JPH02290257A - Carrier for catalyst and its manufacture - Google Patents

Abstract

PURPOSE:To manufacture a carrier having physical properties fit for various kinds of reaction without using a bonding agent by using fire-resistant inorganic particles as cores and carrying fire-resistant inorganic powdery grains over said cores. CONSTITUTION:Fire-resistant inorganic particles of a metal oxide such as alumina or silica, a multi-component oxide such as mullite or cordierite and silica on carbide or the like are used as cores. Fire-resistant inorganic powdery grains composed of one or two kinds or more of a metal oxide such as alumina or silica, silicon carbide, a composite oxide such as alumina-silica are carried over said cores. As a bonding agent is not used in said manufacture of carrier, the effect of transferring the bonding agent component into the catalyst substance is not generated. Also, such various properties as surface area, bore, volume of the catalyst carrier can be controlled.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a catalyst carrier and a method for producing the same. Specifically, the surface area, pore diameter, pore volume, and
The present invention relates to a method for producing a catalyst carrier that allows the distribution, acidity/basicity, distribution, etc. of the catalyst carrier to be arbitrarily designed, and to a catalyst carrier having a novel structure.

[Conventional technology]

Conventionally, porous inorganic carriers have aggregates made of powder and granules made of various metal oxides such as alumina, silica, titania, and zirconia, or refractory materials such as silicon carbide and silicon nitride, and are bonded with these materials mainly made of clay. It is manufactured by mixing the ingredients, forming them by granulation, etc., and then firing them.

The carriers produced in this way are widely used industrially because the physical properties that the carrier should have, such as surface area, pore diameter, and distribution thereof, are adjusted to suit various reactions. However, catalysts using this type of carrier are usually used at relatively high temperatures, and during the reaction, components of the binder contained in the carrier migrate into the catalyst material, resulting in catalytic activity. , a phenomenon occurs in which selectivity changes over time. In particular, alkali metals are used in the binder for the purpose of lowering the firing temperature during support production, but alkali metals such as sodium and potassium are easily mobile, and even a trace amount of alkali metals generally impairs catalyst performance. have a significant impact. Therefore, high-purity carriers are also manufactured that do not use binders, which can be considered as impurities for carriers. For example, as a substitute for the binder, there is a method of using a sol or salt of the same metal as the aggregate, or as in the case of SiC, the range in which the anti-resistance can be changed is narrow, and the actual situation is that the functionality as a carrier is low.

[Problem to be solved by the invention]

Therefore, an object of the present invention is to provide a novel catalyst carrier and a method for producing the same.

Another object of the present invention is to provide a carrier whose physical properties can be easily adjusted to suit various reactions without using the above-mentioned binder.

Still another object of the present invention is to provide a method for producing a carrier that can be easily carried out and is industrially advantageous.

[Means to solve the problem]

These objects are achieved by a catalyst carrier comprising refractory inorganic particles as a core and refractory inorganic powder particles supported on the core.

These objects can also be achieved by a catalyst carrier comprising refractory inorganic particles as a core and refractory inorganic powder and whiskers supported on the core.

These objects can also be achieved by a catalyst carrier comprising a core of refractory inorganic particles and a refractory inorganic powder and an inorganic oxide sol supported on the core.

These objects can also be achieved by a catalyst carrier comprising a core of refractory inorganic particles and a refractory inorganic powder, whiskers, and inorganic oxide sol supported on the core.

These objectives are achieved by applying a slurry of refractory inorganic powder to refractory inorganic particles and drying the refractory inorganic particles as a core, and the refractory inorganic powder is supported on the core. This can also be achieved by a method for producing a catalyst carrier.

These objectives are to form a core of refractory inorganic particles by applying a mixed slurry of refractory inorganic powder and whiskers to refractory inorganic particles, and drying the mixture. This can also be achieved by a method for producing a catalyst carrier on which whiskers are supported.

These objectives are to form a core of refractory inorganic particles by applying a mixed slurry of a refractory inorganic powder and an inorganic oxide sol to refractory inorganic particles and drying the mixture, and to apply a refractory inorganic particle onto the core. This can also be achieved by a method for producing a catalyst carrier on which an inorganic powder and an inorganic oxide sol are supported.

