WO2001056926A1 - Composition d'alumine et son procede de preparation - Google Patents

Composition d'alumine et son procede de preparation Download PDF

Info

Publication number
WO2001056926A1
WO2001056926A1 PCT/JP2000/000620 JP0000620W WO0156926A1 WO 2001056926 A1 WO2001056926 A1 WO 2001056926A1 JP 0000620 W JP0000620 W JP 0000620W WO 0156926 A1 WO0156926 A1 WO 0156926A1
Authority
WO
WIPO (PCT)
Prior art keywords
alumina
acid
preparation
moles
gel
Prior art date
Application number
PCT/JP2000/000620
Other languages
English (en)
Japanese (ja)
Inventor
Goro Sato
Masayoshi Sato
Original Assignee
Goro Sato
Masayoshi Sato
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Goro Sato, Masayoshi Sato filed Critical Goro Sato
Priority to PCT/JP2000/000620 priority Critical patent/WO2001056926A1/fr
Priority to JP2001556805A priority patent/JP4105870B2/ja
Publication of WO2001056926A1 publication Critical patent/WO2001056926A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
    • C01F7/447—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by wet processes
    • C01F7/448—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by wet processes using superatmospheric pressure, e.g. hydrothermal conversion of gibbsite into boehmite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • pseudoboehmite see, for example, -7 14 No. 56 and Japanese Patent Publication No. 61-26512.
  • this method has a problem that the pore structure of the alumina carrier cannot be sufficiently controlled.
  • 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.
  • 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.
  • 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).
  • alumina having a p- and —-crystal structure hereinafter referred to as / 0—alumina having a crystal structure
  • / 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.
  • Alumina composition was once prepared from aluminum hydroxide such as ⁇ 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
  • 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.
  • 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.
  • a is the number of moles in terms of alumina in preparation to A 1 2 ⁇ 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.
  • 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.
  • 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.
  • 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.
  • alumina having the crystal structure alumina previously treated with a monobasic acid may be used.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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. .
  • 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.
  • 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.
  • 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.
  • 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.
  • an acidic aqueous sol and Z or aqueous gel containing fibrous boehmite particles (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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.)
  • 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.
  • 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. ,
  • 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.
  • 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.
  • 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.
  • 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.
  • the k value is preferably in the range of 0.001 to 0.20.
  • 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.
  • nitric acid is about 0.1 to 0.3 mole per mole of alumina.
  • the preferred range is about 0.2 to 0.6 mol.
  • the concentration of alumina in preparation liquid in terms of A l 2 ⁇ 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.
  • alumina having higher solubility than boehmite may be added to the preparation solution.
  • alumina having higher solubility than boehmite include gibbsite, bayerite, amorphous alumina hydrate, amorphous alumina, ⁇ -alumina, ⁇ -alumina, and 7-alumina.
  • the addition of alumina having higher solubility than these boehmite is effective for obtaining an alumina composition having a relatively small specific surface area.
  • a pore structure controlling agent for controlling the pore structure of the alumina composition can be added to the above-mentioned preparation liquid.
  • 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.
  • 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.
  • an aqueous alumina sol-gel is formed, which has the effect of increasing the specific surface area and the pore volume.
  • starch, agar, gelatin, mannan and CMC have a thickening effect on the preparation at low concentrations.
  • 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.
  • 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.
  • polyhydric alcohols increase the pore diameter
  • polyhydric carboxylic acids and certain oxycarboxylic acids both increase the specific surface area
  • 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.
  • 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.
  • 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.
  • the ion potential is represented by the following equation.
  • 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.
  • 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.
  • the atomic ratio is preferably in the range of 0.0002 to 0.2 per mole of atom.
  • 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.
  • 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.
  • 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.
  • 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.
  • the aqueous sol-gel thus obtained is dried, and then calcined at 400 or more to obtain an alumina composition.
  • the sintering may be performed in a temperature range of 400 to 600 ° C.
  • formation of a-alumina suitable for a catalyst carrier is confirmed.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • catalyst components such as Mo, W, Ni, and Co
  • 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.
  • 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.
  • an alumina composition having a high specific surface area and a large pore volume can be easily obtained.
  • 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.
  • 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.
  • 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 ⁇ 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.
  • 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 : 99.83 ⁇ 4, 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 0.73 ⁇ 1 ⁇ g, and the center pore diameter was 220 A.
  • Example 13 400 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 / ⁇ 1 2 0 3 0.20, with HN0 3 / H 2 0 is 0.021, k value Was 0.0042.
  • 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.
  • Example 1 12- L5, Comparative Example-6-9
  • Table 3 shows the specific surface area, pore volume, and compressive fracture strength of the obtained alumina molded product.
  • Example 1 016 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 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 1.5 ⁇ , 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 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
  • Comparative Example 1 10 112 g 0.3 Disintegrated during firing
  • 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
  • Example 1 26 HS-320 Al (NO dalconic acid 0.02 234
  • 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.
  • 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 7 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.
  • 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.
  • 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 weight ratio of alumina was 0.02.
  • 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.
  • 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. ⁇ 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.
  • 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 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 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.
  • the product showed a desulfurization activity of 75% of the contained sulfur.
  • the hydrogenation activity of the polycyclic aromatic ring was also observed.
  • composition A1 2 0 3 concentration calculated 35.5% ⁇ 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne une composition d'alumine capable de subir une modification régulée importante par rapport à une zone de surface spécifique, au volume des pores et à la répartition du diamètre des pores. Cette composition est préparée selon un procédé caractérisé en ce qu'il consiste à obtenir un liquide modifié présentant une concentration prédéterminée d'alumine, d'acide et d'eau par mélange d'une alumine contenant de l'acide obtenue par chauffage d'hydroxyde d'aluminium en présence d'un acide monobasique ou d'un sel dudit acide à une température comprise entre 70 et 400 °C et/ou d'une alumine dotée de structures ς- et ψ-cristallines avec de l'eau et/ou un acide monobasique ou un sel dudit acide, à soumettre ce liquide modifié à une réaction hydrothermique éventuellement en présence d'un composé organique contenant de l'oxygène et/ou d'un acide polybasique inorganique utilisé comme agent de régulation de structure des pores, puis à sécher le sol-gel d'alumine aqueux et acide résultant en vue d'une calcination. L'invention concerne également un procédé de préparation de cette composition d'alumine, ainsi qu'un catalyseur comprenant ladite composition d'alumine en tant que support.
PCT/JP2000/000620 2000-02-04 2000-02-04 Composition d'alumine et son procede de preparation WO2001056926A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP2000/000620 WO2001056926A1 (fr) 2000-02-04 2000-02-04 Composition d'alumine et son procede de preparation
JP2001556805A JP4105870B2 (ja) 2000-02-04 2001-02-05 多孔質アルミナ、その製造方法および用途

