WO2000056447A1 - Solid acid catalyst, method for preparing the same and reaction using the same - Google Patents

Abstract

A method for a solid acid catalyst which contains sulfuric acid, exhibits a satisfactorily high activity even when formed into moldings, and also has a satisfactory mechanical strength and an easiness to handle sufficient to practical operation. The carrier of the catalyst is composed of a part comprising zirconia and/or zirconia hydrate and a part comprising alumina and/or alumina hydrate, and the method (a) comprises a step preparing a carrier which has a pore diameter distribution from 0.05 to 10 νm showing a peak in the range of 0.05 to 1 νm and a step supporting sulfuric acid on the carrier, or (b) comprises a step preparing a carrier which has a pore volume of 0.05 to 0.5 ml/g in the range of pore diameter of 0.05 to 1 νm and a pore volume less than 0.05 ml/g in the range of pore diameter more than 1 νm and up to 10 νm and a step supporting sulfuric acid on the carrier.

Description

 Technical Field The present invention relates to a solid acid catalyst having high activity in acid catalysis and excellent in handleability, and a method for producing the same. Kyogi Kagaku Kogyo has known acid catalyzed reactions such as alkylation, esterification, and isomerization. Conventionally, acid catalysts such as sulfuric acid, aluminum chloride, hydrogen fluoride, phosphoric acid, and paratoluenesulfonic acid have been used in this type of reaction. However, these acid catalysts have the property of corroding metals, so that it was necessary to use expensive anticorrosion materials or perform anticorrosion treatment on the production equipment. In addition, it is usually difficult to separate the reactants from the reactants after the reaction, and waste acid treatment is required, and complicated steps such as alkali washing have to be performed. It was also very difficult to reuse the catalyst.

To solve this problem, a sulfate group obtained by bringing a Group IV metal hydroxide or hydrated oxide into contact with a sulfuric acid-containing solution and then calcining at 350 to 800 ° C. A solid acid catalyst containing nitrogen has been proposed (Japanese Patent Publication No. 59-6181). This solid acid catalyst has a stronger acid strength than 100% sulfuric acid (Hammett's acidity function H. is -1.19.3). Due to their strong acid strength, these solid acid catalysts have high catalytic performance for various acid catalyzed reactions, have low corrosiveness, are easily separated from reactants, and do not require waste acid treatment. It has the advantage of being able to reuse catalysts, and is expected to replace conventional acid catalysts in various industrial reactions. <Catalysts obtained by calcining zirconia gel containing sulfuric acid White It is already known that gold-containing catalysts show good activity in hydrocarbon isomerization reactions (US Pat. No. 3,032,599).

 As a method for producing a metal oxide catalyst containing a platinum group metal and sulfuric acid mainly for the purpose of isomerization of hydrocarbons, a calcination between a treatment with a sulfuric acid compound and a step of supporting the platinum group metal is performed. Japanese Patent Publication No. 5-29503, JP-A-5-29553, discloses a manufacturing method in which the manufacturing method is omitted, a manufacturing method in which the order of treatment with the sulfuric acid-containing compound and the loading of the platinum group metal is changed, and a manufacturing method in which the type of the sulfuric acid-containing compound is changed. This is disclosed in Japanese Patent Publication No. Hei 5-295504, Japanese Patent Publication No. 5-29505 and Japanese Patent Publication No. 5-295506.

 It is also known that a solid acid catalyst obtained by adding a sulfuric acid-containing compound to an aluminum hydroxide or oxide and calcining the same shows a stronger acid strength than 100% sulfuric acid. (Japanese Unexamined Patent Publication No. Hei 5-96971, Arata; Trends in Physical Chemistry, 2nd volume, Item 1 (1991)).

 Japanese Patent Application Laid-Open No. 9-38494 discloses a method for producing a sulfated metal oxide catalyst molded article. This is characterized in that a molded body formed using a metal hydroxide and boehmite is pre-baked at a temperature of 300 ° C. or more and 500 ° C. or less, and then subjected to a sulfate treatment. This is a catalyst molding method using alumina as a binder. However, its catalytic activity is lower than that of a powdered catalyst without boehmite, because it was formed by adding boehmite. Also, when the molded body obtained by using the metal hydroxide and the boehmite powder is dried at a temperature of less than 300 ° C., it becomes powdery and breaks when water is added thereto. Zirconia catalyst powder (a powdery catalyst made of zirconia supporting platinum and sulfuric acid) is mixed with boehmite powder, kneaded with water, molded, and calcined. Is also disclosed.

As a solid acid catalyst, a shaped catalyst that is easy to separate from the reactants and reuse, rather than powder, is required. However, even if it has sufficient catalytic activity as a powder, if it is molded, the mechanical strength required during reaction and production cannot be obtained, or Catalyst activity is reduced. As described above, no method has been reported for producing a solid acid catalyst which satisfies the required characteristics as a catalyst and has a required mechanical strength. DISCLOSURE OF THE INVENTION The present invention solves such a problem, and has a sufficiently high activity even though it is a molded product of a solid acid catalyst containing a sulfuric acid component, and has sufficient practical handleability and necessary mechanical properties. An object of the present invention is to provide a solid acid catalyst having high strength, a method for producing the solid acid catalyst, and a reaction method using the catalyst.

 The present inventors have conducted intensive studies on a method for producing a solid acid catalyst, and as a result, kneaded zirconium hydroxide having specific physical properties, pseudo-boehmite having specific physical properties, and ammonium sulfate to form a mixture. After calcining, it was found that a solid acid catalyst having excellent catalytic activity and sufficient mechanical properties could be obtained, and the present invention was completed by conducting research on the catalyst.

 The method for producing a solid acid catalyst according to the first aspect of the present invention comprises a portion composed of zirconia and / or hydrous zirconia and a portion composed of alumina and Z or hydrous alumina, and has a pore diameter of 0.05 to 10 μm. The method includes a step of preparing a carrier having a peak in a range of 0.05 to 1 μm in a pore size distribution of μm, and a step of supporting a sulfuric acid component on the carrier.

 The method for producing a solid acid catalyst according to the second aspect of the present invention comprises a part comprising zirconia and Z or hydrated zirconia and a part comprising alumina and Z or hydrated alumina, and has a diameter of at least 0.05 μιη. Step of preparing a carrier with a pore volume of less than 1 μm of 0.05 to 0.5 ml Zg and a pore volume of more than 1 μm and less than 10 βm less than 0.05 ml And supporting a sulfuric acid component on the carrier.

