JPS5843237A - Catalyst composition fixed with silicone resin - Google Patents

Abstract

PURPOSE:To obtain a catalyst composition high in activity and durability, by fixing the catalyst to a silicone resin having gas permeability. CONSTITUTION:Ordinarily used catalyst, especially nonstereospecified catalyst, such as Pd, Pt, or the like noble metal, its oxide, that contained in activated carbon, alumina, or the like inorganic carrier, Ni, or the like metal, activated Raney type metal, and/or that held on carrier, is fixed to a silicone resin having gas permeability and solidifying at normal temp. to obtain a catalyst composition characteristic of gas permeability, gas diffusivity, etc. This catalyst composition is obtained, for example, by kneading Raney nickel catalyst or the like with said silicone resin, molding it into an optional form, and further processing it into a desired form and size.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel catalyst composition in which a catalyst component is immobilized using an air-permeable silicone resin.

Conventionally, as a catalyst in which a catalyst component is immobilized by a polymer, JP-A-54-1235913 discloses that a reactive metal compound is contained in a water-soluble water-wettable polymer in the form of a solution, and ammonia, amine, etc. Catalytic membranes have been proposed consisting of polymers mixed with metals and/or metal compounds through gaseous precipitants such as sulfurized water. Although this catalyst membrane is used to decompose hydrogen peroxide, it is not a catalyst with general use and is provided only for limited uses. Moreover, the specification of JP-A-55-99345 is
A catalyst containing catalyst particles inside fine fibers or a fine film, or partially exposed from the inside, and the active surface of the catalyst particles is connected to the outside of the fine fibers or fine film by fine voids. is provided. This material is obtained by mixing catalyst particles with a synthetic fiber raw material such as polyolefin or polyester and spinning it by a known spinning method, or by processing it into a lever, and simply uses the synthetic fiber material as a carrier.

Some polymeric substances have solid solvent properties that allow gases or liquids to pass through or to be contained therein. From this point of view, we believe that the catalytic reaction of gaseous and/or liquid chemical substances passing through the compound matrix can be effectively carried out in polymeric substances, and that it is convenient for maintaining and preserving catalytic activity. As a result of extensive research into the types of polymer compounds suitable for this purpose, their properties, combinations with catalysts, methods of preparing polymer-catalyst composites, etc., we found that certain gases such as hydrogen, nitrogen, and carbon oxides Let it pass;
and can contain and retain organic solvents; the present invention was completed based on the discovery that the above object could be achieved by using a silicone resin.

That is, the present invention provides a silicone resin with air permeability of 1'4F and solidification at room temperature, using commonly used catalysts, especially catalysts that are not asymmetrically modified, such as noble metals such as palladium, platinum, ruthenium, and rhodium. Metals, oxides, metals such as metals supported on inorganic carriers such as activated carbon and alumina, minerals, nickel, cobalt, iron, copper, etc.

By immobilizing activated Raney type metals and/or those supported on carriers, we take advantage of the properties of this silicone resin, such as gas permeability and magnification:, -. A novel catalyst composition is provided.

To obtain the catalyst composition gold of the present invention, (1) Raney nickel catalyst, palladium carbon catalyst.

(3) A method in which a catalyst such as a platinum oxide catalyst and a silicone resin that solidifies at room temperature are kneaded and molded into an arbitrary shape, and this is further processed into a desired shape and two dimensions.

(2) A solution of salts such as palladium acetate is passed through the silicone resin, which has been molded into a sheet or tube shape in advance, and after the salts are adsorbed to the resin, it is reduced with hydrogen or a reducing agent. method to immobilize the catalyst.

The catalyst composition thus obtained can be further coated with a silicone resin solution that solidifies at room temperature to prevent exposure of the catalyst.

As the silicone resin used in the present invention, (1)
Examples of materials used for kneading and solidification include one-component type TV rubber, which solidifies with moisture in the air at room temperature; etc. To explain in more detail, 1-liquid type R, T
When V-rubber solidifies at room temperature, there are acetic acid-removal types that solidify by liberating acetic acid, as well as alcohol-removal (4) types, oxime-removal types, amination-removal types, and acetone-removal types. There are also two-component RTV rubbers, such as those for electric use and those for electric use.

