JPS62201830A - Production of cycloolefin - Google Patents

Abstract

PURPOSE:To obtain a cycloolefin by the partial reduction of a monocyclic aromatic hydrocarbon with H2 in the presence of water using a stable catalyst system produced by adding an oxide of a metal selected from Al, Ga, Nb, Ta, Fe, Co, Ti and Si to a hydrogenation catalyst. CONSTITUTION:A cycloolefin is produced by the partial reduction of a monocyclic aromatic hydrocarbon with hydrogen in the presence of a catalyst and water. The catalyst used in the above reaction is a stable catalyst system produced economically on an industrial scale by compounding a granular hydrogenation catalyst composed mainly of metallic ruthenium with one or more kinds of metal oxides selected from oxide of aluminum, gallium, niobium, tantalum, chromium, iron, cobalt, titanium and silicon. The average particle size of the oxide is preferably about 0.005-100mu and the amount of the oxide is about 1X1/10<3>-0.3pts.wt. per 1pt. of water. USE:Raw material for polyamide, lysine, etc.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention uses an industrially advantageous and stable catalyst system to partially reduce monocyclic aromatic hydrocarbons, thereby reducing the corresponding cycloolefins, especially cyclohexene. The present invention relates to a method for stably producing .

Cyclohexenes have high value as intermediate raw materials for organic chemical industry products, and are particularly important as raw materials for polyamides, lysine, etc.

(Prior art) As a method for producing such cyclohexanes, for example, (
1) A method using a catalyst composition containing water, an alkaline agent, and an element of Group I of the periodic table (Japanese Patent Publication No. 56-22850), (2) Supported on oxides of nickel, conomalt, chromium, titanium, or zirconium. A method using a ruthenium catalyst and an alcohol ester as an additive (% Publication No. 52-3933), (3) copper,
A method using a ruthenium catalyst containing silver, copper, or potassium, water, and a phosphate compound (Japanese Patent Publication No. 56-4536), (4) Ruthenium catalyst and a group IA metal of the periodic table, a group IIA metal A method of reacting in the presence of a neutral or acidic aqueous solution containing a salt of at least one cation selected from metals, manganese, zinc and ammonia (Japanese Unexamined Patent Publication No. 142536/1982), (5) Reaction of ruthenium and rhodium A solid catalyst containing at least one type of metal as a main component is a group IA metal of the periodic table, a group metal, manganese,
A method of reacting in the presence of water using an aqueous solution containing a salt of at least one cation selected from the group consisting of iron and zinc (Japanese Patent Laid-Open No. 51-98243)
(6) A method of reacting using a ruthenium catalyst and adding at least one of zinc oxide and zinc hydroxide as an activating component to the reaction system (Japanese Patent Application Laid-Open No. 184138-1982)
Publication No. 2), etc. have been proposed.

(Problems to be Solved by the Invention) However, in these conventionally known methods, in order to increase the selectivity of the target cyclohexene, it was necessary to significantly suppress the conversion rate of the raw material, and the reaction rate decreased. At present, the yield and productivity of cyclohexenes are generally low due to their extremely small size, and there is no practical method for producing cyclohexenes.

Furthermore, according to the studies of the present inventors, for example, when metallic ruthenium particles are used alone as a catalyst, the catalyst adheres to the reactor made of a general metal material and the parts in contact with the reaction liquid. It has been found that there are many cases in which it is difficult to maintain a stable reaction system, such as deposition.

(Means for Solving the Problems) In order to solve these problems, the present inventors have developed a catalyst system for partial reduction of monocyclic aromatic hydrocarbons in order to obtain a stable catalyst system that is industrially advantageous. That is, the present invention was arrived at after intensive study on a system consisting of a main catalyst and other components.

In other words, when monocyclic aromatic hydrocarbons are partially reduced with hydrogen in the presence of water using particles mainly made of metal ruthenium as a hydrogenation catalyst, apart from the hydrogenation catalyst, group A elements other than boron, vanadium, etc. By carrying out the reaction by adding an oxide of at least one metal selected from group VB elements, chromium, iron, conomalt, titanium, or silicon, adhesion and deposition of the catalyst on the metal surface of the reactor can be prevented. This is an industrially advantageous method for producing stable cycloolefins.