The method for producing a solid acid catalyst according to the third aspect of the present invention is characterized in that the zirconium hydroxide and / or the average particle diameter of the aggregated particles are 0.2 to 10 μm. Or kneading a powder composed of a hydrated oxide and a powder composed of an aluminum hydroxide and / or a hydrated oxide having a fibrous particle shape, and forming a carrier by molding. However, the method includes a step of supporting sulfuric acid on the carrier. In this case, the carrier has a peak in the range of 0.5 to 1 μπι in a pore distribution of 0.05 to 10 μm in the pore diameter of 0.05 to 10 μm, and the diameter is 0.05 to 5 μm or more. Pore volume force of μm or less 0.05 to 0.5 ml / g, pore volume of more than 1 μm and less than 10 μm is preferably less than 0.05 m1 / g . In the present invention, it is preferable that the step of preparing a carrier and the step of supporting a sulfuric acid component are simultaneously performed in the same step.

 The solid acid catalyst according to the present invention is a catalyst comprising a portion composed of zirconia and Z or hydrated zirconium and a portion composed of alumina and Z or hydrated alumina, contains a sulfuric acid component, and is used in an acid catalyzed reaction. It has a peak in the range of 0.05 to 1 μm in the pore distribution with a pore diameter of 0.05 to 10 μm. Or a catalyst composed of a part composed of zirconium and Z or hydrous zirconia and a part composed of alumina and / or hydrous alumina, containing sulfuric acid, and used for acid-catalyzed reaction, and having a diameter of 0.05 μm or more. The pore volume of 1 μm or less is 0.05 to 0.5 m 1 Zg, and the pore volume of more than 1 μm and less than 10 μm is less than 0.05 ml, g. The acid-catalyzed reaction is preferably used for a conversion reaction of hydrocarbons. BEST MODE FOR CARRYING OUT THE INVENTION

[Zirconia powder]

Powders composed of zirconium hydroxide and / or hydrated oxide used in the production of solid acid catalysts (hereinafter also simply referred to as zirconium powders) are amorphous, which do not have a clear crystal structure by X-ray and electron diffraction. By doing so, the crushing strength of the catalyst is improved, and the zirconia is easily stabilized. In addition, the average particle size of the aggregated particles is 0.2 to 10 μιη, particularly 0.2 to 5 μm, and more preferably 0.5 to 2 μm. It is preferable for improving mechanical strength. The average particle size of the agglomerated particles can be measured by a method of irradiating a group of particles dispersed in water with a laser beam and obtaining from the scattered light.

 The zirconia powder can neutralize any force that can be produced, generally zirconium salts or organometallic compounds, such as oxychloride, alcoholate, chloride, sulfate, nitrate, oxysulfate, etc. It can be obtained by hydrolysis. The main component of the zirconium powder is a mixture of zirconium hydroxide and zirconium hydrated oxide, zirconium hydroxide, or zirconium hydrated oxide. Further, the zirconia powder can be used as a composite metal hydroxide and / or a composite metal hydrated oxide. The hydroxide and / or hydrated oxide of zirconium may contain a hydroxide and / or hydrated oxide and / or salt of another metal. As other metals, titanium, hafnium, vanadium, chromium, manganese, iron, silicon, tin, gallium and the like are preferably used. These other metal compounds may be complex metal compounds. However, the zirconia powder has substantially only zirconium as a metal component. Specifically, of the total metal weight in the zirconia powder, 70% by weight or more of zirconium as the metal weight is used. More preferably, 90% by weight or more is preferably used.

 [Alumina powder]

The powder of aluminum hydroxide and / or hydrated oxide (hereinafter, also simply referred to as alumina powder) used in the production of the solid acid catalyst has a fibrous particle shape. This is preferred for improving the water content of the molded pellet, particularly for improving the water stability of the molded pellet. As the fibrous particle shape, specifically, it is preferable that the aspect ratio is more than 10, especially more than 20. Usually, the upper limit of the aspect ratio is about 200. Here, the aspect ratio refers to the ratio of the length of the minor axis to the major axis of the particle ([major axis length] / [minor axis length]). Observation with a microscope can measure the ratio of the length of the minor axis to the major axis of the particle, and it can be obtained from the average. If the particles are spherical, the aspect ratio will be a minimum of 1. Typically, such a particle shape is obtained as a primary particle having a major axis of 0.1 μπι or more or a secondary particle in which the primary particles are oriented in a certain direction. Further, particles having a shape other than fibrous shape, for example, plate-like particles, may be included in a range where the average value, that is, the aspect ratio is larger than 10, particularly larger than 20.

 The alumina powder preferably has an average particle size of the aggregated particles of 0.5 to 50 μπι, particularly 1 to 40 μπι, and more preferably 1 to 20 μm. Usually, the aggregated particles are formed by aggregating fibrous particles. As the alumina powder, the ability to use powders obtained by various manufacturing methods can be used. In particular, the use of aluminum hydrated oxide having a boehmite structure, such as pseudo-boehmite, is a catalytic activity. This is preferable because it can improve When α-alumina or γ-alumina is used as the alumina powder, the mechanical strength of the molded catalyst decreases relatively, and the catalytic activity decreases.

 [Carrier]

The carrier preferably used in the present invention has a peak in the pore diameter range of 0.05 to 1 μπι in a pore distribution of 0.05 to 10 μm, in particular, the diameter of 0.05 to 10 μm. The pore volume from μm to 1 μm is from 0.05 to 0.5 ml Zg, and the pore volume from more than 1 μm to less than 10 μm is less than 0.05 ml Zg. In the pore distribution with a pore diameter of 0.05 to 10 μπι, it has a peak in the range of 0.05 to 1 μπι, especially in the range of 0.05 to 0.5 μππι. Has no peak, and the pore volume from 0.05 to 1 μm in diameter is from 0.05 to 0.3 S ml / g, especially from 0.5 to 0.3 ml / g. The pore volume having a diameter of more than 1 μm and not more than 10 μm is preferably less than 0.05 m 1 Zg, particularly less than 0.02 ml Zg in order to increase the mechanical strength of the catalyst. The pore distribution can be measured using the mercury intrusion method, assuming that the contact angle of mercury is 140 °, the surface tension is 480 dynes / cm, and all pores are cylindrical. . The pore distribution having a peak is defined as the value obtained by differentiating the cumulative pore volume with respect to the pore diameter, It means that the so-called pore distribution curve which has been filtered has a distinct maximum value.

 The carrier is not a powder but a molded shape. A carrier having a size of 0.5 to 20 mm can be easily obtained. Usually, the particle size (length of the cross section) is as follows. 0.2 to 50 mm, in particular, 0.5 to 20 mm is preferably used. The alumina portion and the zirconia portion are present as particles of 0.01 to 100 μm in the carrier. Such a carrier can be prepared by kneading and molding the above-described zirconia powder and alumina powder, but if the carrier has a predetermined pore structure, it can be prepared by another method. Can be used.

