 inch (1.59 cm) height and then pulverized to 3.5-4 mesh size. Using the catalyst, a steam reforming test of methane is performed, in which 25 cc of the catalyst is charged in a reactor of 1 inch (2.54 cm) diameter, with reaction conditions of a reaction pressure of 10 kg/cm²G, a reaction temperature of 650-870°C, GHSV of 15,000 hr⁻¹, and inlet H₂O/CH₄ mol ratio of 3.0. After measuring the initial activity, the reaction temperature is set to 870°C and only steam is passed for further 16 hrs, and then again the steam reforming reaction at the temperature of 650-870°C is performed to measure an extent of decrease of the catalyst activity. Catalyst activity is measured by the content of unreacted CH₄ in the dry exit gas at the outlet of the reactor. In commercial reforming apparatuses, it frequently happens that only steam is flowed into a steam reformer to keep its temperature while an apparatus other than the steam reformer has some other trouble. In such case of operation called as steaming, if the reactivity of the catalyst carrier is high, nickel metal supported on the carrier reacts with aluminum in the carrier to form nickel aluminate which decreases activity of the catalyst. As a method of reproducing such phenomenon in an experiment, only steam is flowed into the reactor at 870°C (steaming), and stability of the carrier is measured by a succeeding methane-steam reforming test. The result is shown in the following Table 8. Referential Example 11 A catalyst carrier is produced in the same manner as in Referential Example 8, except that the raw materials of the carrier are first shaped into rings of 5/8 inch (1.59 cm) outer diameter, 1/4 inch (0.64 cm) inner diameter and 5/8 inch (1.59 cm) height and then pulverized to 3.5-4 mesh. The catalyst is used in a steam reforming test of methane in a same method as in Example 27. The result of the test is shown in the following Table 8. As seen clearly from the Comparative Examples shown above, such catalysts have splendid advantages that the activity for steam reforming reaction is high and that nickel aluminate or cobalt aluminate is hardly produced even when it is exposed to an oxidizing atmosphere due to air and steam at high temperature. The difficulty of formation of nickel aluminate or cobalt aluminate means that the activity of the catalyst is slightly decreased, even if the atmosphere in the reformer becomes to an oxidizing atmosphere by some reasons. This is a great advantage in operating an apparatus of steam reforming. Comparative Example 28 A catalyst carrier consisting essentially of BaO·6Aℓ₂O₃ is produced in the same manner as in Comparative Example 21, then impregnated with an aqueous solution of cobalt nitrate, and calcined at 600°C for 5 hours to obtain a catalyst for reforming hydrocarbons. Supported amount of cobalt is 5 wt% calculated as cobalt oxide. Thus produced catalyst is calcined in air at 900°C, 1,100°C, 1,300°C or 1,400°C for 5 hrs to examine formation of cobalt aluminate. Formation of cobalt aluminate is judged by disappearance of NiO peak of 2ϑ=43.51° in X-ray diffraction measurement using Cu-Kα ray. The results are shown in the following Table 9. Comparative Examples 29 and 30 and Referential Example 12 A CaO·6Aℓ₂O₃ carrier same as that of Comparative Example 22, an SrO·6Aℓ₂O₃ carrier same as that of Comparative Example 23 and an Aℓ₂O₃ carrier the same as that of Referential Example 8, are impregnated with an aqueous solution of cobalt nitrate, and calcined at 600°C for 5 hrs to obtain hydrocarbon reforming catalyst. Supported amount of Co of these catalysts are 5 wt% each. The catalysts are examined in the same manner as in Comparative Example 28 to examine formation of cobalt aluminate. The test results are shown in the following Table 9. Carrier Formation of cobalt aluminate 900°C 1,100°C 1,300°C 1,400°C Comparative Example 28 BaO·6Aℓ₂O₃ ○ ○ ○ X Comparative Example 29 CaO·6Aℓ₂O₃ ○ ○ X X Comparative Example 30 SrO·6Aℓ₂O₃ ○ ○ X X Referential Example 12 Aℓ₂O₃ X X X X ○ No formation of cobalt aluminate X Formation of cobalt aluminate Comparative Examples 31-33 As starting raw materials, barium carbonate, calcium hydroxide and aluminum hydroxide are fed to a ball mill, and pulverized and mixed for 12 hours to produce a mixture. The mixture is