JP2000051713A - Production of spherical carrier for carrying catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a spherical carrier for carrying a catalyst comprising a boria-alumina compsn. or a boria-silica-alumina compsn., having a pore structure almost similar to that of a boria-alumina hydrate paste or a boria-silica-alumina hydrate paste used as a principal starting material and having a uniform spherical shape, a smooth surface and homogeneousness from the outer surface to the interior. SOLUTION: A polysaccharide soln. is added to a boria-alumina hydrate paste prepd. by adding boron to an alumina hydrate gel or a boria-silica-alumina hydrate paste prepd. by adding boron to a silica-alumina hydrate gel, they are mixed and the concn. of the resultant slurry is adjusted. The slurry is then dropped into a soln. contg. multivalent metal ions to form a spherical hydrogen and this hydrogel is aged, washed, dried and thereafter, fired.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a boria-alumina spherical carrier or a boria-silica-alumina spherical carrier used as a catalyst carrier or as an adsorbent. -A spherical carrier having a pore structure substantially similar to the pore structure of an alumina hydrate paste or a boria-silica-alumina hydrate paste, and a homogeneous boria-alumina composition from the outer surface to the inner portion Or boria
The present invention relates to a method for producing a spherical carrier for carrying a catalyst comprising a silica-alumina composition.

[0002]

2. Description of the Related Art A carrier comprising a boria-alumina composition or a boria-silica-alumina composition has a larger specific surface area and is more excellent in acid resistance and heat resistance than an alumina carrier.
In addition, since it has a high solid acid concentration, it is widely used as an adsorbent, a catalyst, and a catalyst carrier in the chemical industry, petrochemical, and the like.

[0003] Generally, a spherical carrier carries a catalytically active metal and is used after being filled in a fixed bed reactor or a moving bed reactor. However, since the spherical carrier is spherical, it can be uniformly filled in the reactor and can be easily extracted. In addition, there is an advantage that so-called channeling, which causes a bypass of a flow of a reactant during operation, can be suppressed. Further, in a moving bed reactor, it is an essential requirement that the carrier be spherical in a reaction mode in which the carrier gradually moves downward by flow or its own weight in the reactor. Such a spherical carrier is manufactured by an in-oil dripping method, a tumbling granulation method, or the like. For example, the alumina spherical carrier by the drop-in-oil method uses a reagent that decomposes at high temperature to generate ammonia, such as hexamethylenetetramine or urea, and employs a method of gelling the alumina sol by its alkalinity. A spherical carrier having a smooth surface and a relatively uniform spherical shape can be produced. In order to gel the alumina sol, the alumina sol is uniform from the outer surface to the inside, and the pore structure is mostly formed of micropores having a diameter of 50 Å or less.

[0004] On the other hand, in the case of an alumina spherical carrier obtained by the tumbling granulation method, the humidified alumina hydrate powder is tumbled to form particles, and then water spray and supply of the humidified alumina hydrate powder are performed. Since the grains are grown alternately and densely, a spherical carrier having a somewhat rough surface and a wide spherical distribution and a slightly low sphericity is produced. Then, a layer is formed between the outer surface and the inside to roll the hydrated alumina hydrate powder and grow the grains,
Although the pore structure has the disadvantage of having micro to macro pores, it is widely used because of its low production cost.

[0005]

By the way, a spherical carrier for a moving bed reactor is particularly required to have abrasion resistance because the carrier is a reaction type in which the carrier flows and / or moves. It is important that the surface is smooth. Therefore, as a spherical carrier for a moving bed reactor, a spherical carrier produced by an in-oil dripping method is mainly used.

However, as described above, the spherical carrier produced by the in-oil dripping method has a uniform spherical shape, a smooth surface, and a uniform shape from the outer surface to the inside, but most of the micropores have a diameter of 50 angstroms or less. Due to the occupancy, the effect of pores appears, and use under conditions such as exhaust gas purification catalysts where the reaction rate is particularly large and the decrease in activity is due to pore blockage or physical poisoning covering the surface Is difficult. In general, since the performance of a catalyst is closely related to the pore characteristics of a support, a support having physical properties suitable for the type of reaction and reaction conditions is required.

