JP2001122810A - Method for reducing oxygen-containing organic compound with hydrogen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for using a catalyst capable of improving the hydrogen reduction activity of an oxygen-containing organic compound and the selectivity for the corresponding hydride and further improving the catalyst life when reducing the oxygen-containing organic compound with hydrogen and producing the corresponding hydrogenated oxygen-containing organic compound. SOLUTION: A nickel catalyst is subjected to an alkali treatment and drying and then a treatment with hydrogen to provide an alkali-treated nickel catalyst as a catalyst used for a hydrogen reducing reaction of the oxygen-containing organic compound. Thereby, the oxygen-containing organic compound is reduced with hydrogen in the presence of the resultant alkali-treated nickel catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for reducing an oxygen-containing organic compound with hydrogen in the presence of an alkali-pretreated nickel catalyst. The hydrogenated oxygen-containing organic compound obtained by the method of the present invention is useful as a raw material for producing lactams, lactones, or dibasic acids, and these are useful as raw materials for polyester or polyamide.

[0002]

2. Description of the Related Art A method for reducing an oxygen-containing organic compound such as epoxycyclododecane with hydrogen in the presence of a nickel catalyst is known. For example, Japanese Patent Publication No. 47-38437 discloses a method for reducing hydrogen to epoxycyclododecane. A method is disclosed in which Raney nickel is used as a catalyst in the production of cyclododecanol and isomerized cyclododecane by contacting and hydrogenating the same. However, the above publication does not describe the yields of cyclododecanol and cyclododecanone. Therefore, when the above method was subjected to additional tests, the results showed that upon hydrogen reduction of epoxycyclododecanes, a deoxygenation reaction of the epoxy group occurred and hydrocarbons such as cyclododecadienes, cyclododecenes and cyclododecanes. Was produced in large quantities, and the selectivity of the desired products, namely cyclododecanol and cyclododecanone, was found to be unsatisfactory.

Also, Neftekhimiya, 16 (1), 114-119, 1
976, using a nickel catalyst supported on chromium oxide,
A method for the hydrogen reduction of 1,2-epoxy-5,9-cyclododecadienes is described. However, in this method, a toxic chromium compound is used, so that practical use is difficult. In general, it is widely known that a hydrogenation reaction of an epoxy compound using a nickel catalyst generates a large amount of various by-product compounds by a deoxygenation reaction (Tokyo Kagaku Dojin, Lecture Organic Reaction Mechanism 13, Catalytic Reduction Reaction ( 2nd volume), written by Ikuo Mitsui).

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a corresponding hydrogen reduction compound in high yield by contacting hydrogen with an epoxy group-containing organic compound. Furthermore, the present invention provides a method for producing a target hydrogen reduction product in high yield by suppressing the by-product of a hydrocarbon compound due to a deoxygenation reaction by contacting hydrogen with an epoxy group-containing organic compound. What you want to do.

[0005]

The above object is achieved by the following method for reducing hydrogen of an oxygen-containing organic compound according to the present invention.
The method for reducing hydrogen of an oxygen-containing organic compound according to the present invention is a method for reducing an oxygen-containing organic compound with hydrogen in the presence of an alkali-treated nickel catalyst prepared by treating a nickel catalyst with an aqueous alkali solution, drying and further subjecting the nickel catalyst to hydrogen treatment. To produce a hydrogenated oxygen-containing organic compound. In the method of the present invention, the oxygen-containing organic compound is preferably selected from epoxy group-containing organic compounds, and the hydrogenated oxygen-containing organic compound is preferably a hydroxyl group-containing organic compound corresponding to the epoxy group-containing organic compound. In the method of the present invention, the nickel catalyst may include a nickel-containing catalyst component and a carrier component supporting the same. In the method of the present invention, the epoxy group-containing organic compound is preferably selected from epoxycyclododecadienes, epoxycyclododecenes, epoxycyclododecanes, epoxycyclooctenes, epoxycyclooctanes, epoxycyclohexenes, and epoxycyclohexanes. In the method of the present invention, the alkali is an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, an alkaline earth metal carbonate, an alkali metal alkoxide, and an alkaline earth metal. It preferably contains at least one selected from basic oxides of rare earth metals.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The alkali-treated nickel catalyst used in the method for reducing hydrogen of an oxygen-containing organic compound according to the present invention comprises:
It is prepared by treating a nickel catalyst with a treatment solution containing an alkali, drying and subjecting this to a hydrogen treatment. In the method of the present invention, the raw material nickel catalyst is selected from metal nickel such as Raney nickel, nickel oxide, and stabilized nickel, and these may be supported on a carrier.