(2) As a pre-molded silicone resin product,
There are sheets (rubber rice) used for pavkin wood, etc., and tubes (circular pipes) used for medical purposes.

Catalysts used in the present invention include (1) those used for kneading and solidification, including activated Raney nickel, cobalt, iron, copper, and other metal components and/or two or more types of metal components including additives; precious metals such as palladium, platinum, rhodium, and ruthenium supported on carriers such as activated carbon and alumina,
Metals such as palladium, platinum, rhodium, and ruthenium, and their vanishing products and/or their complex salt compounds are used. Palladium (acetic acid), such as radium acetylacetonate.

A method is used in which soluble salts such as platinum and ruthenium are adsorbed onto a silicone resin molded product and then reduced with hydrogen or chemically reduced with a reducing agent.

The catalyst composition of the present invention can be obtained in various types and shapes by the method described above. After removing water and gold by washing etc., 3 parts silicone resin to 1 part catalyst component.
Mixed wire solidification has been prepared in a ratio of 1 to 5 parts of silicone resin to 1 part of palladium/carbon catalyst. A catalyst composition with high activity and excellent durability can be obtained.

The catalyst composition of the present invention is made of silicone [1N] which has good air permeability through which gases commonly used in chemical reactions such as hydrogen, oxygen, nitrate, and carbon oxide are immobilized. It can be used in reactions such as hydrogenation, oxidation, and oxidation in the same way as conventionally known powdered or granular catalysts.In addition, silicone resin acts as a solid solvent, so it helps the catalyst itself. 0 Therefore, although the initial reaction rate may be inferior to the initial reaction rate when using the powdered catalyst as it is due to differences in contact area, etc., it is influenced by the numbered substances (trace amounts of contaminants), etc. Therefore, the catalyst composition of the present invention can maintain stable activated gold over a long period of time, have few side reactions, etc., and can extend the life of the catalyst.Furthermore, the properties as a solid solvent make it possible to utilize gold and the solvent used. By selecting , the field in the reaction can be changed and it can be used for reactions with various selectivity tW. Furthermore, since it has good gas permeability, it can also be used for gas phase reactions. I can do it.

The reaction method using the catalyst composition of the present invention is similar to conventional catalysts in the liquid phase under normal pressure, .

Furthermore, since the silicone resin acts as a solid solvent, the catalyst composition of the present invention is also effective in reactions in the gas phase, and therefore can be used in any of the commonly used catalytic reactions. It can also be used in this method.

In gas phase reactions, activated Raney nickel catalysts, which normally have problems in use in gas phase reactions, can be used without any problems in the present invention due to the function of the silicone resin itself as a solid solvent. Furthermore, the catalyst composition of the present invention has excellent heat resistance compared to catalyst compositions using other general resins, and can fully exhibit its properties. The catalyst is less affected by poisoning of the catalyst by contaminants, which is often a problem in phase reactions, and therefore a stable catalyst that can maintain extremely high activity can be obtained.

The catalyst composition obtained in the present invention can be solidified and molded into any form, can be used in reactors of various shapes, etc., and has excellent weather resistance and is easy to store.
,,SatoshiThe conventionally used catalyst is made of silicone resin.
Examples of the products of the present invention will be described below.゛Examples 1 to 3. Comparative Example 1 Commercially available one-component silicone 1 (three types of TV rubber, (8) namely, deacetated type-KIf14iFv), dealcolated type 7Kg47RTV, and deoxime type-Kg4
41⇠1゛V type (all of the above are manufactured by Shin-Etsu Chemical ■, hereinafter simply referred to as deacetic acid type and dealcohol type, respectively).

(abbreviated as oxime-free type) was prepared. 5-ring palladium-elementary catalyst all the above-=m class silicon 14 'l' V
Mix and assimilate the silicon RTV rubber in a ratio of 1 part catalyst weight to 5 parts silicon RTV rubber weight, respectively, and make a 47 ton thick sheet.3 days and 10 days after this sheet was prepared. One month later, the hydrogenation activity of crotonaldehyde and the ignitability test using methanol were conducted as follows. As a comparison, silicon l(,'l' V
The catalyst was also tested in the same manner before being kneaded with the rubber. −
1' (a) The above catalyst sheet containing 0.05 t of 5-tone palladium carbon and 1 strip of the catalyst, 0.035 t of crotonaldehyde and 1.5 t of methanol in 3Q*lf glass magen. The reaction was carried out at room temperature and pressure, and the reaction and the production rate of butyraldehyde in the acid were determined by gas chromatography using a wax lid. 5. Palladium carbon catalyst 0. uSg
A similar reaction was also carried out. The results are shown in Table 1.

