JPS6168137A - Manufacture of solid acid catalyst - Google Patents

Abstract

PURPOSE:To manufacture a catalyst exhibiting catalytic activity in the skeletal isomerization of hydrocarbons by treating the hydroxide or oxide of a group IV metal carrying a group VIII metal and/or the hydroxide or oxide of a group III metal with sulfuric acid, etc., and calcining the material. CONSTITUTION:The hydroxide or oxide of a group IV metal carrying 0.01-10wt% group VIII metal and/or the hydroxide or oxide of a group III metal are pretreated at 50-550 deg.C, then treated with a treating agent contg. a sulfate radical, and calcined and stabilized at 450-800 deg.C. The solid acid catalyst thus obtained has excellent stability of activity, and exhibits catalytic activity in the skeletal isomerization of hydrocarbons, alkylation, aromatization, polymerization, decomposition, and synthesis of gasoline fractions from methanol-synthesis gas. Accordingly, useful products can be obtained selectively by using said catalyst.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a method for producing a solid acid catalyst, in particular a method for producing a solid acid catalyst, in particular a method for producing a solid acid catalyst,
The present invention relates to a method for producing a solid acid catalyst supported on a hydroxide or oxide of a group (1) metal and/or a hydroxide or oxide of a group (1) metal.

[Prior art and its problems]

Reactions in petroleum refining and petrochemical industries include catalytic cracking, catalytic reforming, hydrodesulfurization, isomerization, alkylation of aliphatic hydrocarbons and aromatic hydrocarbons, and polymerization. An overview of the catalyst recognizes that the acidity of the catalyst is one of the important factors for reaction activity. Furthermore, those skilled in the art are well aware that solid acid catalysts represented by metal silicates play an important role in the field of so-called 01 chemistry, which uses methanol, synthesis gas, etc. as raw materials, and has been actively researched and developed in recent years. By the way.

Generally, it is thought that there is an optimal value for the solid acid strength required for a certain reaction, but 100% is defined as a super strong acid.
By using an acid stronger than sulfuric acid (Super Strong Acids/Super Strong Bases, co-authored by Kozo Tabe and Ryoji Noyori, Kodansha Scientific (1980)), the skeletal isomerization reaction of paraffins at low temperatures, which is advantageous for chemical equilibrium, is possible. It is known that the solid superacids produced by conventional techniques produce a large amount of by-products, mainly decomposition products, in addition to the desired products, and that carbonaceous matter is produced as a secondary product. There are problems such as poisoning of the active sites due to oxidation, shortening the life of the catalyst, making it unsuitable for practical use, etc. Therefore, the activity of the catalyst can only be evaluated by using a closed circulation system reaction test device, etc., to increase the efficiency by increasing the contact time extremely long. The current situation was that

[Structure of the invention]

The present invention is characterized by the following method:
A solid acid catalyst characterized in that a hydroxide or oxide of a group metal and/or a hydroxide or oxide of a group metal is treated with a treatment agent containing a sulfate group, and then stabilized by calcination. This is the manufacturing method.

As a result of intensive studies to solve the problems of the prior art, the inventors discovered a solid strong acid catalyst with excellent catalyst life, established a method for producing the same, and arrived at the present invention.

That is, a hydroxide or oxide of a group III metal supporting a group III metal and/or a hydroxide or oxide of a group III metal is treated with a treatment agent containing a sulfate group, and then stabilized by firing. The solid acid catalyst obtained by this method has excellent stability and is suitable for reactions such as skeletal isomerization of linear paraffins, production of gasoline fraction from methanol, alkylation of paraffins and aromatics, and polymerization and decomposition of paraffins and olefins. It was found that it exhibits catalytic activity. Here, group III metals refer to metals such as platinum, nickel, iron, cobalt, palladium, etc., or their compounds, and these can be introduced onto the carrier by ordinary impregnation methods, ion exchange methods, etc. It is possible. The carrier used may be a hydroxide or oxide of a group III metal, and/or a hydroxide or oxide of a group III metal; specific examples include titanium, zirconium, nickel, thorium, silica, and germanium. A metal hydroxide or metal oxide containing at least one of tin, aluminum, gallium, and indium can be used. According to the present invention, a solid strong acid catalyst can be prepared by supporting these metals on a carrier, treating the carrier with a treatment agent containing a sulfate group, and then stabilizing by firing. As a treatment agent containing a sulfate group to be used in this case, sulfuric acid of α01 to 1ON, preferably 0.1 to 5N, ammonium sulfate of 0.1 to 10 molar concentration, etc. are used in an amount of 1 to 10 times the weight of the catalyst. In addition, the same effect can be achieved by using a processing agent that generates sulfate radicals during the firing process, such as hydrogen sulfide or sulfur dioxide gas.

