JPH07232068A - Preparation of hydrogenation catalyst for preparing alcohol - Google Patents

Abstract

PURPOSE:To prepare a hydrogenation catalyst for preparing an alcohol with high activity and high filtration properties and contg. no chromium by reducing basic carbonate contg. copper and zinc with hydrogen, and oxidizing partially it with an oxygen-contg. gas. CONSTITUTION:A copper- and zinc-contg. insoluble basic carboriate is obtd. by mixing a soluble copper salt- and soluble zinc salt-contg. water soln. with a water soln. of a precipitant contg. an alkali carbonate or an alkali hydrogen carbonate. The formed precipitation is recovered, washed with water and dried in an inert gas. Then, this insoluble carbonate contg. copper and zinc is reduced with hydrogen without burning as it is and then, the copper reduced by bringing it into catalytic contact with an oxygen-contg. gas is partially oxidized. A hydrogenation catalyst for preparing alcohol is obtd. thereby. In addition, it is pref. that in the partial oxidation after reduction with hydrogen, 10-80% reduced copper is usually oxidized to copper oxide to obtain practical activity and filtration properties.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a highly active and highly filterable hydrogenation catalyst for producing alcohol, which is used for producing a useful alcohol by hydrogenolysis of carboxylic acid ester with hydrogen. Alcohol is a compound useful as a raw material for polyurethane, unsaturated polyester, plasticizer and the like, and also as a fragrance, a solvent, a resin modifier and the like.

[0002]

Alcohols are generally produced by hydrogenolysis of carbonyl compounds such as carboxylic acid esters with hydrogen in the presence of a catalyst. For example, as an alcohol, a diol such as 1,6-hexanediol is a mixture of carboxylic acids by-produced in the oxidation reaction in liquid-phase air oxidation of cyclohexane to produce cyclohexanol and cyclohexanone useful as a synthetic raw material for ε-caprolactam. Is esterified with alcohol, and the produced esterified product is hydrolyzed with hydrogen (Japanese Patent Publication No. 49-27164 and Japanese Patent Publication No. 53-3).
3567 gazette).

In the production of such a diol, a copper-chromium-based catalyst is often used as a hydrogenation catalyst. However, since the copper-chromium-based catalyst contains harmful chromium, it is necessary to handle the catalyst during its use. It has the drawbacks that special dust-proof measures are required and that special equipment is required for the treatment of wastewater and waste liquid discharged in the catalyst manufacturing process. Especially when carrying out the reaction under the condition of liquid phase suspension,
Since some of the catalyst components are dissolved in the reaction solution, there is a problem in treating the residue of the distillation still after the product diol such as 1,6-hexanediol is distilled off from the reaction solution.

In order to make up for the above-mentioned drawbacks, a method using a hydrogenation catalyst containing no chromium is known as a method for producing higher alcohols, but this method is also industrially sufficiently satisfactory. Absent. For example, as a method for producing a corresponding alcohol from coconut oil fatty acid methyl ester, a method using a hydrogenation catalyst in which copper oxide and iron oxide are supported on aluminum oxide is known (Japanese Patent Publication No. S58-58-
No. 50775), when applied to the production of diols as described above, this catalyst has a problem that its filterability is equivalent to that of the copper-chromium catalyst, but its activity is considerably low. As a method for producing lauryl alcohol from lauric acid methyl ester, a method using a hydrogenation catalyst composed of copper oxide and zinc oxide has been proposed (see Japanese Patent Laid-Open No. 63-141937), but as described above. When applied to the production of diols, this catalyst has a problem that its activity is higher than that of the copper-chromium-based catalyst, but its filterability is extremely poor.