Activated carbon, metal oxides, or diatomaceous earth can be used as the nickel catalyst carrier. As the metal oxide for the carrier, alumina, silica, zirconia, titania, zeolite, titanosilicate, magnesia and the like or a mixture thereof, preferably alumina, silica, zeolite or a mixture thereof, more preferably alumina Is used. Examples of the type of alumina include γ-alumina and α-alumina, and preferably γ-alumina is used.

[0008] The starting nickel catalyst used in the present invention is prepared by a known method. For example, a catalyst in which a nickel oxide is supported can be obtained by impregnating a carrier with a predetermined amount of an aqueous solution of nickel nitrate, evaporating to dryness, and then calcining. Furthermore, the catalyst supporting nickel oxide can be reduced by hydrogen by a known method to obtain a catalyst supporting metal nickel. The amount of nickel supported in the raw material nickel catalyst of the present invention is 0.1 to 90% by weight, preferably 5 to 70% by weight, more preferably 10 to 70% by weight, as a ratio of metallic nickel to the weight of the carrier. is there.

In the present invention, the alkali used for the alkali treatment of the nickel catalyst is, for example, an alkali metal such as sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, barium hydroxide, strontium hydroxide and the like. And alkaline earth metal hydroxides: alkali metal and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and barium carbonate: alkali metal alkoxides such as sodium methoxide and sodium ethoxide: alkaline earth metals and Basic metal oxides such as rare earth elements and the like are preferred, and alkali metal hydroxides, alkali metal carbonates and basic metal oxides of alkaline earth metals are preferred, and alkali metal hydroxides are more preferred. Is used. These alkaline substances may be used alone or in combination of two or more.

In the alkali treatment method of the present invention using an alkali-containing treatment solution for a nickel catalyst, for example, when an alkali metal hydroxide is used, a specified amount of the alkali metal hydroxide solution is added to the nickel catalyst at 0 to 100 ° C. Preferably, it is impregnated at a temperature of 0 to 30 ° C. and dried uniformly in the air or under an inert gas atmosphere. As the solvent for dissolving the alkali metal hydroxide, any solvent can be used as long as it is inert to the catalyst.
Water, alcohol or a mixed solution thereof is used.

In the method of the present invention, the alkali treatment of a nickel catalyst with an alkaline earth metal hydroxide includes:
For example, a nickel catalyst was immersed in a prescribed amount of a solution of an alkaline earth metal salt, and a solution containing hydroxide ions was added thereto to precipitate an alkaline earth metal hydroxide on the nickel catalyst surface. Thereafter, the solid is filtered and washed, and the obtained solid is uniformly dried in air, under an inert gas atmosphere, or under reduced pressure.

In the method for alkali treatment of a nickel catalyst with a basic metal oxide in the method of the present invention, for example,
In the same manner as in the case of using the alkaline earth metal salt, the nickel catalyst is immersed in a solution of the basic metal salt, a solution containing hydroxide ions is added thereto, and the metal prepared on the surface of the nickel catalyst is added. The nickel catalyst supporting the hydroxide is filtered and washed, and the obtained solid is thermally decomposed uniformly in air or under an inert gas atmosphere.

In the method of the present invention, the amount of alkali used is determined according to the molar amount of nickel atoms of the nickel catalyst used, and the total molar amount of alkali is determined by the molar amount of nickel atoms in the nickel catalyst used. 0.01 ~
It is preferably 10 times, more preferably 0.05 to 5 times, still more preferably 0.05 to 1.0 times, and still more preferably 0.05 to 0.5 times. . When the amount of the alkali added is less than 0.01 times the molar amount, after the reduction treatment, the effect of suppressing the deoxygenation reaction of the obtained reduction reaction system is insufficient, and the yield of the obtained target compound is insufficient. When the amount exceeds 10 times the molar amount, the effect of the basic substance is saturated, which not only causes an economic disadvantage, but also greatly reduces the activity and by-products from the oxygen-containing organic compound. May increase.

In the method of the present invention, the above-mentioned alkali-treated nickel catalyst is subjected to hydrogen reduction. The temperature at which the hydrogen reduction is performed is 50 to 1000 ° C, preferably 70 to 800 ° C,
More preferably, it is 100 to 700 ° C. As a method for performing hydrogen reduction, a method in which gas-phase hydrogen is passed while an alkali-treated nickel catalyst is placed in a fixed-bed flow reactor, and a method in which a nickel catalyst is dispersed in an inert solvent in an autoclave and stirred. A method of enclosing or circulating hydrogen while using such a method is used.