 For kneading, a kneader generally used for catalyst preparation can be used. Usually, a method in which raw materials are added, water is added, and the mixture is mixed with a stirring blade is suitably used, but there is no particular limitation on the order of charging the raw materials and additives. Water is usually added at the time of kneading, but there is no particular need to add water when the raw material powder is in a slurry form. The liquid to be added may be an organic solvent such as ethanol, isopropanol, acetone, methyl ethyl ketone, and methyl isobutyl ketone. The kneading temperature and kneading time differ depending on the zirconia powder and the alumina powder as the raw materials, but are not particularly limited as long as a preferable pore structure can be obtained. Similarly, as long as the catalytic properties of the present invention are maintained, an acid such as nitric acid, a base such as ammonia, an organic compound, a binder, a ceramic fiber, a surfactant, a zeolite, etc. may be added and kneaded. I do not care.

 For molding after kneading, a molding method generally used for catalyst preparation can be used. In particular, extrusion molding using a screw type extruder or the like is preferably used because it can be efficiently formed into an arbitrary shape such as a pellet shape or a honeycomb shape. The size of the molded product is not particularly limited, but is usually formed to have a cross-sectional length of 0.5 to 20 mm. For example, a cylindrical pellet having a diameter of about 0.5 to 10 mm and a length of about 0.5 to 15 mm can be easily obtained.

Firing after molding is performed in a gas atmosphere such as air or nitrogen. Will be This calcination is simple and preferable because the calcination is also performed for carrying the sulfuric acid component on the carrier.

 [Sulfuric acid loading]

 Sulfuric acid can be carried by bringing a sulfuric acid-containing compound into contact with a carrier and performing a heat treatment. Examples of the sulfuric acid-containing compound include sulfuric acid, ammonium sulfate, sulfurous acid, ammonium sulfite, and thionyl chloride. Among them, ammonium sulfate and ammonium sulfite are preferable because of low corrosiveness of the production equipment. The sulfuric acid-containing compound may be used as it is or as a solution such as an aqueous solution. The sulfuric acid-containing compound may be in a solid state or a liquid state, and there is no particular limitation on the concentration of the solution, and it can be prepared in consideration of the amount of the solution necessary for kneading. The addition amount of the sulfuric acid-containing compound is preferably such that the sulfur content in the finally obtained solid acid catalyst is 0.2 to 10% by weight, particularly 1 to 10% by weight.

It is preferable to carry out the supporting of the sulfuric acid simultaneously with the preparation of the carrier. The catalyst of the present invention can be prepared by kneading zirconia powder, alumina powder, and a compound containing a sulfuric acid component, forming the mixture, and then firing. Kneading and molding can be performed in the same manner as in the preparation of the carrier. The weight of the sulfuric acid-containing compound is preferably 3 to 40% by weight, particularly 10 to 30% by weight based on the total weight before calcination, which is preferable from the viewpoint of catalytic activity. The firing is preferably performed at a temperature at which zirconium oxide having a tetragonal structure is obtained. This structure can be confirmed by X-ray diffraction. Specifically, the area ratio of the X-ray diffraction peaks at 2Θ = 28.2 ° and 2Θ-30.2 ° by the Cu Ka ray (hereinafter, referred to as the following) Abbreviated as ratio S 28.2 / S 30.2 S 28.2 is the area of the monoclinic zirconia peak at 2 ピ ー ク = 28.2 °, and S 30.2 is 2Θ = 3 (The area of the peak of the tetragonal zirconia at 0.2 °) is 1.0 or less, preferably 0.05 or less. High catalytic activity is obtained when almost no monoclinic structure is present. When pseudo-boehmite-type alumina is used as the alumina powder, the preferable firing temperature is 450 to 800 ° (: especially 500 to 800 ° C, more preferably 600 to 800 ° C). 800 ° C., and a preferable firing time is 0.1 to 20 hours. If the calcination temperature is too high, the proportion of monoclinic crystals in the crystal structure of zirconium oxide increases, and the S28.2 / S30.2 ratio may exceed 1, resulting in reduced catalytic activity. Not preferred. On the other hand, if the firing temperature is too low, zirconium oxide does not crystallize, and the catalytic activity decreases, which is not preferable.

 In the case of supporting a sulfuric acid component after preparing the carrier, the sulfuric acid-containing compound may be used in any form, for example, in the form of a gas or an aqueous solution, as long as it can sufficiently contact the carrier. However, it is preferable that it is in a liquid form for easy handling. The method of contact is not particularly limited, and an impregnation method such as force, spray, or immersion, or a method of passing the catalyst layer in the form of gas is preferably used. After contact with the sulfuric acid-containing compound, it is calcined at a temperature higher than 300 ° C, lower than 800 ° C, preferably higher than 400 ° C, and lower than 800 ° C. Obtain the desired solid acid catalyst. The firing time is usually 0.5 to 10 hours.

 [Spent catalyst]

 As the carrier used in the present invention, a used solid acid catalyst having reduced activity can be used. Before use, the solid acid catalyst contains a carrier composed of a zirconium portion and an alumina portion having a tetragonal crystal structure, and sulfuric acid carried on the carrier. Even after use, it is preferable that a carrier composed of a zirconia portion having a tetragonal crystal structure and an alumina portion remains. Depending on the conditions of use, it may not contain sulfuric acid after use.

 It is preferable that the solid acid catalyst before use is manufactured by kneading zirconia powder, alumina powder, and a compound containing sulfuric acid, molding, and then firing. In this case, kneading and molding can be performed in the same manner as in the preparation of the carrier described above. In this case, the weight of the sulfuric acid-containing compound is 3 to 40% by weight of the total weight before calcination, particularly 10 to 40% by weight.

30% by weight is preferable from the viewpoint of catalytic activity. The firing is performed at a temperature at which zirconium oxide having a tetragonal structure is obtained.

 [Solid acid catalyst]

The solid acid catalyst of the present invention comprises zirconia and / or hydrated zirconia. And a carrier composed of a portion composed of alumina and / or hydrated alumina (hereinafter also referred to as an alumina portion), and a sulfuric acid component supported on the carrier. In the pore distribution with a diameter of 0.05 to 10 μm, it has a peak in the range of 0.05 to 1 μπι, especially when the pore volume is more than 0.05 μππι and less than 1 μm. The pore volume of more than 0.05 to 0.5 ml / g and a diameter exceeding Ιμπι and less than 10μm is less than 0.055m1Zg. The pore structure of the catalyst can be measured in the same manner as in the case of the support, and the pore structure having a pore diameter of 0.0 or more is almost the same as before carrying the sulfuric acid component. In particular, in the pore distribution with a pore diameter of 0.05 to 10 μm, there is a peak in the range of 0.05 to 1 μm, especially in the range of 0.05 to 0.5 μm. There is no other peak, and the pore volume from 0.05 μm to 1 μm in diameter is from 0.05 to 0.5 ml / g, especially from 0.05 to 0.3 ml. Zg, and a pore volume of more than 1 μm and less than 10 μm in diameter is less than 0.05 ml Zg, especially less than 0.02 m1 Zg enhances the mechanical strength of the catalyst Preferred for.