The catalyst obtained in the present invention is a new catalyst.

The catalyst produced according to the present invention exhibits excellent catalytic performance under hydrogen flow. In other words, it is considered that the group (III) metal acts as a center of active hydrogen supply to the solid strong acid site formed by the sulfate radical and the surface of the metal oxide. Surprisingly, it has been found that group (1) metals are effective in improving the catalyst life and suppressing undesirable side reactions without any particular operation such as reduction after introduction. Group metals, for example platinum, can be supported in the form of an aqueous solution of chloroplatinic acid, tetraammineplatinum complex, etc., but after being supported, treatment with a sulfate group-containing treatment agent (previous drying treatment alone is enough to achieve sufficient catalytic performance) demonstrate. In addition, after supporting the group metal, 50 to 550℃
Air calcination may be performed preferably at a temperature of 100 to 400°C for 1 to 24 hours, but according to the present invention, after treatment with a sulfate group-containing treatment agent, the temperature is 450 to 800°C, preferably 500 to 650°C. It is necessary to carry out a firing stabilization treatment in an oxidizing atmosphere for 05 to 10 hours. If the calcination stabilization treatment is performed in a reducing atmosphere, the catalytic activity will be significantly reduced due to changes in the bonding state of sulfate groups or reductive decomposition, which is undesirable.

The invention also relates to a process for the catalytic conversion of hydrocarbons in the presence of hydrogen, wherein the catalyst used is a solid acid catalyst prepared in the process. In other words, by using this catalyst, reactions commonly known as acid-catalyzed reactions such as hydrocarbon skeletal isomerization, alkylation, aromatization, polymerization, decomposition, and synthesis of gasoline fraction from methanol/synthesis gas can be performed. Useful products can be selectively obtained using the catalyst according to the invention.

Taking the skeletal isomerization reaction of hydrocarbons as an example, feedstock oil with an octane number of 60 to 70 containing about 50 to 80% of linear paraffins, known as a light naphtha fraction, is reacted with 70 to 70 octane in the presence of this catalyst.
Temperature ~250°C, pressure 1-50 bar, α5-10
With a liquid hourly space velocity of 1 to 10 hr, and a molar ratio of hydrogen to raw material supplied of 1 to 10, a product oil useful as a gasoline fraction having an octane number of 80 to 90 can be selectively obtained catalytically.

The present invention will be explained in more detail by the following examples.

Example 1 Commercially available zirconium oxychloride (Kanto Kagakuten) 900f was dissolved in pure water 7009, and an appropriate amount of ammonia water was added.
H was brought to 10 to form a precipitate. This precipitate was aged day and night, filtered, washed and dried to obtain Zr(OH)4 white powder 5001. This white powder was impregnated in an aqueous solution of chloroplatinic acid (concentration such that the amount was 0.5 parts by weight in terms of platinum metal per 100 parts by weight of the carrier).
After drying at 650° C. for a day and night, this powder was introduced into 1N sulfuric acid 650, and after filtering off excess sulfuric acid, it was calcined at 600° C. for 3 hours to obtain catalyst A. Table 1 shows the results of measuring solid acid strength by titration using a NO-MET indicator in a benzene solvent.

Example 2 Zr(OR) prepared in the same manner as in Example 1.

The powder was impregnated with a palladium chloride aqueous solution, a nickel nitrate aqueous solution, a ferric nitrate aqueous solution, a nitrate aqueous solution, a ruthenium chloride aqueous solution, and a rhodium chloride aqueous solution, and was treated with sulfuric acid in the same manner as in Example 1 to obtain catalyst B. OXD,E
, obtained FXG. Table 1 shows the results of measuring the solid acid strength by titration using a Hammett indicator in a benzene solvent.

Comparative example 1 Zr(OH) prepared in the same manner as in Example 1.

The powder was impregnated in an aqueous solution of chloroplatinic acid (at a concentration of 0.5 parts by weight in terms of platinum metal per 1-100 parts by weight of the carrier type), dried at 110°C, and then calcined at 600°C for 3 hours. This was designated as Catalyst E. Table 1 shows the results of measuring solid acid strength by titration using a NO-MET indicator in a benzene solvent.

Comparative example 2 zr(on) prepared in the same manner as in Example 1.

The powder was dried at 110°C, introduced into 1N sulfuric acid, filtered to remove excess sulfuric acid, dried at 110°C, and then calcined at 600°C for 5 hours to obtain a catalyst. Table 1 shows the results of measuring the solid acid strength by titration using a Hammett indicator in a benzene solvent.

