WO2001056926A1

WO2001056926A1 - Alumina composition and method for preparing the same

Info

Publication number: WO2001056926A1
Application number: PCT/JP2000/000620
Authority: WO
Inventors: Goro Sato; Masayoshi Sato
Original assignee: Goro Sato; Masayoshi Sato
Priority date: 2000-02-04
Filing date: 2000-02-04
Publication date: 2001-08-09
Also published as: JP4105870B2

Abstract

An alumina composition capable of being widely changed with controllability with respect to specific surface area, pore volume and pore diameter distribution, which is prepared by a method characterized in that it comprises providing an adjusted liquid having a predetermined ratio of alumina, acid and water through mixing an acid-containing alumina obtained by heating aluminum hydroxide in the presence of a monobasic acid or a salt thereof at a temperature ranging 70 to 400 °C and/or an alumina having ς- and ψ-crystal structures with water and/or a monobasic acid or a salt thereof, and subjecting the adjusted liquid to a hydrothermal reaction optionally in the presence of an oxygen-containing organic compound and/or an inorganic polybasic acid as a pore structure-controlling agent, and drying the resultant acidic aqueous alumina sol-gel followed by calcination; a method for preparing the alumina composition; and a catalyst comprising the alumina composition as a carrier.

Description

Description Alumina composition and method for producing the same Technical field

The present invention relates to a method for producing an alumina composition and an alumina composition obtained therefrom. More specifically, a method for producing an alumina composition capable of controlling the specific surface area and the pore structure, which is suitable for a hydrotreating catalyst for petroleum refining or another catalyst carrier, an alumina composition obtained by the production method, and The present invention relates to a catalyst using an alumina composition as a carrier.

Background technology

Heretofore, it has been desired to establish a technique for adjusting the specific surface area, the pore volume, and the pore size distribution of the alumina support for a catalyst.

In particular, hydrotreating catalysts for petroleum refining perform a catalytic reaction while performing molecular fractionation. Therefore, the emergence of an alumina carrier having a wide specific surface area and various pore sizes has been desired. In particular, for a carrier for a gas oil deep desulfurization catalyst, an alumina carrier having a high specific surface area and a small average pore diameter is desired, and a carrier having a low specific surface area and a large pore diameter is desired for a demetallizing catalyst. However, a catalyst having both the desulfurization function and the demetallization function is also desired, and an alumina carrier having a new pore structure for that purpose has been desired.

In producing such an alumina carrier for a hydrotreating catalyst, an alumina salt is hydrolyzed in an aqueous solution of an aluminum salt, and alumina is used via pseudoboehmite (see, for example, -7 14 No. 56 and Japanese Patent Publication No. 61-26512). However, with such a method, a material having a certain specific surface area, pore volume, and pore size distribution has been obtained, but this method has a problem that the pore structure of the alumina carrier cannot be sufficiently controlled. Was. In addition, this method has many problems such as a complicated production process, a large amount of consumption of raw materials and energy, and a need for wastewater treatment.

In addition, a method for converting aluminum hydroxide or alumina having a P-crystal structure to boehmite by rapid thermal dehydration of aluminum hydroxide is not necessarily intended as an alumina carrier for catalysts. 134446, JP-A 64-96511, and JP-A-6-263437.

However, according to the results of the additional test conducted by the present inventor in Japanese Patent Publication No. 56-134446, the specific surface area and pore volume of the obtained alumina molded product were insufficient as a carrier for a catalyst for petroleum refining. Also, this publication does not show how to control them. In addition, it is not possible to obtain alumina with the sharp pore size required for hydrotreating catalyst carriers in terms of pore size distribution, possibly due to the inclusion of aggregates of boehmite fibrous particles in bundles. There was a defect.

The present inventor has previously proposed an alumina sol in which fibrous boehmite is dispersed suitable for a hydrotreating catalyst carrier and a method for producing the same (W097 / 32817). In this publication, alumina having a p- and —-crystal structure (hereinafter referred to as / 0—alumina having a crystal structure) is mixed with other aluminum sources as necessary, and After adjusting the composition of monobasic acid and water to a specific molar ratio, it is subjected to hydrothermal treatment to produce a transparent aqueous alumina sol (fibrous boehmite sol). It is disclosed that an alumina molded body is produced using this alumina sol.

However, the method described in W097 / 32817 is not always satisfactory in control of the specific surface area and the pore volume. Alumina composition was once prepared from aluminum hydroxide such as ト via aluminum having p-crystal structure, but directly from aluminum hydroxide without passing through this alumina having p-crystal structure. It was also desired to produce an alumina composition.

The present invention relates to an improvement of the invention described in the above-mentioned W097 / 32817, and has a high specific surface area, a large pore volume, a sharp pore size distribution, and a wide range. It is an object of the present invention to provide a controllable method for producing an alumina composition and to provide such an alumina composition. Still another object is to provide a catalyst using these alumina compositions as a carrier. Disclosure of the invention

As a method for producing the alumina composition according to the present invention,

As a raw material of alumina, acid-containing aluminum hydroxide and / or aluminum hydroxide obtained by heat-treating aluminum hydroxide in the presence of at least one monobasic acid or a salt thereof at a temperature in the range of 70 to 400. Using Mina (hereinafter referred to as “acid-containing alumina source”), a solution prepared by adding water and, if necessary, a monobasic acid to this acid-containing alumina source so that the k value represented by the following formula has the following range. Is subjected to a hydrothermal treatment at a temperature in the range of 70 to 250 ° C. to obtain an aqueous alumina sol and Or alumina gel and drying and calcining the aqueous alumina sol and / or alumina gel.

0. 0 0 0 1 ≤ k≤ 0. 2 0

Where k = (b / a) X (b Z c)

(Wherein, a is the number of moles in terms of alumina in preparation to A 1 ₂ 〇 3, b is the number of moles of acid generated by the dissociation of the monobasic acid or a salt thereof in the preparation liquid, c is prepared solution Number of moles of water.)

In the above-mentioned preparation solution, an oxygen-containing organic compound or an inorganic polybasic acid containing an element having an ionic potential of 4.5 or more represented by the following formula or a polybasic acid thereof is produced as a pore structure controlling agent. At least one compound may be mixed.

Element valence

Ion potential =

Element Ion Radius Also, in the method for producing alumina according to the present invention, alumina having a P-crystal structure is further used as an alumina raw material, and water and at least one kind of alumina are added to the alumina having the P-crystal structure. A solution prepared by mixing at least one of the basic acid or its salt and at least one of the above pore structure controlling agents so that the k value has the following range is adjusted to a range of 70 to 250. Aqueous alumina sol and Z or alumina gel are obtained by hydrothermal treatment at a temperature, and the aqueous alumina sol and / or alumina gel are dried and calcined.

0. 0 0 0 1 <k≤ 0.20

When alumina having a | 0-crystal structure is used, A solution prepared by mixing at least one kind of inorganic monobasic acid or a salt thereof so that the k value has the following range is subjected to hydrothermal treatment at a temperature in the range of 70 to 250 ° C. It is characterized in that an aqueous alumina sol and Z or alumina gel are obtained, and the aqueous alumina sol and / or alumina gel is dried and calcined.