 The distribution of pores having a pore diameter of 0.05 μm or less can be measured by a nitrogen adsorption method or the like. Within this range, it is preferable to have an average pore diameter according to the size of the reaction target compound, and it is usually from 20 to 200 A, particularly from 30 to 12 OA. Regarding the crystal structure of the zirconia portion in the catalyst, the ratio of S28.2ZS30.2 is preferably 1.0 or less, particularly preferably 0.05 or less. High catalytic activity is obtained when almost no monoclinic structure is present. The solid acid catalyst according to the invention has an acid strength H higher than 100% sulfuric acid. (Hammett's acidity function) can show an acidity stronger than — 1.1.93.

It is more preferable that the weight of the alumina part in the total weight of the alumina part and the zirconia part in the catalyst is 5 to 90% by weight, preferably 5 to 50% by weight, particularly 10 to 40% by weight. Below this range, the mechanical strength of the catalyst decreases and the zirconia is difficult to stabilize. Exceeding this range results in a relatively low catalytic activity. The total weight of the zirconia and alumina portions in the catalyst is determined by the It is preferably at least 70% by weight, more preferably at least 80% by weight, from the viewpoint of the strength of the shaped article.

 The solid acid catalyst of the present invention preferably contains a Group 8, Group 9, or Group 10 metal component, if necessary, for example, when used in a conversion reaction such as isomerization. . Platinum, palladium, ruthenium, nickel, and the like are preferably used as the metal component selected from Group 8, Group 9, and Group 10 used in the catalyst of the present invention. It is preferable to use those in the form of a compound rather than the metal itself. These metal compounds can be used both as anhydrides and hydrates. Further, these metal compounds may be used alone or in combination of two or more. The amount of the metal compound added is preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total amount of the elements belonging to Group 8, Group 9 and Group 10 in the solid acid catalyst. % Is preferable.

 The method for supporting these metal components is not particularly limited, but an impregnation method such as spraying or immersion, or an ion exchange method is preferably used. The above supported catalyst can be calcined in a gas atmosphere such as air or nitrogen at a temperature of 300 ° C. to 700 ° C. for 0.1 to 20 hours to enhance the activity of the catalyst. Preferred.

 The catalyst of the present invention is not a powder but a molded shape, and a catalyst having a size of 0.5 to 20 mm can be easily obtained, and usually has an average particle diameter of 0.2 to 50. mm, particularly preferably 0.5 to 20 mm.

The mechanical strength of the catalyst is 2 kg or more, more preferably 3 kg or more, and even more preferably 4 to 20 kg, as the side crushing strength of a cylindrical pellet having a diameter of 1.5 mm. The shape of the solid acid catalyst formed according to the present invention is maintained even when left in water. Pellet whose shape is not maintained in water is not preferable in practical use because the pellet may be powdered or cracked during the supporting process or the catalyst reaction during the production of the catalyst, leading to a decrease in yield and process trouble. . [Acid catalysis]

 The acid catalyzed reaction to which the solid acid catalyst according to the present invention is applied may be an acid catalyzed reaction using a Lewis acid catalyst typified by an aluminum chloride-based catalyst or a Brenstead acid catalyst typified by sulfuric acid. Can be. Examples of the reaction include various reactions such as isomerization, disproportionation, nitration, decomposition, alkylation, esterification, acylation, etherification, and polymerization, and specifically, methacrylic acid and the like. It can be used for esterification reaction, decomposition reaction of cumene hydroxide, alkylation reaction of phenol, ring-opening polymerization reaction of tetrahydrofuran, decomposition reaction of chlorofluorocarbons, oxidative coupling reaction of methane, and the like. In particular, it is preferably used for conversion reactions such as isomerization, decomposition, acylation, etherification, and esterification. The main reaction targets are hydrocarbons, that is, hydrocarbons and hydrocarbon derivatives obtained by adding a substituent to the hydrocarbons, particularly hydrocarbons or oxygen-containing hydrocarbon compounds. In particular, it is preferably used for a conversion reaction of hydrocarbons. The conversion reaction includes isomerization, decomposition, acylation, etherification, alkylation and the like.

 As a target of the isomerization reaction, it is preferably used for hydrocarbons in a petroleum fraction having a boiling point of about 120 ° C to 150 ° C. In particular, it is preferably used in a reaction in which a linear paraffin is isomerized into a branched paraffin, and an orifice-aromatic compound is hydrogenated into a linear or cyclic paraffin, and further isomerized. As the reaction conditions for the isomerization of hydrocarbon compounds, the preferable reaction temperature range is 100 to 300 ° C. (: particularly, 120 to 240 ° C., and the preferable reaction pressure range is 1 to 100 ° C.). ~ 50 kgf / cm \ The preferred range of LHSV is 0.2 ~ 10 / hr, and the preferred range of hydrogen source ratio is 0.2 ~ 1 Omo1 / mo1.

 [Treatment in oxidizing atmosphere]

The catalyst of the present invention can be improved in catalytic activity by heat treatment in an oxidizing atmosphere before or after use. Usually, ripening treatment is performed at 300 to 500 ° C. in an atmosphere in which oxygen such as air is present. The oxygen content of the atmosphere is 0.1 to 50% by volume, especially 1 to 30% by volume. Preferably, a mixture of nitrogen and oxygen, a mixture of nitrogen and air, and air are suitably used. In particular, a processing temperature of 350 to 480 ° C. and a processing time of 0.1 to 100 hours are preferable. The processing can be performed under reduced pressure, normal pressure, or pressurized pressure, but processing at normal pressure is simple and preferable. It is considered that the catalyst is dried by the treatment in the oxidizing atmosphere, and is activated by oxidizing and removing adsorbed substances and deposits adhered by use. The use of air with reduced impurities is preferred, especially before the catalyst is used. Specifically, an atmosphere in which the relative humidity at 20 ° C. is dehumidified to 5% or less is preferably used. If the treatment temperature is too high, the properties of the catalyst will change. If the treatment temperature is too low, the catalyst will not be dried sufficiently, and in any case, the activity will decrease. After a heat treatment such as calcination during the production of the catalyst, this treatment is applied to the catalyst that has been in the air for more than one day, especially more than 10 days, or the catalyst used for the acid catalyst reaction. Is valid. In addition, even if the treatment is performed in a non-oxidizing atmosphere (air flow containing no oxygen), the activity of the catalyst is reduced.