In the present invention, in drying the alkali-treated nickel catalyst, it is possible to simultaneously perform reduction and drying by the above-mentioned method in a hydrogen atmosphere. It is preferable to perform hydrogen reduction. The alkali-treated nickel catalyst which has been subjected to the hydrogen reduction treatment may be subjected to the reaction as it is, or may be used after being subjected to a stabilization treatment by a known method using an oxygen-containing gas.

In the method of the present invention, an oxygen-containing organic compound is subjected to hydrogen reduction in the presence of an alkali-treated and hydrogen-treated nickel catalyst prepared as described above (hereinafter referred to as an alkali-treated nickel catalyst). .

The oxygen-containing organic compound used in the method of the present invention is preferably selected from epoxy group-containing organic compounds, and the epoxy group-containing organic compound is an epoxy group-containing alicyclic organic compound having 6 to 12 carbon atoms. Preferably, it is a compound. Such alicyclic organic compounds include, for example, cyclododecene oxide, 1,2-epoxy-
5,9-cyclododecadienes, cyclohexene oxides and the like. These compounds may be substituted by one or more, preferably 1 to 3 alkyl groups, preferably alkyl groups having 1 to 4 carbon atoms. These compounds may be used alone or as a mixture of two or more. Although many isomers exist in these compounds, there is no limitation on the type of isomer.

In the method of the present invention, the reduction reaction of the oxygen-containing organic compound with hydrogen is carried out using a batch reactor, a continuous reactor such as a trickle bed reactor or a fixed bed flow reactor. An inert organic solvent can be used in this reaction.

The nickel catalyst used in the method of the present invention may be in the form of a powder or a molded pellet. Generally, in the case of a powdered nickel catalyst, it is subjected to a liquid phase suspension bed catalytic reaction, and in the case of a molded pellet, it is used for a fixed bed catalytic reaction. The fixed bed catalytic reaction can be performed by a trickle reaction, a liquid phase reaction, a gas phase reaction or the like depending on conditions. In the case of a powdery catalyst used for a liquid phase suspension bed reaction, its average particle size is 5 μm to 300 μm.
μm, and in the case of a shaped pellet catalyst used in a fixed bed catalytic reaction, the average length of the pellets is as follows:
Preferably it is 1 to 10 mm. In the method of the present invention, the use amount of the nickel catalyst is not particularly limited,
In the case of a reactor of the liquid-phase suspension bed type, the ratio of the molar amount of nickel atoms in the nickel catalyst to the molar amount of the organic compound containing an epoxy group used is generally 1 / 300,000.
Or more, more preferably 1 / 10,000 or more, still more preferably 1 / 5,000 or more.
0 to 2/1. If the amount of nickel catalyst is too small, the catalytic effect may be insufficient, and if it is too large, the catalytic effect may be saturated and economically disadvantageous. In such a case, the load of the stirrer may be too large.

In the method of the present invention, the hydrogen reduction reaction of the oxygen-containing organic compound may be performed in an organic solvent, or may be performed without using a solvent. As an organic solvent,
It is preferable to use those that do not adversely affect the hydrogen reduction reaction of the method of the present invention and do not generate by-products. Examples of such organic solvents include liquid alkanes such as n-hexane, n-heptane and cyclohexane, dimethyl ether and the like. Ethers such as dioxane and the like, alcohols such as propanol and butanol, and esters such as ethyl acetate and butyl acetate can be used, and these can be used alone or in combination of two or more. It may be used as a mixture. When a reaction solvent is used, the control of the reaction may be facilitated. The amount of the organic solvent to be used is preferably 100 times or less, more preferably 10 times or less, the weight of the oxygen-containing organic compound.

In the method of the present invention, the raw material containing the oxygen-containing organic compound may contain the corresponding reaction product such as an alkanone compound and / or an alkanol compound.

In the method of the present invention, the oxygen-containing organic compound is treated with a treatment solution containing an alkali, dried,
The mixture is further mixed with an alkali-treated nickel catalyst which has been subjected to a hydrogen treatment, and if necessary, the mixture is heated and reacted at normal pressure or under pressure while stirring. At this time, the reaction temperature is preferably from 80 to 280 ° C, more preferably from 100 to 250 ° C, and
It is more preferable that the temperature is 0 to 230 ° C.
More preferably, it is 00 ° C. In the method of the present invention, the hydrogen pressure is preferably from 98 kPa to 98,000 kP.
a (1 to 1000 kg / cm ² ), more preferably 490 kP
a to 39000 kPa (5 to 400 kg / cm ² ), more preferably 980 kPa to 20000 kPa (10 to 200 kg
/ Cm ² ).