These objectives are achieved by applying a mixed slurry of refractory inorganic powder, whiskers, and inorganic oxide sol to refractory inorganic particles, and then drying the refractory inorganic particles as a core. This can also be achieved by a method for producing a catalyst carrier on which refractory inorganic powder, whiskers, and inorganic oxide sol are supported.

According to the present invention, it has become possible to arbitrarily design various properties of the catalyst carrier such as surface area, pore diameter, pore volume, their distribution, acidity/basicity, and their distribution. This makes it possible to control the heat transfer properties and the carrier strength, and has the excellent effect of providing catalysts suitable for various target reactions.

The present invention will be described in more detail.

In the present invention, the core refractory inorganic particles are loaded with refractory inorganic powder as an aggregate material, and then heat treated as required to produce #carrier.

Therefore, the core particles are used simply for the purpose of forming the aggregate powder into the shape of a carrier, and are not required to have functionality as a carrier in themselves. As the nuclear particle material,
Metal oxides such as alumina, zirconia, titania, and silica, composite oxides such as mullite, cordierite, and zircon, and non-oxides such as silicon carbide and silicon nitride are used. A sintered body sintered without sintering, a sintered body using the same kind of metal oxide sol or metal salt as a sintering agent, or a molten product thereof are used. The shape of the core particles is not particularly limited, such as amorphous, spherical, cylindrical, cylindrical, Raschig ring, veil saddle, etc., but should have good rolling properties so that the aggregate powder is supported with a uniform thickness. A shape is desirable. In addition, the size of the core particle has a representative diameter of 0. The length is appropriately selected within the range of 3 to 12 mm, preferably 1 to 8 mm.

It is important to select an aggregate material that determines its functionality as a carrier, such as physical and chemical properties such as surface area, pore diameter, pore volume, acidity and basicity. These characteristic values greatly affect the activity, selectivity, and durability of the catalyst, and it is necessary to design a support that is compatible with the target reaction.

Aggregate materials include metal oxides such as alumina, titania, zirconia, magnesia, and silica, non-oxides such as silicon carbide, silicon nitride, and alumina nitride, or alumina silica, alumina titania, titania silica, and titania zirconia. Powder or granules made by mixing one or more of complex oxides such as , cordierite, mullite, and zircon are used.

When these materials are used as aggregate powder, the surface area, pore diameter, pore diameter distribution, acidity/basicity, and their distribution are adjusted to suit the physical properties required as a carrier. For example, a carrier having two or more peaks in its pore size distribution can be produced by mixing desired amounts of two or more types of powder particles having different pore sizes.

In addition, although the shape of the particles constituting powder and granules is usually amorphous, by controlling the particle shape such as spherical, flaky, and strip-like shapes, it is possible to more precisely control the physical properties of the carrier, such as pore diameter and pore volume. control is possible.

The average particle size of these powders is 0.05 to 1200 μm,
Preferably it is 0.1 to 500 μm.

The granular material is then supported on the core particles, but if the granular material is difficult to be supported on the core particles and the supporting yield is poor, or if the supporting strength of the supported granular material is weak, a supporting aid may be used. It is preferable to use whiskers as In addition to whiskers, there are also inorganic fibers such as glass fibers as materials that improve the support strength, but the shape of whiskers was the most desirable in the carrier manufacturing method of the present invention, which will be described later. The use of whiskers is highly effective in improving the loading yield and loading strength, and since whiskers are fire resistant, they also serve as a component of the carrier and exert the effect of adjusting the physical properties of the carrier.

The whiskers used in the present invention are manufactured by a known method, and their materials include metal whiskers such as tungsten, iron, and nickel, silicon carbide, silicon nitride, aluminum oxide, titanium oxide, helium oxide,
Examples include boron carbide, titanium carbide, potassium titanium oxide, and calcium phosphate.

The shape of the whiskers used in the present invention preferably has an average diameter of 0. 1 to 5 μm, more preferably 0. 3 ~
1 μm, the length is preferably 5 to 1000 μm, more preferably 70 to 500 μm, and the aspect ratio is preferably 10 to 500, more preferably 20 to 30.

The amount of whiskers used is 1 to 1 relative to the amount of aggregate material.
An amount of 50% by weight, preferably in the range from 1 to 20% by weight, is effective in improving the retention and strength of the aggregate material.