Hereinafter, specific embodiments of the present invention will be described.

In the present invention, in addition to the hydrogenation catalyst mainly consisting of metal ruthenium particles, at least one selected from the following group elements excluding boron, VB group elements excluding nonadium, chromium, iron, conomalt, titanium, or silicon is used. The reaction is carried out by adding an oxide of one type of metal. More specifically, Altos, Ga20g.

In*Os*TI! Os, Nb0z*Ta
xes, 0rzO3e Taxes e 0030
4 *The reaction is carried out by adding at least one selected from TiO2 and 5iOt.

The amount of oxide added is based on the water coexisting in the reaction system.
1 x 10-s to 0.3 times by weight, preferably U I
It is 10-2 to 0.1 times the weight.

The oxide to be added is preferably in the form of fine powder, with an average particle size of 0.005 to 100μ, and 0.0
It is more preferable that it is 05 to 10μ. -The average particle diameter is determined by using ethanol as a dispersion medium and adding 1% to the dispersion medium.
After adding oxides of less than % by weight and performing dispersion operation for 30 to 60 minutes in an ultrasonic oscillation tank of several hundred watts, determine the change in absorbance of the dispersion using normal sedimentation methods (natural sedimentation method, centrifugal sedimentation method). This is the value calculated by

The effects obtained by adding such oxides are extremely useful, suppressing fluctuations in the reaction system due to adhesion of the hydrogenation catalyst to the reactor metal surface and agglomeration of the hydrogenation catalyst, and stabilizing the reaction system. This is particularly effective when continuously producing cycloolefin over a long period of time. It also has the effect of making it easier to handle the slurry containing the hydrogenation catalyst, for example, by apparently diluting and increasing the amount of the hydrogenation catalyst, making it easier to charge and recover the catalyst.

On the other hand, what should be specified is that the immersion method,
When a supported ruthenium catalyst prepared by supporting ruthenium and reducing it by a conventional method such as a drying method or a precipitation method is used as a hydrogenation catalyst, the selectivity of cycloolefins is as follows.
This is extremely low compared to the method of the present invention, and the addition of oxides in the method of the present invention is different from that of the ruthenium supported catalyst.
They are essentially different.

The monocyclic aromatic hydrocarbons used as raw materials for the present invention refer to benzene, toluene, xylenes, and lower alkylbenzenes having an alkyl group having 4 or less carbon atoms.

The particles mainly composed of metallic ruthenium used as a hydrogenation catalyst in the method of the present invention are those obtained from a ruthenium compound by a conventional reduction method, or particles containing other metals, e.g. The main component is zinc or ruthenium with the addition of chromium, molybdenum, tungsten, manganese, copper, nickel, iron, copper, etc., which are known per se. There are no particular restrictions on the various ruthenium compounds, but for example,
Chlorides, bromides, iodides, nitrates, sulfates, hydroxides, oxides, ruthenium r1 or various ruthenium-containing complexes can be used. Reduction methods include reduction with hydrogen gas, formalin, hydrogen This can be carried out by a chemical reduction method using sodium boronate, hypurazine, or the like.

Furthermore, in the method of the present invention, if a reduced product of ruthenium containing zinc in advance is used, the yield of cycloolefin can be further increased, and it is effectively used. Such a catalyst is a reduced product obtained by first impregnating a valuable ruthenium compound with a zinc compound and then reducing the compound, in which ruthenium is reduced to a metallic state.

Valuable ruthenium compounds that can be used include, for example, salts such as chlorides, nitrates, and sulfates, complexes such as ammine complexes,
Among the hydroxides, oxides, etc., trivalent or tetravalent ruthenium compounds are particularly preferred because they are easily available and easy to handle. A wide range of lead compounds can be used, including chlorides, sulfates, salts such as sulfates, complexes such as ammine complexes, hydroxides, and oxides.