If the reaction and / or temperature is excessively low, the hydrogenation reaction of the oxygen-containing organic compound with respect to oxygen and the hydrogenation reaction with respect to the double bond do not proceed sufficiently, and the yield of the target compound is insufficient. It may be. Also, when the pressure is excessive, the hydrogen reduction reaction proceeds sufficiently, but the effect is saturated and may be disadvantageous economically.When the temperature is excessively high, by-products such as high Boiling compound formation increases. The reaction time and contact time
Although there is no particular limitation, usually a reaction time of 3 hours or less is sufficient.

In the method of the present invention, the reaction product can be isolated and separated from the reaction system, if necessary, for example, by distillation, crystallization, etc., and purified.

[0025]

The method of the present invention will be further described by the following examples. However, these examples do not limit the scope of the method of the present invention.

Example 1 Activated alumina powder carrier (specific surface area 150 m ² / g)
0 g is immersed in 200 ml of an aqueous solution containing 7.44 g of nickel nitrate hexahydrate.
, And 100 ml of a warm aqueous solution (40 ° C.) containing 2.04 g of sodium hydroxide was added thereto.
The mixture was allowed to stand at 0 ° C for 2 hours. The resulting precipitate was suction-filtered using Nutsche and filter paper, and the pH of the filtrate was adjusted to 8 using pure water.
Washing was repeated until the following (approximately 500 ml). After the obtained solid was simultaneously dried and pulverized at 120 ° C., the obtained powder was fired in an electric furnace at 500 ° C. for 3 hours in air. The calcined powder is transferred to a quartz fixed bed flow-type reactor, reduced at 500 ° C. for 1 hour in a hydrogen stream at 40 ml / min, cooled to room temperature, and stabilized with nitrogen gas containing 3% diluted oxygen. To obtain a nickel catalyst in which 30% by weight of nickel was supported on a carrier.

The nickel catalyst was pretreated as described below and used for the reaction. Sodium hydroxide (0.204 equivalent to 0.2 equivalent to metallic nickel contained in the catalyst)
The nickel catalyst was immersed in 10 cc of an aqueous solution containing g), dried at 120 ° C. and pulverized to obtain an alkali-supported nickel catalyst. Next, the catalyst was transferred to a quartz fixed-bed flow-type reactor, and reduced at 500 ° C. for 1 hour in a hydrogen stream of 40 ml / min. After cooling to room temperature, the catalyst was converted to nitrogen gas containing 3% diluted oxygen. And stabilized.

1.50 g of the pretreated nickel catalyst
Was charged in a stainless steel autoclave (volume: 120 ml), 20 ml of cyclohexane was added, hydrogen gas was sealed at normal temperature at a pressure of 5100 kPa (50 atm), and a preliminary reduction treatment was performed at 230 ° C. for 1 hour. After cooling, 1,2-epoxy-
5,9-cyclododecadiene (hereinafter referred to as ECD "):
8.92 g (50 mmol) and 7 ml of cyclohexane were added, and a hydrogen reduction reaction was performed at 150 ° C. for 1 hour while always keeping the hydrogen partial pressure in the reaction system at 5100 kPa (50 atm).

After the completion of the reaction, the reaction product was filtered, and the reaction solution was analyzed by gas chromatography. as a result,
The raw material ECD "has been completely consumed and 8.85 g (48.0) of cyclododecanol (hereinafter referred to as CDOL).
mmol) and cyclododecanone (hereinafter referred to as CDON):
0.02 g (0.1 mmol) was obtained. Epoxycyclododecane (hereinafter referred to as ECD) as a by-product was not obtained, and deoxygenated by-product cyclododecane (hereinafter referred to as CD) was not obtained.
AN8): 0.28 g (1.7 mmol) was obtained.
That is, the content of the by-product was only 1.7 mmol.

Example 2 ECD ″ was hydrogen reduced in the same manner as in Example 1, except that
A catalyst support was prepared as described below. 5.0 g of the above-mentioned activated alumina powder carrier was immersed in 200 ml of an aqueous solution containing 2.51 g of magnesium nitrate hexahydrate and placed in a water bath.
The mixture was heated to 100 ° C, 100 ml (40 ° C) of a hot aqueous solution containing 0.79 g of sodium hydroxide was added, and the mixture was sufficiently stirred and left standing at 40 ° C for 2 hours. The obtained precipitate was suction-filtered using Nutsche and filter paper, and the washing was repeated with pure water until the pH of the filtrate became 8 or less (about 500 ml). After drying and grinding the obtained solid at 120 ° C.,
C. for 3 hours in air, and Al ₂ O
_{A 3-} MgO mixture was obtained.