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2000/000620 WO2001056926A1 (fr) 2000-02-04 2000-02-04 Composition d'alumine et son procede de preparation

Publications (1)

Publication Number Publication Date
WO2001056926A1 true WO2001056926A1 (fr) 2001-08-09

Family

ID=11735659

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2000/000620 WO2001056926A1 (fr) 2000-02-04 2000-02-04 Composition d'alumine et son procede de preparation

Country Status (2)

Country Link
JP (1) JP4105870B2 (fr)
WO (1) WO2001056926A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112745105A (zh) * 2020-12-24 2021-05-04 深圳技术大学 一种高烧结活性氧化铝陶瓷粉体及其制备方法
EP4050130A4 (fr) * 2019-10-25 2022-12-14 China Petroleum & Chemical Corporation Grain d'alumine, son procédé de préparation et utilisation associée

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4344928A (en) * 1979-02-26 1982-08-17 Rhone-Poulenc Industries Process for preparing alumina particulates, at least a fraction of which being ultrafine boehmite
JPH02293371A (ja) * 1989-04-17 1990-12-04 Hermann C Starck Berlin Gmbh & Co Kg α―Ａｌ↓２Ｏ↓３焼結物体の製造
EP0885844A1 (fr) * 1996-03-05 1998-12-23 Goro Sato Sol d'alumine, son procede de preparation, procede de preparation d'un moulage d'alumine l'utilisant, et catalyseur a base d'alumine ainsi prepare