Besides, as a chromium-free hydrogenation catalyst, the synthesis of methanol from syngas (Japanese Patent Laid-Open No. 64-2).
6526) or the synthesis of cumene and ethylbenzene from methylstyrene and acetophenone (DD21).
8090), a hydrogenation catalyst composed of copper metal-copper oxide-zinc oxide obtained by reducing copper oxide-zinc oxide is known. When applied to manufacturing, it has a problem of poor filterability. Further, this catalyst has a problem that handling is very complicated because the catalyst usually has high activity and generates heat or ignites when it is exposed to air.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing a hydrogenation catalyst for alcohol production which has high activity and high filterability, does not contain harmful chromium, and is easy to handle, and uses the catalyst. It is an object of the present invention to provide an industrially suitable method for producing alcohol.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies on a chromium-free copper-based catalyst in order to achieve the object of the present invention, and as a result, have obtained a base containing copper and zinc obtained under specific conditions. The present invention has been completed by finding that after the reduction of the acidic carbonate, the activity of the catalyst obtained by partially oxidizing the reduced copper is extremely high and the filterability is also excellent. That is,
The present invention reduces a basic carbonate containing copper and zinc obtained by mixing an aqueous solution containing a soluble copper salt and a soluble zinc salt with an aqueous solution containing an alkali carbonate or an alkali hydrogencarbonate with hydrogen, and then oxygen. The present invention relates to a method for producing a hydrogenation catalyst for alcohol production, which comprises partial oxidation with a contained gas.

First, a method for preparing an insoluble basic carbonate containing copper and zinc, which are precursors of the hydrogenation catalyst for alcohol production of the present invention, will be described. The insoluble basic carbonate containing copper and zinc is obtained by mixing an aqueous solution containing a soluble copper salt and a soluble zinc salt with an aqueous solution of a precipitating agent containing an alkali carbonate or an alkali hydrogen carbonate to recover a precipitate. Prepared by The soluble copper salt and the soluble zinc salt used at this time may each be water-soluble, for example, copper nitrate, copper sulfate, an inorganic acid salt of copper such as copper chloride, an organic salt of copper such as copper acetate. Acid salt, copper ammine complex salts such as tetraammine copper nitrate, zinc nitrate, zinc sulfate,
Examples thereof include inorganic acid salts of zinc such as zinc chloride, organic acid salts of zinc such as zinc acetate, and ammine complex salts of zinc such as hexaammine zinc nitrate. Further, sodium carbonate, potassium carbonate, ammonium carbonate and the like are preferably used as the alkali carbonate, and sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate and the like are preferably used as the alkali hydrogen carbonate. The use ratio of the above-mentioned copper salt and zinc salt is not particularly limited, but in order to obtain practical activity and filterability, the copper / zinc ratio (atomic ratio) is usually 1: 9 to 9: 1, preferably 2 :. 8
˜7: 3, more preferably 2: 8 to 6: 4.

The temperature at which the aqueous solution containing the soluble copper salt and the soluble zinc salt is mixed with the aqueous solution containing the precipitant is usually 50 ° C. or higher and the reflux temperature or lower, preferably 60 to 95 ° C. If this temperature is too low, the crystallinity of the insoluble basic carbonate containing copper and zinc formed will be poor, and the activity and filterability of the hydrogenation catalyst will be poor. In addition to salts, a part of hydroxides of copper oxide or copper or zinc is generated and mixed in the precipitate, and the filterability of the hydrogenation catalyst becomes poor, which is not preferable.

The pH at this time is usually maintained at 6.5 to 9.5 by adjusting the dropping rate of the aqueous solution containing the soluble copper salt and the soluble zinc salt and / or the aqueous solution containing the precipitating agent. Is preferably performed. If the pH is too low, a basic salt containing anions derived from the metal salts used, such as basic copper nitrate and basic copper sulfate, will be formed in addition to the desired basic carbonate, and the activity and filterability of the hydrogenation catalyst will be improved. On the contrary, if it is too high, the amount of the precipitate is reduced, or copper oxide is generated and mixed in the precipitate, which is not preferable because the hydrogenation catalyst has poor filterability. After the dropping of the above solution, in order to age the generated basic carbonate,
It is preferable that the solution is maintained at the temperature at the time of dropping with stirring or allowed to cool. At this time, the pH slightly changes, but it is not particularly necessary to adjust it.