Furthermore, an inorganic oxide sol can also be blended into the refractory inorganic powder and the mixture of the refractory inorganic powder and whiskers. That is, a carrier having sufficient strength for practical use can be easily produced by using whiskers, but when preparing a catalyst using the carrier, it is necessary to prepare the catalyst while stirring the carrier vigorously, for example. In some cases, it may be necessary to minimize the amount of carrier constituent substances brought from the carrier mixed into the catalytically active component. In such cases, good results can be obtained by using an inorganic oxide sol in addition to or without whiskers.

The amount used is 0.5 in terms of oxide based on the amount of aggregate material.
The inorganic oxide sol in an amount of up to 20% by weight, preferably 1 to 10% by weight, may be added to the slurry of the powder and whiskers, or may be used after forming a support. However, the inorganic oxide sol often becomes thickened and gelled by mixing with other #jIJ substances or by heating, so it is desirable to use a highly stable inorganic oxide sol in the present invention.

The present inventors also conducted intensive studies on the method for preparing the sol, and as a result, it was found that the zirconia sol described below has high stability and can be suitably used for producing the carrier of the present invention.

The zirconia sol used in the present invention is prepared by mixing an aqueous zirconyl ammonium carbonate solution and a chelating agent, for example,
It is prepared by first converting zirconyl ammonium carbonate into a zirconium chelate compound, then heating and hydrolyzing the chelate compound, and then, if necessary, filtering and washing using an ultra-I membrane.

In this preparation method, a commercially available zirconyl ammonium carbonate aqueous solution is used, but this zirconyl ammonium carbonate is hydrolyzed into hydrous zirconia with the generation of gases such as ammonia and carbon dioxide, and this reaction solution has an alkaline pH. Then, it began to exhibit properties as a sol. However, if the reaction is continued, the viscosity of the reaction solution increases and gelation occurs in a relatively short period of time, and only a small amount of zirconyl ammonium carbonate can be hydrolyzed. In order to stably continue the hydrolysis reaction of zirconylammonium carbonate, an aqueous zirconylammonium carbonate solution and a chelating agent are mixed to form a reaction product between the zirconylammonium carbonate and the chelating agent, and then the product is The present inventors have discovered a method for obtaining a zirconia sol by heating an aqueous solution containing zirconia to 60°C or higher to carry out a hydrolysis reaction.

Specifically, when an aqueous solution of zirconyl ammonium carbonate is placed in a stirred tank reactor and then a chelating agent is added under stirring, the zirconyl ammonium carbonate and the chelating agent react rapidly at room temperature.

After the reaction, when the reaction solution is heated to 60°C or higher, the hydrolysis reaction of the reactants between zirconyl ammonium carbonate and the chelating agent proceeds while generating gases mainly consisting of carbon dioxide and ammonia. During the reaction, the reaction solution does not increase in viscosity, and the reaction can be completed while maintaining the transparency of the reaction solution.

The reaction solution has almost neutral p}I, and during the above reaction,
As a sol, impurity ions such as ammonium ions and carbonate ions take up ammonia and carbon dioxide.

In addition, minute amounts of unreacted substances, carbonate ions, ammonium ions, etc. remaining in the above reaction solution can be efficiently filtered and washed in a short time by using an ultrafilter membrane, and can be further removed by heating or ultrafiltration. High purity and high concentration zirconia sol can be obtained by concentration using a filtration membrane.

The chelating agents used in the present invention include oxyphenols such as CaT≠cole and pyrogallol; amino alcohols such as diethanolamine and triethanolamine; glycolic acid, citric acid, tartaric acid, lactic acid, mandelic acid, and apple. acids, oxyacids such as hydroxyacrylic acid and their esters such as methyl, ethyl, hydroxyethyl, oxyaldehydes such as glycolaldehyde; polycarboxylic acids such as oxalic acid and malonic acid; amino acids such as glycine and alanine; β-diketones such as acetylacetone, penzoylacetone, stearoylacetone, stearoylbenzoylmethane, dibenzoylmethane, and β-ketonic acids such as acetoacetic acid, propionylacetic acid, benzoylacetic acid, and their methyl, ethyl, n-probyl, and isoprovil , n-butyl, L-butyl, or a combination of two or more esters can be used. Among these, oxyacids such as glycolic acid, citric acid, tartaric acid, lactic acid, mandelic acid, malic acid, and hydroxyacrylic acid, and β-diketones such as acetylacetone are preferably used. More preferably α. β, and γ-oxyacid necks with functional groups having oxygen atoms on α, β, and γ carbons, respectively. β-, γ-ketonic acids or their esters.