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4344928A (en) * 1979-02-26 1982-08-17 Rhone-Poulenc Industries Process for preparing alumina particulates, at least a fraction of which being ultrafine boehmite
JPH02293371A (ja) * 1989-04-17 1990-12-04 Hermann C Starck Berlin Gmbh & Co Kg α―Ａｌ↓２Ｏ↓３焼結物体の製造
EP0885844A1 (fr) * 1996-03-05 1998-12-23 Goro Sato Sol d'alumine, son procede de preparation, procede de preparation d'un moulage d'alumine l'utilisant, et catalyseur a base d'alumine ainsi prepare

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JANUSZ T. TRAWCZYNSKI: "Effect of Aluminium Hydroxide Precipitation Conditions on the Alumina Surface Acidity", IND. ENG. CHEM. RES., vol. 35, no. 1, 1996, pages 241 - 244, XP002928256 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4050130A4 (fr) * 2019-10-25 2022-12-14 China Petroleum & Chemical Corporation Grain d'alumine, son procédé de préparation et utilisation associée
CN112745105A (zh) * 2020-12-24 2021-05-04 深圳技术大学 一种高烧结活性氧化铝陶瓷粉体及其制备方法
CN112745105B (zh) * 2020-12-24 2022-06-14 深圳技术大学 一种高烧结活性氧化铝陶瓷粉体及其制备方法

Also Published As

Publication number Publication date
JP4105870B2 (ja) 2008-06-25

Similar Documents

Publication Publication Date Title
JP3304360B2 (ja) アルミナゾル及びその製造方法、及びそれを用いたアルミナ成型体の製造方法、及びそれによって得られたアルミナ系触媒
US6884406B2 (en) Process for preparing an alumina composition
US6930217B2 (en) Catalyst containing microporous zeolite in mesoporous support and method for making same
Kim et al. Synthesis of thermo-stable high surface area alumina powder from sol–gel derived boehmite
US7208446B2 (en) Quasi-crystalline boehmites containing additives
JP5404056B2 (ja) 酸化物混合物
JP6134334B2 (ja) シリカ含有アルミナ担体、それから生じさせた触媒およびそれの使用方法
Yang et al. Novel synthesis and characterization of nanosized γ-Al2O3 from kaolin
JP5117657B2 (ja) 安価な前駆体から擬結晶性ベーマイトを製造する方法
US6506358B1 (en) Process for the preparation of quasi-crystalline boehmites
MXPA02006039A (es) Compuestos de oxido de aluminio de gran area superficial, alto volumen de poros, derivados de trihidrato de alumina y metodos para su preparacion y uso.
EP1204596A2 (fr) Boehmites quasi-cristallines contenant des additifs
van Garderen et al. Improved γ-alumina support based pseudo-boehmite shaped by micro-extrusion process for oxygen carrier support application
BR0016511B1 (pt) compósitos de óxido de alumìnio/argila intumescìvel hidrotermicamente estáveis com alto volume de poros e métodos para sua preparação e uso.
EP0950638B1 (fr) Poudre de pseudo-boehmite pour support catalytique et son procede de fabrication
JP4264852B2 (ja) アルミナ押出し物、その調製方法および触媒または触媒担体としてのその使用
EP2392548B1 (fr) Procédé de préparation de composition de silice-alumine amorphe et composition de silice-alumine amorphe associée
do Carmo et al. Synthesis of highly porous alumina-based oxides with tailored catalytic properties in the esterification of glycerol
WO2001056926A1 (fr) Composition d'alumine et son procede de preparation
JP2003507289A (ja) 耐摩耗性の成形された、結晶性のＭｇ−Ａｌ−Ｓｉ含有粘土を含む物体
JP4119144B2 (ja) 多孔質無機酸化物の製造方法
WO2010013428A1 (fr) Procédé de production de poly(hydrate) de sel d'acide monobasique d'aluminium inorganique et/ou de sol aqueux d'alumine, et sel d'acide monobasique d'aluminium inorganique et/ou sol aqueux d'alumine ainsi obtenus
RU2584951C1 (ru) Способ получения носителя катализатора превращений углеводородного сырья на основе мезопористого материала
US20030180214A1 (en) Process for the preparation of quasi-crystalline boehmites
RU2026111C1 (ru) Способ приготовления катализатора для гидроочистки нефтяных фракций

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN JP KR SG US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): DE DK FR GB IT NL

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase