JPH11188261A - Solid acid catalyst and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid acid catalyst having higher activity in hydrocarbon isomerization and the like and a method for producing the same. (A) Tungsten containing substantially no Group VIII metal and containing tungsten (B) a portion comprising a zirconium hydrate oxide and / or oxide substantially containing no tungsten and containing a Group VIII metal, and It is something that is mixed. Further, the method for producing a solid acid catalyst according to the present invention comprises: (a) particles comprising a zirconium hydrated oxide and / or an oxide containing tungsten;
(b) a zirconium hydrate containing a Group VIII metal and / or
Alternatively, oxide particles are mechanically mixed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solid acid catalyst useful for an acid catalyzed reaction such as a hydrocarbon conversion reaction, and a method for producing the same. This catalyst is used for hydrocarbon conversion reaction, carbon increase reaction,
Promotes decomposition reaction, polymerization reaction, hydrogenation reaction, dehydrogenation reaction, etc.

[0002]

2. Description of the Related Art A solid acid catalyst has recently been attracting attention as an environmentally friendly catalyst which can be easily recovered, does not corrode equipment, and is environmentally friendly.
Catalysts consisting of oxides of tungsten and zirconium, and catalysts with a Group VIII metal such as platinum added to them,
It is an effective catalyst for hydrocarbon isomerization, low polymerization reaction and the like.

As a method for producing a solid acid catalyst, in Example 2 of International Publication No. WO 96/13328, an aqueous solution of chloroplatinic acid is brought into contact with tungsten oxide and zirconium oxide produced by a known method. Accordingly, a catalyst supporting platinum has been proposed. In addition, Example 4 of the publication discloses a catalyst obtained by adding platinum-supported silica to tungsten oxide and zirconium oxide manufactured by a known method and mechanically mixing the resultant. . However, it is shown in Table 1 of the publication that the catalyst of Example 4 has lower activity (lower isomerization rate to isoparaffin) than the catalysts of other Examples.

[0004]

In the isomerization of hydrocarbons, it has been desired to further increase the activity of a solid acid catalyst. The present invention solves such a problem and provides a solid acid catalyst having higher activity and a method for producing the same.

[0005]

Means for Solving the Problems The present inventors have found that higher activity can be obtained by combining and mechanically mixing specific solid acid catalysts, and completed the present invention.

That is, the solid acid catalyst according to the present invention comprises:
(a) a zirconium hydrate oxide and / or an oxide substantially containing no Group VIII metal and containing tungsten and (b) a zirconium hydrate oxide containing substantially no tungsten and containing a Group VIII metal and And / or an oxide portion, and these portions are mixed. In particular, the weight of tungsten is
30% by weight, and 0.1 wt.
It is preferred that the content be 5 to 5% by weight.

The method for producing a solid acid catalyst according to the present invention comprises the steps of: (a) particles containing a zirconium hydrated oxide and / or an oxide containing tungsten; and (b) particles containing a zirconium hydrated oxide and / or a group VIII metal. Alternatively, oxide particles are mechanically mixed.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Zirconium hydrated oxides and / or oxides containing tungsten can be obtained by (1) contacting a hydroxide or / and oxide of zirconium with an aqueous solution of a tungsten compound such as a tungsten ammonium salt; It can be produced by a method obtained by baking, or (2) a coprecipitation method in which a tungsten compound and a zirconium compound are made into an aqueous solution and an alkali is added thereto to generate a precipitate. The tungsten content in the zirconium hydrated oxide containing tungsten and / or the oxide is arbitrary, but is preferably 5 to 35% by weight, particularly preferably 7 to 25% by weight as the metal weight of tungsten. Any known tungsten source and zirconium source may be used and are not particularly limited. In the present application, the hydrated oxide includes a hydroxide, an oxide obtained by removing water from the hydroxide, an oxide containing water of crystallization, and the like.

The Group VIII metal, that is, the Group 8-10 metal, is at least one selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.
Particularly, platinum or palladium is preferable. The content of the Group VIII metal in the zirconium hydrated oxide and / or oxide containing the Group VIII metal is optional, but is 0.01 to 10% by weight, particularly 0.2 to 1.5% by weight as the metal weight. Is preferred. As the Group VIII metal, one kind may be used, or two or more different kinds may be used in combination.

The form in which the group VIII metal component is supported is not particularly limited, but those containing a small amount of a catalyst poison such as an alkali metal can be suitably used.
Oxides, chlorides, sulfates, nitrates, sulfides, ammonium salts of oxyacids, complexes with chloride ions, complexes with ammonium ions, complexes with cyanide ions, complexes with thiocyanate ions, complexes of the above ions Examples of the complex include an ammonium salt of the complex.