0. 0 1≤ k≤ 0. 2

As the alumina having the crystal structure, alumina previously treated with a monobasic acid may be used.

When using the above-described / 0-crystal structure-treated alumina with a monobasic acid, the k value has the following range by mixing water and at least one monobasic acid or a salt thereof. The aqueous solution prepared above is subjected to hydrothermal treatment at a temperature in the range of 70 to 250 ° C. to obtain an aqueous alumina sol and Z or alumina gel. It is characterized by firing.

0. 0 0 0 1≤ k <0. 0 1

Further, aluminum hydroxide and Z or alumina having higher solubility than boehmite can be mixed with the above-mentioned preparation liquid within a range not exceeding 95% by weight based on the alumina in the preparation liquid.

The acidic aqueous alumina sol and / or alumina gel obtained by the above method is further added with an alkali to increase the specific surface area and the pore volume of the alumina composition. Hydrothermal treatment may be performed at a temperature within the range.

The alumina composition according to the present invention is a alumina composition produced by the above method, having a specific surface area and pore volume controlled in a wide range, and suitable for a catalyst carrier. The catalyst according to the present invention uses an alumina composition having a controlled specific surface area and pore volume as described above as a carrier, on which a catalyst component is supported. When these catalysts are prepared, the resulting alumina composition does not affect the obtained alumina composition even when the aqueous alumina sol and the components not involved in the Z or alumina gel formation reaction coexist in the above-mentioned preparation solution. The desired catalyst can be prepared by mixing the components. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows a composition ratio in which the monobasic acid is nitric acid, the alumina concentration in the preparation is in the range of 5 to 60% by weight, and the k value is in the range of 0.0001 to 0.20. FIG. 2 shows pore size distribution curves of the alumina compositions prepared in Examples 11 and 56. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

Alumina raw material

In the method for producing an alumina composition according to the present invention, an acid-containing alumina source obtained by heating aluminum hydroxide in the presence of an acid or alumina having a p-crystal structure is used as an alumina raw material.

The aluminum hydroxide used in the present invention is also referred to as alumina hydrate, and typically includes gibbsite, bayerite, Nordstrandite, amorphous aluminum hydroxide and the like. Examples of the alumina having a P-crystal structure include those obtained by subjecting a gibbsite or the like to vacuum heating dehydration or high-temperature rapid dehydration. First, a method for preparing an acid-containing alumina source obtained by heat-treating aluminum hydroxide, which is one of the alumina raw materials of the present invention, in the presence of a monobasic acid will be described.

Examples of the acid or its salt used in the heat treatment of aluminum hydroxide include monobasic acids such as nitric acid, hydrochloric acid, formic acid, and acetic acid, and aluminum salts such as aluminum nitrate and basic aluminum acetate. .

Such amount of such acid, to alumina 1 mole when converted to aluminum hydroxide A 1 ₂ 〇 _3, 0.0 5 to 1.0 mols you and the preferred.

In the present invention, heat treatment is performed on aluminum hydroxide in the presence of at least one of the above monobasic acids. The heat treatment temperature of the acid-mixed aluminum hydroxide is preferably in the range of 70 to 400. At this time, the heating temperature is preferably in the range of 100 to 300 in a period of several minutes to several tens of hours. When aluminum hydroxide is heated in the presence of a monobasic acid in the manner described above, the water of crystallization of aluminum hydroxide is partially dehydrated, and the acid groups are adsorbed in the pores formed by the dehydration, and the reactivity is reduced. It is believed that an acid-containing alumina source with a high concentration is formed. When using a high vapor pressure acid, heat treatment is performed in a closed vessel, but when using a low vapor pressure acid salt, the heat treatment can be performed in an open state.

The concentration of aluminum hydroxide during the heat treatment is preferably in the range of 50 to 80% by weight in terms of Al ₂ (.

The acid-containing alumina source obtained by the above method has properties similar to P-alumina obtained by rapid heat dehydration such as gibbsite, and the reaction rate is higher than when P-alumina is used as an alumina raw material. Slow but A similar alumina composition can be obtained under the same preparation liquid composition conditions. Alumina having a / 0-crystal structure may be previously treated with a monobasic acid. Specifically, alumina having a p-crystal structure is added to a nitric acid aqueous solution of about 10% or more, and the treatment is performed at a temperature of room temperature to 400. When alumina having a P-crystal structure subjected to such an acid treatment is used, an alumina composition having a high specific surface area can be obtained.

Preparation of preparation solution

In the present invention, first, the acid-containing alumina source obtained by the above method or alumina having a p-crystal structure (hereinafter collectively referred to as raw alumina) is mixed with water and an acid at a predetermined molar ratio. To prepare an acidic aqueous sol and Z or aqueous gel containing fibrous boehmite particles. The term “acidic aqueous sol and Z or aqueous gel” as used in the present invention refers to an aqueous sol or fibrous boehmite particles in which the fibrous boehmite particles obtained by the above hydrothermal treatment are dispersed. It refers to an aqueous gel having a structure or a mixture of both, and in the present invention, may be referred to as an acidic aqueous sol-gel.

Such an aqueous sol-gel has the property of swelling when contacted or kneaded with water, and is different from a mere precipitate that does not have such a property.

The particle size of the raw material alumina in the preparation solution is not particularly limited, but if the particle size is too large, the raw material alumina is likely to settle in the preparation solution. If the mixture is stirred at high speed, the resulting fibrous boehmite particles may be bound in a bundle, and the alumina composition obtained from the fibrous boehmite bound in such a bundle may be obtained. The product may have a low pore volume and an increase in macropores. For this reason, it is effective to use a pressure-resistant reaction vessel or a rotary pressure-resistant reactor equipped with a low-speed stirring mechanism in order to prevent the raw material alumina from settling at the beginning of the reaction.

In addition, aluminum hydroxide having a low Na content can be used as the raw material alumina. A very small amount of sodium contained in the raw material alumina can be washed at the powder stage before the reaction, or it can be washed at the hydrogel or molded body stage in the subsequent process. Acids or salts thereof added to the preparation solution include inorganic monobasic acids such as hydrochloric acid and nitric acid, and lower aliphatic monocarboxylic acids such as formic acid, acetic acid and propionic acid.Also, aluminum nitrate and basic acetic acid Monobasic acids generated by dissociation of salts with ionic potentials of 4.5 or higher, such as aluminum and zirconyl nitrate, are also effective. In the present invention, one or more of these acids or salts are used, and particularly when an inorganic monobasic acid and a lower aliphatic monocarboxylic acid are used in a mixture, the pore volume of the alumina composition obtained by the ratio is used. Can be controlled.

In the present invention, the molar ratio of alumina, monobasic acid and water in the above prepared solution is one of the important factors in controlling the specific surface area and pore structure of the obtained alumina composition.

