JPH02178235A - Preparation of perhydroacenaphthene - Google Patents

Abstract

PURPOSE:To provide the subject substance in a high yield in the reduced production of by-products by hydrogenating acenaphthene in the presence of a Ni catalyst using diatomaceous earth as a carrier thereof in a specific solvent such as a paraffinic hydrocarbon or a naphthenic hydrocarbon. CONSTITUTION:Acenaphthene is hydrogenated in the presence of a Ni catalyst using diatomaceous earth as a carrier thereof at 160-190 deg.C (preferably 170-190 deg.C) under a hydrogen pressure of >=50kg/cm<2>G in a solvent to provide the subject substance. The solvent includes a paraffinic hydrocarbon, naphthenic hydrocarbon, perfectly hydrogenated condensed cyclic hydrocarbon or their mixture which have a boiling point of <=200 deg.C (preferably 50-150 deg.C). The Ni catalyst is preferably one prepared by hydrogenating a Ni compound in a dry state, cooling the hydrogenated Ni, substituting hydrogen gas in the hydrogenation chamber with CO2 gas and subsequently gradually adding air to the gas in the chamber to slightly oxidize the surface of the hydrogenated Ni for the stabilization of the prepared catalyst whereby the prepared catalyst is inexpensive and does substantially not cause the lowering of the catalytic activity thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for hydrogenating acenaphthene to produce perhydroacenaphthene.

More specifically, the present invention relates to a method for producing perhydroacenaphthene in high yield by catalytically hydrogenating acenaphthene in a solvent in the presence of a specific nickel catalyst to suppress the production of by-products.

[Prior Art] Perhydroacenaphthene (decahydroacenaphthene) is industrially useful as a raw material for 1,3-dimethyladamancune, which is an important intermediate for synthesizing pharmaceuticals, polymers, synthetic lubricating oils, etc. It is a substance.

As a method for producing perhydroacenaphthene, a method of catalytic pressure reduction of acenaphthene using a Raney nickel catalyst (Yamada, Coal Tar, Idan, p. 34 (1)
961)), hydrogenation of acenaphthene at a reaction temperature of 80 to 200°C using a Ru-based catalyst and/or Rh-based catalyst to obtain perhydroacenaphthene with the cis isomer as the main product. -265238), a method of hydrogenating acenaphthene at 200 to 300°C using Ni as a catalyst and using diatomaceous earth as a carrier to obtain perhydroacenaphthene with trans isomer as the main product (JP-A No. 63-2203).
Publication No. 6) etc. have been proposed.

However, in Yamada's method, the temperature is 100 atm and 250°C.
About 90% of perhydroacenaphthene was obtained by hydrogenation, but about 10% of the acenaphthene remained unreacted.

The method disclosed in JP-A No. 62-265238 uses an expensive precious metal catalyst to generate a hydrogen pressure of 100 to 200 kg/ci/G.
Since the hydrogenation is carried out under high pressure, there is a drawback that the catalyst cost and equipment cost are high.

The method of JP-A No. 63-22036 has a reaction temperature of 20
0~300℃, hydrogen pressure 100~200kg/crtf・
It requires high temperature and high pressure of G, which causes difficulties in terms of equipment and is industrially disadvantageous. Furthermore, according to the inventors' research, when the hydrogenation reaction is carried out at a high temperature as disclosed in this invention, in addition to the four isomers of perhydroacenaphthene, there are also octyl and It has been confirmed that hydroacenaphthene is also produced as a by-product, and both the yield and purity of perhydroacenaphthene cannot be said to be sufficient.

[Problem to be solved by the invention] There are four types of isomers of perhydroacenaphthene.
The most important use of perhydroacenaphthene is the production of 1,3-dimethyladamancune by isomerization. -Dimethyladamancune is obtained. On the other hand, 1.3-
Since dimethyladamancune cannot be obtained, even if it is a mixture of various isomers, a material with few impurities other than perhydroacenaphthene is suitable as a raw material for producing 1,3-dimethyladamantane. A method for easily synthesizing acenaphthene under mild conditions has been desired.

[Means for Solving the Problems] The present inventors have conducted extensive research and testing on a method for producing perhydroacenaphthene inexpensively and efficiently by catalytic reduction of acenaphthene, while eliminating the drawbacks of the conventional methods. As a result, in the presence of a solvent, if acenaphthene is hydrogenated under specific conditions using a nickel catalyst with a nickel content of about 45 to 55% supported on diatoms as a catalytic reduction catalyst, acenaphthene can be converted to benzene nuclei. It has high hydrogenation activity, produces perhydroacenaphthene in high yield, suppresses poisoning by impurities contained in acenaphthene, and prevents catalyst deterioration due to sintering at the temperature where catalyst activity is expressed. The present invention was achieved by discovering that the catalyst can be used repeatedly.