The precipitate produced by the above operation is recovered and washed with water, and the insoluble basic carbonate containing copper and zinc is usually precipitated in the air or an inert gas such as nitrogen gas. It can be obtained by drying at 100 to 120 ° C. The obtained insoluble basic carbonate containing copper and zinc is an auricalcite (Zn, Cu) ₅ (CO ₃ ) which is a basic carbonate containing copper and zinc according to X-ray diffraction.
_The main component is a double salt of the same type as ₂ (OH) ₆ and a part of basic zinc carbonate is contained.

Next, a method for preparing the hydrogenation catalyst for alcohol production comprising copper metal-copper oxide-zinc oxide of the present invention from the insoluble basic carbonate containing copper and zinc will be described. The hydrogenation catalyst for alcohol production consisting of copper metal-copper oxide-zinc oxide of the present invention is an insoluble basic carbonate containing copper and zinc, which is directly reduced with hydrogen without calcination, and then the oxygen-containing It is prepared by partial oxidation of reduced copper in contact with gas. Hydrogen used for reduction is pure gas or inert gas such as nitrogen, 1% by volume
It may be diluted to the concentration of, but if the concentration of hydrogen in the gas is too low, the treatment time must be lengthened,
If it is too high, it will be difficult to remove the reaction heat generated by the reduction and the catalytic activity will decrease due to copper sintering. Therefore, hydrogen is usually diluted with an inert gas to a concentration of 2 to 60% by volume before use. To be done. The gas flow rate at this time is usually 1 to 100 l / g.cat.hr. If the temperature at this time is too low, the treatment time will be long, and if it is too high, the catalytic activity will decrease due to the sintering of the reduced copper. Therefore, the temperature is usually 100 to 400 ° C., preferably 1 ° C.
It is maintained in the range of 20 to 350 ° C.

Partial oxidation after hydrogen reduction is carried out by bringing the insoluble basic carbonate containing the above-mentioned reduced copper and zinc into contact with an oxygen-containing gas, but in order to obtain practical activity and filterability. It is preferred that usually 10-80% of the reduced copper is oxidized to copper oxide. In this treatment, the reduced catalyst is usually contacted with oxygen gas or air diluted with nitrogen gas so as to have an oxygen concentration of 0.1 to 5% by volume at room temperature, and then the oxygen concentration is further increased to 20%. It is carried out by contacting with oxygen gas diluted with nitrogen gas so as to have a volume% or air. Although the temperature rises during the partial oxidation, it is preferable to keep the treatment temperature at 100 ° C. or lower in order to suppress sintering. The thus obtained hydrogenation catalyst for alcohol production comprising copper metal-copper oxide-zinc oxide is used as it is as a catalyst for hydrocracking of the present invention.

The copper metal-copper oxide-zinc oxide hydrogenation catalyst obtained by the present invention can be used in the production of alcohols by hydrogenolysis of various carboxylic acid esters as described below. it can. (1) Production of 1,6-hexanediol from adipic acid diesters such as dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, and diesters of adipic acid and diols such as 1,6-hexanediol. (2) Production of 1,5-pentanediol from glutaric acid diesters such as dimethyl glutarate, diethyl glutarate, dipropyl glutarate and dibutyl glutarate. (3) Production of 1,4-butanediol from succinic acid diesters such as dimethyl succinate, diethyl succinate, dipropyl succinate and dibutyl succinate. (4) Production of propylene glycol from lactic acid esters such as methyl lactate, ethyl lactate, propyl lactate and butyl lactate. (5) Oxalic acid diesters such as dimethyl oxalate, diethyl oxalate, dipropyl oxalate and dibutyl oxalate, and ethylene glycol from glycolic acid esters such as methyl glycolate, ethyl glycolate, propyl glycolate and butyl glycolate. Manufacturing. (6) Methyl caproate, ethyl caproate, methyl octanoate, ethyl octanoate, methyl oleate, ethyl oleate, methyl laurate, ethyl laurate,
Production of higher alcohols from esters of saturated or unsaturated carbon atoms having 6 or more carbon atoms, such as methyl linoleate and ethyl linoleate, or linear or branched carboxylic acids and lower alcohols having 1 to 4 carbon atoms. (7) Production of polyol and amino alcohol from carboxylic acid ester having hydroxyl group or amino group.