In the present invention, an acid-containing alumina source or an alumina raw material such as alumina having a | 0-crystal structure is mixed with water and the acid or a salt thereof such that the k value represented by the following formula has the following range. Prepare liquid

0. 0 0 0 1≤ k≤ 0 .2 0… (1)

k = (b / a) x (b / c) (Wherein, a is the number of moles in terms of alumina in preparation to A 1 ₂ 03, b is the number of moles of acid generated by the dissociation of the monobasic acid or a salt thereof in the preparation liquid, c is in the preparation Indicates the number of moles of water.)

Such a relational expression is expressed as shown in FIG. 1 when the acid is nitric acid and the alumina concentration in the preparation is 5 to 60% by weight.

When the k value in the above formula (1) is less than 0.0001, even if an oxygen-containing organic compound or an inorganic polybasic acid described later is added, the particles do not become an aqueous sol-gel but heavy sedimentable particles. Is generated. Such particles have no plasticity and have a low compressive strength even when the obtained alumina composition is molded. If the k value is larger than 0.20, the effect of increasing the specific surface area of the obtained alumina composition is not recognized even if an oxygen-containing organic compound or an inorganic polybasic acid described later is added, and the pore volume is not increased. Can get only small things. Also, the molded body may be broken during firing.

Regardless of whether the raw material alumina is an acid-containing alumina source, an alumina having a P-crystal structure, or an alumina having a p-crystal structure previously treated with a basic acid, the k value is basically unchanged. Also, the k value does not change regardless of whether the monobasic acid is an organic monocarboxylic acid, an inorganic acid, a pore structure controlling agent, or an improvement in a subsequent process. ,

0. 0 0 0 1≤ k≤ 0.20

Meets the range. The k value is subdivided depending on the fine setting conditions at the time of preparing the alumina, and will be described below including the improvement of W097 / 32817 of the prior invention.

In W097 / 32817 proposed earlier by the present inventors, when alumina having a p-crystal structure was used as the raw material alumina, the lower fat In the case of group monocarboxylic acids, the k value is in the range of 0.02 to 0.20, and in the case of inorganic monobasic acids, the k value is in the range of 0.001 to 0.01. A translucent aqueous alumina sol was produced, and an alumina composition having a large micropore volume of 60 nm or less and a small Mac pore volume of 60 nm or more was obtained.

As a result of further study by the present inventors, when the monobasic acid is a lower aliphatic monocarboxylic acid, even if the k value is less than 0.002, some of the acids (oxy acid, inorganic polyvalent acid) in the pore structure controlling agent are used. It was found that the addition of an acid, etc.) increased the total acid content and produced an aqueous sol-gel, although not transparent, and an effective alumina composition. In addition, in the case of inorganic monobasic acid, an aqueous sol-gel having no transparency was generated beyond 0.01 irrespective of the presence or absence of the pore structure controlling agent, but in a later step after obtaining the alumina sol-gel. It was found that an effective alumina composition can be obtained by improving the shear stress and the like.

That is, when alumina having a P-crystal structure is used as the raw material alumina, the above-mentioned pore structure controlling agent is used together with at least one kind of inorganic monobasic acids and lower fatty acid monocarboxylic acids or salts thereof. For example, the k value is preferably in the range of 0.001 to 0.20.When alumina having a p-crystal structure is used as the raw material alumina and an inorganic monobasic acid or a salt thereof is used, Even if a pore structure controlling agent is not used, the k value is changed to 0.01≤k≤0.20 other than the range described in W097 / 32917 by improving the shear stress in the post-process. It was confirmed that the range was effective.

As the specific acid amount, when the alumina concentration in the preparation is 30 to 40% by weight, nitric acid is about 0.1 to 0.3 mole per mole of alumina. In the case of toluene or acetic acid, the preferred range is about 0.2 to 0.6 mol. The concentration of alumina in preparation liquid, in terms of A l ₂ 〇 _3, 5-6 0% by weight is preferably in the range of. If the alumina concentration is lower than 5% by weight, the low-viscosity state continues for a long time during the hydrothermal treatment, and a problem occurs in that the fibrous boehmite is bound in a bundle by prolonged stirring. If the amount exceeds 60% by weight, the obtained alumina hydrate loses its plasticity and molding becomes difficult. If the concentration is 30% by weight or more, the produced alumina hydrate can be directly kneaded and extruded without special concentration operation.

Further, alumina having higher solubility than boehmite may be added to the preparation solution. Examples of alumina having higher solubility than boehmite include gibbsite, bayerite, amorphous alumina hydrate, amorphous alumina, χ-alumina, α-alumina, and 7-alumina. Such higher solubility than pots one My Bok alumina, acid-containing alumina source preparation liquid or [rho - mixed in an amount of 9 5 wt% or less in Alpha 1 ₂ 0 ₃ in terms of relative alumina having a crystal structure Is preferred. The addition of alumina having higher solubility than these boehmite is effective for obtaining an alumina composition having a relatively small specific surface area.

In the present invention, a pore structure controlling agent for controlling the pore structure of the alumina composition can be added to the above-mentioned preparation liquid. Examples of such a pore structure controlling agent include an oxygen-containing organic compound, or an inorganic polybasic acid or a compound which is dissolved in water to generate an inorganic polybasic acid.

Oxygenated organic compounds include starch, agar, gelatin, carbohydrates such as mannan and CMC, mono- or polyhydric alcohols, ketones, Examples thereof include esters, higher aliphatic monocarboxylic acids, aromatic monocarboxylic acids, oxycarboxylic acids, and polycarboxylic acids. These oxygen-containing organic compounds may be compounds such as sodium, ammonium, and aluminum.

When monohydric alcohols, ketones and esters are added among the oxygenated compounds, the resulting product is an aqueous alumina sol, and the alumina composition obtained therefrom has a small effect on increasing the specific surface area, but an effect on increasing the pore volume. Is big. In the case of carbohydrates, an aqueous alumina sol-gel is formed, which has the effect of increasing the specific surface area and the pore volume. Among them, starch, agar, gelatin, mannan and CMC have a thickening effect on the preparation at low concentrations. As the aliphatic monocarboxylic acid has a lower molecular weight, a more transparent aqueous sol is generated, but the effect of increasing the specific surface area and the pore volume is small, and the effect of increasing the molecular weight is larger when the molecular weight is higher. In the case of carboxylic acids, polyhydric alcohols, and polycarboxylic acids, an aqueous sol-gel composed mainly of hard gel is formed, and the effect of increasing the specific surface area and the pore volume is recognized.

Regarding the effect of controlling the pore distribution, polyhydric alcohols increase the pore diameter, and polyhydric carboxylic acids and certain oxycarboxylic acids both increase the specific surface area, and the pore volume decreases from a small value. An alumina composition having a sharp pore distribution over a wide range up to a large value can be obtained, and an alumina composition having a bimodal pore distribution can be obtained. In addition, most of the oxygen-containing compounds have an effect of improving the mechanical strength of a molded article of the alumina composition.

Such an oxygen-containing organic compound is preferably added in the range of 0.002 to 0.2 part by weight per 1 part by weight of alumina. 0. Double If the amount exceeds the above range, the macropore volume of the obtained alumina composition may increase, and the mechanical strength of the molded product may decrease.