The present invention has been made to solve these problems, and has a pore having substantially the same pore structure as a boria-alumina hydrate paste or a boria-silica-alumina hydrate paste used as a main raw material. A boria-alumina composition or boria-silica having a structure, a uniform spherical shape, a smooth surface, and a uniform outer surface to the inner portion.
It is an object of the present invention to provide a method for producing a catalyst-supporting spherical carrier comprising an alumina composition.

[0008]

In order to achieve the above object, the present invention provides a boria-alumina hydrate paste obtained by adding boron to an alumina hydrate gel or a boria-alumina hydrate gel obtained by adding boron to a silica-alumina hydrate gel. -A polysaccharide solution is added to and mixed with the silica-alumina hydrate paste, and the slurry whose concentration has been adjusted is dropped into a solution containing polyvalent metal ions to form a spherical hydrogel, which is then aged and washed. Characterized by drying and firing,
The polysaccharide solution added to the hydrate paste has a concentration of 1.0 to
3.0 wt% of low methoxyl pectin or sodium alginate, and the amount of the polysaccharide solution added to the hydrate paste is 3 to 10 times the weight of the hydrate paste in terms of oxide. The concentration of the slurry is adjusted to be in the range of 5 to 20% by weight in terms of oxide of boria-alumina or boria-silica-alumina, and the polyvalent metal ion solution has a concentration of 0.5 to 3%. .0
% By weight of at least one of calcium, aluminum, magnesium, barium and strontium, and the spherical boria-alumina hydrogel after the washing has a drying temperature of 60 to 120 ° C and a calcination temperature of 500 to 120 ° C. The drying temperature of the spherical boria-silica-alumina hydrogel after the washing is 1300 ° C. or 60 to 120 ° C., and the firing temperature is 500 to
A method for producing a spherical carrier for carrying a catalyst at 1400 ° C. is characterized.

[0009]

DETAILED DESCRIPTION OF THE INVENTION As a method for producing a boria-alumina hydrate paste, which is one of the main raw materials in the present invention, a general production method can be applied, for example, a water-soluble compound containing aluminum as a main component. Can be used by adding and / or kneading boron and / or an aqueous solution of boron to an alumina hydrate gel obtained by filtering and washing an alumina hydrate slurry produced by hydrolyzing the resultant. In addition, as a method for producing a boria-silica-alumina hydrate paste as another main raw material, an aqueous solution containing silicon as a main component is added to an alumina hydrate slurry produced in the same manner as described above, and silica-alumina-hydrate is added. A hydrate slurry can be obtained, and a mixing method of adding boron and / or an aqueous boron solution to a silica-alumina hydrate gel obtained by filtering and washing the slurry in the same manner as described above and kneading the resultant can be used.

As the water-soluble compound containing aluminum as a main component, an aqueous solution such as aluminum nitrate, aluminum sulfate, aluminum chloride, and sodium aluminate can be used.
Water-soluble salts such as metaboric acid and ammonium borate can be used. As the aqueous solution containing silicon as a main component, an aqueous solution such as sodium silicate, silicon tetrachloride, and colloidal silica can be used.

Next, a polysaccharide solution having a concentration of 1.0 to 3.0% by weight is added to the boria-alumina hydrate paste or the boria-silica-alumina hydrate paste to obtain a weight of the hydrate paste in terms of oxide. Is added in an amount of 3 to 10 times. In the present invention, the polysaccharide solution to be added to the boria-alumina hydrate paste or the boria-silica-alumina hydrate paste is low methoxyl (LM) pectin, sodium alginate, etc., and has a solubility in warm water. Considering the concentration of the polysaccharide solution from 1.0 to
It is preferred to be in the range of 3.0% by weight. 3.0% by weight
However, if the concentration is less than 1.0% by weight, the dissolution time is slightly shortened, but the concentration of the solution decreases, so that the amount added increases, and thus the concentration increases. It becomes difficult to adjust the concentration of the mixed slurry to which the saccharide solution has been added. Further, the amount of the polysaccharide solution added was 3 to the weight of boria-alumina hydrate paste or boria-silica-alumina hydrate paste in terms of oxide.
When the amount is from 10 to 10 times, a suitable spherical carrier cannot be obtained with an addition amount of less than 3 times, while when added in an amount of more than 10 times, a further effect of increasing the sphericity can be obtained. Because there is no.