The hydrogenation catalyst for alcohol production obtained in the present invention is an oxidation reaction liquid of cyclohexane, that is, an oxidation reaction liquid when cyclohexane is liquid-phase air-oxidized to produce cyclohexanol and cyclohexanone, and this cyclohexanol. And a mixture of carboxylic acids separated and recovered by water extraction or alkali washing from an oxidation reaction solution for producing adipic acid by nitric acid oxidation of cyclohexanone is esterified with an alcohol, particularly a diol such as 1,6-hexanediol. It can also be suitably used as a catalyst for hydrocracking an esterified compound (see, for example, JP-B-49-27164 and JP-B-53-33567).

This esterified product is obtained by esterifying an alcohol with a mixture of a carboxylic acid containing a dibasic acid such as adipic acid, glutaric acid and succinic acid and an oxyacid such as oxycaproic acid which are separated and recovered by the above method. It can be easily obtained by converting At this time, as the alcohol, for example, monohydric alcohol such as methanol, ethanol, propanol, butanol, or 1,4-butanediol, 1,5-pentanediol,
A diol such as 1,6-hexanediol can be used, but preferably 1,6-hexanediol,
Particularly preferably, a hydrocracking reaction liquid of the above esterified product containing 50% or more of 1,6-hexanediol is used.

The amount of alcohol used in the above esterification is usually the acid value (AV) of the starting carboxylic acid mixture.
Value), the hydroxyl group of alcohol is 1.2 to
It is chosen to be in the range of 1.5 times. If this is less than 1.2 times, the esterification will be very slow and the reaction will not be completed, so that the AV value of the obtained esterified product will be high, which is not preferable as a raw material for hydrocracking. Further, when it is larger than 1.5 times, there is no problem in the esterification, but the apparatus becomes large because the amount of the reaction solution to be treated in the esterification and the hydrogenolysis becomes large, and the target diol is recovered. It requires a large amount of energy, which impairs economic efficiency.

Other esterification conditions are not particularly limited, but usually, at a reaction temperature of 200 to 250 ° C., the AV value of the obtained esterified product is 5 mg-KOH / g or less, particularly 2 mg-KOH / g or less. It is preferable to carry out esterification until that time. This is an esterified AV
This is because when the value is higher than 5 mg-KOH / g, the action of the acidic substance in the hydrocracking causes the components of the hydrogenation catalyst to be remarkably dissolved and its activity to be reduced.
Since esterification is an equilibrium reaction, the reaction can be completed promptly by vaporizing and removing the produced water with an inert gas such as nitrogen gas.

The hydrocracking of the ester is usually carried out in the presence of the above-mentioned hydrogenation catalyst at a reaction temperature of 200 to 300 ° C., preferably 250 to 300 ° C. and a hydrogen pressure of 150 to 300 kg / cm ² (at the reaction temperature). (Gauge pressure), preferably 200 to 300 kg / cm ² (gauge pressure) under conditions of hydrogenation of the esterification product of the carboxylic acid ester or adipic acid and 1,6-hexanediol obtained as described above with hydrogen. It is performed by chemical decomposition. When the reaction temperature is higher than 300 ° C., the amount of by-products of water increases, and when the hydrogen pressure is higher than 300 kg / cm ² (gauge pressure), the safety of the equipment must be taken into consideration.