According to the same operation as in Example 1, 30% by weight of reduced nickel was supported on the carrier, and the carrier was further subjected to a stabilizing treatment. Hydrogen reduction of ECD ″ was carried out in the same manner as in Example 1. However, 1.50 g of the pretreated catalyst was used as a catalyst. As a result, the raw material ECD ″ was completely consumed, and CDOL: 8 .32 g (45.
2 mmol) and CDON: 0.03 g (0.2 mmol) were obtained. The by-product is ECD: 0.00g (0.0mmo
l), CDAN: 0.73 g (4.4 mmol).
That is, 4.4 mmol of by-product was produced.

Example 3 The hydrogen reduction of ECD ″ was carried out in the same manner as in Example 1. However, the hydrogen reduction reaction temperature was set at 140 ° C. As a result, the raw material ECD ″ was completely consumed, and CDOL: 8.7
0 g (47.2 mmol), CDON: 0.00 g (0.0
mmol) were obtained. The by-product is ECD: 0.09 g (0.
5 mmol) and CDAN: 0.34 g (2.0 mmol). That is, 2.5 mmol of by-product was produced.

Comparative Example 1 ECD ″ was reduced with hydrogen in the same manner as in Example 1, except that
The catalyst was not subjected to an alkali treatment. As a result, the raw material ECD ″ was completely consumed, and CDOL: 8.04
g (43.6 mmol) and CDON: 0.03 g (0.2
mmol) were obtained. The by-product is ECD: 0.00g (0.
0 mmol) and CDAN: 0.98 g (5.9 mmol). That is, 5.9 mmol of by-product was produced.

Comparative Example 2 The hydrogen reduction of ECD ″ was carried out in the same manner as in Example 1. However, the reduction treatment after the alkali treatment of the catalyst was not carried out.
As a result, the raw material ECD ″ has been completely consumed, and
DOL: 8.45 g (45.9 mmol) and CDON:
0.06 g (0.4 mmol) was obtained. By-product is EC
D: 0.17 g (1.0 mmol), CDAN: 0.54 g
(3.2 mmol). That is, the by-product is 4.2mm
ol had been generated.

Examples 4 to 8 (Catalyst Life) Using 30% by weight nickel-supported catalyst prepared in the same manner as in Example 1, the same reaction conditions as in Example 1 (starting material EC
D "using 50 mmol), and the batch reaction was repeated. The product obtained in each reaction was analyzed. The number of moles of the product (mmol)
Are shown in Table 1.

[0036]

[Table 1]

Comparative Examples 3 to 6 (Catalyst Life) In each of Comparative Examples 3 to 6, the batch reaction was repeated the same number of times as shown in Table 2 under the same reaction conditions as Comparative Example 1.

[0038]

[Table 2]

[0039]

According to the method of the present invention, the oxygen-containing organic compound is hydrogen-reduced, and when the corresponding hydride is produced, the nickel catalyst to be used is subjected to an alkali treatment before being hydrogen-reduced, whereby the organic compound is reduced. The hydrogen reduction activity and the selectivity of the corresponding hydride can be improved, and further the catalyst life can be improved.

Claims (5)

[Claims] 1. An oxygen-containing organic compound is reduced by hydrogenation in the presence of an alkali-treated nickel catalyst prepared by treating a nickel catalyst with a treatment solution containing an alkali, drying and further subjecting the nickel treatment to hydrogenation. A method for reducing hydrogen of an oxygen-containing organic compound, comprising producing an oxygen-containing organic compound. 2. The oxygen-containing organic compound is selected from an epoxy-containing organic compound, and the hydrogenated oxygen-containing organic compound is a hydroxyl-containing organic compound corresponding to the epoxy-containing organic compound. The method described in. 3. The method according to claim 1, wherein the nickel catalyst comprises a nickel-containing catalyst component and a carrier component supporting the same. 4. The method according to claim 2, wherein the epoxy group-containing organic compound is selected from epoxycyclododecadienes, epoxycyclododecenes, epoxycyclododecanes, epoxycyclooctenes, epoxycyclooctanes, epoxycyclohexenes and epoxycyclohexanes. . 5. The method according to claim 1, wherein the alkali is an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, an alkaline earth metal carbonate, an alkali metal alkoxide, and an alkaline earth metal. 2. The composition according to claim 1, comprising at least one selected from basic oxides of rare earth metals.
The method described in.