Then, the concentration of the slurry obtained by adding and mixing the polysaccharide solution is adjusted to a range of 5 to 20% by weight in terms of boria-alumina oxide or boria-silica-alumina oxide. In the present invention, the reason why the slurry concentration is 5 to 20% by weight in terms of boria-alumina oxide or boria-silica-alumina oxide is that when the slurry is dropped from a dropper having a fixed diameter, the concentration is 20% by weight. If the concentration exceeds 5% by weight, the viscosity of the slurry becomes high, and it is difficult to control the falling speed of the droplets to a constant value, which results in the formation of an elliptical sphere of non-uniform size. This is because a spherical shape is formed.

Next, a polysaccharide solution is added to and mixed with the boria-alumina hydrate paste or boria-silica-alumina paste, and the slurry whose concentration has been adjusted is dropped into a solution containing polyvalent metal ions to form a spherical boria-alumina paste. An alumina hydrogel or a spherical boria-silica-alumina hydrogel is formed, aged, washed, dried and calcined to obtain a spherical carrier comprising a boria-alumina composition or a boria-silica-alumina composition.

The solution containing a polyvalent metal ion used in the present invention is preferably selected from metal salts containing a divalent metal ion such as calcium, aluminum, magnesium, barium and strontium. Mixed solutions of the species can also be used. The concentration of the solution containing the polyvalent metal ion is preferably in the range of 0.5 to 3.0% by weight. If the concentration is less than 0.5% by weight, a suitable spherical carrier cannot be obtained. If the content exceeds 0% by weight, the effect of obtaining a suitable spherical carrier cannot be obtained.

The spherical hydrogel mainly composed of boria-alumina or boria-silica-alumina obtained by the procedure described above is aged. In the case of a spherical boria-alumina hydrogel, the temperature is 10 to 15 at a temperature of 60 to 120 ° C.
Dry for hours, bake at a temperature in the range of 500-1300 ° C,
On the other hand, in the case of a spherical boria-silica-alumina hydrogel, the boria-alumina composition or boria-silica-alumina composition is dried at a temperature of 60 to 120 ° C. for 10 to 15 hours and calcined at a temperature of 500 to 1400 ° C. Can be produced.

[0016]

EXAMPLES Examples of the present invention will be described together with comparative examples.
The pore characteristics shown below were measured by the mercury intrusion method, and the surface tension of mercury was calculated at 480 dyn / cm, and the contact angle between silver and the measurement sample was calculated at 140 °. [Example 1] A stainless steel reaction vessel equipped with a stirrer having an internal volume of 100 liters, (as _Al 2 _{O 3} 516g) Water 50 l aluminum sulfate solution 6360g and put, heated to 70 ° C., and held, stirred 4620 g of sodium aluminate aqueous solution (580 as Al ₂ O ₃₎
g) was added dropwise, and the hydrated alumina hydrate slurry having a pH of 9.5 was filtered and washed until Na ₂ O became 0.1% by weight or less to obtain an alumina hydrate cake. .

Next, 3520 g of the cake (650 g in terms of Al ₂ O ₃ ) and 128 g of a special grade of orthoboric acid (B
72.2 g as ₂ O ₃ ) was thoroughly kneaded in a double-armed kneader equipped with a heating jacket to obtain 10% by weight as B ₂ O _3.
Containing boria-alumina hydrate paste (a) was obtained. A portion of this boria-alumina hydrate paste (a) was
C. for 15 hours and calcined at a temperature of 600.degree. C. for 3 hours to obtain a boria-alumina solid (a ').

On the other hand, the boria-alumina hydrate paste
(A) 476 g (B₂O₃-Al₂O ₃As 100
g) a 1.5 wt% sodium alginate solution 5
00g (B₂O₃-Al₂O₃5 times the amount) and water 2
5 cc and mix well with stirring.₂O₃-Al₂O
₃A slurry having a solid content of 10% by weight was obtained. About
The slurry was supplied through a dropping port having a diameter of 4.5 mm to a concentration of 1.2.
10 liters internal volume containing calcium chloride solution by weight
Into a Pyrex reactor with a stirrer
Form hydrogel and after 5 minutes aging, spherical hydrogel
Is taken out, washed with water, dried at a temperature of 80 ° C. for 15 hours,
Boria-alumina spheres fired at a temperature of 600 ° C for 3 hours
Carrier A was prepared.