The hydrocracking of the ester is carried out in conventional liquid phase suspension bed equipment. That is, the raw material carboxylic acid ester and the hydrogenation catalyst were charged into a pressure resistant reactor, and under pressure of hydrogen,
The reaction is carried out in a batch system in which the temperature is raised to the reaction temperature while stirring and the reaction is performed. Further, it may be carried out by a continuous reaction in which the hydrogenation catalyst is suspended in a raw material carboxylic acid ester in advance and heated under hydrogen pressure, and then continuously introduced into the lower part of the reactor to react. it can. In addition, as the hydrogenation catalyst, one having a particle size distribution of 5 to 100 μm and a median diameter of 15 to 25 μm is usually used, and the usage amount thereof is usually 0.1 to 0.1 with respect to the carboxylic acid ester as a raw material.
It is 3.0% by weight, preferably 0.3 to 1.5% by weight.

The alcohol produced by the hydrogenolysis of the carboxylic acid ester is easily separated and purified from the reaction solution taken out from the above reactor by a conventional method. For example,
After separating the hydrogenation catalyst from the reaction solution using a filter-type filtration device, a vacuum distillation device was used to remove 1,6-hexanediol, 1,5-pentanediol, 1,4-butanediol, ethylene glycol, and lauryl alcohol. Etc. can be separated and purified to obtain the desired products.

[0022]

EXAMPLES Next, the method of the present invention will be specifically described with reference to Examples and Comparative Examples. The esterified product of adipic acid and 1,6-hexanediol in each of the Examples and Comparative Examples is a carboxylic acid prepared according to the method of water extraction of a liquid phase air oxidation reaction liquid of cyclohexane described in JP-B-49-27164. (Adipic acid: 26.8% by weight, oxycaproic acid: 31.9% by weight, glutaric acid: 6.1% by weight, succinic acid: 1.2% by weight)
It was prepared by esterification with a hydrogenolysis reaction liquid containing 50% or more of 6-hexanediol. The obtained esterified product contained 3.1% by weight of 1,6-hexanediol,
It contains 1.1% by weight of 5-pentanediol and 0.06% by weight of 1,4-butanediol, and has an acid value (AV) of 0.8 mg-KOH / g and a saponification value (SV) of 343 m.
It was g-KOH / g.

The hydrogenolysis reaction solution used for this esterification was obtained by the method of Example 1 described in JP-A-3-115237, and 1,6-hexanediol was added at 61. 1% by weight, 8.5% by weight of 1,5-pentanediol and 0.1% of 1,4-butanediol.
It contains 8% by weight. The analysis of the product was carried out by the same method as in the following examples.

Example 1 [Preparation of catalyst] 250 ml of a 14.5% by weight ammonium carbonate aqueous solution was placed in a glass container (catalyst preparation tank) having an internal volume of 2 l and kept at 80 to 85 ° C. A solution prepared by dissolving 0.157 mol of copper nitrate and 0.125 mol of zinc nitrate in 250 ml of water so as to maintain 6.5 was added dropwise over 30 minutes. After the completion of dropping, the mixture was allowed to cool with stirring, and during this period, the pH of the solution in the catalyst preparation tank rose to 8.2. The precipitate formed is filtered and washed,
After drying in air at 120 ° C., 4 g of a basic carbonate (precursor of hydrogenation catalyst) containing copper and zinc was obtained through a 70-mesh sieve. This basic carbonate was placed in a glass boat-shaped container, charged into a glass tube having an inner diameter of 25 mm, and 12 l of hydrogen gas diluted with nitrogen (hydrogen concentration: 2% by volume) was charged.
110 ° C, 170 ° C, 27 while flowing at a flow rate of / hr
Hold in the order of 0 ° C for 1 hour each, and then adjust the hydrogen concentration to 3
The content was reduced to 0% by volume and held at 270 ° C. for 1 hour. After the hydrogen reduction was completed, it was cooled to room temperature in a nitrogen stream.