The solid acid catalyst according to the present invention comprises (a) particles comprising a zirconium hydrated oxide and / or oxide containing tungsten, and (b) a zirconium hydrated oxide and / or oxide containing a Group VIII metal. It can be preferably produced by mechanically mixing the particles. The size of the particles to be mixed is usually about 0.1 μm to 100 μm, preferably about 0.5 μm to 20 μm. The mixing ratio is not particularly limited, but is 1: 5 to 5: 1 by weight.
In particular, 1: 3 to 3: 1 is preferable. Mechanical mixing
It is preferable that the two types of particles are uniformly mixed without chemically reacting. The mixed solid acid catalyst preferably contains 5 to 30% by weight of tungsten as a metal weight and 0.1 to 5% by weight of a metal of Group VIII as a metal weight.

The catalyst according to the invention usually exhibits an acid strength higher than 100% sulfuric acid (Hammett's acidity function Ho is -11.93) and is suitable for all reactions which proceed with an acid catalyst or with a hydrogenation catalyst. Can be applied. Reactions that proceed with an acid catalyst include, for example, isomerization, alkylation,
Examples include alkylation, dehydration, esterification, hydrogenation, dehydrogenation, polymerization, acylation, and etherification.

[0013] These reaction conditions are not limited to a specific range because they naturally vary depending on the raw materials. To give an example here, for example, the conditions for isomerization may vary depending on the raw material, but the temperature, space velocity, pressure, etc. are as follows. The temperature is between 150 ° C and 300 ° C, preferably 250 ° C.
° C or lower and the space velocity is 0.1 to 10 / h, preferably 0.5 to 5 / h. The pressure is above normal pressure and 50 megapascals, preferably 20 to 30 megapascals. However, these numerical values do not limit the claims of the present invention. The type of reaction when using the present catalyst can take any form depending on the reaction. Fixed bed flow reaction, liquid phase heterogeneous reaction, batch reaction, semi-batch reaction,
Such as a continuous reaction.

[0014]

EXAMPLES (Example) to pH = 8 with aqueous ammonia solution was added to zirconyl chloride (ZrOCl ₂ · 8H ₂ O) aqueous solution, recovering the precipitate thus obtained zirconium hydroxide, washed with water, dried for 24 hours at 100 ° C. Thus, dried zirconium hydroxide was obtained.

The dried zirconium hydroxide was put into an aqueous solution of ammonium metatungstate, the water content was evaporated by an evaporator, and further dried and fired at 700 ° C. for 3 hours to obtain zirconia supporting tungsten oxide. The tungsten concentration of the tungsten-supported catalyst thus obtained was 15 wt% with respect to zirconium hydroxide, and 14.2 wt% with respect to the tungsten-supported catalyst after calcination.

Further, dried zirconium hydroxide was placed in an aqueous solution of chloroplatinic acid hexahydrate, the water content was evaporated by an evaporator, dried, and calcined at 700 ° C. for 3 hours to obtain platinum-supported zirconia. The platinum concentration of the thus-obtained platinum-supported catalyst was 0.5% with respect to zirconium hydroxide.
wt%.

The catalyst a was obtained by mechanically mixing 0.2 g of the tungsten-supported catalyst and 0.4 g of the platinum-supported catalyst with a kneader equipped with a motor-driven stirring blade.

Comparative Example 1 A platinum-supported titania, a platinum-supported iron oxide, and a platinum-supported titania were prepared in the same manner as the platinum-supported catalyst of the embodiment by using another metal oxide in place of dry zirconium hydroxide.
Platinum supported tin oxide was prepared. These catalysts were prepared by using a hydroxide obtained by adding an aqueous ammonia solution to an aqueous solution of titanium chloride, ferric nitrate, and tin chloride, and using the same manufacturing method as that of the platinum-supported catalyst of the example under other conditions. 0.4 g of the platinum-carrying catalyst and 0.2 g of the tungsten-carrying catalyst were mechanically mixed with a kneader equipped with a motor-driven stirring blade to obtain a catalyst b, a catalyst c, and a catalyst d.