then formed into rings of 5/8" (1.59 cm) outer diameter, 3/8" (0.95 cm) inner diameter and 1/4" (0.64 cm) height. After forming, the rings are calcined in an electric furnace at 1,300°C for 3 hrs to obtain three carriers of Ba-Ca-Aℓ series. Crush strengths of these carriers, and BaO:CaO:Aℓ₂O₃ mol ratios are shown in Table 10. BaO : CaO : Aℓ₂O₃ mol ratio Crush strength (kg) Comparative Example 31 11.9 : 2.6 : 85.5 18 Comparative Example 32 10.4 : 4.6 : 85.0 24 Comparative Example 33 9.3 : 6.1 : 84.6 18 Example A Setting BaO:CaO:Aℓ₂O₃ mol ratio to 10.4:4.6:85.0, barium acetate, alumina cement and aluminum hydroxide are fed to a ball mill, and mixed in wet state for 30 min. Here the alumina cement used is composed of 80.5% of Aℓ₂O₃ and 19.5% of CaO. The mixture is dried at 400°C for 4 hrs, formed into rings of 5/8" (1.59 cm) outer diameter x 3/8" (0.95 cm) inner diameter x 1/4" (0.64 cm) height, and then cured for 24 hrs. The rings are dried at 400°C, and then calcined at 1,300°C for 5 hrs to obtain a catalyst carrier. Crush strength of the catalyst is 28 kg, and the composition of the catalyst carrier is mixed crystals of BaO·Aℓ₂O₃, CaO·6Aℓ₂O₃ and α-Aℓ₂O₃ by an X-ray diffraction analysis. The catalyst carrier is impregnated with an aqueous solution of nickel nitrate, and calcined at 600°C for 5 hrs to obtain an NiO/Ba-Ca-Aℓ series catalyst. Supported amount of Ni is 5 wt% calculated as nickel oxide. Referential Examples 13-20 Using barium acetate, barium nitrate, barium carbonate or barium hydroxide as barium sources, and boehmite or aluminum hydroxide as aluminum source, raw materials of a BaO:Aℓ₂O₃ mol ratio of 1:6 are fed to a ball mill, and kneaded in wet state. The mixture is dried at 400°C, then formed into rings of 5/8" (1.59 cm) outer diameter x 3/8" (0.95 cm) inner diameter and 1/4" (0.64 cm) height. The rings are calcined at 1,300°C for 5 hrs, and crush strength thereof are shown in the following Table 11. Ba source Aℓ₂O₃ source Crush strength (kg) Referential Example 13 barium acetate AℓOOH 11.7 Referential Example 14 barium acetate Aℓ(OH)₃ 1.2 Referential Example 15 barium nitrate AℓOOH 9.3 Referential Example 16 barium nitrate Aℓ(OH)₃ <1.0 Referential Example 17 barium carbonate AℓOOH 1.8 Referential Example 18 barium carbonate Aℓ(OH)₃ 1.8 Referential Example 19 barium hydroxide AℓOOH 10.1 Referential Example 20 barium hydroxide Aℓ(OH)₃ 6.3 Referential Example 21 The process of Example 1 is repeated using aluminum hydroxide as a starting raw material to obtain an α-Aℓ₂O₃ carrier. The carrier is impregnated with an aqueous solution of nickel nitrate, and calcined at 600°C for 5 hrs to obtain an NiO/α-Aℓ₂O₃ catalyst. Crust strength of the catalyst is 10.1 kg. Example 35 Spalling tests are performed on the catalysts prepared in Example Comparative Example 32 and A and Referential Examples 13 and 21. In the spalling test, catalyst is rapidly heated to 1,000°C in aerial atmosphere and held thereat for 15 min, quenched in a flowing water for 3 min, left in a room temperature for 2 min then rapidly heated again to 1,000°C, and the operations are repeated for 10 times. Thereafter, crush strengths of the catalysts are measured. This is a test for examining thermal shock resistant property of the catalysts by measuring differences of crush strengths of the catalysts before and after the test, wherein a smaller difference of crush strengths means a better spalling property of the catalyst. The results of the spalling test are shown in Table 12. Catalyst Crush strength before test (kg) Crush strength after test (kg) Comparative Example 32 24.0 9.0 Example A 28.0 19.4 Referential Example 13 11.7 8.7 Referential Example 21 10.1 5.2 As apparent from the foregoing explanations, the steam reforming catalyst of the present invention exhibits high activity, splendid mechanical strength, heat resistant property, chemical stability, and thermal shock resistant property, retains a high specific surface area at high temperatures, and does not form nickel aluminate or cobalt aluminate in steam reforming reactions of hydrocarbons, so that the reforming catalyst of the present invention can retain its activity for a long period of use and is very useful and economical. Therefore, the present invention is eminently useful in industry.