Other pore structure controlling agents used in the present invention are inorganic polybasic acids or compounds which dissociate or decompose in hot water to produce inorganic polybasic acids.

Among these, preferred polybasic acids include inorganic polyacids containing elements having an ionic potential of 4.5 or more (for example, B, C, Si, P, S, Ti, V, MOW, Zr). A basic acid or a compound thereof, specifically, boric acid, caic acid (ion-exchanged of sodium silicate with a cation exchange resin), polycaic acid (hydrolyzate of ethyl silicate), phosphoric acid, Examples include aluminum phosphate, sulfuric acid, sulfosalicylic acid, ammonium sulfate, peroxotitanic acid, vanadic anhydride, molybdic acid, molybdenum trioxide, suigustenoic acid, and zirconyl acetate.

The ion potential is represented by the following equation.

Element valence

Ion potential =

Element ion radius Among these, polybasic acids composed of light elements such as B, S i, and P have the effect of increasing the specific surface area and pore volume of the alumina composition with a small amount of addition Mo, W, etc. In the case of a polybasic acid composed of the following heavy elements, the effect of increasing the specific surface area of the alumina composition was not recognized unless added in a large amount. Most inorganic polybasic acids have a higher alumina composition than the oxygen-containing organic compound described above. Has the effect of increasing the specific surface area of the product, and it is also effective to use both It is.

When the above-mentioned inorganic polybasic acid is added in a large amount, the mechanical strength of the molded product when the alumina composition is molded may be reduced. The atomic ratio is preferably in the range of 0.0002 to 0.2 per mole of atom.

Hydrothermal treatment

In the present invention, the prepared solution prepared as described above is added with the various pore structure controlling agents described above, if necessary, to obtain 70 to 25.0, preferably 90 to 200. Hydrothermal treatment is performed in a pressure vessel such as an autoclave at a temperature in the range of. As a result, an acidic aqueous sol-gel of fibrous boehmite particles is formed.

The acidic aqueous sol-gel obtained by the above method contains an acid and may be molded as it is for a catalyst carrier. Shrinkage occurs, and only a molded product having a pore volume of, for example, about 0.5 to 0.7 ml / g is obtained, and a molded product having a larger pore volume may not be obtained.

Therefore, the pore volume of the alumina composition can be increased by neutralizing the acid in the sol-gel with an alkali. The alkali used is preferably ammonia gas or aqueous ammonia. The amount of addition is preferably smaller than 1.5 in terms of molar ratio (ammonia Z-acid) to the total amount of acid in the sol-gel. Can be controlled.

After neutralization with alkali, hydrothermal treatment may be performed again if necessary. The temperature of the hydrothermal treatment is desirably in the range of 70 to 200 ° C, preferably in the range of 110 to 150. When hydrothermal treatment is performed after alkali neutralization, an alumina composition having a larger pore volume can be obtained. This It is not clear why the pore volume is increased by re-hydrothermal treatment after alkali neutralization as described above, but the nodules in the three-dimensional network structure of the fibrous matrix in the aqueous gel are strong. It is presumed that bonding occurs, shrinkage due to the capillary condensation of water during dehydration in the drying process is reduced, and a large pore structure is maintained.

Drying and firing

The aqueous sol-gel thus obtained is dried, and then calcined at 400 or more to obtain an alumina composition. In particular, the sintering may be performed in a temperature range of 400 to 600 ° C. When sintering is performed in this temperature range, formation of a-alumina suitable for a catalyst carrier is confirmed. Since the aqueous sol-gel obtained in the present invention can have an alumina concentration of 30% by weight or more, it can be formed into an arbitrary shape by extrusion molding or the like as it is. Therefore, an alumina molded body useful for a catalyst carrier or the like can be obtained by drying and calcining after molding.

Alumina composition

The alumina composition according to the present invention obtained by the above-described method has a very wide range in both the specific surface area and the pore volume, and for example, is calcined in the range of 400 to 600 ° C. The alumina composition thus obtained has a specific surface area of 100 to 400 m ² Z g, a pore volume of 0.5 to 1.5 ml Z g and an average pore diameter of 50 to 30 OA. have. Such an alumina composition is useful as various types of catalyst carriers, and has a pore structure that is particularly suitable as a carrier for a hydrotreating catalyst in the petroleum refining industry.

In hydrotreating catalysts, asphaltene in petroleum fractions diffuses into the pores of the catalyst, and pores close due to the deposition of nickel and vanadium metals. It is said that various phenomena such as clogging and the formation of carbon due to the overcracking of heavy hydrocarbons depend on the pore size of the catalyst. Although carriers having different pore structures are required, the alumina composition according to the present invention can be obtained by selecting an alumina composition having an optimum pore structure according to each purpose.

Catalyst

The catalyst using the alumina composition according to the present invention as a carrier is obtained by molding the alumina composition obtained by the above method into an appropriate shape and then impregnating the molded body with a catalyst component by a usual method. be able to.

In the present invention, the desired catalyst can be obtained by mixing the above-mentioned aqueous sol-gel with a catalyst component, followed by molding, drying and calcining. Further, since the preparation liquid of the alumina raw material contains substances not related to the formation of the alumina sol gel, and aqueous alumina sol gel can be generated in the coexistence of these substances, the catalyst component is added to the preparation liquid. It is also possible to add. For example, when preparing a hydrotreating catalyst for petroleum refining, first add the compound of Mo and W as a catalyst component to a preparation solution to prepare an aqueous sol-gel by the above-mentioned method, and then mold, dry, and calcine it. Further, catalyst components such as Ni and Co can be supported by an impregnation method. The catalyst obtained by this preparation method has sufficient performance for desulfurization activity and nuclear hydrogenation activity. In addition, even if the desired catalyst is prepared by simultaneously adding catalyst components such as Mo, W, Ni, and Co to the preparation solution, the formation of nickel aluminate and cobalt aluminate compounds having an inactive composition will not occur. unacceptable.

Mo and W at this time are, for example, molybdic acid, Acid is useful as the above-mentioned polybasic acid as a pore structure controlling agent.If such a compound is used as a controlling agent, it acts as a controlling agent and at the same time becomes a catalyst component as it is. This simplifies the catalyst manufacturing process.

Further, a compound of Zr and Ce may be added to the preparation solution of the alumina raw material in advance and subjected to hydrothermal treatment to obtain an aqueous sol-gel, which may be molded, dried, and fired. The alumina composition thus obtained has sufficient heat resistance as an exhaust gas purifying catalyst carrier. The invention's effect

According to the method for producing an alumina composition of the present invention, an alumina composition having a high specific surface area and a large pore volume can be easily obtained. In addition, since the pore structure such as specific surface area, pore volume, and pore distribution can be arbitrarily controlled, alumina compositions having various pore structures suitable for use as a catalyst carrier used in the petroleum refining industry and the like can be obtained. It can be easily prepared with the same manufacturing equipment by changing some conditions.