The amount of the chelating agent used varies depending on the type of chelating agent used, but the ratio of chelating agent (molar ratio)/zirconia (molar ratio) is 0.02/1 to 4/1, preferably 0.02/zirconia (molar ratio).
1/1 to 3/1, more preferably 0. 5 /
It is preferable to select a value in the range of 1 to 2/1.

If the amount of chelating agent used is too small, certain organic zirconium salts formed by the reaction between the chelating agent and zirconyl ammonium carbonate will be degraded when hydrolyzed by the method of the present invention compared to when zirconyl ammonium carbonate alone is used. The same behavior was observed, and the use of chelating agents was ineffective as the hydrolysis reaction could not be continued; on the other hand, even if used at a ratio exceeding 4/1, no special effects could be obtained and it was not economical. do not have.

? The hydrolysis reaction in the invention may be carried out at a temperature of 60° C. or higher, and the reaction is preferably carried out under a pressurized atmosphere in order to promote the reaction.

Practical reaction temperature is 60 to 300°C, and there is no particular limit to the concentration of zirconyl ammonium carbonate (higher concentrations can be economically advantageous, but the economic stability of the aqueous zirconyl ammonium carbonate solution is Considering this, 10 to 25% by weight of ZrO is desirable.

The zirconia sol obtained in this way is stabilized with a chelating agent, so it is highly stable and stable over a wide p}I range, especially stable even when alkaline substances are added, and has a low viscosity. It can be prepared up to a concentration of 45% by weight and has a transparent appearance and a minute sol particle size, and exhibits high strength when used as an inorganic binder as in the present invention.

The following method is employed to support the aggregate powder on the core particles.

The granular material alone or the granular material and the whiskers and/or the inorganic oxide sol with adjusted particle size are added to a solvent, and the mixture is stirred and mixed uniformly using a homogenizer or the like.

In order to improve the dispersibility of the inorganic oxide sol, it is effective to add a small amount of a dispersant or surfactant.

The slurry thus obtained was then heated at 50 to 500°C.
Preferably, it is sprayed onto core particles that have been fluidized by heating and stirring at 100 to 400"C to evaporate the solvent and support them. Alternatively, inorganic particles are immersed in the slurry and then heated and dried. The slurry concentration is 3 to 60"C. % by weight, preferably 10
It is adjusted to ~40% by weight. If the slurry concentration is too low, it will take a long time to support the slurry, which is economically disadvantageous; if the slurry concentration is too high, the viscosity of the slurry will increase, making spraying impossible.

Alternatively, a centrifugal fluid coating device may be used to easily support the particles. That is, a coating liquid (binder such as water) is quantitatively sprayed onto core particles flowing in a centrifugal fluid coating device, and at the same time, if necessary, aggregate powder with whiskers uniformly mixed therein is quantitatively sprayed. This is a method of obtaining spherical carriers with controlled particle size by granulating the particles by dispersing the particles. By introducing air or the like into the apparatus to carry out the support without accelerating drying, and by using heated air or the like if necessary, the support can be carried out in a relatively short time. It is also effective to increase the supporting strength by adding an inorganic oxide sol to the coating liquid if necessary and further dissolving an organic binder such as an acrylic binder in advance. This method of application and subsequent drying is repeated several times if necessary.

Regardless of the manufacturing method, the supported amount of aggregate particles is 1 to 500 g, preferably 20 to 20 g, per 100 ml of core particles.
The supported amount is determined mainly by the pore volume, specific surface area, etc. required for the carrier.

The supported type carrier thus obtained has sufficient supporting strength as it is and can be used as a carrier, but it may be heat-treated to further improve the strength or to decompose and remove mixed organic matter. desirable. Heat treatment at 200~1600"C, preferably 400~
l0. within the range of 200°C. It takes place for 5-5 hours. The support obtained in this manner has sufficient strength for practical use, and the method of the present invention can be applied to a low surface area type support mainly used in catalytic gas phase partial oxidation reactions or a high surface area type support used in catalytic gas phase complete oxidation reactions. Supports with various physical properties controlled, including surface area type supports, can be easily produced.