Claims: A steam reforming catalyst for hydrocarbons having at least one of Ni oxide, Co oxide and a platinum group metal supported on a carrier consisting essentially of aluminum oxide Al2O3 and a metal oxide MeO wherein Me is selected from Ca, Ba and Sr, the metal oxide MeO and the aluminum oxide Al2O3 being present in a mole ratio MeO/(MeO + Al2O3) of 10/100-15/100 and being essentially in the form of a complexed oxide expressed mainly as MeO.6Al2O3, at least a part of said metal Me being added in the form of calcium aluminate cement as a moulding binder in an amount of from 10-40 wt% relative to the essential components of the carrier A steam reforming catalyst as defined in claim 1, comprising from 3-50 parts by weight of at least one of nickel oxide and cobalt oxide supported on the carrier relative to 100 parts by weight of the carrier. A steam reforming catalyst as defined in claim 1, comprising from 0.03-3 parts by weight of at least one platinum group noble metal supported on the carrier relative to 100 parts by weight of the carrier. A steam reforming catalyst as defined in claim 1, comprising from 3-50 parts by weight of at least one of nickel oxide and cobalt oxide, and from 0.03-3 parts by weight of at least one platinum group noble metal, supported on the carrier relative to 100 parts by weight of the carrier. A method of producing the steam reforming catalyst for hydrocarbons as claimed in claim 1, comprising mixing carrier components consisting essentially of Al₂O₃ and/or aluminium hydroxide Al₂O₃.nH₂O and a metal oxide compound MeO wherein Me is selected from Ca, Ba and Sr to make a mixture, the metal oxide MeO and the aluminium oxide Al₂O₃ being present in a mole ratio MeO/(MeO + Al₂O₃) of 10/100 - 15/100, adding calcium aluminate cement as a moulding binder in an amount of from 10-40 wt% relative to the essential components of the carrier and moulding the mixture, calcining the mixture to provide a catalyst carrier at a temperature of not less than 900°C essentially in the form of a complexed metal oxide expressed mainly as MeO.6Al₂O₃ wherein Me is provided at least partly in said cement, impregnating the catalyst carrier with an aqueous solution of at least one of a nickel compound, a cobalt compound, and a platinum group noble metal compound, and calcining the impregnated catalyst carrier. A method of producing a steam reforming catalyst as defined in claim 5, wherein the mixture of aluminum oxide Al₂0₃ and/or aluminum hydroxide Al₂0₃·nH₂O and Me compound is a coprecipitate or a hydrolysis product or a heat decomposition product obtained from a mixed solution of a water soluble or alcohol soluble aluminum compound and a water soluble or alcohol soluble compound of Me. A method of producing a steam reforming catalyst as defined in claim 5, wherein a portion or the whole of the mixture of aluminum oxide Al₂0₃ and/or aluminum hydroxide Al₂0₃·nH₂O and Me compound is a hydrolysis product or a heat decomposition product of mixed or complexed alkoxides of aluminum and the metal Me. A method of producing a steam reforming catalyst as defined in claim 5, wherein a portion or the whole of the mixture of aluminum oxide Al₂0₃ and/or aluminum hydroxide Al₂0₃·nH₂O contained in the mixture before calcination is a hydrolysis product or a heat decomposition product of at least one aluminum alkoxide. A method of producing a steam reforming catalyst as defined in claim 5, wherein the catalyst carrier is produced by mixing and/or kneading powdery aluminum oxide Al₂0₃ and/or a powdery Me compound or a solution of Me compound, and calcining.

Inventors: ARAI HIROMICHI, KITAGAWA JUN SHIMONOSEKI FACT, NISHIOKA YASUO SHIMONOSEKI FAC, ARAI, HIROMICHI, KITAGAWA, JUN SHIMONOSEKI FACT. CATAL. CHEM. INC., NISHIOKA, YASUO SHIMONOSEKI FACT. CATAL. CHEM. INC
Applicants: CATALYSTS & CHEM INC, CATALYSTS AND CHEMICALS INC, FAR EAST
Application year: 1989
Main classification: C01B3
IPC codes: B01J23, C01B3, B01J32