 After treatment in an oxidizing atmosphere, the catalyst must avoid adsorption of moisture and the like. For this reason, it is preferable that this treatment is performed after introducing the catalyst into the reaction device or the reactor in which the reaction is performed, and that the target acid-catalyzed reaction be started without substantially introducing air. If the desired acid-catalyzed reaction is carried out in a reducing atmosphere such as a hydrogen atmosphere, replace the atmosphere with an inert atmosphere such as a rare gas such as nitrogen gas or argon gas before starting the reaction. Is preferred. Since the activity does not decrease significantly even when exposed to air for about one day, in a small-scale reactor, treatment in this oxidizing atmosphere is performed outside the reactor, and then the reactor is A catalyst may be introduced.

Further, the treatment in the oxidizing atmosphere can be applied to the regeneration of a catalyst which has been used in a reaction in a reaction apparatus or a reactor and has reduced activity. In particular, when carbonaceous material such as coke is precipitated on the catalyst, the oxygen concentration is set to 0.1 to 20% by volume, particularly 0.2 to 5% by volume, and the carbonaceous material is rapidly increased. It is preferable not to oxidize. Example Hereinafter, an example will be described in detail.

 The measurement method and the like in this example were based on the following method.

[Method for measuring average particle size of aggregated particles]

 Nikkiso Co., Ltd. Measured by a wet measurement method using a MI CRO TRAC particle size analyzer. This involves dispersing the powder in water, irradiating the flowing aggregated particles with laser light, and performing particle size analysis using the forward scattered light.

 [Method of measuring the aspect ratio]

 Observation of the powder using a Hitachi H-900 UHR transmission electron microscope, random extraction of 10 particles from the particles present in the image field, and the long and short axes of the particles It measures the ratio of the lengths and calculates the average.

 [Method of measuring pore distribution]

 The pore diameter in the range of 0.05 to 1Ομπι was measured by a mercury intrusion method using an AutoPore 9002 type measuring instrument manufactured by Microsoft Corporation. The pore diameter in the range of 0.05 μm or less was measured by a nitrogen adsorption method using an ASAP2400 type measuring instrument manufactured by Microsoft Corporation.

 [Water stability test]

A random selection of 50 cylindrical pellets with a diameter of 1.5 πιπι and a length of 5 mm, and immersed in 10 ml of water at room temperature and left for 15 minutes to observe the change in the shape of the pellets It has been examined. The shape is maintained, 5 0 All pellet force ^5; without cracked or powdered, means that maintains the shape before immersion in water.

 [Measurement method of average crushing strength]

Toyama Sangyo Co., Ltd. TH-203 CP tablet breaking strength measuring device was used to measure the side crushing strength of a sample extruded into a cylindrical shape, dried and fired. The measuring probe has a circular tip with a diameter of 4.5 mm. Was used. The operation of applying the measurement sample to the center of the side surface of the cylindrical sample and repeating the measurement was repeated 20 times, and the average value was calculated.

 [Calculation method of S28.2 / S30.2 ratio]

 The peaks of tetragonal and monoclinic zirconia were separated from the X-ray diffraction chart, and the area of the monoclinic zirconia peak at 2 2 = 28.2 ° and 2Θ = 30.2. The ratio (S28.2 / S30.2 ratio) to the area of the tetragonal zirconia peak in was calculated. When the ratio of S28.2 / S30.2 was less than 0.02, the monoclinic peak was unclear and could not be detected. The X-ray diffraction chart was measured under the following conditions. Wide-angle X-ray measuring device; RAD-1C manufactured by Rigaku Corporation

 Horizontal goniometer

 X-ray tube; sealed tube type Cu tube (output 30 kV—20 mA,

 (Wavelength 1.505 A)

 Measurement area (2Θ); 3 to 90 °

 Step width; 0.0 2 °

 Scan speed; 4 ° min

 Slit width; divergent slit (DS) = 1 °

 Scattering slit (S S) = 1 °

 Receiving slit (R S) = 0.3 mm Smoothing condition; weighting of 15 points of Savitzky, Golay

 Smoothing method

 Peak separation use area (2Θ); 26.5 to 32.5 °

 Number of peaks to be separated: 4 (2 monoclinics, 1 tetragonal, 1 amorphous) Peaks used for crystal seed ratio calculation;

Monoclinic; 2 Θ = 28.2 ° (d = '3.163, hk 1 = 1 1 1) Tetragonal; 2 Θ = 30.2 ° (d = 2.960, hk 1 = 1 1 1) [Catalyst A]-Among the commercially available dry hydrated zirconia, a powder having an average particle size of 1.2 μπι was used as the zirconia powder. In addition, among commercially available hydrated alumina (pseudo-boehmite) powders, alumina powder having a fibrous particle shape was used. The alumina powder has a small ratio of 58 and an average particle size of Ο Ομπι Met. The zirconia powder (1200 g) and the alumina powder (800 g) were added, and ammonium sulfate (383 g) was further added. The mixture was kneaded for 45 minutes while adding water using a kneader equipped with stirring blades. The obtained kneaded material was extruded from an extruder having a circular opening having a diameter of 1.6 mm to form a cylindrical pellet, and dried at 110 ° C to obtain a dried pellet. When a water stability test was performed on the dried pellets, all pellets maintained their shapes without cracking or powdering. Subsequently, the dried pellet was calcined at 65 ° C. for 2 hours to obtain a catalyst A. When the pore distribution of catalyst A with a pore diameter of 0.05 to 10 μm was measured, it had a clear peak at a pore diameter of 0.18 μm, and other clear peaks. And a pore distribution with no. The pore volume of pores with a pore diameter of 0.5 μm or more and 1 μm or less is 0.18 m1 Zg, and the pore volume with a pore diameter of more than 1 μm and 10 μm or less is 0.0. It was 1 m 1 / g or less. Further, when the pore distribution with a pore diameter of 50 OA or less was measured, the average pore diameter was 50 A.

 The molded catalyst A was cylindrical with an average diameter of 1.5 mm and an average length of 5 mm.As a result of a water stability test, all pellets remained intact without cracking or powdering. Was maintained. The average crushing strength was 4.5 kg. The S28.2 / S30.2 ratio of catalyst A was 0.04, and there was almost no monoclinic structure.