Example 5 Soot of titanium tetrachloride (manufactured by Wako Tsumugi Co., Ltd.) was soaked in pure water at 800 f.
K was dissolved, the pH was adjusted to produce a precipitate, and the mixture was aged, filtered, and dried to obtain 150f of white powder of τ1 (OH). This powder was impregnated in an aqueous solution of chloroplatinic acid (concentration such that n, s parts by weight in terms of platinum metal per 100 parts by weight of the carrier) was dried at 110°C, and then a 1 molar ammonium sulfate aqueous solution was added. After introducing into 500ca and filtering the excess ammonium sulfate aqueous solution, drying at 110℃.
Catalyst J was obtained by firing at 00°C for 3 hours. Table 2 shows the results of measuring solid acid strength by titration using a Hammett indicator in Pe/Zen solvent.

Example 4 Aluminum nitrate (Wako Tsumugi Co., Ltd.) 701] IF was mixed with pure water 9
Dissolved in 50 tons of water, adjusted the pH to produce a precipitate, aged, filtered, and dried to obtain 220 tons of white powder of MuZ (Oa).
I got it. This powder was mixed with a chloroplatinic acid aqueous solution (carrier weight 10
After drying at 110°C, the mixture was introduced into 500 ac of a 2 molar ammonium sulfate aqueous solution to remove excess ammonium sulfate aqueous solution. After filtering, it was dried at 110°C and then calcined at 600°C for 3 hours to obtain a catalyst. Table 2 shows the solid acid strength measurement results by titration using a Hammett indicator in benzene solvent.

Example 5 81(
OE[), -Zr(OH), 8n(OH).

--A/(OH)m powder was obtained. These powders were impregnated in an aqueous solution of chloroplatinic acid (concentration such that Q, calculated as platinum gold fiK, was 5 parts by weight per 100 parts by weight of the carrier), dried at 110°C, and then diluted with ammonium sulfate at a 2 molar concentration. The mixture was introduced into an aqueous solution, and after filtering off the excess ammonium sulfate aqueous solution, it was calcined at 600° C. for 3 hours to form a catalyst. Table 2 shows the solid acid strength measurement results by titration using a Hammett indicator in benzene solvent.

Example 6 (skeletal isomerization reaction of linear paraffins) Catalyst A prepared by the method of Example 1 was used at a concentration of 0.59 to 1. OO,
The hydroisomerization reaction of n-pentane was carried out in a high-pressure flow reactor having a length of 2200 mm and an inner diameter of 1 mm.

The reaction conditions for the hydroisomerization reaction are as follows.

Temperature: 200°C Total pressure: 10 bar Hydrogen/n-be/tan molar ratio 2 5/1 mo//no
/liquid hourly space velocity: 1.5 tlI #-n 4-1 catalyst/hour Table 3 shows the results of continuous gas chromatography analysis of the gas composition at the outlet of the reaction tube.

Comparative Example 5 A hydroisomerization reaction was carried out in the same manner as in Example 5 using Catalyst H and Catalyst. The results are shown in Table 3.

Table 3 shows that the melting medium prepared according to the present invention showed activity in the skeletal isomerization of n-pentane even after a reaction time of 16 hours, indicating that it is a catalyst with high activity and excellent catalyst life. It can be seen that the presence of group II metals and sulfate groups has a significant effect.

Claims (1)

[Claims] 1. A hydroxide or oxide of a group IV metal supporting 0.01 to 10% by weight of a group VIII metal, and/or a hydroxide or oxide of a group III metal containing a sulfate group. 1. A method for producing a solid acid catalyst, which comprises treating it with a treating agent, and then stabilizing it by firing. 2. The method for producing a catalyst according to claim 1, wherein the Group VIII metal is at least one metal selected from nickel, platinum, iron, cobalt, ruthenium, rhodium, palladium, osmium, and iridium or a compound thereof. . 3. Claim 1, wherein the hydroxide or oxide of a group IV metal is a hydroxide or oxide of at least one metal selected from titanium, zirconium, hafnium, thorium, silica, germanium, and tin. term or second
2. Method for producing the catalyst described in Section 1. 4.Claims 1 and 2, wherein the hydroxide or oxide of the Group III metal is a hydroxide or oxide of at least one metal selected from aluminum, gallium, indium, and thallium. A method for producing a catalyst according to item 1 or 3. 5. Claim 1 in which the sulfuric acid radical-containing treatment agent is sulfuric acid
2. A method for producing a catalyst according to item 2, item 3, or item 4. 6. The method for producing a catalyst according to claim 1, 2, 3, or 4, wherein the sulfate group-containing treatment agent is ammonium sulfate. 7. 50-55 before treatment with sulfate root-containing treatment agent
The method for producing a catalyst according to any one of claims 1 to 6, wherein the pretreatment is performed at a temperature of 0°C. 8. A method for producing a catalyst according to any one of claims 1 to 7, wherein the calcination stabilization is carried out at a temperature of 450 to 800°C.