JPS61153140A - Production of solid acid catalyst - Google Patents

Abstract

PURPOSE:To enhance the catalytic activity and to prolong the life time of a catalyst by treating the hydroxides and oxides of group IV metals and/or the hydroxides and oxides of group III metals with a treating agent contg. a sulfate group, and then by supporting a specified amt. of group VIII metals. CONSTITUTION:The hydroxides and oxides of group IV metals and/or the hydroxides and oxides of group III metals are treated with the treating agent contg. a sulfate group. Then, 0.01-10wt% group VIII metals is supported on this treated substance to form a solid acid catalyst. Group VIII metals include nickel, platinum, iron, cobalt, ruthenium, rhodium, palladium, osmium and iridium. Group IV metals include titanium, zirconium, hafnium, silicon, germanium and tin. Group III metals include aluminum, gallium, indium and thallium.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to 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, in which a group m
The present invention relates to a method for producing a solid acid catalyst supported on a group metal hydroxide or oxide.

[Prior art and its problems]

Reactions in the petroleum refining and petrochemical industries include catalytic cracking, catalytic reforming, hydrodesulfurization, isomerization, aliphatic hydrocarbon processing, aromatic hydrocarbon alkylation, and polymerization. An overview of the catalysts used in this study indicates that the acidic nature of the catalyst is one of the important factors for the reaction activity. In addition, so-called C1.
Those skilled in the art are well aware that solid acid catalysts represented by metal silicates play an important role in the field of chemistry as well.

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.
Sulfur FF Engineering 9 Strong Acids (Super Strong Acids/Super Strong Bases, co-authored by Kozo Tabe and Ryoji Noyori, Kodansha Scientific (1980>)
? It is known that by using this method, the skeletal isomerization reaction of paraffins at low temperatures, which is advantageous in terms of chemical equilibrium, proceeds even at room temperature. However, with conventional solid super strong acids, in addition to the desired products, by-products mainly consisting of decomposition products are generated, and the active sites are poisoned by secondary carbonaceous substances, etc. There are problems such as a short lifespan that makes it unsuitable for practical use, and currently the catalyst activity is only evaluated by using a closed-circulation reaction test device, etc., and increasing the contact time by 9 y$. Ta.

[Structure of the invention]

The present invention provides a hydroxide or oxide of a group metal, and/or
Alternatively, the hydroxide or oxide of group m metal is treated with a treatment agent containing a sulfate group, and then 1LO1~10wt-V
This is a method for producing a solid acid catalyst characterized by supporting a group I metal.

The inventors conducted extensive studies to solve the problems of the prior art, and as a result, discovered a solid strong acid catalyst with excellent catalyst life, established its manufacturability, and arrived at the present invention.

That is, a solid acid obtained by treating a hydroxide or oxide of a group II metal and/or a hydroxide or oxide of a group M metal with a treatment agent containing a sulfate group, and then supporting a Vm group metal. The catalyst has excellent stability and is suitable for skeletal isomerization of straight-chain paraffins, production of gasoline fraction from methanol, alkylation of paraffins and aromatics, paraffins and
It was discovered that it exhibits catalytic activity in reactions such as polymerization and decomposition of olefins. Here, ■M group metals refer to metals such as platinum, nickel, iron, cobalt, palladium, etc., or their compounds, and these are introduced onto the carrier by ordinary impregnation methods, ion exchange methods, etc. It is possible to do so. The carrier used is a hydroxide or oxide of group metal,
It is a hydroxide or oxide of an M-group metal, such as ffin, zirconium,
The following treatment agents can be used for all treatments, including nickel, thorium, silica, germanium, tin, and aluminum.

The treatment agent containing the sulfate group mentioned here is usually (L
Ol ~1ON preferably cL1~5N sulfuric acid, (L1
~10 molar concentration of ammonium sulfate, etc. is used in an amount 50 times the catalyst weight (1), but in addition, processing agents that generate sulfate radicals during the calcination treatment, such as hydrogen sulfide, sulfur dioxide gas, etc. It is possible to achieve the same effect by using

When supporting group VI metal gold on a carrier that has been treated with a sulfate group-containing treatment agent, the carrier may be used as is or with 50 to 6
Although it is possible to use a method that performs the firing treatment at a temperature of 00°C, after supporting the Vl group metal, the firing treatment is performed at a temperature of 450 to 800°C.
Preferably α5~ in an oxidizing atmosphere at 500~650℃
It is necessary to stabilize the firing for 10 hours.