 [Catalyst B]

 Among commercially available dry hydrated zirconia powders having an average particle size of 15 μπι were used as the zirconia powder. In addition, among commercially available hydrated alumina (pseudo-boehmite) powders, plate-like alumina powder was used. The aspect ratio of this alumina powder was 2, and the average particle size was 20 μm. Using this zirconia powder and alumina powder, the rest was prepared in the same manner as catalyst A, and catalyst B was obtained. In addition, a water stability test was performed on the dried pellets during preparation, and all pellets were powdered.

When the pore distribution of catalyst B with a pore diameter of 0.05 to 10 μm was measured, it had a clear peak at a pore diameter of 1.7 μπι and no other clear peak. The pore distribution was shown. The pore diameter is 0.05 The pore volume from μm to 1 μm was 0.07 ml Zg, and the pore volume from 1 μπι to 10 μm was 0.12 ml / g. Further, when the pore distribution with a pore diameter of 500 A or less was measured, the average pore diameter was 45 A.

 The molded catalyst B was cylindrical with an average diameter of 1.5 mm and an average length of 5 mm, and was subjected to a water stability test, but 10 out of 50 pellets were cracked or powdered. . The average crushing strength was 2.8 kg. The S 28.2 / S 30.2 ratio of catalyst B was 0.04, indicating that almost no monoclinic structure was present.

 [Catalyst C]

 An aqueous solution of chloroplatinic acid was spray-loaded onto 50 g of Catalyst A so that the amount of platinum in the catalyst was 0.5%. After drying, it was calcined at 550 ° C. for 2 hours to obtain catalyst C. The pore distribution and crystal structure of catalyst C were almost the same as catalyst A. When a water stability test was performed on Catalyst C, all pellets maintained their shape without cracking or powdering. The average crushing strength was 4.0 kg.

 [Catalyst D]

 An aqueous solution of chloroplatinic acid was spray-supported on 50 ^ of catalyst 8 so that the amount of platinum in the catalyst was 0.5%. After drying, this was calcined at 550 ° C. for 2 hours to obtain Catalyst D. The pore distribution and crystal structure of catalyst D were almost the same as catalyst B. When a water stability test was performed on Catalyst D, 8 out of 50 pellets cracked or powdered. The average pylon strength was 2.5 kg.

 [Catalyst E, F]

A dried hydrated zirconium powder having an average particle diameter of 1.2 μπι obtained by drying commercially available zirconium hydroxide was used as the zirconium powder. Among the commercially available hydrated alumina (pseudo-boehmite) powders, alumina powders having a fibrous particle shape were used. The alumina powder had an aspect ratio of 58 and an average particle size of 10 μm. 150 g of this zirconia powder and 500 g of alumina powder were added, and 383 g of ammonium sulfate were further added. The mixture was kneaded for 45 minutes while adding water using a kneader equipped with stirring blades. went. The obtained kneaded material was extruded from an extruder having a circular hole having a diameter of 1.6 mm and dried at 110 ° C to obtain a dried pellet. A water stability test was performed on this dried pellet, and as a result, the shape of the pellet was maintained without cracking or powdering. Subsequently, the dried pellet was calcined at 65 ° C. for 2 hours to obtain catalyst E, which is a catalyst of a zirconia molded article supporting sulfuric acid.

 When the pore distribution of catalyst E with a pore diameter of 0.05 to 10 μm was measured, a clear peak was observed at a pore diameter of 0.22 μm, and the other peaks were clear. The pore distribution showed no significant peak. The pore volume of pores with a pore diameter of 0.05 μm or more and 1 μm or less is 0.18 ml Zg, and the pore volume with a pore diameter of more than 1 μm and 10 μm or less is 0.01 m. 1 Zg or less. When the pore size distribution of pores having a pore diameter of 500 A or less was measured, the average pore diameter was 48 A.

 The molded catalyst E was cylindrical with an average diameter of 1.5 mm and an average length of 5 mm, and was subjected to a water stability test.As a result, all pellets remained intact without cracking or powdering. Was maintained. The average crushing strength was 3.5 kg. The ratio of S28.2 / S30.2 of catalyst E was 0.05, and there was almost no monoclinic structure.

 To 50 g of this catalyst E, 125 ml of an aqueous solution of chloroplatinic acid was added so that the amount of platinum in the catalyst was 0.5%. After drying, the mixture was calcined at 550 ° C. for 2 hours to obtain catalyst F, which is a catalyst for a zirconia alumina compact supporting platinum and sulfuric acid. The pore distribution and crystal structure of Catalyst F were almost the same as Catalyst E. The catalyst F was subjected to a water stability test. As a result, all the pellets maintained their original shapes without breaking into powder. The average crushing strength was 3.3 kg.

 [Catalyst G]

Among commercially available dry hydrated zirconia, powder having an average particle size of 1.2 μπι was used as the zirconia powder. In addition, among commercially available hydrated alumina (pseudo-boehmite) powders, alumina powder having a fibrous particle shape was used. The alumina powder had an aspect ratio of 58 and an average particle size of 10 μm. 300 g of this zirconia powder and 300 g of alumina powder In addition, kneading was performed for 2 hours while adding water with a kneader equipped with stirring blades. The obtained kneaded material was extruded from an extruder having a circular opening having a diameter of 1.6 mm to form a cylindrical pellet, and dried at 110 ° C to obtain a dried pellet. Subsequently, the dried pellet was calcined at 65 ° C. for 2 hours to obtain a carrier G.

 When the pore distribution of the carrier G with a pore diameter of 0.05 to 10 μm was measured, a clear peak was observed at a pore diameter of 0.25 μπι, and other clear peaks were observed. It showed a pore distribution without. The pore volume of pores with a pore diameter of 0.05 μm or more and 1 μm or less is 0.20 ml / g, and the pore volume with a pore diameter of more than 1 μm and 10 m or less is 0.01. m 1 / g or less. Further, when the pore distribution with a pore diameter of 50 OA or less was measured, the average pore diameter was 65 A.

 The molded carrier G is cylindrical with an average diameter of 1.5 mm and an average length of 5 mm.As a result of a water stability test, all pellets were broken and did not change into powder. Was maintained. The average crushing strength was 4.8 kg. The S 28.2 / S 30.2 ratio of the support G was 0.02 or less, and almost no monoclinic structure was present.

 To this support G, 125 ml of an aqueous solution of chloroplatinic acid was added so that the amount of platinum in the catalyst was 0.5% by weight. After drying this, 0.5 mo 1/1 aqueous sulfuric acid solution (125 ml) was added, dried again, and calcined at 600 ° C for 2 hours to obtain catalyst G. The formed catalyst G had a cylindrical shape with an average diameter of 1.5 mm and an average length of 5 mm. The S28.2 / S30.2 ratio of catalyst G was 0.02 or less, and there was almost no monoclinic structure.