Although the catalyst can be prepared using the carrier of the present invention in the same manner as when using a conventional carrier, it is preferable to prepare the catalyst by a method called an impregnation method. The carrier is immersed in a solvent containing a catalytically active component, dried, and then catalyzed by thermal decomposition and activation of the salt. In addition, if the affinity between the carrier and the catalyst component liquid is weak or the adsorption amount is small, the catalyst component may be supported on the carrier by immersing the carrier in the catalyst component liquid and then evaporating the solvent while stirring. A method of spraying the catalyst component liquid while constantly maintaining the dry state can be adopted.

The support of the present invention obtained as described above is a porous inorganic support suitable for use in catalysts on which metals and/or metal oxides are dispersedly supported and used in various gas phase catalytic reactions. The reaction to be used is not particularly limited, but
Examples include catalysts for producing ethylene oxide through ethylene gas-phase oxidation reactions that use silver as the main catalyst, ammonia synthesis reactions that mainly use one or more of iron, nickel, zinc, copper, etc., water gas reactions, methanol synthesis reactions, etc. Catalysts for gas-phase reduction reactions, catalysts using expensive noble metals such as platinum, palladium, and gold, catalysts for producing benzaldehyde from benzoic acid hydrogen and using chromium, manganese, etc. as the main catalyst material, and the like.

Hereinafter, the present invention will be explained in more detail based on Examples.

Example 1 Zirconium oxychloride was dissolved in pure water to prepare an aqueous solution having a concentration of 0.2 mol/l. Pour 1.2 liters of pure water into a stirred reactor with an overflow tube, and then add ammonia water.
H was set to 8.0. Add the above aqueous solution to this at a liquid rate of 190 per minute.
mf, and aqueous ammonia (28% by weight aqueous solution)
were injected with stirring at a rate of 200+cj2 per hour using a constant-air pump.

The reaction solution flowed out from the overflow tube, and the neutralization reaction was continuously carried out under conditions where the amount of solution in the reactor was kept almost constant. The neutralization reaction was carried out while finely adjusting the liquid speed of ammonia water so that pll was 8±0.2 during the reaction.

Hydroxide in the effluent was separated from the mother liquor by filtration, and then ammonium chloride was removed by washing with water. The water in the hydroxide was dehydrated by dispersing the obtained hydroxide in 1-propanol and heating it to remove the water in the yarn as a mixture with 1-propanol from the system. After dehydration and drying, the resulting body was calcined at 700°C for 1 hour to obtain fine zirconia powder with a specific surface area of 32 rff/g.

500 g of the thus obtained zirconia fine powder and 80 g of pure water
A homogeneous slurry was obtained using a ball mill from 0 mf.

The average particle size is maintained in an externally heated rotary furnace. 5mmφ
300L of SiC self-sintered porous spherical particles as core particles
Add Tlβ, spray the above slurry while heating to 250-300'C, and add 25% of zirconia as an aggregate material.
0g was supported. By calcining the obtained carrier at 900°C, the carrier has an average pore diameter of 0.1 μm and a specific surface area of 3r.
A supported zirconia carrier with high strength and a pore volume of 0.15 mffi/g and a pore volume of 0.15 mffi/g was obtained.

Example 2 Mixing α-alumina with different particle sizes, specific surface area 8rd
/g of α-alumina powder was prepared. The particle size distribution of this alumina powder is 50% by weight of 0.5μm or less, 0.5~2%
The size of 35 μm was 1% by weight, and the size of 2 μm or more was 15% by weight.

50 g of SiC whiskers and 60 g of pure water are added to 1 kg of the powder.
0 mf was added, and the mixture was stirred and mixed uniformly using a homogenizer. The whiskers have an average diameter of 0.6 μm and an average length of 15 μm.
The dimensions were

The average particle size is 2 months in a rotary furnace with external heating. 5mmφ
300L of SiC self-sintered porous spherical particles as core particles
II! The above slurry was sprayed while heating to 250-300°C to support 350g of alumina as an aggregate material. By calcining the obtained carrier at 1400°C, the carrier has an average pore diameter of 0.15 μm, a specific surface area of 2 pores/g,
A high-strength supported alumina carrier with a pore volume of 0.25 mff/g was obtained.