Boria-alumina solid obtained (a ')
Table 1 below shows the pore characteristics and physical properties of the porous carrier A and the pore characteristics of the boria-alumina spherical carrier A. As can be seen from Table 1, according to the method for producing a boria-alumina spherical carrier according to Example 1 of the present invention, the boria-alumina hydrate paste of the main raw material has pore characteristics almost equivalent to those of the paste. An almost spherical boria-alumina spherical carrier having a high breaking strength was produced.

Example 2 Alumina water in Example 1
1053 g of Japanese cake (Al₂O₃200g)
The amount of orthoboric acid to be added was 11 g (B₂O₃
6.2 g), 62.5 g (B₂O₃35.
3g) except that the boria in Example 1 was changed.
-Almost the same as the method for obtaining the alumina hydrate paste (a)
B in the way ₂O₃-Alumina containing 3% by weight as
Hydrate paste (b) and B₂O₃15% by weight
Boria-alumina hydrate paste (c), and boria
-Alumina solids (b ') and (c') were obtained. Meanwhile it
Each of the boria-alumina hydrate pastes (b, c)
In the same manner as in Example 1 in which spherical carrier A was obtained using
Rear-alumina spherical supports B and C were prepared.

The resulting boria-alumina solid (b ',
c ') the pore properties and the boria-alumina spherical support B;
The pore properties and physical properties of C are also shown in Table 1 below. As can be seen from Table 1, according to the method for producing a boria-alumina spherical carrier according to Example 2 of the present invention, even when the boria content of the boria-alumina hydrate paste as the main raw material was changed, each boria-alumina hydrate paste was changed. An almost spherical boria-alumina spherical carrier having pore characteristics almost equal to those of the alumina hydrate cake and having high breaking strength was obtained.

Comparative Example 1 The concentration of 1.5% by weight added to the boria-alumina hydrate paste (a) obtained in Example 1
Amount of the sodium alginate solution of B ₂ O ₃ —Al
Boria-alumina spherical carriers D and E were prepared in substantially the same manner as the method for obtaining the boria-alumina spherical carrier A in Example 1 except that the amount was 1 and 15 times the amount of ₂ O ₃ , respectively. .

The resulting boria-alumina spherical supports D, E
Table 1 below shows the pore characteristics and physical properties of the sample.
As can be seen from Table 1, the boria-alumina spherical carrier D obtained by the method according to Comparative Example 1 in which the amount of the polysaccharide solution added is out of the range of the present invention is good in the pore characteristics but the shape of the carrier Became elliptical, and the pore characteristics of the boria-alumina spherical carrier E were changed, and the breaking strength was weak.

[Comparative Example 2] Boria-Al obtained in Example 1
1.5 wt% Argi in Mina Hydrate Paste (a)
Add 5 times the volume of sodium phosphate solution and water and mix thoroughly
Slurry B ₂O₃-Al₂O₃Triple solids concentration
% And the slurry is concentrated by heating₂O
₃-Al₂O₃Except that the solid concentration was 25% by weight
Obtained a boria-alumina spherical carrier A in Example 1.
Boria-alumina spherical carrier F, in substantially the same manner as
G was prepared.

The obtained boria-alumina spherical supports F, G
Table 1 below shows the pore characteristics and physical properties of the sample.
As can be seen from Table 1, the boron obtained by the method according to Comparative Example 2 in which the concentration of the slurry is out of the range of the present invention.
The alumina spherical supports F and G had good pore characteristics, but had a tear-like or elliptical shape and irregular particle sizes.

[Example 3] In the method for producing a boria-alumina spherical carrier A shown in Example 1, instead of a calcium chloride solution having a concentration of 1.2% by weight, an aluminum chloride solution having a concentration of 1.5% by weight was used. A boria-alumina sphere was produced in substantially the same manner as in Example 1 except that a mixed solution of 1.2% by weight of calcium chloride solution and 1.5% by weight of aluminum chloride solution at a weight ratio of 1: 1 was used. Carriers H and I were prepared.

