JPH05329380A - Cubic catalyst and its manufacture - Google Patents

Abstract

PURPOSE:To make it possible to manufacture a cubic catalyst with a sharp granular distribution and high sphericalness efficiently by using a cellulose- contained cubic carrier as a core and a catalytic component as the coat. CONSTITUTION:This cubic catalyst is composed of a cubic carrier containing Z 10% powdery cellulose as a core and a catalytic component as the coat. This catalytic component is nickel, cobalt, molybdenum or iron catalytic material together with the catalytic carrier material. Consequently, it is possible to manufacture a cubic catalyst with a sharp granular distribution and high sphericalness efficiently. In addition, it is possible to manufacture a cubic catalyst with a varying specific gravity or a hollow cubic catalyst, so that catalytic reaction conditions can be optimized easily. Further, the use quantity of a valuable catalyst can be reduced by the use quantity of the cubic catalyst and thereby, reducing the manufacturing cost of catalyst is possible.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spherical catalyst containing a cellulose-containing spherical carrier as a core and a method for producing the same.

[0002]

2. Description of the Related Art A catalyst is granulated for the purpose of improving the flow of a reaction system fluid and accelerating the movement of substances and heat to improve the reaction efficiency. Further, the granulated product is desired to be more spherical because of its wear resistance and restriction of reaction conditions. As a method of obtaining such a granulated material, a method of kneading the catalyst component with other auxiliary agents to granulate it, and a method of coating the catalyst component around the spherical carrier as a core are considered. As the former method, a method of charging a catalyst component in a rotary container such as an inclined dish type and spraying a binding solution while rolling to granulate (Japanese Patent Application Laid-Open No. 54-28780) or a crystalline cellulose for the catalyst component. A method of kneading with water, kneading with water, forming into pellets, and then spheroidizing with a rolling granulator (Japanese Patent Publication No. 46-20683) is known. As the latter method, non-pareil (Freund Industries Co., Ltd.)
Made of sugar, or spherical granules of which sugar and starch are raw materials), granulated sugar, crystalline lactose, salt, silicon carbide, mullite, α-alumina, quartz sand, etc. are transferred to a CF granulator (made by Freund Sangyo Co., Ltd.) or the like. A method of granulating while spraying a binding solution and simultaneously applying powder while rolling with a dynamic granulator (edited by Japan Powder Industrial Technology Association (1991); "Granulation Handbook" p425-426, JP Sho 52-11
7292 and JP-A-54-149379), etc., but the idea of improving the production yield and the like by specifying the core component is not known in this method.

[0003]

The latter method is more advantageous than the former method in terms of easiness of granulation, sharpness of product particle size distribution, and roundness of product shape, but it is suitable as a spherical carrier for a catalyst. Since such materials were not available, the production yield was particularly poor, and they have not been widely used.

[0004]

The present inventors have arrived at the present invention as a result of diligent studies on a spherical catalyst in view of the above circumstances. That is, the present invention uses 1
The present invention relates to a spherical catalyst containing 0% or more of a spherical carrier as a core, and a method for producing the same.

The present invention will be described below. The spherical carrier in the present invention needs to contain 10% or more of cellulose. When the content of cellulose is less than 10%, the water retention property is lowered, so that when the catalyst component is coated, the particles are likely to be aggregated and the yield is lowered. Further, since the mechanical strength is lowered, it is not preferable because it is worn away when coating the catalyst component. The effect of containing cellulose is remarkable when it contains 50% or more of cellulose, and a spherical carrier composed of 100% of cellulose is particularly preferable.

The raw material of cellulose is preferably in powder form. Cellulose powder, for example, linter,
Use those produced by subjecting cellulosic raw materials such as pulp and recycled fibers to chemical treatment (acid hydrolysis, alkali oxidation decomposition, etc.) and / or mechanical treatment (crushing, grinding, etc.) You can As the cellulose used in the present invention, crystalline cellulose is particularly preferable from the viewpoint of easy production of the spherical carrier.

As components other than cellulose, asbestos, zeolite, diatomaceous earth, magnesia, activated clay, activated alumina, bauxite, silica gel, silicate, graphite,
Powders of stearic acid, stearates, polyacrylic acid, polyacrylates, starch, lactose and the like can be used. These components may be selected in consideration of the final physical properties of the spherical catalyst, that is, specific gravity and strength. Also,
As the binder component used for producing the spherical carrier, starch paste, methyl cellulose, polyvinyl alcohol, sodium carboxymethyl cellulose, hydroxypropyl cellulose and the like can be used.

The spherical carrier used in the present invention is produced, for example, by the following methods, but is not limited to these methods. A powder containing 10% or more of cellulose powder is charged into a mixing and agitation granulator to uniformly add water. An aqueous solution of methyl cellulose or the like may be used as a binder instead of water. If necessary, extrusion granulation may be subsequently performed using an extruder. After that, these are transferred to a tumbling type granulator, and while spraying distilled water or a binding solution as necessary, granulation and spheroidization are performed, followed by drying and sieving if necessary to obtain a spherical carrier. obtain.