Example 3 (1) 10 liters of zirconia sol having a concentration of 10% by volume was added to a solution prepared by dissolving 180 g of a surfactant having an H'L B of approximately 6 and consisting of a sorbitan fatty acid ester in 5β n-octanol while stirring with a homogenizer. This premixed solution was sent to a colloid mill and further stirred for 1 hour to prepare a W/O type slurry emulsion. Next, 100% ammonia gas was blown into this W/0 type sol emulsion with stirring at a flow rate of 250 mj2/min for about 2 hours to gel the sol emulsion. The gel emulsion was then evaporated to dryness while stirring and mixing in a vacuum dryer to remove water and n-octanol from the system.

The thus obtained spherical fine particles were calcined at 600° C. for 2 hours to obtain highly dispersible spherical zirconia fine particles having an average particle diameter of 0.1 μm.

800 g of the thus obtained spherical zirconia fine particles and 25 g of SiC whiskers were stirred in methanol and mixed uniformly. After drying, it was then crushed using a jut mill to obtain aggregate material powder.

Coating granulation equipment with average particle size. 5 φ Si
400 self-sintered porous spherical particles of C were placed as core particles in a plate, and while fluidly mixed, pure water as a coating liquid and the above-mentioned aggregate substance powder were simultaneously quantitatively sprinkled, and hot air was sent to the coating tank to dry them. The loading was carried out continuously while

As a result, 100 g of spherical zirconia fine powder as an aggregate material was supported per 100 mf of core particles. Then, by firing at 1000°C, the average wire pore diameter was reduced to 0. 2
a m, specific surface area 1 rrf/g, pore volume 0.
A supported zirconia carrier with a high strength of 1...l/g was obtained.

Example 4 ZrO. 1300 g of a commercially available aqueous zirconyl ammonium carbonate solution containing 13% by weight was added. Add 10% glycolic acid to this while stirring. 4 g was added gradually. At this time, odorless gas was generated.

? Then, the flask was heated with a mantle heater to carry out a hydrolysis reaction. As the temperature rose, it bubbled violently, and the reaction proceeded while slowly exhausting gases generated from unnecessary ions in the sol, such as ammonia and carbon dioxide, out of the system. By reacting for about 3 hours at a reaction solution temperature of about 100°C, the foaming subsided, and heating was continued for an additional 12 hours while adding pure water to the flask as needed to reach a concentration of 25% as ZrO■.
A zirconia sol with a pH of 7 in weight percent was obtained.

200 g of the fired body obtained in Example 3 was placed in 500 mff of the clay and heated to boil for 1 hour. By boiling, the air in the carrier was replaced with the sol, and the sol penetrated into the interior of the carrier. Next, the carrier was taken out from the sol, excess sol adhering to the carrier was removed, and then calcined at 800°C for 1 hour.

In the obtained carrier, the aggregate material layer is bonded and bonded with zirconia.
The wear resistance of the carrier was significantly improved.

Example 5 The zirconia fine powder having a specific surface area of 32 m/g obtained in Example 1 was further calcined at 800°C for 1 hour to obtain a zirconia fine powder having a specific surface area of 23 nf/g. 600 g of pure water was added to 500 g of this fine zirconia powder, and 100 g of the zirconia sol obtained in Example 4 was added to obtain a homogeneous slurry using a ball mill.

The average particle size is 1.5 mm in an externally heated rotary furnace. 5 nun
SiC self-sintered porous spherical particles with a diameter of 300 mm are used as core particles.
The above slurry was sprayed while heating at 150 to 200° C. to support 300 g of zirconia as an aggregate material.

The support obtained after the support was calcined at 600°C to obtain a supported zirconia support with high strength having an average pore diameter of 0.15 μm, a specific surface area of 4rrf/g, and a pore volume of 0.2mf/g.

Example 6 100 cc of the zirconia carrier obtained in Example 5 and 200 cc of a mixed solution of chromium nitrate and manganese nitrate were placed in an eggplant-shaped flask, and the flask was placed in a rotary evaporator. While evacuating the inside of the flask, the zirconia carrier was impregnated with chromium nitrate and manganese nitrate and dried at 70 to 80°C, and then the carrier was heat-treated in a tubular electric furnace for 600°C for 600°C directly under a nitrogen gas flow. 5 as chromium
A composition was obtained in which 2 g/β of manganese was loaded.