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

The catalyst prepared according to the present invention exhibits excellent catalytic performance under hydrogen flow. That is, it is considered that the group VI metal acts as a center of active hydrogen supply to the solid strong acid site formed by the sulfate radical and the metal oxide surface. Surprisingly, it has been found that group Vl metals are effective in improving catalyst life and suppressing undesirable side reactions without any particular reduction or other operations after introduction.

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, the use of this catalyst can be used in reactions known as acid-catalyzed reactions such as skeletal isomerization, alkylation, aromatization, polymerization, public accounting of F hydrocarbons, and the synthesis of gasoline fractions from methanol and synthesis gas. Useful products can be selectively obtained using the catalyst according to the invention.

In all examples of skeletal isomerization reactions of hydrocarbons, feedstock oil with an octane number of 60 to 70 containing about 50 to 80% of straight chain paraffins, known as the light soot fraction, is heated to 70% in the presence of this catalyst.
Temperature ~250°C, pressure 1-50 bar, 1lL5
A product oil useful as a gasoline fraction with an octane number of 80S9G can be selectively obtained catalytically at a liquid hourly space velocity of ~10 hr'''! and a molar ratio of hydrogen to raw material supplied of 1 to 10.

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

Example 1 Commercially available zirconium oxychloride 900fff pure water yoai
A suitable amount of aqueous ammonia was added to make put-10, and a precipitate was produced. This precipitate was aged for a day and night, filtered, washed, and dried to obtain a white powder of Zr (OH) a.
00 f'i Tokuji. After drying this white powder at 110°C for a day and night, 650% of 1N sulfuric acid was introduced into it, and an excess of 1 t of sulfuric acid was added.After cooling, the powder was dried at 110°C for a day and night.
The mixture was calcined at 0° C. for 5 hours and the carrier B t-191 was developed.

Supports A and B were each impregnated in a gold chloride platinic acid aqueous solution (concentration such that cL5 parts by weight in terms of platinum metal per 100 weight of the carrier) and dried at 110°C overnight.
Catalyst 1.2 was prepared by calcining at ℃ for 3 hours. Table 1 shows the results of solid acid strength measurements by water titration using a No. 1 knot indicator in a benzene solvent.

Example 2 The carrier Ai of Example 1 was impregnated in a palladium chloride aqueous solution, a rhodium chloride aqueous solution, and a ruthenium chloride aqueous solution, and heated at 110°C.
After drying for a day and night, the mixture was calcined at 600° C. for 5 hours to prepare catalysts 5 and 4.5 in which palladium, tetradium, and ruthenium were each supported on 100 parts by weight of the carrier (15 parts by weight).

Mayu carrier At? It was impregnated in an aqueous ferric nitrate solution, a cobalt nitrate aqueous solution, and a nickel nitrate aqueous solution, dried at 110°C for a day and night, and then fired at 600°C for 3 hours. 6.7.8 tl of supported catalyst was prepared. Table 1 shows the results of measuring the solid acid strength by titration using a Hammett indicator in a benzene solvent.

Comparative Example 1 vI4 was manufactured using the same method as in Example 1 and 721. Zr(O
H) 4 powder was impregnated in a chloroplatinic acid aqueous solution (concentration equivalent to 5 parts by weight of platinum metal based on 100 parts by weight of the carrier), dried at 110°C, and then calcined at 600°C for 3 hours. This was designated as Catalyst 9. Table 1 shows the results of measuring the solid acid strength by a titration method using a Hammett indicator in a benzene solvent.

Comparative Example 2 72-Zr(OH
) 4 powder was dried at t-110°C, introduced into 1N sulfuric acid, filtered off excess sulfuric acid, dried at 110°C, and calcined at 600°C for 3 hours to obtain catalyst 10. First, the results of solid acid strength measurement using a Hammett indicator in a benzene solvent were determined by a titration method.
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~〈-1 Example 3, Titanium tetrachloride (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) 500 f'i pure water 80
Dissolve 0fVC, adjust the pH to 111ml to produce a precipitate, age, filter, and dry to obtain a white powder of 1(OH)a.
0fi profit. This powder was introduced into 500 ac of an ammonium sulfate aqueous solution having a molar concentration of t-1, and after filtration and drying over an excess ammonium sulfate aqueous solution, a chloroplatinic acid aqueous solution (carrier weight 1
00 parts by weight, impregnated in λ at a concentration of 15 parts by weight in terms of platinum metal, dried at 110°C,
After baking for 3 hours, the catalyst was heated to 11'tv14m. Solid strength measurement results by titration using a Hammett indicator in benzene solvent are shown in t-g2.