The particle size of the spherical carrier to be used may be determined from the target particle size of the spherical catalyst and the content of the catalyst.
It must be 1 mm or more. If it is less than 0.1 mm, it is difficult to roll the spherical carrier, and it is very difficult to coat the catalyst component. Since it is possible to produce a spherical catalyst having a diameter of 1 mm or more by the conventional technique, it is worth the present invention to produce a spherical catalyst having a smaller particle size.

The shape and particle size distribution of spherical catalysts depends largely on the nature of the spherical support used. Therefore, if a spherical carrier having a narrow particle size distribution is used, a spherical catalyst having a narrow particle size distribution can be produced, and if a spherical carrier having a high sphericity is used, a spherical catalyst having a high sphericity can be manufactured. can do. Conventionally, it is difficult to manufacture a spherical carrier having a sharp particle size distribution, a small average particle size, and high sphericity, and even if it can be manufactured, a catalyst component is coated around a small spherical carrier. If this is attempted, the particles will agglomerate, making it very difficult to produce a spherical catalyst in good yield. However, in the present invention, a spherical carrier having a sharp particle size distribution, a small average particle size and a high sphericity can be easily produced by blending 10% or more of cellulose. Moreover, since it contains 10% or more of cellulose, it has an appropriate water absorption, so that the aggregation of particles is suppressed when coating the catalyst component, and as a result, the particle size distribution is sharp and the average particle size is small. Makes it possible to produce a spherical catalyst with high sphericity in good yield.

As the catalyst component in the present invention, nickel-based, cobalt-molybdenum-based, iron-based, platinum-based, copper-based, zinc-based, alumina-based, silica-alumina-based, vanadium,
Catalyst materials such as silica gel and catalyst support materials are used. When using the catalyst material activated by calcination, use it as it is. When a catalyst substance before calcination activation or a catalyst carrier substance is used, it is used after being coated (coated) on a spherical carrier and then calcined (activated). At this time, if the calcination temperature is 350 ° C. or higher, the cellulose will be burned out, and a hollow or porous spherical catalyst will be formed. For the purpose of facilitating the coating on the spherical carrier, other additives such as mineral substances and natural organic substances may be mixed with the catalyst component and used. The size of these particles provided for coating is preferably about 1/4 or less of the major axis and 1/7 or less of the minor axis with respect to the diameter of the spherical carrier. It is necessary to screen.

The spherical catalyst used in the present invention is produced, for example, by the following methods, but is not limited to these methods. When coating the catalyst component in the form of powder, the spherical carrier is placed in a centrifugal tumbling type coating device or a dish type granulator and rolled, and the binder such as methyl cellulose aqueous solution is continuously sprayed. Then, the catalyst component is supplied to coat the catalyst component on the spherical carrier, and then the carrier is dried. If the catalyst components are to be coated in a state of being suspended in a liquid for reasons such as before activation by calcination, a spherical carrier is placed in a fluidized bed coating machine or a rolling fluidized bed type coating device to flow or roll. After the slurry-like catalyst component is sprayed and coated on the spherical carrier in a fluidized state, it is dried if necessary. The weight ratio of the spherical carrier and the catalyst component may be appropriately determined, but is about 1/100 to 50/1.

The spherical catalyst thus obtained is used as it is if the catalyst substance is after calcination activation, and is used after calcination activation if necessary. Further, when the catalyst component is only the catalyst carrier substance, it is also possible to use it after calcination into a spherical catalyst carrier, and then supporting the catalyst substance according to a conventional method.

[0014]

The present invention will be described in detail below with reference to examples. The methods for measuring the physical properties of the spherical carrier and the spherical catalyst in Examples and Comparative Examples are as follows. Particle size range (μm) 30 g of a sample is sieved for 10 minutes using a JIS standard sieve (Z8801-1987) with a low tap type sieve shaker (Sieve Shaker A type manufactured by Hiraiko Seisakusho), and a sieve opening containing 90% by weight or more. The range of opening was defined as the particle size range.

• Sphericity An optical micrograph of 100 particles was taken, the minor axis and major axis of each particle were measured, and the average value of the values obtained by dividing the minor axis by the major axis was taken as the sphericity. -Coating efficiency (%) The value obtained by dividing the recovery amount of the spherical catalyst by the total amount of the used raw materials (as a dried product) and multiplying by 100 was defined as the coating efficiency.

Agglomeration rate (%) From 2 g of the spherical catalyst, the agglomerated one was taken out, its weight was measured, divided by 2 and multiplied by 100 to obtain the agglomeration rate. The spherical carrier and spherical catalyst samples used in Examples and Comparative Examples were prepared by the following method.