Also, high concentration of alumina can be prepared, and it can be directly molded from a sol or gel without a concentration operation, or a catalyst component can be added at a preparation liquid stage. The production process of the alumina composition or the catalyst can be greatly shortened. Example

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 _ 1 Gibbsite with a center particle size of 0.5 zzm to an aqueous solution containing 28.4% Al (NOs) ₃ [C-3005, manufactured by Sumitomo Chemical Co., Ltd., adhering water 0.17% Al (0H) ₃ : 99.5 535 g of 0.35% of impurities such as Na ₂ O, etc.] and heat-treated at 250 ° C. to obtain an acid-containing alumina block made of χ-alumina. And grinding the blocks 352 g contained in Alpha 1 ₂ 0 ₃ in terms of a powder, by addition of ion-exchanged water 720ml, alumina concentration was prepared 30 wt% of the preparation.

Raw materials used were calculated on the basis, the number of moles of acid in the preparation (b) ZA 1 ₂ 0 ₃ mole number (a) is 0.20, the number of moles of acid (b) the number of moles of Z water ( c) was 0.016 and the k value ((b / a) X (b / c)) was 0.0032. The prepared solution was placed in a rotary pressure-resistant container, and subjected to hydrothermal treatment at 160 ° C. for 24 hours while rotating to obtain an acidic aqueous sol-gel. The aqueous sol-gel was neutralized by adding the same molar number of aqueous ammonia as nitric acid and converted to an aqueous gel, and subjected to hydrothermal treatment at 135 for 3 hours.After kneading, the mixture was cylindrical with a 1.5-band φ die. It was extruded, dried at 140 and calcined at 560 to produce an alumina molded product.

The obtained alumina molded product had a specific surface area of 171 m ² Z g, a pore volume of less than 60 nm and a pore volume of 0.90 mlZ g, and alumina having a sufficiently large pore volume was obtained.

Example 1 2

Median particle size is 8.8 m low source one Dagibusai bets [manufactured by Showa Denko KK, HS - 32 0, water attached 0.11%, Al (0H) 3 : 99.8¾, Na 2 0 and the like impurities: 0.0 «] to 77g of 10 g of acetic acid was added, and the mixture was filled in a closed container and heated at 150 ° C for 12 hours to obtain 87 g of an acid-containing gibbsite. After the acid-containing gibbsite was pulverized, 80 ml of ion-exchanged water was added to prepare a preparation. Acid of this preparation _{_{(b) / Al 2 0 3}} (a) is 0.34, acid (b) / 0 (c) is 0.028, k value was 0.0095. The prepared solution was subjected to hydrothermal treatment under the same conditions as described in Example 11 to obtain an acidic aqueous sol containing a small amount of translucent gel. Aqueous ammonia with the same mole number as the acetic acid contained in this aqueous sol was added, hydrothermally treated at 135 for 3 hours, kneaded, extruded into a 1.5-strand cylinder, dried at 140 ° C, and dried at 560. It was fired to produce an alumina molded product. The specific surface area of the obtained alumina molded product was 132 m ² Z g, the pore volume was 0.73ΙΠ1Ζ g, and the center pore diameter was 220 A.

Example 1 3

Median particle size of alumina with a P- crystal structure (manufactured by Sumitomo Chemical Co., _{_{Ltd., BK- 540 Al 2 0 3:}} 93.6%, impurities such as Na ₂ 0: 0.3%, water: 6.1%) to 320 g Was added to ion-exchanged water together with 65 g of aluminum nitrate 9-hydrate, wet milled, and then 8.8 g of 70% glycolic acid and 85% phosphoric acid were added to prepare a prepared solution. .

Alumina concentration in the preparation liquid to 30%, the molar ratio of the predetermined three components, calculated from aluminum nitrate two © beam was used HN0 ₃ / Al ₂ (but with _{_{0. 17, HN0 3 / H 2}} 0 0.01 3 The k value was 0.0022, the weight ratio of alumina glycolic acid was 0.02, and the primitive ratio of P / A1 was 0.0014.

This prepared solution was placed in a pressure-resistant container and subjected to hydrothermal treatment at 100 at 48 hours and at 140 at 16 hours under static conditions. As a result, an acidic aqueous sol-gel was obtained. Ammonia water is added in a molar amount to neutralize 40% of the nitric acid contained in the acidic aqueous sol-gel, and the mixture is subjected to hydrothermal treatment at 135 for 3 hours. After kneading, the mixture is extruded into a 1.5-band cylindrical shape. in after drying 500, a result of firing at at 550T :, 600, respectively the specific surface area of the obtained alumina molded ^{^{270m 2 Z g, 252m 2 /}} g, was 233m ² Bruno g. Example 1 4-8

400 g of the same alumina as that used in Example 13 was mixed in advance with nitric acid having different concentrations shown in Table 1, and after aging, ion-exchanged water was added to prepare 1070 g of each of the prepared solutions. 35% alumina concentration of these preparation, respectively, the molar ratio of the predetermined three components of alumina, nitric acid and water thigh 0 _₃ / Α 1 ₂ 0 ₃ 0.20, with HN0 ₃ / H ₂ 0 is 0.021, k value Was 0.0042.

These prepared solutions were hydrothermally treated at 135 ° C. for 28 hours by the method described in Example 11 to obtain an acidic aqueous sol-gel. These aqueous acidic sol gels are neutralized by adding ammonia water in the same number of moles as the acid contained in the acidic aqueous sol gel, kneaded, extruded into a 1.5 mm column, dried at 140 ° C, and fired at 560 As a result, the specific surface area of each obtained alumina molded body is shown in Table 1.

From the results in Table 1, it was found that the higher the nitric acid concentration in the initial addition, the higher the specific surface area of alumina.

Example—9-11, Comparative Example— ~ Five

Acetic acid aqueous solution (Comparative Examples 1 to 5) to which acetic acid was not added or 6.4 g was added to 560 ml of ion-exchanged water, and 19.1, 48.7, and 84.7 g were added (Examples 9 to 11). An aqueous solution was prepared, and oxalic acid, glycolic acid, citric acid and the like shown in Table 2 were added thereto. To these 385 g of alumina having a p-crystal structure of Example 13 was added to prepare a preparation liquid. The composition was such that A (was 36% by weight and the weight ratio of the above carboxylic acid to alumina was 0.02. An alumina molded article was produced from the obtained preparation in the same manner as in Example_4. .

Table 2 shows the specific surface area, pore volume, and compressive strength of the obtained alumina molded product. Table 2

Example Molar ratio and k value Additive SA PV Compressive strength Comparative example b / ab / ck Type Weight ratio mVg ml / g kg Comparative example 1 1 0.000 0.000 0.00000 Glycolic acid 0.02 158 0 42 1.0 or less Comparative Example 1 2 0.03 0.003 0. 00009 Not added 145 0.37 1.0 or less Comparative Example—3 0.03 0.003 0. 44 1.0 or less Comparative example 1 4 0.03 0.003 0.00009 Oxalic acid 0.02 166 0.41 1.0 0 or less Comparative example 1 5 0.03 0.003 0. 00009 Cunic acid 0.02 172 0 401.0 or less Example 1 9 0.09 0. 009 0.0008 Glycolic acid 0.02 198 0.54 1.3 Example 1 10 0.23 0. 028 0. 0.75 2.2 Example 1 11 0.40 0.046 0.019 Glycolic acid 0.02 248 0.59 2.7

From Table 2, it was found that, when the k value was small as in Comparative Examples 1 to 5, only an alumina molded product having a sufficient specific surface area, pore volume, and compressive fracture strength could be obtained. Further, it was found that 0.0008 of the k value in Example-9 was effective in increasing the specific surface area and the pore volume.

