JPS623129B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for selectively isomerizing endo-trimethylenenorbornane (hereinafter referred to as endo-TMN) to produce highly pure exo-trimethylenenorbornane (hereinafter referred to as exo-TMN). . Conventionally, acid catalysts such as aluminum chloride and Friedel-Crafts type catalysts such as anhydrous aluminum chloride are known as catalysts for isomerizing endo-TMN to exo-TMN, but both have short catalyst lifetimes and cannot be used continuously. However, it was difficult to manufacture, and it also corroded the equipment. The object of the present invention is to solve the above-mentioned drawbacks, and to provide a method for producing exo-TMN under industrially advantageous conditions using a solid catalyst with high selectivity and long life. That is, the present invention provides the formula By isomerizing the endo-trimethylenenorbornane represented by the formula In producing exo-trimethylene norbornane represented by This is a method for producing exo-trimethylenenorbornane, which is characterized by using zeolite ion-exchanged with the above metal ions. In the method of the present invention, the catalysts used include alumina, silica-alumina, H-X type and H
Either -Y-type zeolite or zeolite ion-exchanged with one or more metal ions selected from the group consisting of alkaline earth metals and rare earth metals is used. Alumina and silica-alumina may be produced by any method and are not particularly limited. Therefore, commercially available products can also be used. In addition, H-X type and H
The -Y type zeolite does not need to be a special one, and a conventional commercially available product can be used, or it can be obtained by calcining NH ₄ -Y type zeolite. In particular, H-Y type zeolite has excellent heat resistance and is therefore preferable when used at high temperatures or for long periods of time. On the other hand, the ion-exchanged zeolite mentioned above is
Na ⁺ , K ⁺ , NH ₄ ⁺ in zeolites such as type and Y type
The cation sites of , etc. are ion-exchanged with alkaline earth metals such as Ca, Mg, or rare earth metals such as La, Ce, Nd, Yb, Y, etc., and the ions of the alkaline earth metal or rare earth metal are exchanged with, for example, metal It can be obtained by treating it in the form of an aqueous salt solution, introducing it into zeolite, followed by drying and calcining. In this case, the above-mentioned metals should not be supported on the zeolite, but should be introduced in the form of ion exchange with the cation sites in the zeolite. The ion exchange rate is not critical, but is usually 20-100%, preferably 45-90%. Preferred catalysts used in the present invention include, in addition to the above-mentioned catalysts, the above-mentioned alumina, silica-alumina, H-X type and H-Y type zeolites, or ion-exchanged zeolites, as well as iron, cobalt, nickel, platinum, and rhenium. There are catalysts containing one or more metals, such as, and catalysts further treated with carbon tetrachloride. Among these catalysts, those containing platinum, rhenium, and iron group metals such as iron, nickel, and cobalt are particularly preferred. The content ratio of platinum and rhenium is 0.1 to 5% of the catalyst weight in total for both metals, and platinum:rhenium=
It is preferable to set it as 19:1-1:3 (atomic ratio). The iron group metal is preferably contained in an amount of 0.1 to 10% of the weight of the catalyst. Note that when these metals are contained in zeolite, any method such as an ion exchange method or an impregnation method can be employed. In other words, the special public official court in 1977-
It can be obtained by the method described in the specifications of No. 12706, No. 53-35942, and No. 53-35944. Activation of the catalyst can be performed, for example, in an inert gas stream at approx.
It is carried out by heating at a temperature of 350-570°C. Further, the shape of the catalyst may be arbitrary, such as powder or granule. The isomerization reaction is usually carried out in the presence of a catalyst at a reaction temperature of approximately
The reaction is carried out at a temperature of 130 to 350°C and a reaction pressure of normal pressure or pressurized up to 20 atm. As for the reaction format, a flow type is preferred, but a batch type is also possible. Normally for flow type
LHSV 0.5 to 30 is sufficient, and irrigant-filled tower type,
A boiling type etc. can be adopted. In order to increase the reaction yield, hydrogen chloride gas may be supplied together with hydrogen gas, and in this case, the amount of hydrogen chloride gas is suitably 0.05 to 1.0 mol% relative to the hydrogen gas. Further, instead of hydrogen chloride gas, it is also possible to use an organic halide that generates hydrogen chloride gas by hydrogenolysis, such as propylene dichloride. Catalyst regeneration involves heating the used catalyst under vacuum for 150 to 250 minutes.