Sample A: Commercially available spherical granules of crystalline cellulose (Selfia <registered trademark> CP-203, manufactured by Asahi Kasei Kogyo Co., Ltd.) were used as Sample A. Table 1 shows the basic physical properties of Sample A. Sample B: Commercially available crystalline cellulose spherical granules (Selfia <registered trademark> CP-305, manufactured by Asahi Kasei Corporation) were used as Sample B. Table 1 shows the basic physical properties of Sample B. Sample C; crystalline cellulose (Avicel <registered trademark> PH-
101, manufactured by Asahi Kasei Kogyo Co., Ltd., and 500 g of gamma-alumina powder are mixed in a plastic bag, placed in a planetary mixer (Can Tho Mixer SS71, manufactured by Kanto Mixer Kogyo), and 700 g of water is added and kneaded for 30 minutes. did. Extrusion granulator (RG-5 type (screen pore size: 0.
5 mm), manufactured by Kikusui Seisakusho). 800 g of this extruded granulated product was used as a marumerizer (Q-230 type,
Charged to Fuji Paudal Co., Ltd., 30 at 500 rpm
Rolled for a minute to make it spherical. Thereafter, it was dried at 40 ° C. for a whole day and night, and particles of 300 to 500 μm obtained by sieving were used as sample C. Table 1 shows the basic physical properties of Sample C.

Sample D: 100 g of crystalline cellulose and 900 g of gamma-alumina powder were mixed in a plastic bag, placed in a planetary mixer, 540 g of water was added, and the mixture was kneaded for 15 minutes. Next, this kneaded product was crushed with a flash mill (screen pore size: 5 mmφ, manufactured by Fuji Paudal Co., Ltd.). Charge 800 g of this crushed material to a marumerizer, and
Spheroidized by rolling at rpm for 15 minutes. After that, it was dried at 40 ° C for 24 hours and then 300-500μ obtained by sieving.
Particles of m were used as sample D. Table 1 shows the basic physical properties of Sample D.

Sample E: Sample E was prepared in the same manner as in Sample D except that crystalline cellulose was changed to 50 g, gamma-alumina was changed to 950 g, and water was changed to 510 g. The basic physical properties of Sample E are shown in Table 1.

[0020]

Example 1 400 g of sample A was placed in a centrifugal rolling coating device (CF-360 type, manufactured by Freund Sangyo Co., Ltd.),
Slit air temperature 40 ℃, Rotor speed 160rpm
And spraying a 3% sodium carboxymethyl cellulose aqueous solution at a rate of 8 g / min while firing in air at 350 ° C. for 1.5 hours to activate copper-chromium catalyst powder 216 g and sodium polyacrylate (degree of polymerization). 20,000 ~
70,000) 24 g (both using a 38 μm sieve fraction) were supplied at a rate of 20 g / min for coating.
The spherical granules were dried in air at 110 ° C. for 16 hours to obtain a spherical catalyst. Table 2 shows the coating efficiency, aggregation degree and basic physical properties of the spherical catalyst.

[0021]

Example 2 A spherical catalyst was obtained in the same manner as in Example 1 except that Sample B was used. Table 2 shows the coating efficiency, aggregation degree and basic physical properties of the spherical catalyst.

[0022]

Example 3 A spherical catalyst was obtained in the same manner as in Example 1 except that Sample C was used. Table 2 shows the coating efficiency, aggregation degree and basic physical properties of the spherical catalyst.

[0023]

Example 4 A spherical catalyst was obtained in the same manner as in Example 1 except that Sample D was used. Table 2 shows the coating efficiency, aggregation degree and basic physical properties of the spherical catalyst.

[0024]

Comparative Example 1 A spherical catalyst was obtained in the same manner as in Example 1 except that Sample E was used. Table 2 shows the coating efficiency, aggregation degree and basic physical properties of the spherical catalyst. As described above, when the spherical catalyst is produced using the spherical carriers (Samples A to D) having a cellulose content of 10% or more, the coating yield is 97.3%.
As described above, the agglomeration rate is 5.3% or less, and the sphericity is 0.82 or more, which is a very preferable result for the production of the spherical catalyst. However, when a spherical catalyst is produced using a spherical carrier having a cellulose content of less than 10% (Sample D), the coating efficiency, the degree of aggregation, and the sphericity all have unsatisfactory results.

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

Industrial Applicability By using a spherical carrier containing 10% or more of cellulose as the core, it is possible to efficiently produce a spherical catalyst having a sharp particle size distribution and a high sphericity. Further, since it is possible to produce spherical catalysts having different specific gravities or hollow spherical catalysts, it becomes easy to optimize the catalytic reaction conditions. Furthermore, since a spherical carrier is used,
Since the amount of expensive catalyst used can be reduced, the catalyst cost can be reduced.

Claims (2)

[Claims] 1. A spherical catalyst comprising a spherical carrier containing 10% or more of cellulose as a core. 2. A method for producing a spherical catalyst, which comprises coating a spherical carrier containing 10% or more of cellulose with a catalyst component.