This was filled into an atmospheric pressure gas phase flow reactor and used as a catalyst for hydrogenating benzoic acid to synthesize benzaldehyde.

The reaction conditions were as follows: catalyst temperature: 320°C, pressure: normal pressure, hydrogen space velocity: 150011r'' and benzoic acid concentration: 2%.The reaction was carried out by blowing hydrogen into the benzoic acid melt to make the benzoic acid isotropic. The yield of benzaldehyde was 98%.

Example 7 100 cc of the amine carrier obtained in Example 2 and 200 cc of the chloroplatinic acid aqueous solution were placed in an eggplant-shaped flask, and the same procedure as in Example 6 was carried out to obtain a composition in which 1 g/l of platinum was supported. However, the heat treatment was performed by firing at 600°C for 3 hours under air circulation.

This was charged into a gas phase flow reactor, and 500% of carbon monoxide was added.
ppm (air balance) gas to reactant gas (air velocity 1
The gas temperature at the catalyst inlet is 30 as 0000+1,'')
CO combustion performance at 0°C was evaluated.

Further, the catalyst was aged for 24 hours at 900° C. under air circulation, and the performance was evaluated in the same manner. As a result, the CO conversion rate of the Frensch catalyst was 97%, and the CO conversion rate after aging was 88%, which were good results.

Claims (1)