When the pore distribution of catalyst G with a pore diameter of 0.05 to 10 μm was measured, it had a clear peak at a pore diameter of 0.22 μπι, and other clear peaks. It showed a pore distribution without. The pore volume of pores with a pore diameter of 0.05 m or more and 1 μm or less is 0.18 ml / g, and the pore volume with a pore diameter of more than 1 μm and 10 μm or less is 0.01 m. 1 / g or less. Further, when the pore distribution with a pore diameter of 50 OA or less was measured, the average pore diameter was 6 OA. The molded catalyst G was cylindrical with an average diameter of 1.5 mm and an average length of 5 mm.As a result of a water stability test, all pellets remained intact without cracking or powdering. Was maintained. The average crushing strength was 4.6 kg. The S 28.2 / S 30.2 ratio of the support G was 0.02 or less, and there was almost no monoclinic structure.

 [Degradation catalyst H]

Degraded catalyst H was obtained by treating 40 g of catalyst G in a hydrogen stream of 10 kg, cm ² —G, 600 m 1 / min at 450 ° C. for 24 hours. The pore distribution and crystal structure of the deteriorated catalyst H were almost the same as those of the catalyst G. In addition, a water stability test was conducted on the deteriorated catalyst H. As a result, all the pellet forces maintained the shape without cracking or powdering.

 [Treatment catalyst I]

 10 g of the deteriorated catalyst H was calcined in the air at 550 ° C. for 2 hours to obtain a treated catalyst I. The pore distribution and crystal structure of the treated catalyst I were almost equivalent to those of the catalyst G. In addition, when the water stability test was performed on treated catalyst I, all the pellets maintained their shape without cracking or powdering.

 [Treatment catalyst J]

 After adding 0.5 mo 1 Z1 aqueous sulfuric acid solution (150 m1) to 10 g of the deteriorated catalyst H and bringing them into contact, excess sulfuric acid aqueous solution was removed by filtration, dried, and dried at 550 ° C. After calcination for a time, a treated catalyst J was obtained. The pore distribution and crystal structure of the treated catalyst J were almost the same as those of the catalyst G. In addition, a water stability test was conducted on the treated catalyst J. As a result, all the pellets were broken and the shape was maintained without powdering.

 [Treatment catalyst K]

To 0.5 g of 0.1 g of degraded catalyst H was added 0.5 ml of an ammonium sulfate aqueous solution (150 ml), and the mixture was brought into contact with the catalyst.The excess aqueous ammonium sulfate solution was removed by filtration, dried, and dried at 550 ° C. For 2 hours to obtain a treated catalyst K. The pore distribution and crystal structure of the treated catalyst K were almost the same as those of the catalyst G. In addition, when a water stability test was conducted on treated catalyst K, all pellets were maintained in their original shape without cracking and powdering. did.

 [Acylation reaction]

 To improve the stirring efficiency, 20.0 g of the catalyst crushed in a mortar and sieved to 32 mesh or less was placed in an autoclave, and pretreated at 400 ° C for 1 hour in an air atmosphere. . Then, without introducing air, the inside of the autoclave was set to a nitrogen atmosphere, and 225 g of benzene and 35 g of p-chlorobenzene were added, and the reaction was carried out while stirring at 135 ° C. went. After the reaction for 3 hours, the reaction solution was analyzed by gas chromatography.

 The yields of dichlorobenzophenone as the acylated product were 27% when using catalyst A, 24% when using catalyst B, and 29% when using catalyst E. For comparison, when the atmosphere of the pretreatment was changed to nitrogen using catalyst E, and the other acylation reactions were performed, the yield of dichlorobenzophenone was 26%.

 [n-hexane isomerization reaction 1]

 4 cc of catalyst (Catalysts C and D) sized to 16 to 24 mesh is packed into a fixed bed flow-through reactor with a length of 50 cm and an inner diameter of 1 cm. An isomerization reaction of xan was performed. The pretreatment was performed at a temperature of 400 ° C., a pressure of normal pressure, and an atmosphere of air for one hour. Then, without introducing air, the reactor was set to a nitrogen atmosphere and then to a hydrogen atmosphere, and then the isomerization reaction was started.

hexane isomerization reactions to n-, reaction temperature: 2 0 0 ° C, reaction pressure (gauge pressure): 1 0 Bruno ^{0:. 111 2, LHSV =} 1 5 / hr, hydrogen Z oil ratio (H ₂ / 〇 i 1): Performed at 5 (mo I / mo 1).

 The conversion and selectivity indicating the activity of the catalyst were calculated and evaluated as follows using the conversion to n-hexane and the value of 2,2'-dimethylbutane / chain C6.

 n Hexane conversion =

 [1 — (% by weight of n-hexane in product oil)

Weight of n-hexane in Z feed oil ° / ₀ )] X 100 (%) 2, 2'-dimethylbutano chain C 6 =

 (% By weight of 2,2'-dimethylbutane in product oil /% by weight of total chain hydrocarbons having 6 carbon atoms in product oil) X 100 (%)

 As a result of analyzing the composition of the outlet of the reaction tube 20 hours after the start of oil passage by gas chromatography, the n-hexane conversion rate was 88.6% for the catalyst C and 86.3% for the catalyst D. The value of 2,2′-dimethylbutane / chain C 6 was 26.2% for catalyst C and 20.5% for catalyst D.

 [η-hexane isomerization reaction 2]

Using a catalyst F, hexane isomerization reactions to the same n- isomerization reaction 1 above, reaction temperature: 1 8 0 ° C, reaction pressure (gauge ^{pressure): 1 0 kgf Zc m 2} , LHSV = 1 . 5Zh r, at the reaction conditions of a hydrogen / oil ratio (H ₂ Z_〇 i 1) 5 (mo \ / o 1), was conducted by changing the pretreatment conditions. Table 1 shows the results of gas chromatographic analysis of the outlet composition of the reaction tube 20 hours after the start of oil passage in a reaction in which the temperature, atmosphere, and pressure under the pretreatment conditions were changed.

 table 1

 Atmospheric pressure n-hexane 2,2'-dimethylbut

° c Conversion (%) Tan Z chain C 6 (%)

400 Normal air pressure 86.4 2 1.0

 5 0 0 Air Normal pressure 8 6.1 2 0.2

 3 0 0 Air Normal pressure 8 6.0 2 0.1

 3 0 0 Air 1 0 8 6.2 2 0, 5

 6 0 0 Air Normal pressure 84.5 15.2

 2 0 0 Air Normal pressure 8 5.0 1 7.5

 4 0 0 Normal pressure 8 5.3 1 8.5

 4 0 0 Hydrogen Normal pressure 2 0 .0 0.5

3 0 0 Hydrogen 1 0 84.8 16.2 [n-hexane isomerization reaction 3]

 The catalyst whose activity was reduced by the reaction was activated. The catalyst F was degraded by performing a reaction for 100 hours using nitrogen instead of hydrogen in the above-mentioned isomerization reaction 2 using the catalyst F. The catalyst was pretreated in different atmospheres and the change in activity was measured. The atmosphere was a nitrogen atmosphere, a nitrogen atmosphere, or nitrogen containing 2% by volume of oxygen, and was performed at 400 ° C. for 2 hours. The activity was evaluated by conducting the same reaction as the above-mentioned isomerization reaction 2 and analyzing the composition of the reaction tube outlet 20 hours after the start of oil passage by gas chromatography. Table 2 shows the results.