The resulting boria-alumina spherical supports H, I
Table 1 below shows the pore characteristics and physical properties of the sample.
As can be seen from Table 1, the boria according to the third embodiment of the present invention.
According to the method for producing an alumina spherical carrier, even if an aluminum chloride solution is used instead of a calcium chloride solution, or if a mixed solution of a calcium chloride solution and an aluminum chloride solution is used, the pores of the boria-alumina hydrate cake It has pore characteristics almost equivalent to those of the above, and has a high breaking strength, so that a substantially spherical boria-alumina spherical carrier can be produced.

[0028]

[Table 1]

Example 4 Using the boria-alumina spherical carrier A shown in Example 1, 1000 ° C., 1100 ° C., 12
The sintering temperature was changed to 00 ° C. and 1300 ° C. to prepare boria-alumina spherical supports J, K, L and M. The specific surface areas of these carriers were measured by a nitrogen gas adsorption method and determined by a calculation formula by the BET method. The specific surface areas of the boria-alumina spherical carriers J, K, L, and M were 91 m ² / g, respectively.
It was 49 m ² / g, 24 m ² / g, and 10 m ² / g.
As described above, it was found that the spherical support comprising the boria-alumina composition had a high specific surface area even when fired at a high temperature, and had excellent heat resistance.

Example 5 25 liters of water and 3180 g of an aqueous solution of aluminum sulfate (258 as Al ₂ O ₃₎ were placed in a stainless steel reactor equipped with a stirrer having an inner volume of 50 liters.
g), and heated and maintained at 70 ° C., and while stirring, 2310 g of an aqueous sodium aluminate solution (425 g as Al ₂ O ₃ ) was added dropwise in total, and the mixture was aged to obtain an alumina hydrate slurry having a pH of 9.5. I got

Next, nitric acid 2 having a concentration of 30% was added to the slurry.
After adding 2 g to adjust the pH to 6.0, 607 g of an aqueous solution of sodium silicate (85 g as SiO ₂ ) was added dropwise.
After aging, an alumina hydrate slurry having a pH of 8.5 was obtained.
Thereafter, the slurry was filtered and washed until Na ₂ O became 0.1% by weight or less to obtain a silica-alumina hydrate cake containing 11% by weight as SiO ₂ .

Then, 3520 g of the cake (SiO _2-
650 g of Al ₂ O ₃ ) and 60.6 g of a reagent-grade orthoboric acid (34.2 g as B ₂ O ₃ ) are sufficiently kneaded in a double-arm kneader equipped with a heating jacket, and 5% by weight as B ₂ O _3. boria containing 10.5 wt% as -SiO ₂ - silica - to obtain an alumina hydrate paste (n). A part of the boria-silica-alumina hydrate paste (n) was dried at a temperature of 80 ° C for 15 hours, and dried at a temperature of 600 ° C for 3 hours.
Calcination time for boria-silica-alumina solid (n ')
I got

On the other hand, 476 g of the above boria-silica-alumina hydrate paste (n) (B ₂ O ₃ —SiO ₂ —Al ₂
O ₃ as 100g) in a concentration of 1.5 wt% sodium alginate solution _{500g (B 2 O 3 -SiO 2} -Al 2
(5 times the amount of O ₃ ) and 25 cc of water were added and sufficiently stirred and mixed to obtain a slurry having a B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ solid content concentration of 10% by weight.

Thereafter, the slurry was dropped from a 4.5 mm diameter dropping port into a 10 liter Pyrex reaction tank equipped with a stirrer containing a 1.2% by weight calcium chloride solution to form a spherical hydrogel. After aging for 5 minutes, the spherical hydrogel was taken out, washed with water, dried at a temperature of 80 ° C. for 15 hours, and then calcined at a temperature of 600 ° C. for 3 hours to prepare a boria-silica-alumina spherical carrier N.

The pore properties and physical properties of the obtained boria-silica-alumina solid (n ') and the pore properties of the boria-silica-alumina spherical carrier N are shown in Table 2 below. As can be seen from Table 2, according to the method for producing a boria-silica-alumina spherical carrier according to Example 5 of the present invention, the pores substantially equal to the pore characteristics of the main raw material boria-silica-alumina hydrate paste. A boria-silica-alumina spherical support having substantially true spheres having characteristics and high breaking strength was able to be produced.