That is, the present invention uses acenaphthene in a solvent in the presence of a nickel catalyst having diatomaceous earth as a carrier at a reaction temperature of 160 to 1
This is a method for producing perhydroacenaphthene, which is characterized by hydrogenation at 90°C.

In the present invention, the acenaphthene used as a raw material may be a synthetic product or acenaphthene separated and recovered from coal tar, coal liquefied oil, or petroleum hydrocarbon oil.

A nickel catalyst using diatomaceous earth as a carrier is used after dry reduction, cooling, replacing hydrogen with CO2 gas, and then gradually adding air to stabilize the surface by slightly oxidizing it. This nickel catalyst, which uses diatomaceous earth as a carrier, has the surface of metallic nickel covered with an oxide film, so it is highly resistant to catalyst poisons, especially organic sulfur compounds, has high catalytic activity, and can be used repeatedly. However, deterioration is unlikely to occur.

The amount of nickel catalyst using diatomaceous earth as a carrier is 2 to 10% by weight based on the acenaphthene used as a raw material.
is appropriate.

The amount of nickel catalyst using diatomaceous earth as a carrier is 2% by weight.
If the amount is less than 10% by weight, it is difficult to proceed the hydrogenation reaction efficiently, and even if the amount is more than 10% by weight, no effect of improving the reaction rate is observed, and the production cost increases due to the increase in the amount of catalyst used. This not only causes an economic disadvantage, but also adversely affects the stirring condition.

In the present invention, it is important to perform hydrogenation in a solvent. That is, the present invention is characterized in that hydrogenation is carried out at a temperature of 190°C or lower in order to suppress the formation of by-products, but if a solvent is not used, acenaphthene is hydrogenated at a reaction temperature of 190°C or lower to form perhydrocarbon. In order to produce acenaphthene in high yield, the hydrogen pressure must be 130 kg/ctf.
6 or more is required, but if a solvent is used, 50 to 70k
A sufficient effect can be obtained even if the hydrogen pressure is lowered to g/cr+fG.

Various solvents can be used, but examples include pentane-5-hexane, heptane, cyclohexane, methylcyclohexane, decalin, etc. with a boiling point of 200.
It is preferable to use paraffinic hydrocarbons, naphthenic hydrocarbons, fully hydrogenated condensed ring hydrocarbons, or mixtures thereof having a temperature of 50 to 150°C or lower.

The appropriate amount of the solvent to be used is 0.5 times or more by weight, preferably 1 to 2 times the weight of the raw material acenaphthene.

The reaction conditions for the hydrogenation reaction are a reaction temperature of 160 to 190°C.
, preferably 170 to 190°C.

If the reaction temperature is lower than 160°C, hydrogen absorption of the reactants will hardly occur (the hydrogenation reaction will hardly proceed; on the contrary, if the reaction temperature is lower than 190°C)
When the temperature is higher, tetrahydroacenaphthene or octahydroacenaphthene dehydrogenated from the target product perhydroacenaphthene is produced as a by-product, and the production rate of the target perhydroacenaphthene decreases.

Further, the hydrogen pressure is preferably 50 kg/crrr・G or more, and 50 kg/crr? - If it is lower than G, the reaction rate will be too slow, resulting in a long reaction time and poor productivity.

Although the upper limit of the hydrogen pressure is not particularly limited, in the present invention hydrogenation is performed in a solvent so that hydrogen can be produced at a sufficient reaction rate without using high pressures such as 130 kg/crri'-G or higher in conventional methods. Since the reaction can be carried out under mild conditions, the degree of freedom in selecting the reactor and operating conditions is increased, which is economically advantageous.

In principle, the reaction time is until the absorption of hydrogen is completed, but if the nickel catalyst is used, an equilibrium state can be reached in a short period of time. It is enough.

Note that the hydrogenation reaction can be carried out in the presence of a large excess of hydrogen gas in a batch system or a flow system, but a batch system is preferred since the catalyst used is in the form of a powder.

After the hydrogenation reaction is completed, the catalyst is separated by means such as decantation or filtration, and then the solvent is distilled off from the reaction mixture, and perhydroacenaphthene can be obtained in high yield.