The following margin (tg) Next, each catalyst 1 was preheated to 60 t': and brought into contact with methanol gas Vcll that evaporated into the air, and when it came into contact with the 5-width palladium carbon catalyst, it ignited.
Even when it came into contact with the product of the present invention processed with silicone rubber, it did not catch fire.

Examples 4-6. Comparison Daj2: Activated Raneni-Soquel catalyst (Suzuki Fine Chemicals (Ceramics NDT-90)) Washed with methanol three times to remove moisture, and used the same dispersion type used in Example 1.

silicone) tTV rubber to 1 nickel content of the catalyst
0% ratio type 1 ratio) and mix both metals in one building,
1 wholesale solidified into a sheet of J thickness 〇 Assimilated 2 weeks 11 JI
Later, an amount of this catalyst containing 0.89 nizukel was cut off and fixed on the stirring rock of a stirring autoclave.The autoclave was heated with acetomethyl 0, 1 molar f force 11 5 hydrogen side pressure LlO'vi, and heated at 100" CFC. Then, reaction '1□1 was carried out, and the reaction time was defined as the time until hydrogen absorption was completed.After the reaction was completed, the autoclave was cooled, the reaction product *ffi was taken out, and then the new menal human acetate 0.1 The reaction was carried out at a hydrogen pressure of 9 mouths (12) by increasing the molar amount.The reaction was carried out repeatedly (11) to confirm the durability of the catalyst.The reaction solution was distilled to form methyl 23-hydroxybutyrate. The total yield was determined. The reaction was carried out in the same manner with Raney nickel that was not fixed with silicone rubber. These results are shown in Table 2. From these results, the catalyst of the present invention has excellent durability (of activity). That was nZ's fault.

Catalyst 4: When an ignition test using methanol was conducted in the same manner as the catalysts of Examples 1 to 3, no ignition of methanol was observed.

Below are blank spaces Examples 7 to 9 The catalyst compositions obtained in Examples 4 to 6 and cross-wired and solidified with the all-silicone resin were stored in the air to improve the weather resistance (changes over time) of the catalysts. .

The conditions for hydrogenating methyl acetoacetate using this catalyst composition were the same as in Example 4, and the results shown in Table 3 were obtained. As a result, the catalyst composition crosslinked and solidified with the silicone resin did not show any decrease in activity even when stored in air for 6 months.

Table 3 Example io, Comparative Example 31) Adams type platinum oxide catalyst 0.311't-catalyst component is l
A catalyst was prepared by kneading acetic acid-removed Kg41R, TV-liquid silico (15) and solidifying it into a 1 mm thick sheet. This catalyst, 5 mmol of 1-octene, and 30 me of methanol. f Put in a glass mardan and introduce hydrogen gas to carry out the reaction at room temperature and normal pressure, and the reaction was completed in 95 minutes.Next, this reaction product was removed, and the same procedure was carried out using fresh l-octene and methanol. The reaction was completed in 130 minutes. When a similar reaction was carried out using an Adams-type platinum oxide catalyst that was not immobilized with silicone rubber, the first reaction completed in 70 minutes and reached 7 tons, and the second time, after 100 minutes, the amount of hydrogen absorbed was 14, resulting in a poor reaction. Example 11 4 g of the Raney nickel-immobilized catalyst obtained in Example 5 was cut into long strips with a thickness of 1 mm and a width of 5 mm, placed in a glass reaction tube, and heated to 85°C. Hydrogen gas was blown into the methyl acetoacetate maintained at 8 FI Q to this catalyst I@ to create a hydrogen-methyl acetoacetate mixed gas, which was passed through the catalyst layer and then cooled with dry ice to recover all the reaction liquid. Hydrogen gas was further sent to the raw material (16) and circulated. This operation was carried out for 3 days, and 5810.5 moles of methyl acetoacetate)'! i? Processed.