[n-heptane conversion reaction]

1 g of catalyst formed into granules of 16 to 24 mesh was packed in a fixed bed flow reactor having a length of 50 cm and an inner diameter of 1 cm, and the reaction temperature was 200 ° C and the reaction pressure was 4 kgZc. m ² — G, WH SV: 3.4 / h, hydrogen source ratio (H ₂ Z0 i 1): 5 mo 1 / mo 1 As a pretreatment of the catalyst, hydrogen reduction at 300 ° C. for 1 hour was performed before the conversion reaction. The conversion indicating the activity of the catalyst was calculated and evaluated using the conversion to n-heptane as follows.

 n-Heptane conversion =

 [1-(-% by weight of n-heptane in product oil

 N-Heptane weight% of feedstock)]

 X 100 (%)

Two hours after the start of the reaction, the conversion of n-heptane was analyzed by gas chromatography to evaluate the heptane conversion activity. The result The results are shown in Table 3.

 Table 3

産業上の利用可能性 本発明は、 特定の細孔構造を持った担体を有する成形された固体 酸触媒に関するものであリ、 成形された触媒が特定の細孔構造を有 することにより、 機械的に十分な強度が得られると同時に優れた触 媒活性を発揮することができる。 また、 成形品であるため反応物質 との分離が容易であるから、 触媒の再利用も容易である他、 使用済 み触媒の再生も容易である

Industrial Applicability The present invention relates to a molded solid acid catalyst having a carrier having a specific pore structure, and the molded catalyst has a specific pore structure. In addition, it is possible to obtain sufficient catalytic strength and at the same time to exhibit excellent catalytic activity. In addition, since it is a molded product, it can be easily separated from the reactants, so that the catalyst can be easily reused and the used catalyst can be easily regenerated.

 Further, the solid acid catalyst of the present invention is widely useful for acid-catalyzed reactions such as isomerization, disproportionation, alkylation, esterification, acylation, etherification, and polymerization.

Claims

Scope of word blue 1. It is composed of a part composed of zirconia and / or hydrous zirconia and a part composed of alumina and / or hydrous alumina. The pore diameter is 0.05 to 1 μπι in a pore distribution of 0.05 to 10 μm. A method for producing a solid acid catalyst, comprising the steps of: preparing a carrier having a peak in the range described above; and supporting a sulfuric acid component on the carrier.  2. The carrier has a pore volume of 0.05 to 0.5 μπι or more and a pore volume of 0.05 to 0.5 ml Zg, and a pore volume of a diameter exceeding Ι μπι and 10 μm or less 0.0. 2. The method for producing a solid acid catalyst according to claim 1, wherein the amount is less than 5 ml Zg.  3. The step of preparing the carrier includes the step of: A powder of 10 μm of zirconium hydroxide and / or hydrated oxide and a powder of fibrous particle-shaped aluminum hydroxide and / or hydrated oxide are kneaded and molded. 3. The method for producing a solid acid catalyst according to claim 1, which is a step comprising:  4. The method for producing a solid acid catalyst according to claim 1, wherein the step of preparing the carrier and the step of supporting a sulfuric acid component on the carrier are performed in the same step.  5. The step of supporting a sulfuric acid component on the carrier, wherein after the carrier is prepared, a sulfuric acid-containing compound is brought into contact with the carrier and calcined at a temperature higher than 300 ° C and lower than 800 ° C. 3. The method for producing a solid acid catalyst according to 3. 6. Using a solid acid catalyst produced by the production method according to any one of claims 1 to 5, using the catalyst whose activity has been reduced as a carrier, and bringing the catalyst into contact with a sulfuric acid-containing compound; A method for producing a solid acid catalyst, comprising a step of supporting sulfuric acid which is calcined at a temperature higher than 0 ° C and lower than 800 ° C. 7. The method _t for producing a solid acid catalyst according to any one of claims 1 to 6, wherein the solid acid catalyst includes at least one metal component selected from Group 8, Group 9, and Group 10. 8. A step of using the solid acid catalyst produced by the production method according to any one of claims 1 to 7 and treating the catalyst with reduced activity at a temperature of 300 to 500 ° C. in an oxidizing atmosphere. A method for producing a solid acid catalyst comprising:  9. The carrier is composed of a part composed of zirconia and / or hydrous zirconia and a part composed of alumina and hydrated or hydrated alumina. It contains sulfuric acid and has a pore distribution of 0.05 to 10 μm. A solid acid catalyst having a peak in the range of 0.05 to 1 μπι in diameter and used for acid catalysis.  10 0.Solid acid catalyst with a diameter of 0.05-5 μm or more and 1 μm or less, pore volume of 0.05-0.5 m1 / g, finer than 1 μm and less than 10 μm in diameter 10. The solid acid catalyst according to claim 9, having a pore volume of less than 0.05 ml / g. 11. The solid acid catalyst according to claim 9, wherein the acid-catalyzed reaction is a conversion reaction of hydrocarbons.  12. The solid acid catalyst according to claim 9, wherein the solid acid catalyst further contains one or more metal components selected from Group 8, Group 9, and Group 10 groups. 1 3. An acid catalyst using the solid acid catalyst according to claims 9 to 12 and using a solid acid catalyst obtained by treating a substance having reduced activity at a temperature of 300 to 500 ° C in an oxidizing atmosphere. An acid-catalyzed reaction method for performing a reaction.  1 4. A solid acid catalyst according to claims 9 to 12 is charged into a reaction vessel, treated at a temperature of 300 to 500 ° C. in an oxidizing atmosphere, and then an acid catalyst reaction is performed. Acid catalyst reaction method.  1 5. Fill the reaction vessel with the solid acid catalyst according to claims 9 to 12 and treat it in an oxidizing atmosphere at a temperature of 300 to 500 ° C., then replace it with an inert atmosphere, and replace it with hydrogen. A method for isomerizing hydrocarbons, which comprises contacting with hydrocarbons in an atmosphere.