As the platinum-supported silica, a hydroxide obtained by adding a nitric acid aqueous solution to silica was used, and other conditions were prepared in the same manner as in the platinum-supported catalyst of the example. Platinum-supported alumina was prepared by supporting platinum on gamma-type alumina by the same method as the platinum-supported catalyst of the example. 0.4 g of these platinum-supported catalysts and 0.2 g of tungsten-supported catalysts
Were mechanically mixed by a kneader equipped with a motor-driven stirring blade to obtain a catalyst e and a catalyst f.

[0020] (Comparative Example 2) zirconyl chloride (ZrOCl ₂ · 8
H ₂ O) Aqueous ammonia solution was added to the aqueous solution to adjust the pH to 8, and the resulting precipitate of zirconium hydroxide was collected, washed with water,
It was dried at 100 ° C. for 24 hours. This dried zirconium hydroxide is put into an aqueous solution of ammonium metatungstate, and the water is evaporated by an evaporator.
Dry at 0 ° C. for 3 hours. This dried tungsten oxide-supported zirconium hydroxide is placed in an aqueous solution of chloroplatinic acid hexahydrate, and the water is evaporated by an evaporator and dried.
By baking at 700 ° C. for 3 hours, zirconia carrying platinum-containing tungsten oxide (catalyst g) was obtained. The thus obtained catalyst had a tungsten concentration of 15 wt% and a platinum concentration of 1 wt%.

[0021] (Comparative Example 3) zirconyl chloride (ZrOCl ₂ · 8
H ₂ O) Aqueous ammonia solution was added to the aqueous solution to adjust the pH to 8, and the resulting precipitate of zirconium hydroxide was collected, washed with water,
It was dried at 100 ° C. for 24 hours. This dried zirconium hydroxide was put into an aqueous solution of chloroplatinic acid hexahydrate, the water content was evaporated by an evaporator, and further dried at 300 ° C. for 3 hours. The dried product was placed in an aqueous solution of ammonium metatungstate, the water was evaporated by an evaporator, and the product was further dried and calcined at 700 ° C. for 3 hours to obtain platinum-containing tungsten oxide-supported zirconia (catalyst h). The thus obtained catalyst had a tungsten concentration of 14.2 wt% and a platinum concentration of 0.52 wt%.

(Evaluation of catalytic activity) In the presence of the above catalyst, butane isomerization was carried out under the following conditions, and catalysts a to h were evaluated. The reaction was performed using a fixed bed catalyst pulse type reactor. The reaction was carried out at a temperature of 180 to 280 ° C., a helium gas flow rate of 20 ml / min, and a pulse size of 0.05 ml, and the product was analyzed by direct gas chromatography. The catalyst was dried at 300 ° C. for 1 hour before the reaction and used. As the value of the conversion, the average value of the sixth to tenth pulses obtained by performing the pulse experiment 10 times was used. Table 1 shows the results.

As can be seen from Table 1, in the isomerization of butane, the catalyst a, which is an embodiment of the present invention, is different from the other catalysts b to
It turns out that it has activity significantly higher than h.

[0024]

[Table 1]

FIG. 1 shows the conversion (%) of a catalyst prepared in the same manner as the catalyst a except that the tungsten concentration (relative to zirconium hydroxide) of the tungsten-supported catalyst was changed in the example. The weight of tungsten in the tungsten-supported catalyst is 5 to 30 wt%, particularly 10 to 20 wt%
%, A high conversion rate can be obtained.

FIG. 2 shows the conversion (%) of the catalyst prepared in the same manner as the catalyst a except that the calcination temperature of the tungsten-supported catalyst in the example was changed. Firing temperature 650-850
It is understood that a high conversion rate can be obtained at ℃, particularly at 670 to 800 ° C. In FIG. 2, when the weight of tungsten in the tungsten-supported catalyst is 5 wt%,
The case of 15 wt% is indicated by ●, and the case of 30 wt% is indicated by ○.

The calcination temperature of the platinum-supported catalyst was changed,
FIG. 3 shows the conversion (%) of the catalyst prepared in the same manner as in a. In FIG. 3, the case where 0.5 g of a platinum-supported catalyst containing 0.2 wt% of platinum is used is represented by Δ, the case where 0.2 g of a platinum-supported catalyst containing 0.5 wt% of platinum is used is represented by ●, and platinum is 1
The case of using 0.1 g of a platinum-supported catalyst containing wt% is indicated by ○. It can be seen that a high conversion rate can be obtained when the firing temperature is 650 to 800 ° C. The tungsten weight of each catalyst in FIG. 3 is constant.