On the other hand, the separated catalyst and recovered solvent can be recycled for the next reaction.

[Examples] The present invention will be explained below using Examples, but the present invention is not limited to these Examples. The composition of the hydrogenated product was analyzed by gas chromatography. The gas chromatograph analysis conditions are as follows.

Column: 0V-1 (0.25φ x 50m) [Shimadzu ■Product] Detector: FID Vaporization temperature: 250℃ Detection temperature: 250℃ Initial setting temperature: 120℃ Heating rate: 2℃/min Final temperature: 200℃ Example↓ Acenaphthene (99.9% purity) 100g and hexane 1
00g and nickel catalyst with diatomaceous earth as a carrier (manufactured by JGC Chemical ■, trade name N-103, [nickel 49-52%, diatomaceous earth 27-29%, graphite 4-5%]) 3g at 500mf
The mixture was charged into an autoclave No. 2, and hydrogenated for 2.5 hours at a reaction temperature of 160° C. and a hydrogen pressure cuff of 0 kg/crrr·G. The reaction mixture was filtered and hexane was distilled off under reduced pressure to obtain 106.0 g of a reaction product.

As a result of compositional analysis of this reaction product using gas chromatography, a chart as shown in FIG. 1 was obtained. No. 1 in Figure 1. No, 2°No, 3 and No,
The peak 5 is the four isomers of perhydroacenaphthene, and N004 is the by-product octahydroacenaphthene. The analysis results showed that the concentration of perhydroacenaphthene (total of 4 isomers) was 97.7%, and the yield of perhydroacenaphthene was 97.4 mol%.

The reaction temperature was 190℃ and the hydrogen pressure was 70kg/crr?・
G. Acenaphthene was hydrogenated in the same manner as in Example I, except that the reaction time was 1.5 hours, and the reaction product was 106
．． 3g was obtained.

The concentration of perhydroacenaphthene in this reaction product is 98
, 5%, the yield of perhydroacenaphthene was 98.4 mol%.

Dashi Guangdan reaction temperature 170℃, hydrogen pressure 50 kg/crt
f.G, acenaphthene was hydrogenated in the same manner as in Example 1 except that the reaction time was 2 hours, and the reaction product 106.
3g was obtained.

The concentration of perhydroacenaphthene in this reaction product is 98
, 0%, the yield of perhydroacenaphthene was 97.8 mol%.

The reaction temperature was 220℃ and the hydrogen pressure was 70kg/crd・G.
, Acenaphthene was hydrogenated in the same manner as in Example 1, except that the reaction time was 4 hours, and the reaction product was 105.8
I got g. The concentration of perhydroacenaphthene in this reaction product is 75.0%, the concentration of tetrahydroacenaphthene is 25.0%, a large amount of by-products are produced, and the yield of perhydroacenaphthene is 74.5 mol%. there were.

Comparison: 3° Reaction temperature: 240°C, hydrogen pressure: 130kg/crrf
-G, acenaphthene was hydrogenated in the same manner as in Example 1 except that the reaction time was 2 hours, and the reaction product was 105
．． I got 4g.

The concentration of perhydroacenaphthene in this reaction product is 68
．． 4%, the concentration of by-product tetrahydroacenaphthene is 31
．． At 5%, the yield of perhydroacenaphthene was 67.8 mol%.

Raiseden A Reaction temperature: 190℃, hydrogen pressure: 130k[/crrr
・G, acenaphthene was hydrogenated in the same manner as in Example 1 except that the reaction time was 1.5 hours, and the reaction product 105
．． Obtained 0g.

The concentration of perhydroacenaphthene in this reaction product is 96
．． At 2%, the yield of perhydroacenaphthene was 94.9 mol%.

Comparative 180g of fallen acenaphthene and nickel catalyst (manufactured by JGC Chemical ■,
Product name N-103) 5.4g was placed in a 500mβ autoclave. 2. Reaction temperature was 190°C and hydrogen pressure cuff was 0k.
g/crr?・Hydrogenation reaction was carried out for 2 hours under the conditions of G. The reaction mixture was divided into portions, and hexane was distilled off under reduced pressure to obtain 185.9 g of a hydrogenated product.

The perhydroacenaphthene concentration of this hydride is 71.3
%, the concentration of tetrahydroacenaphthene is 23.1%, the concentration of octahydroacenaphthene is 5.4%, by-products are generated, and the yield of perhydroacenaphthene is 69.2%.
It was mol%.