It is not necessarily clear why such catalysts are effective as catalysts for the production of cycloolefins, but
It can be considered that during the process in which a valuable ruthenium compound is reduced to a metallic state, the coexisting zinc compound reveals or increases active sites that are advantageous for the production of cycloolefins.

The zinc content in such catalysts is 0.1 to ruthenium.
The content is adjusted to 50% by weight, preferably 2 to 20% by weight. Therefore, the main component of the catalyst is ruthenium, and zinc is not a carrier.

Valuable ruthenium compounds containing such zinc are
It may be obtained as a solid by a general coprecipitation method using a mixed solution of zinc and ruthenium compounds, or it may be obtained as a homogeneous solution.

The catalyst of the present invention is prepared by reducing a valuable ruthenium compound containing zinc and lead until the ruthenium is reduced to a metallic state.
A general ruthenium reduction method can be applied. For example, reduction with hydrogen in the gas phase, hydrogen or a suitable chemical reducing agent, e.g. NaBH, in the liquid phase.
A method of reduction using 4, formalin, etc. is preferably applied, and a method of reduction using hydrogen in the gas phase or liquid phase is particularly preferable.

When reducing with hydrogen in the gas phase, it is recommended to avoid extremely high temperatures or dilute the hydrogen with another inert gas in order to avoid an increase in crystallite size. Further, when the reduction is carried out in a liquid phase, it may be carried out by dispersing a solid valuable ruthenium compound containing zinc in water or alcohol, or it may be carried out in the state of a homogeneous solution. At this time, in order to facilitate the reduction,
It is advisable to carry out appropriate stirring, heating, etc. Furthermore, instead of water, an aqueous alkaline solution or an appropriate aqueous metal salt solution, such as an aqueous alkali metal salt solution, may be used.

Further, the same effect can be obtained by using a reduced product of ruthenium in which iron is pre-contained in zinc oxide as a hydrogenation catalyst. Such a catalyst can be obtained by the same method as a reduced product of ruthenium containing zinc in advance. A wide range of iron compounds can be used, including chlorides, nitrates, salts other than sulfates, hydroxides, and oxides. The iron content in this catalyst is relative to ruthenium.
0.01-50% by weight, 0.1-20% by weight for economic conditions
is adjusted to Therefore, the main component of the catalyst is also ruthenium. The diffraction angle in X-ray diffraction of this catalyst is characterized by being shifted to a higher angle side than that of ruthenium metal.

The hydrogenation catalyst particles described above exist in the reaction system mainly as crystallites made of ruthenium and/or aggregated particles thereof, but in order to increase the selectivity and yield of cycloolefins, it is necessary to The average crystallite diameter is preferably 200 λ or less, more preferably 100 λ or less. Therefore, the average crystallite diameter is calculated by a general method, that is, from the expansion of the diffraction line width obtained by the X-ray diffraction method, using the 5cherrer formula. Specifically, when 0uKa rays are used as an X-ray source,
The broadening of the diffraction line having a maximum around 44° at the diffraction angle (2θ) is calculated from .

The present invention requires the presence of water. The amount of water varies depending on the reaction type, but it can coexist with 0.01 to 100 times the amount of monocyclic aromatic hydrocarbons used, but under the reaction conditions, the raw materials and products An organic liquid phase mainly composed of
It is necessary to form a phase, and the coexistence of a very small amount of water that becomes a homogeneous phase under the reaction conditions, or the coexistence of a very large amount of water will reduce the effect, and the amount of water is too large. Therefore, it is necessary to increase the size of the reactor, so in practical terms F
It is desirable to increase the economy by 20 times.

In addition, in the present invention, unlike the known methods that have been proposed, elements of group IA of the periodic table, group IIA elements, Mn
, Fe, Zn, Co, and other salts of various metals may be added. In particular, the presence of zinc salts gives good results. Here, as the salts of various metals, for example, weak acid salts such as carbonate 1 and acetate, and strong acid salts such as hydrochloride, nitrate, and sulfate are used. The amount used is from 1X10-5 times the weight of water coexisting during the reaction to a saturated dissolution amount at room temperature.