FIG. 4 shows the conversion ratio (%) of the catalyst in which the weight of platinum contained in the whole catalyst was changed. In FIG. 4, 0.1 g, 0.2 g,
○ when 0.4g, 0.6g or 0.8g is used
As a result, a platinum-supported catalyst containing 1 wt% of platinum
g, 0.05 g, 0.1 g, 0.2 g, 0.4 g, or 0.8 g when using 0.1 g, 0.2 g, or 0.4 g of a platinum-supported catalyst containing 2 wt% platinum The case of performing is shown by ◎, respectively. In this case, the weight of platinum contained in the entire catalyst is equivalent between a catalyst using 0.4 g of a platinum-supported catalyst containing 0.5 wt% of platinum and a catalyst using 0.2 g of a platinum-supported catalyst containing 1 wt% of platinum.
A particularly high conversion is obtained when the platinum content of the platinum-supported catalyst is 0.5 wt%.

The conversion ratios (%) of the catalysts prepared in the same manner as the catalysts g and h except for changing the weight of platinum contained in the catalysts are also shown in FIG. It can be seen that a high conversion rate can be obtained when the weight of platinum in the platinum-supported catalyst is 0.2 to 1.5 wt%, particularly 0.3 to 1 wt%.

FIG. 5 shows the conversion (%) of each catalyst when the reaction temperature for isomerization was changed. When a catalyst equivalent to catalyst a was used except that 0.2 g of a tungsten-supported catalyst and 0.1 g of a platinum-supported catalyst containing 1 wt% of platinum were mixed, a reaction with 0.1 g of a platinum-supported catalyst containing 1 wt% of platinum was made with ○. Then, each catalyst was not mixed so as to react with 0.2 g of the tungsten-supported catalyst and reacted as a two-layer catalyst.
And a platinum-supported catalyst containing 1 wt% of platinum.
Each catalyst was not mixed so as to react with 1 g, and the reaction was performed as a two-layer catalyst. The case where the reaction was performed with only 0.2 g of the catalyst is indicated by ▲. In FIG. 5, the composition of the product according to each catalyst and reaction temperature indicated by A, B, C, D and E is shown in Table 2.

As is apparent from the results, the catalysts of the present invention which are mixed as a tungsten-supported catalyst and a platinum-supported catalyst are a catalyst in which tungsten and platinum are supported on the same carrier, or a tungsten-supported catalyst and a platinum-supported catalyst. Shows an activity superior to the case where is independently and sequentially reacted.

[0032]

[Table 2]

[0033]

The solid acid catalyst according to the present invention comprises: (a) a zirconium hydrate oxide and / or an oxide substantially containing no Group VIII metal and containing tungsten;
(b) a part containing zirconium hydrated oxide and / or oxide substantially containing no tungsten and containing a Group VIII metal, and a mixture thereof, and hydrocarbon such as hydrocarbon isomerization It has a high activity in the conversion reaction of, and is a very effective catalyst for acid catalyzed reactions such as hydrocarbon conversion reaction, carbon increase reaction, decomposition reaction, polymerization reaction, hydrogenation reaction and dehydrogenation reaction.

[Brief description of the drawings]

FIG. 1 is a graph showing the isomerization conversion rate (%) depending on the tungsten concentration of a tungsten-supported catalyst in Examples.

FIG. 2 is a graph showing the isomerization conversion rate (%) depending on the calcination temperature of a tungsten-supported catalyst in an example.

FIG. 3 is a diagram showing the isomerization conversion rate (%) depending on the calcination temperature of a platinum-supported catalyst in an example.

FIG. 4 is a graph showing the isomerization conversion (%) based on the weight of platinum contained in the entire catalyst in Examples.

FIG. 5 is a diagram showing conversion rates (%) of each catalyst when the reaction temperature of isomerization is changed.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI C07C 9/12 C07C 9/12

Claims (3)

[Claims] (1) a portion comprising a zirconium hydrate oxide and / or oxide substantially containing no Group VIII metal and containing tungsten; and (b) substantially containing no tungsten and containing a Group VIII metal. A solid acid catalyst comprising a part composed of a zirconium hydrated oxide and / or an oxide, and these parts are mixed. 2. Tungsten having a metal weight of 5 to 30
Weight%, and 0.1 to 5 in terms of metal weight
The solid acid catalyst according to claim 1, wherein the solid acid catalyst comprises 0.1% by weight. 3. Particles comprising (a) a zirconium hydrated oxide and / or oxide containing tungsten, and (b) VII.
A method for producing a solid acid catalyst in which particles composed of a zirconium hydrated oxide and / or an oxide containing a Group I metal are mechanically mixed.