When the reaction product was quantified by gas chromatography, it was found that 934 3-hydroxybutyric acid and the remainder were unreacted products.

Example 12 1-decene was used instead of methyl acetoacetate in Example 11, and the reaction was carried out in the same manner as in Example 11 except that hydrogen gas was blown into the decene at room temperature. 7011 (0.5 mol) was reacted for 3 days, and the reaction solution was analyzed by 7tn gas chromatography, and it was found that the production rate of decane was 100%.

Example 13 A tube (inner diameter 2 mm) obtained by processing silicone resin commercially available for medical use, etc. was cut into T-1501 lengths, one cut end was sealed with a glass rod, and ethyl acetate was placed in the tape. A solution of palladium acetate dissolved in water was added.

The ethyl acetate passed through the silicone resin and volatilized through the pores, and the radium acetate was adsorbed onto the silicone resin. After repeating this operation two more times, the height was 600′″G.
After drying, the palladium acetate was reduced to metal palladium by passing hydrogen gas.

The tube was immersed in a silicone resin solution (KE428-TV) to which toluene was added in an amount twice as much by weight, taken out, and dried to destroy the outer surface. This operation was repeated two more times, and at this time the palladium content was 0.3.

In this way, one end of the silicone tube palladium catalyst was sealed while the other end was completely sealed.
It was connected to hydrogen gas maintained at M.

Add 5 mmol of octene to 30 mmol of methanol in this tube.
When the silicone tube was immersed in a helical shape and allowed to stand in such a state that hydrogen gas passed through the silicone tube and entered the reaction solution, 30% progress of hydrogenation was observed after 4 hours.

Example 13 An RB rubber sheet (thickness: 0.5 mm) containing commercially available silicone as the main component.
5M) was impregnated with palladium acetate by absorbing an enal acetate solution of palladium acetate, and after drying, the palladium catalyst was immobilized by reduction in an aqueous gas stream. The catalyst composition thus obtained was cut into strips with a width of 1 to 2 mm, and in order to prevent fine palladium particles from depositing on the surface of the catalyst assembly, a toluene solution of silicone resin ( 1 (E 428-gTV) vcfl shite table m'
I was exposed to 1r4fB fat. After drying, the resin on the dried surface was dipped in the resin solution again to cover it and left in the air for two weeks to completely solidify, and the catalyst was treated so that no catalyst particles were exposed on the surface. Example 10 using
Atmospheric pressure hydrogenation of a methanol solution of 1-octene was carried out in the same manner as in 0. Even though the catalyst particles were not exposed at all on the surface, the silicone resin acted as a solid solvent and the reaction progressed very quickly. did. At that rate, palladium acetate was separately reduced and the product obtained was almost the same as when palladium gold was used. As a result, hydrogenation of 1-octene proceeded rapidly with extremely high activity (19).
t.) The reaction solution was collected and quantitatively analyzed by gas chromatography, and octane was obtained with a conversion rate of 1004. ] Patent, applicant Jj: Iken Fine Chemical Co., Ltd., Patent application agent'! lI Patent Attorney Akira Yoiki Patent Attorney Kazuyuki Nishidate Patent Attorney Akira Yamaguchi (20) Procedural Amendment (Voluntary).

Haruki Shimada, Commissioner of the Japan Patent Office, January 1, 19811, Indication of the case, Patent Application No. 141644, filed in 1982, Title of the invention, Catalyst composition fixed by silicone resin, 3, Person making the amendment; Relationship between patent applicant name Yoken Fine Chemical Co., Ltd. 4, agent 5, [Detailed Description of the Invention, Column 6, Contents of Amendment (1) Specification 1, page 4, line 2, Correct "silicon resin" to "silicone resin".

(2) In the second line of page 18, "600" is corrected to j60JK.

(3) On page 18, line 13, “octene 5” is changed to “1
-Corrected to ``Octene 5''.

(4) On page 18, line 18, "Example 13J is corrected to "Example 14."

Claims (1)

[Claims] 1. Catalyst composition 02 comprising an air permeable silicone resin and a catalyst fixed thereby; Claim 1, wherein the catalyst composition is in the form of a sheet or a tube. Compositions as described in Section.