Example 6 The amount of the aqueous sodium silicate solution dropped to the alumina hydrate slurry in Example 5 was 2
57 g (36 g as SiO ₂ ), 1215 g (SiO ₂
Silica except that varied as ₂ 170 g) and containing 5% by weight SiO ₂ in substantially the same manner as to obtain an alumina hydrate cake (n) in EXAMPLE 5 - alumina hydrate cake and SiO ₂ as 20% by weight comprising silica - obtain alumina hydrate cake, respectively on the cake B ₂
Orthoboric acid was added so as to contain 5% by weight as O ₃ , and a boria-silica-alumina hydrate paste (o) containing 5% by weight as B ₂ O _{3 and} 4.8% by weight as SiO ₂ respectively, and B ₂ O ₃ as comprising 19 wt% as a 5 wt% -SiO ₂ boria - silica - alumina hydrate paste (p), and boria - silica - alumina solid (o '), (p' was obtained). On the other hand, each of the boria
Boria-silica-alumina spherical carriers O and P were prepared in substantially the same manner as the method for obtaining the spherical carrier N using the silica-alumina hydrate paste (o, p).

The pore properties and physical properties of the obtained boria-silica-alumina solid (o ', p') and the boria-silica-alumina spherical carriers O and P are shown in Table 2 below. Shown. As can be seen from Table 2, according to the method for producing a boria-silica-alumina spherical carrier according to Example 6 of the present invention, even if the silica content of the boria-silica-alumina hydrate paste of the main raw material was changed, A substantially spherical boria-silica-alumina spherical carrier having pore characteristics substantially equal to those of the respective boria-silica-alumina hydrate pastes and high breaking strength was obtained.

Comparative Example 3 The concentration of the boron-silica-alumina hydrate paste (n) obtained in Example 5 was 1.
5 wt% of the added amount of B ₂ O of sodium alginate solution
₃ Each 1 times the -SiO ₂ -Al ₂ O _3, 1
Boria-silica-alumina spherical carriers Q and R were prepared in substantially the same manner as the method for obtaining the boria-silica-alumina spherical carrier N in Example 5, except that the amount was 5 times.

The pore characteristics and physical properties of the resulting boria-silica-alumina spherical carriers Q and R are shown in Table 2 below. As can be seen from Table 2, the boria-silica-alumina spherical carrier Q obtained by the method according to Comparative Example 3, in which the amount of the polysaccharide solution added is out of the range of the present invention, has a good pore property, Has an elliptical shape, and the boria-silica-alumina spherical carrier R has changed pore characteristics and low breaking strength.

Comparative Example 4 The boria-silica-alumina hydrate paste (n) obtained in Example 5 had a concentration of 1.5% by weight.
Sodium alginate solution of 5 times and water were added and sufficiently stirred and mixed. A slurry of B ₂ O ₃ —SiO ₂ —Al ₂
Boria in Example 5 except that the O ₃ solid content concentration was 3% by weight, and the slurry was heated and concentrated to obtain a B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ solid content concentration of 25% by weight. Boria-silica-alumina spherical carriers S and T were prepared in substantially the same manner as the method for obtaining silica-alumina spherical carriers N.

The pore properties and physical properties of the obtained boria-silica-alumina spherical supports S and T are also shown in Table 2 below. As can be seen from Table 2, the boria-silica-alumina spherical supports S and T obtained by the method according to Comparative Example 4 in which the slurry concentration is out of the range of the present invention have good pore characteristics, The shape was tear-like or elliptical, and the particle size was irregular.

Example 7 The concentration of 1.2% by weight was obtained by the method for producing a boria-silica-alumina spherical carrier N shown in Example 5.
1.5% by weight aluminum chloride solution and 1.2% by weight concentration instead of calcium chloride solution
Except that a calcium chloride solution of 1.5% by weight and a mixed solution of aluminum chloride having a concentration of 1.5% by weight in a weight ratio of 1: 1 were used. , V were prepared.

