JPH02268832A - Catalyst for alkylation reaction - Google Patents

Abstract

PURPOSE:To prolong the service life of a catalyst by supporting a group Ib, IIb or VIII metal of the periodic table on a carrier formed by thermally decomposing crystalline aluminosilicate and heteropolyacid. CONSTITUTION:Crystalline aluminosilicate and heteropolyacid (salt) are thermally decomposed to form a modified crystalline aluminosilicate carrier. Alumina powder is dipped in 5-10wt.% aq. soln. of a compd. of a group Ib, IIb or VIII metal of the periodic table, dried and calcined to form alumina supporting the metal. An alumina sol is added to the modified crystalline aluminosilicate carrier and the alumina supporting the metal and they are kneaded, molded, dried and calcined to produce a catalyst for an alkylation reaction.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to thermal decomposition products of heteropolyacid compounds selected from the group consisting of crystalline aluminosilicates, heteropolyacids and heteropolyacids, and The present invention relates to a catalyst for an alkylation reaction comprising gold selected from Group Ib, Group Ib, and Group I, and a method for producing the same. More specifically, the present invention relates to a catalyst having excellent performance in alkylation reactions, particularly in reactions with aromatic compounds and olefins, and a method for producing the same.

[Conventional technology]

Crystalline aluminosilicate is a porous substance known as zeolite (hereinafter, crystalline aluminosilicate may be referred to as zeolite), and many modification methods have been proposed to use it as a catalyst. A representative example of the prior art is a method of modification with a compound containing magnesium, phosphorus, and other elements (Japanese Patent Application Laid-Open No. 1986-
No. 27528), molybdenum, tungsten, etc.
These include a method of modifying with a group B metal (Japanese Patent Application Laid-Open No. 133032/1982), a method of modification with a heteropolyacid compound (Japanese Patent Application Laid-Open No. 14118/1982), and the like. However, these prior art techniques have various problems, particularly the relatively short catalyst life, which is a major problem when using zeolite as a catalyst. That is, although the modified zeolite catalyst has a high initial activity, coking causes a rapid decrease in activity.

Even with catalysts based on pentasil-type zeolites, which are said to have been improved, sufficiently satisfactory results have not been obtained. In addition, catalysts supported on metals such as platinum have been developed as a technology for extending life.

However, in the alkylation reaction of aromatic compounds with olefins carried out in the presence of hydrogen, hydrogenation of the olefins also occurs, which is a practical problem.

Zeolite is a very interesting material as a base for a catalyst for alkylation reactions, but as mentioned above, it has the drawback of short catalyst life, which is one of the most important factors in industrialization.

[Problem to be solved by the invention]

An object of the present invention is to provide a catalyst for alkylation reactions that has shape selectivity equivalent to that of conventional zeolite catalysts and has improved catalyst life, and a method for producing the same.

[Means to solve the problem]

The present inventors have carried out extensive studies in order to find a zeolite-based catalyst that is excellent in shape selectivity and catalyst life in the alkylation reaction of aromatic compounds with olefins. As a result, the inventors discovered that a catalyst composed of zeolite, a thermally decomposed product of a heteropolyacid compound, and a certain metal has excellent shape selectivity and catalyst life in alkylation reactions, and has arrived at the present invention.

That is, the present invention provides a thermal decomposition product of a heteropolyacid compound selected from the group consisting of crystalline aluminosilicates, heteropolyacids, and heteropolyacid salts, and
The present invention relates to a catalyst for alkylation reactions containing a metal selected from Groups IIb and I. Furthermore, the present invention relates to a method for producing the catalyst.

The zeolite used in the present invention is not particularly limited, and examples include synthetic zeolites such as X type, Y type, and pentasil type, and natural zeolites such as mordenite, chabasite, and erionite.