Comparative type A: The reaction temperature was 240°C, which is within the range of the invention of JP-A No. 63-22036, and the hydrogen pressure was 130 kg/crtr・G.
Acenaphthene was hydrogenated in the same manner as in Comparative Example 3, except that the reaction time was 3 hours, to obtain 184.3 g of a hydrogenated product.

According to the results of gas chromatography analysis and mass spectrometry of this hydrogenated product, as shown in FIG. 2, there are four isomers of perhydroacenaphthene (No.
In addition to No. 5), octahydroacenaphthene (No.
4) was observed to occur as a side effect. The concentration of perhydroacenaphthene in the product was 73.9%, the concentration of the by-product octahydroacenaphthene was 25.9%, and the yield of ζ perhydroacenaphthene was 7], 1 mol%.

Comparative Dandan reaction temperature: 240℃, hydrogen pressure cuff: 0kg/crr1″・
G, acenaphthene was hydrogenated in the same manner as in Comparative Example 3 except that the reaction time was 2 hours, and the hydrogenated product was 187. E
I got the lig.

The perhydroacenaphthene concentration of this hydride is 76.8
%, the concentration of by-product octahydroacenaphthene is 22.7
%, the yield of perhydroacenaphthene is 75.2 mol%
Met.

Table 1 summarizes the main reaction conditions and yields of perhydroacenaphthene obtained in each of the above Examples and Comparative Examples.

100g of Niacenaphthene and 1~10g of the same nickel catalyst used in Example 1 (1~10% by weight of acenaphthene)
) and 100 g of hexane in an autoclave, reaction temperature 190°C, hydrogen pressure cuff 0 kg/cr
T? The hydrogenation reaction was carried out for 1 hour under the conditions of -G.

Then, the reaction mixture was treated in the same manner as in Example J, and the relationship between the amount of catalyst added and the yield of perhydroacenaphthene was determined.

The results are shown in FIG. At a catalyst addition rate of 2.0%, the perhydroacenaphthene yield was 97 mol% or more, and no improvement in the yield was observed even if the catalyst was further increased.

Example 1 100 g of acenaphthene, 3 g of the nickel catalyst of Example 1, and 100 g of hexane were charged into an autoclave, and a hydrogenation reaction was carried out for 1 hour under the conditions of a reaction temperature of 190° C. and a hydrogen pressure cuff of 0 kg/Cl.G.

After the reaction was completed, the catalyst was separated and recovered from the reaction mixture by filtration. And recovered catalyst, acenaphthene 100g
and 100 g of hexane were charged into an autoclave, and the hydrogenation reaction was repeated under the same conditions.

The catalyst was recycled seven times, and each reaction mixture was treated in the same manner as in Example 1, to determine the relationship between the number of catalyst cycles and the perhydroacenaphthene yield.

The results are shown in FIG.

As shown in FIG. 4, even when the catalyst is used repeatedly, the yield of perhydroacenaphthene hardly decreases.

This shows that the catalyst of the present invention can be used repeatedly.

[Effects of the Invention] As described above, according to the method of the present invention, when producing perhydroacenaphthene by catalytic reduction of acenaphthene,
By using a nickel catalyst with dry-reduced diatomaceous earth as a carrier, which is inexpensive and has little loss of catalytic activity (and is easy to handle), the hydrogenation reaction is carried out in the presence of a solvent and under mild reaction conditions. It has many advantages, such as being able to catalytically reduce acenaphthene in a short time, producing less by-products, producing perhydroacenaphthene in high yield, and allowing the catalyst to be used for long-term circulation.

[Brief explanation of the drawing]

Figure 1 is a gas chromatography chart of the reaction product of Example 1, Figure 2 is a gas chroma analysis chart of the reaction product of Comparative Example 4, and Figure 3 is the catalyst addition amount and perhydroacenaphthene in Example 5. 4 is a diagram showing the relationship between the number of cycles of the catalyst and the yield of perhydroacenaphthene in Example 6. FIG. 〈−＼ Retention time Retention time

Claims (1)

[Claims] 1. A method for producing perhydroacenaphthene, which comprises hydrogenating acenaphthene in a solvent in the presence of a nickel catalyst using diatomaceous earth as a carrier at a reaction temperature of 160 to 190°C. 2. The solvent is a paraffinic hydrocarbon with a boiling point of 200°C or less,
The method for producing perhydroacenaphthene according to claim 1, wherein the perhydroacenaphthene is a naphthenic hydrocarbon or a completely hydrogenated condensed ring hydrocarbon.