The pore characteristics and physical properties of the obtained boria-silica-alumina spherical carriers U and V are also shown in Table 2 below. As can be seen from Table 2, according to the method for producing a boria-silica-alumina spherical carrier according to Example 7 of the present invention, an aluminum chloride solution was used instead of a calcium chloride solution, or a calcium chloride solution and an aluminum chloride solution were used. Even when a mixed solution of the above is used, it has substantially the same pore characteristics as those of the boria-silica-alumina hydrate paste, has a high breaking strength, and is a substantially spherical boria-silica-alumina spherical carrier. Could be manufactured.

[0044]

[Table 2]

Example 8 The boria-silicone shown in Example 5
1000 ° C., 1100 using car-alumina spherical carrier N
C., 1300 ° C., 1400 ° C.
Preparation of rear-silica-alumina spherical carrier W, X, Y, Z
did. The specific surface area of these carriers is determined by the nitrogen gas adsorption method.
Measured and calculated by BET method, Boria
-Specific surface area of silica-alumina spherical carrier W, X, Y, Z
Is 123m each²/ G, 66m ²/ G, 28m²/
g, 12m²/ G. As described above, boria-silica
-Even if the spherical support made of the alumina composition is fired at a high temperature
It has a high specific surface area and excellent heat resistance.
won.

[0046]

As described above, according to the present invention, the pore characteristics of the used boria-alumina hydrate paste or boria-silica-alumina hydrate paste are substantially the same, and the shape is substantially spherical. A process for producing a catalyst-supporting spherical carrier comprising a boria-alumina composition or a boria-silica-alumina composition having a smooth surface, uniform from the outside to the inside, high breaking strength, and also having heat resistance. And its industrial value is high.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 28, 1998 (1998.8.2
8)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction contents]

[0028]

[Table 1]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction contents]

[0044]

[Table 2]

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G065 AA01 AA02 AA06 AA07 AA08 AA09 AB01Y AB06X AB06Y AB11X AB22X AB30X AB35Y BA09 BB03 BB08 BB10 CA15 CA21 CA30 DA04 EA01 EA03 EA05 EA10 FA01 BA01 A01 BA01 A03 A03 A01 A01 BAA BA27B BA29A BA29B BB04A BB04B BB06A BB06B BB18A BB18B BC09A BC09B BC10A BC10B BC12A BC12B BC13A BC13B BC16A BC16B BD03A BD05A EA04X EA04Y EB18Y EC10Y FB09 FB30 FC07 FC08

Claims (7)

[Claims] 1. A polysaccharide solution is added to a boria-alumina hydrate paste obtained by adding boron to an alumina hydrate gel or a boria-silica-alumina hydrate paste obtained by adding boron to a silica-alumina hydrate gel. And mix
A method for producing a spherical carrier for supporting a catalyst, comprising: dropping a slurry having an adjusted concentration into a solution containing a polyvalent metal ion to form a spherical hydrogel, and then aging, washing, drying and calcining. 2. The catalyst-supporting spherical carrier according to claim 1, wherein the polysaccharide solution to be added to the hydrate paste is low methoxyl pectin or sodium alginate having a concentration of 1.0 to 3.0% by weight. Manufacturing method. 3. The amount of the polysaccharide solution added to the hydrate paste is 3 to 10 times the weight of the hydrate paste in terms of oxide. 3. The method for producing a spherical carrier for supporting a catalyst according to 2. 4. The slurry according to claim 1, wherein the concentration of boria-alumina or boria-silica-alumina is adjusted in the range of 5 to 20% by weight in terms of oxide. A method for producing the spherical carrier for supporting a catalyst according to the above. 5. The polyvalent metal ion solution having a concentration of 0.5
３3.0% by weight of at least one of calcium, aluminum, magnesium, barium or strontium.
5. The method according to claim 1, wherein the seed comprises a seed.
The method for producing a spherical carrier for supporting a catalyst according to the above item. 6. The method according to claim 1, wherein a drying temperature of the spherical boria-alumina hydrogel after the washing is 60 to 120 ° C., and a firing temperature is 500 to 1300 ° C. The method for producing a spherical carrier for supporting a catalyst according to the above item. 7. The drying temperature of the spherical boria-silica-alumina hydrogel after the washing is 60 to 120 ° C.,
The method for producing a spherical carrier for supporting a catalyst according to any one of claims 1 to 5, wherein the calcination temperature is 500 to 1400 ° C.