Products adjusted to various silica-alumina ratios depending on the purpose of use can also be used; for example, Sr 02/A 120
Those having 20 to 100 3 can also be used. Furthermore, in order for zeolite to act as a catalyst, acid sites must exist on the zeolite surface. Commercially available zeolites are in the sodium type, and in order to be used as catalysts, they must be converted into the proton type, and zeolites with various proton exchange rates can be used. There are various exchange methods, but for example, changing the zeolite to ammonium type with ammonium chloride,
After that, it can be made into a proton type by firing. When zeolite is used as a catalyst, it generally has a proton exchange rate of 50 to 100%. Moreover, those subjected to dealumination treatment can also be used.

The heteropolyacid compound used in the present invention is a heteropolyacid compound selected from the group consisting of heteropolyacids and heteropolyacid salts, and is a compound represented by the following format and its salt.

Hj! -X-Y,・Z 12-II” O<o・nfl
Jx: Hetero atom (P, Si, Ge, As) YSZ:
Poly atom (W%!JoSV) Specifically, H, PW, 20. ,,HnSIL20*o,
LPMo+zLo, )+4SIMO+20. . , )I
46eW+2040%)I4Ge! Jot 20
40, HsPVW, 0. o, HaSiVLlo+ 10
40 etc. and those (7)7:/monium salts, alkali metal salts, alkaline earth metal salts and the like.

Here, the alkali metal is Li%Na5KSRbS
Examples of alkaline earth metals include Cs and Fr.
Be,! , 1g5Ca, St, Ba.

An example is Ra. These heteropolyacid compounds are dissolved in a solvent inert to the heteropolyacid compounds and used for preparing a catalyst. Examples of suitable solvents include water, alcohol, etc., but from the viewpoint of industrial implementation, it is preferable to use water.

The metal used in the present invention is a metal selected from Group Ib, Group IIb, and Group 1 of the Periodic Table of the Elements. Chapter I
Examples of group b metals include Cu and ^gSAu.
Examples of group Ib metals include Zn and Cd5Hg, and examples of group 1 metals include Fe, Co, Ni, and Ru.

Examples include Rh, Pd, and 0sSIrSPt. Particularly preferred metals are Cu, Zn, Fe and L.

When preparing the catalyst, these metals are treated as nitrates, sulfates,
Examples of suitable solvents used as chlorides, acid chlorides, hydroxides, etc. and dissolved in solvents inert to these metal forms include water, alcohol, etc. From a practical standpoint, the use of water is preferable.

The catalyst of the present invention may contain a carrier in addition to the above-mentioned components to support a metal. Examples of the carrier include those commonly used as a carrier in catalyst preparation, such as alumina, silica, titania, and zeolite. It can be applied as is. Particular preference is given to using alumina, especially η-alumina.

Furthermore, the catalyst of the present invention can contain a binder for shaping, and common binders such as alumina sol, clay, etc. can be used as the binder.

The method for producing the catalyst of the present invention will be explained below.

The alkylation reaction catalyst of the present invention can be produced by the following method.

(a) A method of mixing, molding, and firing a crystalline aluminosilicate modified with a heteropolyacid compound and a metal supported on a carrier; (b) A method of mixing a crystalline aluminosilicate and a metal supported on a supporter, and then forming a heteropolyacid compound. and (c) a method in which crystalline aluminosilicate is modified with a heteropolyacid compound, fired, and then a metal is supported, molded, and fired.

In producing the catalyst of the present invention, the heteropolyacid compound acts as a modifier for crystalline aluminosilicate as described above.

The method (a) will be specifically explained below.

Proton-exchanged pentasil type zeolite is added to a heteropolyacid aqueous solution prepared at 10 to 50 wt%, and heated to 10 to 90°C, preferably 20 to 60°C, with gentle stirring.
Soak for 5-30 hours. After soaking for a specified time, the zeolite is filtered, dried at 80-150°C, and then heated at 350-150°C in the presence of oxygen, usually air.
2-2 at 700°C, preferably 400-650°C
Bake for 0 hours. In this way, a modified zeolite modified with a thermal decomposition product (oxide) of a heteropolyacid compound is prepared. Thermal decomposition products of heteropolyacid compounds are metal oxides, and vary depending on the heteropolyacid and salt.
WL,! It is thought that it is JOO3, 8102, etc.