This can be done by degassing at a temperature of 180°C to 500°C, but in order to regenerate completely, it is heated to a temperature of 180 to 500°C while supplying hydrogen at a hydrogen pressure of 10 kg/cm ² or higher. The method of the present invention is characterized by a small amount of catalyst used, high catalyst activity, and long catalyst life. It also has advantages such as easy regeneration of the catalyst and no corrosion of equipment. Exo-TMN obtained by the method of the present invention is a colorless, odorless liquid with a boiling point of 187°C (760mmHg), a low melting point (does not crystallize even at -78°C), and is used as a lubricating oil additive, special fuel and fuel additive, and organic It is useful as a synthetic intermediate, high boiling point solvent, etc. Next, the present invention will be explained in more detail with reference to Examples. Example 1 A 1/16 inch extruded product of La-exchanged Y-type zeolite was filled into a fixed bed flow reactor, and the first
Endo-TMN was supplied and the isomerization reaction was carried out under the reaction conditions shown in the table. The results after 250 hours are the first
Shown in the table. Examples 2 to 5 The same operation as in Example 1 was carried out using La-exchanged Y-type zeolite supporting 0.5 wt% of Pt, 0.25 wt% of Re, and 3.0 wt% of Co. The results after 250 hours are shown in Table 1. Example 6 The same operation as in Example 1 was carried out using alumina on which 0.3% of Pt was supported as a catalyst. The results after 250 hours are shown in Table 1. Example 7 The same operation as in Example 1 was carried out using alumina on which 0.3% of Pt was supported and treated with carbon tetrachloride in a nitrogen stream as a catalyst. The results after 250 hours are shown in Table 1. Example 8 The same operation as in Example 1 was carried out using HY type zeolite (Pt/HY) on which 0.3% of Pt was supported as a catalyst. The results after 250 hours are shown in Table 1. Example 9 The same operation as in Example 1 was carried out using Mg-exchanged Y-type zeolite (Pt/MgY) on which 0.3% of Pt was supported as a catalyst. The results after 250 hours are the first
Shown in the table. Example 10 The same operation as in Example 1 was carried out using Ca-exchanged Y-type zeolite (Pt/CaY) on which 0.3% of Pt was supported as a catalyst. The results after 250 hours are shown in Table 1. Example 11 Mixed rare earth-exchanged Y-type zeolite (Y-type zeolite manufactured by Union Carbide containing a mixture of La, Ce, Nd, Y, etc., trade name: SK-500) supported with 0.3% Pt as a catalyst ( The same operation as in Example 1 was performed using Pt/REY). The results after 250 hours are shown in Table 1. Example 12 The same operation as in Example 1 was carried out using H-X type zeolite (Pt/HX) on which 0.3% of Pt was supported as a catalyst. The results after 250 hours are shown in Table 1. Example 13 The same operation as in Example 1 was carried out using Mg-exchanged type X zeolite (Pt/MgX) on which 0.3% of Pt was supported as a catalyst. The results after 250 hours are the first
Shown in the table. Example 14 The same operation as in Example 1 was carried out using Ca-exchanged type X zeolite (Pt/CaX) on which 0.3% of Pt was supported as a catalyst. The results after 250 hours are shown in Table 1. Example 15 The same operation as in Example 1 was carried out using HY type zeolite (HY) as a catalyst. The results after 250 hours are shown in Table 1. Example 16 The same operation as in Example 1 was carried out using Mg-exchanged Y-type zeolite (MgY) as a catalyst. The results after 250 hours are shown in Table 1. Example 17 Mixed rare earth-exchanged Y-type zeolite (Y-type zeolite manufactured by Union Carbide containing a mixture of La, Ce, Nd, Y, etc., trade name:
The same operation as in Example 1 was carried out using SK-500) (REY). The results after 250 hours are shown in Table 1. Example 18 The same operation as in Example 1 was carried out using H-X type zeolite (HX) as a catalyst. The results after 250 hours are shown in Table 1. Comparative Example 1 Aluminum chloride 150 in a 4-necked flask
Dissolve g in benzene 2, endo-TMN650
While dropping n-hexane solution 3 containing g.
Stir at reflux for an hour. After the reaction is completed, add 1 part of water to the reaction solution while stirring for hydrolysis, wash with water, dry,
After the solvent was distilled off, the product was distilled to obtain 588 g of exo-TMN with a purity of 92.9% (yield 90.5%, conversion rate 97.5%). The used catalyst was recovered from the flask and the same operation as above was performed, resulting in a yield of 64.1% and a conversion rate of 70.5%. This catalyst was further recovered and subjected to the same operation as above, resulting in a yield of 31.8% and a conversion rate of 35.0%.

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Claims (1)

[Claims] 1 formula By isomerizing endo-trimethylenenorbornane represented by the formula In producing exo-trimethylenenorbornane represented by A method for producing exo-trimethylene norbornane, characterized by using a zeolite ion-exchanged with the above metal ions. 2 formulas By isomerizing endo-trimethylenenorbornane represented by the formula In producing exo-trimethylenenorbornane represented by Zeolite ion-exchanged with the above metal ions further contains one or more metals selected from the group consisting of iron, cobalt, nickel, platinum, and rhenium, or is further treated with carbon tetrachloride. A method for producing exo-trimethylene norbornane, characterized in that it is used.