Example 1 12-: L5, Comparative Example-6-9

Add 55%, 109, 219, and 437 g of 6% 1% nitric acid to 560 ml of ion-exchanged water to prepare an aqueous solution of nitric acid at room temperature, and add oxalic acid, glycolic acid, and quench acid as shown in Table 3. Acid and the like were added. To these, 385 g of the alumina having the P — crystal structure of Example 3 was added to prepare a preparation solution. The composition was such that AI 2 O 3 was 36% by weight and the weight ratio of the carboxylic acid to alumina was 0.02. The resulting preparation was subjected to alumina treatment in the same manner as in Example-4. A molded product was produced.

Table 3 shows the specific surface area, pore volume, and compressive fracture strength of the obtained alumina molded product.

Table 3

Example Molar ratio and k value Additive SA PV Compressive strength Comparative example b / ab / ck Type Weight ratio iVg ml / g kg Example-12 0.15 0.016 0.0024 Not added 175 0.84 2 2 Example—13 0.15 0. 016 0.0024 Daricolic acid 0.02 247 0.83 2.3 Example 1 14 0.30 0.034 0.010 Glycolic acid 0.02 0.65 3.5 Example-15 0.60 0.077 0.046 Glycolic acid 0.02 227 0.50 3.0 Comparative example 6 1.20 0.205 205.245 Not added 211 0.444 1 2 Comparative Example 1 7 1.20 0.209 0.250 Glycolic acid 0.02 232 0.45 Collapse during firing Comparative Example 1 8 1.20 0.209 0.250 Oxalic acid 0.02 226 0.46 Collapse during firing Comparative Example 1 9 1.20 0.209 0.250 Cunic acid 0.02 235 0.45 Collapse during firing

FIG. 12 shows a pore size distribution curve of the alumina composition of Example 1-12. From the results in Table 3, it was found that a usable alumina carrier was obtained with a k value of 0.46 in Example-15.

Example 1 16 to 21, Comparative Example—10

Example 4 Tartaric acid was added to a diluted aqueous solution of nitric acid at 30 having the same composition as described in Example 4 as shown in Table 4 (from 0.112 g to 112 g in seven steps). —Alumina having a crystal structure was similarly added to prepare a preparation liquid. The resulting preparation was subjected to hydrothermal treatment at 135 for 28 hours in the same manner as in Example-4 to obtain an acidic aqueous sol-gel. The aqueous sol-gel was kneaded while being acidic, extruded into a cylindrical shape of 1.5ππηφ, dried at 140, and fired at 560 to produce an alumina molded product. Table 4 shows the specific surface area, pore volume, and compressive fracture strength of the obtained alumina molded product. Table 4

Example Tartaric acid tartaric acid / alumina SA PV Compressive strength Comparative example Addition amount Weight ratio mVg ml / g kg Example—16 0.12 g 0.0003 223 0.69 3.4

Example 1 17 0.373 g 0.0001 225 0.70 3.7

Example 1 18 1.12 g 0.0003 230 0.72

Example 1 19 3.73 g 0.001 245 0.70 3.9

Example—20 11.2 g 0.03 248 0.56 3.6

Example-21 37.3 g 0.1 222 0.48 2.1

Comparative Example 1 10 112 g 0.3 Disintegrated during firing

Example 1 22 to 28

Using the gibbsites used in Examples 11 and 12, acid-containing alumina hydrate and alumina were prepared and powdered according to the method and conditions described in the same. To a suspension of this powder dispersed in ion-exchanged water, glucose, maleic acid, glycerin, glycolic acid, dalconic acid, oxalic acid dihydrate and lactic acid are shown in Table 5 as pore structure control agents. To prepare seven types of preparation solutions. The prepared solution was subjected to hydrothermal treatment at 160 at 24 hours in the same manner as in Examples 11 and 12 to obtain an acidic aqueous sol-gel. An alumina molded product was produced from this aqueous sol gel according to the method and conditions of Example 11.

Table 5 shows the specific surface area of the obtained alumina molded product. The specific surface area showed higher values than those of Example 11 and Example 12. Table 5

Examples Gibsai Additives during heat treatment SA

Type of acid Type of acid Type to weight ratio of alumina mVg Example-22 C-3005 Al (NO ₃ ) glucose 0.02 188

Example-23 C-3005 Al (NO ₃ ) maleic acid 0.02 203

Example-24 HS-320 CHaCOOH Glycerin 0.02 177

Example-25 HS-320 Al (NO glycolic acid 0.02 237

Example 1 26 HS-320 Al (NO dalconic acid 0.02 234

Example-27 HS-320 Al (NO oxalic acid dihydrate 0.02 206

Example-28 HS-320 Al (NO lactic acid 0.02 235 Comparative Example 1 11 to 13, Example—29 to 5 1

Example 1 of 3! Using 0-crystalline alumina, nitric acid and acetic acid, their addition amount and k value, alumina concentration, types and addition amounts of various organic and inorganic substances, hydrothermal treatment conditions, hydrothermal treatment conditions after alkali neutralization, etc. An alumina molded product was obtained under the conditions shown in Table 6 respectively.

Table 6 shows the specific surface area and pore volume of the obtained alumina molded product.

Table 6

Example 1 5 2

61.7 g of acetic acid and 8.4 g of oxalic acid dihydrate were added to 547 ml of ion-exchanged water, and then 160 g of alumina having a p-crystal structure of Example-3 and Gibci described in Example 14 of W097 / 32817 Publication The composition of this solution was prepared by adding 231 g of the solution, the composition of this solution had an alumina concentration of 30% by weight, an acetic acid concentration of 6.2%, an oxalic acid concentration of 0.60%, a molar ratio of nooacetate acetate of 0.35, and a molar ratio of acetic acid water. Was 0.029 and the k value was 0.010.

This prepared solution was subjected to hydrothermal treatment at 150 at 24 hours in the same manner as in Example-4, and then an alumina molded product was produced in the same manner and under the same conditions as in Example-14. The specific surface area of the obtained molded product was 154 m ² / g, and the pore volume was 0.78 mlZg. The specific surface area of the alumina, oxalic acid had increased W097 / specific surface area of 32817 JP one example embodiment 4, wherein the alumina 107m ² Z g and specific base, 47m ² Z g of additive-free.

Example—53 to 54, Comparative Example—11 to: 14

As shown in Table 7, using P-crystal structure alumina and acetic acid and nitric acid of Example 13 as shown in Table 7, the composition of alumina was 15% by weight and 52% by weight, and the k value was 0.00008, 0.002, And a preparation solution having a composition of 0.2 or more was prepared. Using the obtained preparation liquid, an alumina molded product was produced in the same manner and under the same conditions as in Example 14. Table 7 shows the pore volume and compressive fracture strength of the obtained alumina molded product.