The amount of the modifier, ie, the heteropolyacid, for the zeolite can be selected arbitrarily, but is usually 5 to 30 wt%, preferably 15 to 25 wt%. Moreover, this modification treatment may be repeated several times.

On the other hand, groups Ib, IIb and 1 of the periodic table of elements
Alumina powder is added to a 5 to 10 wt % aqueous solution of a metal selected from the group, and is immersed, dried, and calcined under the same conditions as the zeolite described above to produce metal-supported alumina. The amount of metal supported on alumina is usually about 0.1 to 30 wt%.

Next, 5 to 30 wt% aqueous alumina sol solution is added as a binder to the modified zeolite and metal-supported alumina prepared as described above. The modified zeolite:metal-supported alumina ratio is 70-95:30-5, and the modified zeolite/metal-supported alumina:alumina sol aqueous solution ratio is 70-95.
:30-5 is appropriate. After thorough kneading, the catalyst of the present invention is obtained by molding, drying and calcining under the same conditions as in the case of modifying zeolite.

In the method (b), metal-supported alumina obtained by the same method as the method (a) and crystalline aluminosilicate are thoroughly kneaded. The resulting kneaded product is then modified with a heteropolyacid compound in the same manner as in method (a). The catalyst of the present invention can be obtained by molding, drying, and calcining the obtained modified zeolite in the same manner as in method (a).

Furthermore, in method (c), a modified zeolite is obtained in the same manner as in method (a), and a metal is supported on the modified zeolite in the same manner as in method (a), except that the modified zeolite is used as a carrier. The catalyst of the present invention can be obtained by molding the obtained metal-supported modified zeolite, drying it, and calcining it.

The catalyst of the present invention is used as a catalyst for the alkylation reaction of aromatic compounds with olefins. Examples of the olefin include ethylene, propylene and butene-1, preferably ethylene and propylene, and examples of the aromatic compound include benzene, toluene, ethylbenzene and isopropylbenzene, preferably toluene and benzene.

Various reaction formats can be employed for the reaction, but industrially it is convenient to use a continuous flow reactor equipped with a fixed bed reactor. -If the reaction conditions are as specified by boat, the reaction temperature is 300 to 500℃, and the reaction pressure is normal pressure to 50 kg/c.
tl, weight time space velocity is 1 to 100 h-'.

〔Effect of the invention〕

The catalyst for an alkylation reaction containing a zeolite, a thermal decomposition product of a heteropolyacid compound, and a metal selected from Group Ib, Group IIb, and Group IV of the Periodic Table of the Elements according to the present invention is prepared by a conventional method. Since the accumulation of carbonaceous matter on the catalyst surface is suppressed compared to a catalyst that has been used for a long time, the life of the catalyst can be improved during long-term use. Furthermore, since high yields can be maintained over a long period of time, it is an extremely advantageous catalyst for industrial use.

〔Example〕 The present invention will be explained in more detail with reference to Examples below.

Example 1 100g of pentasil-type zeolite (sodium type with a silica/alumina ratio of 50) was mixed with 0. The mixture was added to a 1,000 ml of IN aqueous ammonium chloride solution and ion-exchanged at 95°C for 6 hours. The zeolite was filtered out, dried at 110°C for 16 hours, and then calcined at 520°C for 5 hours in an air atmosphere. As a result of analyzing sodium in the zeolite by atomic absorption spectrophotometry, the proton exchange rate was 58%. Next, 50 g of proton-exchanged zeolite was added to 150 ml of a 3Qwt% aqueous solution of 12 tungstosilicic acid, and immersed for 16 hours at room temperature with gentle stirring. After filtration, it was dried at 110°C for 12 hours, and then calcined at 610°C for 5 hours in an air atmosphere to obtain a modified zeolite. From the analysis results of 12 tungstosilicic acid before and after soaking, the ratio of modifier to zeolite was 15.3vt.
%Met.