Further, in the present invention, preferable results can be obtained by allowing the coexisting aqueous phase to react under acidic conditions. If the aqueous phase is made neutral or alkaline, the reaction rate will drop significantly, making this a practical production method. Further, to make it acidic, ordinary acids such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid, etc. may be added. In particular, sulfuric acid is extremely effective in increasing the reaction rate. The pH of the aqueous phase introduced into the reaction system is from 0.5 to less than 7, preferably from 2 to 6.5.

The partial reduction reaction in the method of the present invention is usually carried out continuously or batchwise by a liquid phase suspension method, but it can also be carried out by a stationary phase method. The reaction conditions are appropriately selected depending on the type and amount of the catalyst and additives used, but usually the hydrogen pressure is 1.
~200147cm”G, preferably 10-100
The range is A9/cm"G, and the reaction temperature is room temperature to 2.
The temperature is 50°C, preferably in the range of 100 to 200°C. In addition, the reaction time may be selected as appropriate by determining the actual target values for the selectivity and yield of the desired cyclohexene.
Although there is no particular limit, it is usually several seconds to several hours.

(Effects of the Invention) According to the present invention, a stable catalyst system for obtaining cycloolefins is provided, which is industrially extremely valuable.

(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

Examples 1 to 11 Pre-containing Zn(OH)z 9nu(oH)
A hydrogenation catalyst containing 4.8% by weight of zinc obtained by reducing , (average crystallite diameter 51A) 0.5? , water 280d, Z
n804-7H2028, 8f, benzene 140 xi
1. Oxide powder having the average particle diameter shown in Table 1 and 3.
5 tons were placed in an autoclave with an internal volume of 1 liter, whose wetted parts such as the reactor wall and stirring blade were made of titanium, and heated under high-speed stirring for 1 hour.
At 50°C and hydrogen pressure of 50kf/cIn"G, 120
Allowed to react for minutes.

After the reaction, only the oil phase was removed, 140% of benzene was newly added, and the mixture was reacted in the same manner for 120 minutes. This operation was repeated for the 5th and 10th time, and 1 rnl of the reaction solution was extracted over time, and the composition of the oil phase was analyzed by gas chromatography. The results are shown in Table 1.

Margin below The by-product in both cases was cyclohexane.

Even after the 10th repeated reaction, no catalyst was observed to adhere to the reactor walls, etc., regardless of the addition of any of the oxides.

Comparative Example 1 The reaction was carried out in the same manner as in Examples 1 to 11, except that no oxide was added. The results are shown in Table 2.

Table 2 After the 10th repeated reaction, adhesion of catalyst was observed on the inner wall of the reactor, etc., and it was found that it was difficult to maintain a stable reaction system.

From these, by adding the oxide in the method of the present invention,
It can be seen that cyclohexene can be obtained extremely stably.

Examples 12-18 1u(OH) containing pe(OH)s in advance
The reaction was carried out in the same manner as in Examples 1 to 11, except that a hydrogenation catalyst (average crystallite diameter sI!) of 0.7 t containing 2.4% by weight of iron obtained by reducing s was used. Table 3 shows the results.
Shown below.

Comparative Example 2 Comparative Example 2 The reaction was carried out in the same manner as in Examples 12 to 18, except that no oxide was used. The results are shown in Table 4.

Table 4 Examples 19 to 25 Examples 1 to 25 except that 0.7 t of hydrogenation catalyst (average crystallite diameter 55 A) obtained by reducing u(OH)3 was used.
The reaction was carried out in the same manner as in 11. The results are shown in Table 5.

Margin Comparative Example 3 The same operations as in Examples 19 to 25 were performed except that no oxide was used. The results are shown in Table 6.

Table 6 Examples 26 to 32 Zn0J for znS04/7H20! 215.4
The reaction was carried out in the same manner as in Examples 1 to 11 except that f was used.

The results are shown in Table 7.

Comparative Example 4 Comparative Example 4 The reaction was carried out in the same manner as in Examples 26 to 32, except that no oxide was used. The results are shown in Table 8.