As a result, when the alumina concentration is 15% and 52%, the composition having a k value of 0.00008 and a composition of 0.2 or more has a small pore volume, a low compressive strength, and the composition having a k value of 0.002 has a small pore volume. The volume and compressive strength were sufficient.

Example 1 5 5

3950 g of alumina having a p-crystal structure of Example 13 was mixed with a mixed solution obtained by adding 75 g of 61% nitric acid and 7.4 g of glycerin to 755 ml of ion-exchanged water to prepare a prepared solution. The composition of the preparation liquid in 30% concentration of alumina, the molar ratio and k values, HN0 _₃ / A1 ₂ 0 ₃ is 0.20, HNC / ILO is 0. 017, the k value is 0.0034, glycerin Bruno The weight ratio of alumina was 0.02.

Next, using the reaction vessel described in Example 1, the viscosity was increased to 2 O mPa or more at 80 ° C. while rotating, and then hydrothermal treatment was performed at 135 at rest for 28 hours. . The molar ratio of ammonia to be neutralized was changed to 0.00.4 0.6 0.8 1.0 1.20 with respect to HNO ³ of the acidic alumina sol gel synthesized by this method, and then heat treatment was performed at room temperature and 135 ° C. It was molded and dried in the same manner as in Example 11 to produce an alumina molded product. Table 8 shows the specific surface area and pore volume of the obtained alumina molded product. Table 8

When the hydrothermal treatment is performed after the addition of ammonia, the pore volume increases.

Two

Turned out to be.

Example 1 5 6

Example 15 In Example 55, a preparation solution was prepared by using oxalic acid dihydrate instead of glycerin. The composition of this preparation solution had the same alumina concentration, mole ratio and k value as in Example 55, and the weight ratio of nolumina oxalate was 0.02. The resulting preparation was subjected to hydrothermal treatment according to the same method and conditions as in Example 55. Respect synthesized acidic alumina sol HN0 _3, the molar ratio of Nmonia neutralizing, 0.0 (no addition), was added as a 0.5 1.0, the same molding as one example embodiment 1, dry Operations such as drying were performed to produce an alumina molded product.

The specific surface area of the obtained alumina molded product was such that when the ammonia was not added, the molar ratio of force was 243 m ² Z g NH3 / HNO3 was 0.5, and the molar ratio of force was 247 m ² ng NH3 / H NOs was 1.0. The time was 238 m ₂ Z g. FIG. 12 shows the pore size distribution curve of the obtained molded body. It was found that an alumina composition having a sharp pore size distribution curve was obtained without the addition of oxalic acid as compared with Example 1-12 in which the composition of the substantially prepared solution was similar.

Example 1 5 7 This example shows an example in which a large amount of nitric acid is used with respect to alumina and a pore structure controlling agent is not added in a high k value region.

And Ion-exchanged water 420ml 61% added nitric acid 190 g, alumina having a center particle diameter of 15 111 with p- crystal structure thereto (manufactured by Sumitomo Chemical Co., _{_{Ltd., BK-112 Al 2 0 3}} : 93.6%, Na 2 Impurities such as 0: 0.3%, water: 6.1%) 400 g were added to prepare a preparation. The molar ratio of the predetermined three components of the preparation liquid HN0 _₃ / A 1 ₂ 0 ₃ is 0.50, HN0 ₃ / H ₂ 0 is at 0.064, k value was 0.032.

According to the method of Example 14, hydrothermal treatment was carried out at 150 under the reaction conditions of 8 hours to obtain an acidic sol-gel. The sol-gel was divided into three parts, and 100%, 120% and 140% moles of ammonia were added to the contained acid, and then an alumina molded article was prepared by the method and conditions described above. The specific surface area of the obtained aluminum molded product was 144 m ² Z g, 140 m ² / g and 138 m ² / g, respectively, and the pore volume was 0.δδπιΙΖ g, 0.70 ml / g and 0.71 ml, respectively. Alumina having a small specific surface area but a large central pore diameter was obtained, and an effective carrier was obtained with a k value of 0.032.

Example 1 5 8

The dilute aqueous solution of sodium silicate No. 3, through a cation exchange resin to obtain a silicic acid aqueous solution containing 3.0% of Si0 _2. To 269 ml of ion-exchanged water were added 290 g of this aqueous solution of silicic acid, 54.4 g of acetic acid, and 395 g of alumina having the same p-crystal structure as used in Example 13 to prepare a preparation solution. The composition of the adjustment made _{_{solution, A 1 2 0 3: CH}} 3 C00H: H 2 0 , respectively 36.7%: 5.4%: A 57.0% Si (but 0.86% is other impurities 0.12%, molar ratio and the k _{_{value, CH 3 C00H / a 1 2}} 0 3 is _{_{0.25, CH 3 C00H / H 2}} 0 is 0.028, k is 0.007, the atomic ratio of Si / Al was 0.02 .

Thereafter, the prepared solution was stirred at 135 for 28 hours without stirring in the same manner as in Example 13. 3i A hydrothermal treatment was performed with stirring, and a silica-containing alumina molded product was obtained in the same manner as in Example 13.

The specific surface area of the obtained alumina molded body was 226 m ² ng, and the pore volume was 0.98 mlZ g, and the respective values increased.

Example 1 5 9

In 95.5 ml of ion-exchanged water, 3.3 g of acetic acid and zircosol ZA-30 manufactured by Nutex Corporation [Ζ Γ · 0 · (CH ₃ C00) 48.1%] 9.29 g and cerium acetate [Ce (CHsCOO) 3: 92.5%] 17.64 g was dissolved, and 48.1 g of alumina having a p-crystal structure of Example 13 was added to prepare a preparation solution. The composition of the preparation _{_{_{liquid, A1 2 0 3: CH 3}}} C00H: H 2 0 25.9%, respectively: 3.08%: in 59 · 9% Zr0 ₂ 1.62% and impurities and cerium acetate, such as other Na ₂ 0 in 9.47%, molar _{_{ratio, CH 3 C00H / a 1 2}} 0 3 is _{_{0.20, CH 3 C00H / H 2}} 0 is 0.015, k value of 0.003, the atomic ratio of Zr / a 1 was 0.026. The acetic acid group of cerium acetate having an ionic potential of less than 4.5, which is not significantly involved in the reaction, was omitted from the calculation of the molar ratio of the three components and the k value.

The obtained preparation liquid was subjected to hydrothermal treatment at 125 in 56 hours in the same manner as in Example 14, and after drying the obtained acidic aqueous sol-gel, it was pre-baked in 57 O: for 3 hours. After washing a small amount of the contained Na component, it was further baked at 1100 for 3 hours. As a result, the obtained alumina composition had a specific surface area of 53 m ² g, and as a result of X-ray diffraction, the crystal form of alumina was 0-alumina and non-alumina-free, δ-alumina, and It has been demonstrated that it has heat resistance.

Example 1 60

Same as described in Example 13 3 — Washing trace Na component containing 365 g of alumina having a crystal structure with 1380 g of 0.25% nitric acid aqueous solution 630 g of this washed cake was added to a mixture of 70 g of aluminum nitrate nonahydrate and 7 g of oxalic acid dihydrate dissolved in 300 ml of ion-exchanged water, and 73.4 g of molybdenum oxide was further added. A liquid was prepared. Its composition A 1 ₂ 0 ₃ in terms of concentration of 32.4%, the weight ratio of oxalic acid / alumina 0.014, the atomic ratio of Mo / Al was 0.074. This was placed in a pressure vessel and subjected to hydrothermal treatment at 135 for 28 hours to obtain an acidic aqueous sol-gel. After ammonia water was added to neutralize the mixture, it was hydrothermally treated at 135 for 3 hours, kneaded, extruded, dried, and fired at a temperature of 450 ° C to obtain a Mo-containing alumina molded product. Next, an aqueous solution of nickel ammonium complex was impregnated into the Mo-containing alumina molded product, dried and calcined at a temperature of 550 to obtain a catalyst having a specific surface area of 319 m ² g and a pore volume of 0.51 mlZ g.

This catalyst was crushed and sulfurized at a temperature of 400 with hydrogen sulfide, and then 1 part by volume was charged into a batch type reaction tube.

Hydrogenation reaction was carried out by introducing 20 parts by volume of a light oil distillate containing 0.05% by weight of sulfur containing dibenzothiophene and 2400 parts by volume of hydrogen and stirring at 300 and about SOkgZcm ² for 1 hour.

As a result of analyzing the product after the reaction, the product showed a desulfurization activity of 75% of the contained sulfur. The hydrogenation activity of the polycyclic aromatic ring was also observed.

Example 1 6 1

In 448 ml of ion-exchanged water, 70.6 g of aluminum nitrate nonahydrate, 56.7 g of nickel nitrate hexahydrate and 7 g of oxalic acid dihydrate were dissolved, and 57.3 g of molybdic acid was added. 374 g of alumina having the same p-crystal structure as in Example 1 were added. Its composition A1 ₂ 0 ₃ concentration calculated 35.5%丽0 ₃ concentration excludes nitrate nickel nitrate, only the calculation to 3.5% component converted from the nitrate of aluminum nitrate, all H ₂ 0 is 51.9 %, Ni (NOs) ₂ is 3.5%, impurities 0.1% molar ratio, HN0 ₃ / Al ₂ (but 0.160, oxalic acid / H ₂ 0 is 0.0196, k value is 0.031, the weight ratio of oxalic acid / alumina 0.014, the Mo / A1 The atomic ratio was 0.050.

The steps from hydrothermal treatment to molding and firing are performed in accordance with the operating method conditions described in Example 14.Furthermore, a small amount of contained Na is washed and dried at 140, the specific surface area is 261 m ² Z g, and the pore volume is 0.62 ml. / g was obtained.

The resulting molded body did not show the color tone that appeared when the nickel-aluminate compound that inactivates Ni was formed, and the high temperature of 750 and 800 ° C was used to examine the signs of the formation of the compound. An accelerated nickel aluminate crystal growth test during firing was performed. X-ray diffraction showed no formation of the crystal.

Claims

The scope of the claims

1. Obtained by heat-treating aluminum hydroxide in the presence of at least one monobasic acid or a salt thereof at a temperature in the range of 70 to 400 ^. , Water and, if necessary, a monobasic acid to adjust the k value represented by the following formula to the following range, and then subject the alumina sol and the alumina sol to hydrothermal treatment at a temperature in the range of 70 to 250. A method for producing an alumina composition, comprising obtaining Z or alumina gel, drying and calcining the alumina sol and / or alumina gel.

0. 0 0 0 1≤ k≤ 0 .2 0

Where k = (b / a) X (b / c)

(Wherein, a is the number of moles in terms of alumina in preparation to A 1 ₂ 0 _3, b is the number of moles of acid generated by the dissociation of an acid or a salt thereof in the preparation liquid, c is water in the preparation Number of moles)

2. The method for producing an alumina composition according to claim 1, wherein a pore structure controlling agent is added to the preparation liquid.

3. A liquid prepared by mixing water, at least one monobasic acid or a salt thereof, and a pore structure controlling agent with alumina having a p-crystal structure, and adjusting the k value represented by the following formula to the following range. Is subjected to hydrothermal treatment at a temperature in the range of 70 to 250 to obtain an alumina sol and / or alumina gel, and drying and firing the alumina sol and / or alumina gel. . 3b

0. 0 0 0 1≤ k≤ 0 .2 0

Where k = (b / a) X (b / c)

(Wherein, a is the number of moles in terms of alumina in preparation to A 1 ₂ 0, b is the number of moles of acid generated by the dissociation of the monobasic acid or a salt thereof in the preparation liquid, c is in the preparation Number of moles of water)

4. A prepared solution prepared by mixing water and at least one inorganic monobasic acid or a salt thereof with alumina having an ιθ-crystal structure and adjusting the k value represented by the following formula to the following range, A method for producing an alumina composition, comprising obtaining an alumina sol and Z or alumina gel by hydrothermal treatment at a temperature in the range of 0 to 250: drying and firing the alumina sol and Z or alumina gel.

0. 0 1≤ k≤ 0 .2 0

Where k = (b / a) X (b / c)

(Wherein, a is the number of moles in terms of alumina in preparation to A 1 ₂ 〇, b is the number of moles of acid generated by the dissociation of the monobasic acid or a salt thereof in the preparation liquid, c is in the preparation Number of moles of water)

5. The method for producing an alumina composition according to claim 3, wherein the alumina having a p-crystal structure is previously treated with a monobasic acid.

6. A prepared solution was prepared by adding water and, if necessary, a monobasic acid to alumina having a crystal structure previously treated with a monobasic acid to adjust the k value represented by the following formula to the following range. Hydrothermal treatment at a temperature in the range of An alumina sol and / or an alumina gel is obtained by treating the alumina sol and / or the alumina gel.

0. 0 0 0 1 ≤ k <0.0. 1

Where k = (b / a) X (b / c)

7. The pore structure controlling agent comprises: (i) an oxygen-containing organic compound, and

(ii) At least one of an inorganic polybasic acid containing an element having an ion potential of 4.5 or more represented by the following formula or a compound formed by dissociating or decomposing the polybasic acid in hot water. Is a seed

4. The method for producing an alumina composition according to claim 2, wherein:

Element valence

Ion potential =

Element ionic radius

8. An aluminum hydroxide having higher solubility than boehmite and Z or alumina are mixed with the preparation solution in a range not exceeding 95% by weight based on alumina in the preparation solution. 7. The method for producing an alumina composition according to any one of 1 to 6.

9. After adding an alkali to the alumina sol and / or the alumina gel, perform a hydrothermal treatment at a temperature in the range of 70 to 250 ° C. A method for producing an alumina composition according to any one of claims 1 to 8, characterized in that:

10. An alumina composition produced by the method according to any one of claims 1 to 9.

11. A catalyst comprising the alumina composition according to claim 10 as a carrier, and a catalyst component carried on the carrier.