Separately from zeolite, 50g of η-alumina powder was added as metallic copper to a 7wt% copper acetate aqueous solution, and 6% was added at room temperature.
Soaked for an hour. After filtration, it was dried at 110°C for 16 hours, and then calcined in an air atmosphere at 520°C for 5 hours to obtain copper-supported η-alumina. As a result of analysis, the amount of copper supported was 19 wt%.

Next, a 10 wt % alumina sol aqueous solution was prepared as a binder, and the modified zeolite, copper-supported l-alumina, and alumina sol aqueous solution were mixed in a weight ratio of 70:15:15. After kneading, the mixture was molded into a pellet shape with approximately two diameters and a length of 4 mm. After drying at 110° C. for 16 hours, it was fired at 520° C. for 5 hours in a stream of air, and further fired at 520° C. for 16 hours in an electric Matsufuru furnace. After pulverization, a portion with a particle size of 20-42 mesh was sieved and used as a catalyst in the alkylation reaction of toluene with ethylene.

The reaction was carried out using the above catalyst 2.0 in a continuous flow reactor having reaction tubes with an inner diameter of 10 and a length of 100 tubes. The reaction temperature was 400°C and the reaction pressure was 10 kg/crl. The weight hourly space velocity was 30 h-', and toluene, ethylene and hydrogen were fed in a molar ratio of 8:1:3. The reaction results are shown in Table 1.

Example 2 The zeolite prepared in Example 1 with a proton exchange rate of 58% was treated under the same conditions as in Example 1 except that 12-tungstophosphoric acid was used instead of 12-tungstosilicic acid to obtain a modified zeolite. From the analysis results of 12-tungstophosphoric acid before and after soaking, the ratio of modifier to zeolite was 16.
It was 5wt%.

Separately, zinc was supported on the eta-alumina used in Example 1 in the same manner and under the same conditions as in Example 1, except that zinc acetate was used instead of acetic acid steel, to obtain zinc-supported eta-alumina. As a result of the analysis, the amount of zinc supported was 21 wt%.

Next, the modified zeolite, zinc-supported η-alumina, and the alumina sol aqueous solution used in Example 1 were mixed in a weight ratio of 70:
The mixture was mixed at 15:15, and dried and fired under the same conditions as in the example. After pulverization, the part with a particle size of 20-42 mesh was sieved and used as a catalyst for the alkylation reaction of toluene with ethylene. The reaction was carried out using the same reaction apparatus as in Example 1 and under the same conditions as in Example 1. Ta. The reaction results are shown in Table 1.

Comparative Example 1 The modified zeolite modified with 12-tungstosilicic acid of Example 1 and the alumina sol aqueous solution used in Example 1 were mixed at a weight ratio of 70:30, and dried and fired under the same conditions as Example 1. After pulverization, a portion with a particle size of 20-42 mesh was sieved and used as a catalyst in the alkylation reaction of toluene with ethylene.

The reaction was carried out using the same reactor as in Example 1.
It was carried out under the same conditions. The reaction results are shown in Table 1.

Comparative Example 2 The modified zeolite modified with IJ acid and the alumina sol aqueous solution used in Example 1 were mixed at a weight ratio of 70:30, and dried and calcined under the same conditions as Example 1. Ta. After pulverization, a portion with a particle size of 20-42 mesh was sieved and used as a catalyst in the alkylation reaction of toluene with ethylene.

The reaction was carried out using the same reactor as in Example 1.
It was carried out under the same conditions. The reaction results are shown in Table 1.