[Scope of Claims] 1. A catalyst carrier comprising a core of refractory inorganic particles and a refractory inorganic powder supported on the core. 2. The carrier according to claim 1, wherein the proportion of the refractory inorganic powder per 100 ml of the refractory inorganic particles is 1 to 500 g. 3. The particle size of the refractory inorganic particles is 0.3 to 12 mm, and the average particle size of the refractory inorganic powder is 0.05 to 12 mm.
The carrier according to claim 2, which has a diameter of 00 μm. 4. The carrier according to claim 3, wherein the refractory inorganic particles and the powder are at least one ceramic selected from the group consisting of metal oxides, metal composite oxides, and non-oxides. 5. A catalyst carrier comprising refractory inorganic particles as a core, and refractory inorganic powder and whiskers supported on the core. 6. The ratio of the refractory inorganic powder per 100 ml of the refractory inorganic particles is 1 to 500 g, and the amount of whiskers to the refractory inorganic powder is 1 to 50% by weight. The catalyst carrier described above. 7. The particle size of the refractory inorganic particles is 0.3 to 12 mm, and the average particle size of the refractory inorganic powder is 0.05 to 1200 mm.
μm, and the average diameter of the whiskers is 0.1 to 5 μm.
The carrier according to claim 6, having a length in μm of 5 to 1000 μm. 8. The carrier according to claim 7, wherein the refractory inorganic particles and the powder are at least one ceramic selected from the group consisting of metal oxides, metal composite oxides, and non-oxides. 9. A catalyst carrier comprising a core of refractory inorganic particles and a refractory inorganic powder and an inorganic oxide sol supported on the core. 10. The ratio of the refractory powder per 100 ml of the refractory inorganic particles is 1 to 500 g, and the amount of the inorganic oxide sol to the refractory inorganic powder is 0.5 to 2 in terms of oxide.
The carrier according to claim 9, which is 0% by weight. 11. The particle size of the refractory inorganic particles is 0.3 to 12 mm, and the average particle size of the refractory inorganic powder is 0.05 to 1.
The carrier according to claim 10, which has a diameter of 200 μm. 12. The carrier according to claim 11, wherein the refractory inorganic particles and the powder are at least one ceramic selected from the group consisting of metal oxides, metal composite oxides, and non-oxides. 13.Claim 1, wherein the inorganic oxide sol is a zirconia sol.
0. 14. A catalyst carrier comprising a core of refractory inorganic particles and a refractory inorganic powder, whiskers, and inorganic oxide sol supported on the core. 15. The proportion of the refractory inorganic powder per 100 ml of the refractory inorganic particles is 1 to 500 g, and the amount of whiskers to the refractory inorganic powder is 1 to 50% by weight, and the amount of the inorganic oxide sol. The carrier according to claim 14, wherein the amount is 0.5 to 20% by weight in terms of oxide. 16. The particle size of the refractory inorganic particles is 0.3 to 12 mm, and the average particle size of the refractory inorganic powder is 0.05 to 120 mm.
0 μm, and the average diameter of the whiskers is 0.1 to 0.1 μm.
The carrier according to claim 15, which has a length of 5 μm and a length of 5 to 1000 μm. 17. The carrier according to claim 16, wherein the refractory inorganic particles and powder are at least one ceramic selected from the group consisting of metal oxides, metal composite oxides, and non-oxides. 18. The carrier according to claim 15, wherein the inorganic oxide sol is zirconia. 19. A catalyst carrier comprising a core of refractory inorganic particles obtained by applying a slurry of refractory inorganic powder to refractory inorganic particles and drying the same, and a refractory inorganic powder supported on the core. manufacturing method. 20. The method according to claim 19, wherein the proportion of the refractory inorganic powder per 100 ml of the refractory inorganic particles is 1 to 500 g. 21. The particle size of the refractory inorganic particles is 0.3 to 12 mm, and the average particle size of the refractory inorganic powder is 0.05 to 1.
21. The method according to claim 20, wherein the thickness is 200 μm. 22. The method according to claim 19, further comprising applying an inorganic oxide sol to the carrier. 23. The method according to claim 19, further comprising firing. 24. A mixed slurry of a fire-resistant inorganic powder and whiskers is applied to fire-resistant inorganic particles, and then dried to form a core of the fire-resistant inorganic particles, and the fire-resistant powder and whiskers are supported on the core. A method for producing a catalyst carrier. 25. According to claim 24, the proportion of the refractory inorganic powder per 100 ml of the refractory inorganic particles is 1 to 500 g, and the amount of whiskers to the refractory inorganic powder is 1 to 50% by weight. the method of. 26. The particle size of the refractory inorganic particles is 0.3 to 12 mm, and the average particle size of the refractory inorganic powder is 0.05 to 120 mm.
0 μm, and the average diameter of the whiskers is 0.1 to 0.1 μm.
26. The method according to claim 25, wherein the length is 5-1000 [mu]m. 27. The method according to claim 24, further comprising applying an inorganic oxide sol to the carrier. 28. The method according to claim 24, further comprising firing. 29. A mixed slurry of a refractory inorganic powder and an inorganic oxide sol is applied to refractory inorganic particles, and then dried. The refractory inorganic particles are used as a core, and the refractory inorganic powder is placed on the core. and a method for producing a catalyst carrier on which an inorganic oxide sol is supported. 30. The ratio of the refractory inorganic powder per 100 ml of the refractory inorganic particles is 1 to 500 g, and the amount of the inorganic oxide sol to the refractory inorganic powder is 0.5 in terms of oxide.
30. The method of claim 29, wherein the amount is ~20% by weight. 31. The refractory inorganic particles have a particle size of 0.3 to 12 mm, and the refractory inorganic powder has an average particle size of 0.05 to 120 mm.
31. The method according to claim 30, wherein the thickness is 0 μm. 32. The method according to claim 29, further comprising firing. 33. A mixed slurry of a fire-resistant inorganic powder, a whisker, and an inorganic oxide sol is applied to fire-resistant inorganic particles, and then dried to form a core of fire-resistant inorganic particles, and a fire-resistant inorganic powder is placed on the core. A method for producing a catalyst carrier on which particles, whiskers and inorganic oxide sol are supported. 34. The proportion of the refractory inorganic powder per 100 ml of the refractory inorganic particles is 1 to 500 g, and the amount of whiskers to the refractory inorganic powder is 1 to 50% by weight, and the amount of the inorganic oxide sol 34. The method according to claim 33, wherein the amount is 0.5 to 20% by weight in terms of oxide. 35. The particle size of the refractory inorganic particles is 0.3 to 12 mm, and the average particle size of the refractory inorganic powder is 0.05 to 1200 mm.
μm and the average diameter of the whiskers is 0.1 to 5 μm
35. The method according to claim 34, wherein m is 5 to 1000 [mu]m in length. 36. The method according to claim 33, further comprising firing. 37. Claim 1 using a centrifugal fluid coating device.
15. A method for producing a catalyst carrier according to 5, 9 or 14.