Table 8 Comparative Examples 5 to 15 Hydrogenation catalyst prepared by adsorbing ruthenium chloride onto an oxide by a normal equilibrium adsorption method and carrying 1% by weight of ruthenium by hydrogen reduction 5. The reaction was repeated five times in the same manner as in Examples 1 to 11 except that Of was used and no oxide was added. The results are shown in Table 9.

From the following margins, it is clear that the system in which oxides are added in the present invention is completely different from ordinary supported catalyst systems.

Patent Applicant Asahi Kasei Kogyo Co., Ltd. Procedural Amendment (Voluntary) September 1985 Commissioner of the Patent Office Kuro 1) Akio Yu 1, Indication of Case 1985 Patent Application Interval No. 41981
No. 2, Name of the invention Method for producing cycloolefins 3, Relationship with the case of the person making the amendment Patent applicant 1-2-6-4 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture Scope" and column 8 "Detailed Description of the Invention"~,・1・,J-"1"(/" or more Claims (1) Monocyclic aromatic hydrocarbons mainly composed of ruthenium metal oxidation of the hydrogenation catalyst and at least one metal selected from tal, chromium, chromium, iron, cobalt, titanium, moji, or silicon in the presence of water using particles as a hydrogenation catalyst. (2) A method for producing cycloolefin characterized by carrying out the reaction by adding oxides (2) The amount of oxide added is
0.3 times the weight of the cycloolefin according to claim 1 (3) The average particle diameter of the oxide to be added is 0.0O5 to 1
(4) A method for producing a cycloolefin according to claim 1, in which the average crystallite diameter of the hydrogenation catalyst is 200 A or less ( 5) A method for producing a cycloolefin according to claim 1, wherein the hydrogenation catalyst is a reduced product of ruthenium containing zinc in advance. (6) The zinc content in the hydrogenation catalyst is the main component. 0.5-50 for Ruthenium
(7) A method for producing a cycloolefin according to claim 5, in which the hydrogenation catalyst is a reduced product of ruthenium containing iron in advance. Manufacturing method (8) Method for manufacturing a cycloolefin according to claim 7, wherein the iron content in the hydrogenation catalyst is 0.01 to 50% by weight based on ruthenium as the main component (9) A method for producing a cycloolefin according to claim 1, wherein the reaction is carried out under acidic conditions in the presence of at least one water-soluble zinc compound.

Claims (9)

[Claims] (1) When partially reducing monocyclic aromatic hydrocarbons with hydrogen in the presence of water using particles mainly made of metal ruthenium as a hydrogenation catalyst, boron is removed separately from the hydrogenation catalyst.
Group IIIA elements, Group VB elements except vanadium, chromium,
A method for producing a cycloolefin, characterized in that the reaction is carried out by adding an oxide of at least one metal selected from iron, cobalt, titanium, or silicon. (2) The amount of oxide added is 1 x 10^-^ relative to water
A method for producing a cycloolefin according to claim 1, which is 3 to 0.3 times by weight. (3) The average particle diameter of the oxide to be added is 0.005 to 1
A method for producing a cycloolefin according to claim 1 which is 00μ (4) A method for producing a cycloolefin according to claim 1, wherein the hydrogenation catalyst has an average crystallite diameter of 200 Å or less. (5) A method for producing a cycloolefin according to claim 1, wherein the hydrogenation catalyst is a reduced product of ruthenium containing zinc in advance. (6) The method for producing a cycloolefin according to claim 5, wherein the hydrogenation catalyst has a zinc content of 0.5 to 50% by weight based on ruthenium as a main component. (7) A method for producing a cycloolefin according to claim 1, wherein the hydrogenation catalyst is a reduced product of ruthenium containing iron in advance. (8) The method for producing a cycloolefin according to claim 7, wherein the iron content in the hydrogenation catalyst is 0.01 to 50% by weight based on ruthenium as the main component. (9) A method for producing a cycloolefin according to claim 1, wherein the reaction is carried out under acidic conditions in the presence of at least one water-soluble zinc compound.