Example 3 Example 1 except that zeolite with a proton exchange rate of 58% prepared in Example 1 and nickel acetate were used instead of copper acetate.
After mixing nickel-supported η-alumina prepared in the same manner and under the same conditions as 4.6:1 with nickel-supported IL (20 wt%), it was modified with 12-tungstosilicic acid in the same manner as in Example 1, dried, and fired.

From the analysis results of 12 tungstosilicic acid before and after soaking, the ratio of the modifier to the mixture of zeolite and η-alumina was 5.6 wt% I.

Next, the modified nickel-supported l-alumina-containing zeolite and the alumina sol aqueous solution used in Example 1 were mixed at a weight ratio of 85:15, and dried and fired under the same conditions as in Example 1. After pulverization, a portion with a particle size of 20-42 mesh was sieved and used as a catalyst in the alkylation reaction of toluene with ethylene.

The reaction was carried out using the same reactor as in Example 1.
It was carried out under the same conditions. The reaction results are shown in Table 2.

Comparative Example 3 One zeolite with a proton exchange rate of 58% prepared in Example 1 was added without adding the nickel-supported η-alumina of Example 3.
Modified in the same manner as in Example 3 using 2-tungstosilicic acid,
Drying and firing were performed. From the analysis results before and after the modification treatment, the actual amount of the modification agent used was 16.1 wt%. next,
The alumina sol aqueous solution used in Example 1 was 85 in weight/liter ratio.
:15 and dried and baked under the same conditions as in Example 1.

After pulverization, a portion with a particle size of 20-42 mesh was sieved and used as a catalyst in the alkylation reaction of toluene with ethylene.

The reaction was carried out using the same reactor as in Example 1.
It was carried out under the same conditions. The reaction results are shown in Table 2.

Example 4 Zeolite prepared in Example 1 with a proton exchange rate of 58%)
10 (] g and 20 g of η-alumina used in Example 1 were added to 300 ml of an aqueous solution of 30 wt% 12-tungstophosphoric acid.
for 16 hours at room temperature. Drying and firing were performed under the same conditions as in Example 1. From the analysis results of 12-tungstophosphoric acid before and after soaking, the ratio of the modifier that substantially acted on the zeolite and η-alumina was 16.8 wt%.

Next, a mixture of modified zeolite and η-alumina
Citric acid M (II
I) Immersed in 200 g of ammonium aqueous solution at room temperature for 6 hours. After filtration, it was dried at 110°C for 16 hours, and then calcined at 520°C for 5 hours in an air atmosphere. As a result of the analysis, the amount of iron supported on the mixture of modified zeolite and η-alumina was 17 wt%.

The mixture of iron-supported zeolite and η-alumina prepared as described above and the alumina sol aqueous solution used in Example 1 were mixed at a weight ratio of 85:15 and molded.
Dry at ℃ for 16 hours, bake at 520℃ for 5 hours in an air stream,
Further, it was fired in an electric Matsufuru furnace at 520°C for 16 hours.

After pulverization, a portion with a particle size of 20-42 mesh was sieved and used as a catalyst in the alkylation reaction of toluene with ethylene.

The reaction was carried out using the same reactor as in Example 1.
It was carried out under the same conditions. The reaction results are shown in Table 3.

Comparative Example 4 Modification, drying, calcination, molding, etc. were carried out under the same conditions as in Example 4 without performing the treatment with the iron(III) ammonium citrate aqueous solution of Example 4, and the alkylation reaction of toluene with ethylene was performed. It was used as a catalyst.

The reaction was carried out using the same reactor as in Example 1.
It was carried out under the same conditions. The reaction results are shown in Table 3.

Claims (1)

[Claims] Thermal decomposition products of heteropolyacid compounds selected from the group consisting of crystalline aluminosilicates, heteropolyacids and heteropolyacid salts, and alkyl containing metals selected from Group Ib, Group IIb and Group VIII of the Periodic Table of the Elements. Catalyst for chemical reaction.