Example 4 Aluminum nitrate (Wako Tsumugi Yakug) 700ft-H water 95
0 fVCffl-solve, pH! A precipitate was produced by aging, filtering, and drying to obtain 220 tons of white powder of t(OH)s. After filtering and drying the aqueous solution, chloroplatinic acid aqueous solution (converted to platinum metal per 100 parts by weight of the carrier)
12 tons of catalyst was prepared by impregnating the catalyst in a solution (concentration such that the concentration was 100% by weight), drying at 110°C, and calcining at 600°C for 3 hours.Results of solid strength measurement by titration method using a Hammett indicator in benzene solvent. are shown in Table 2.

Example 5 Co-precipitation method using water glass (manufactured by Wako Tsumugi), zirconium oxychloride (Kanto Kagaku jI!!), stannous chloride (manufactured by Wako Tsumugi), and aluminum nitrate (manufactured by Wako Tsumugi) 81 (OH), -Zr (OH), 8n (0111)
! -Mul(OH)m powder was obtained. These powders were introduced into a 2 molar ammonium sulfate aqueous solution, and the excess ammonium sulfate aqueous solution was filtered and dried.
(parts by weight), dried at 110°C and calcined at 600°C for 5 hours to give a catalyst of 15.14'lkv!
4 were made. Table 2 shows the results of measuring the solid brewing strength by a titration method using a Hammett indicator in a benzene solvent.

Example 6 (skeletal isomerization reaction of linear paraffins Example 1)
[159-1.00 m
The entire hydroisomerization reaction of n-pentane was carried out in a high-pressure flow reactor having a length of 22 crn and an inner diameter of 1α. - The reaction conditions for the hydroisomerization reaction are as follows.

Temperature: 200°C Total pressure: 10 bar Ratio in % of hydrogen/n-pentane: 5/1 motAn
ot liquid space velocity: 1.5ml 1-n-penta haze-catalyst/
The gas composition at the outlet of the reaction tube was analyzed continuously by gas chromatography, and the results are shown in Section 5.

Comparative Example 3 A hydroisomerization reaction was carried out in the same manner as in Example 6 using Catalyst 9 and Catalyst #E10. The results are shown in Table 3.

No. 1 showed activity in the skeletal isomerization of n-pentane even after a reaction time of 16 hours, and was found to be a cross-catalyst with high activity and excellent catalyst life, and the presence of sulfuric acid in V-group metals was remarkable. It can be seen that it is effective.

Example 7 (Linear chain paraffin decomposition reaction) Powder f of catalysts 1 to 8 prepared by the method of Example 1.2 was packed into a 200 mf pulse reactor, and n-
Pentane t-1μ was injected to perform a decomposition reaction of n-pentane. The composition of the gas at the outlet of the pulse reactor is shown in Table 4 as a result of total gas chromatography and F analysis.

4. Catalyst lt-60 (300-
A mixture of isobutane and cis-2-butene (weight ratio of isobutane:cis-2-butene =
1o:1) t-Introduced in an amount 1.5 times the weight of the catalyst
After that, the reaction system was sealed, and the reaction temperature was 60°C, 16 kg/l.
Let it react for 5 hours under the same conditions. After the reaction, the reactants were taken out and analyzed, and the results are as follows.

Reaction rate of cis-2-butene: 93-selectivity (by weight)

Claims (1)

[Claims] 1. Hydroxide or oxide of group IV metal, and/or
The hydroxide or oxide of group III metal is treated with a treatment agent containing a sulfate group, and then the group VIII metal 0.01 to 10
1. A method for producing a solid acid catalyst, characterized in that a solid acid catalyst is supported in an amount of % by weight. 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. Claims 1 to 7 in which the group VIII metal is supported and then stabilized by firing at a temperature of 450 to 800°C.
A method for producing a catalyst according to any one of paragraphs.