Next, in order to partially oxidize copper, oxygen gas diluted with nitrogen gas (oxygen concentration: 0.1% by volume) is added to 3 parts.
Flow at room temperature at a flow rate of 6 l / hr for 10 hours,
The treatment was terminated when the oxygen concentration was gradually increased to reach 20% by volume. During this partial oxidation treatment, the treatment temperature is 1
The temperature was maintained below 00 ° C. The copper / zinc ratio (atomic ratio) of the obtained catalyst was 1: 1 and the partial oxidation rate of copper was 19.1%. The copper / zinc ratio (atomic ratio) of the catalyst was obtained by dissolving the catalyst in hydrochloric acid and performing atomic absorption spectrometry.
It was determined by using a thermogravimetric analyzer (TGA-50: manufactured by Shimadzu) and using hydrogen gas as a carrier gas to measure the weight change up to 500 ° C. In this case, since the corresponding weight loss was derived from partially oxidized copper, the partial oxidation rate was calculated assuming that copper and oxygen were bonded at a ratio of 1: 1.

[Hydrolysis of Carboxylic Acid Ester] 350 g of an esterified product of adipic acid and 1,6-hexanediol as a carboxylic acid ester and the above catalyst 3.
5 g and 5 g were charged into an SUS autoclave having an internal volume of 500 ml, and hydrogen gas was injected at 25 ° C. to 180 kg / cm ² (gauge pressure), and then heated to 280 ° C. with stirring. Next, at the reaction temperature of 280 ° C., hydrogen decomposition was carried out for 5 hours while maintaining the hydrogen pressure at a constant pressure of 280 kg / cm ² (gauge pressure) while supplementing hydrogen gas.

After completion of the reaction, the total amount of the reaction solution kept at 55 ° C. was put into a pressure filter equipped with a 10 μm membrane filter (effective diameter: 45 mm), and the pressure was adjusted to 1 kg / cm ² (gauge pressure) with nitrogen gas. Filtration was performed under pressure. The filtration time was determined by measuring the time required for filtration of the next 50 ml after passing the first 50 ml of this reaction solution with a stopwatch. Produced by hydrocracking 1,
Diols such as 6-hexanediol were obtained by analyzing the filtrate obtained by filtration by gas chromatography. As a result, the filterability of the reaction solution was 0.2 minutes, which was extremely good. In the reaction solution, 57.5% by weight of 1,6-hexanediol, 9.5% by weight of 1,5-pentanediol and 0.8% by weight of 1,4-butanediol were added.
Was included.

Example 2 [Preparation of catalyst] A catalyst was prepared and analyzed in the same manner as in Example 1. Table 1 shows the catalyst preparation conditions and the obtained results. [Hydrolysis of Carboxylic Acid Ester] 100 g of the esterified product of adipic acid and 1,6-hexanediol as a carboxylic acid ester and 2 g of the above catalyst were used as the internal volume 5
It was charged in a 00 ml autoclave made of SUS, hydrogen gas was injected at 25 ° C. to 180 kg / cm ² (gauge pressure), and then heated to 280 ° C. with stirring to give a reaction temperature of 2
Hydrogenolysis was carried out at 80 ° C. for 3 hours at a hydrogen pressure of 250 kg / cm ² (gauge pressure) at the start of the reaction. In the following examples and comparative examples, as an index of catalyst activity, instead of measuring the concentration of alcohols in the obtained reaction solution, a gauge pressure of 240 kg / cm ² to 210 kg / c was used during the reaction.
The time to fall to m ² was measured to calculate the hydrogen absorption rate.
The results obtained are shown in Table 1.

Comparative Example 1 In Example 2, the catalyst was a commercially available copper-chromium catalyst (N2
03: manufactured by JGC Chemical Co., Ltd.) Hydrolysis and analysis were performed in the same manner as in Example 2 except that the amount was changed to 2 g. As a result, the hydrogen absorption rate was 0.863 mol / hr, and the filtration time was 3.
It was 2 minutes.

Example 3 [Preparation of catalyst] In Example 1, the ammonium carbonate solution was added to 460 ml of a 10 wt% sodium carbonate aqueous solution, and the copper nitrate and zinc nitrate solutions were added with 0.12 mol of copper nitrate and 0.28 mol of zinc nitrate. A catalyst was prepared and analyzed in the same manner as in Example 1 except that each solution was changed to a solution dissolved in 400 ml of water. Table 1 shows the catalyst preparation conditions and the obtained results. [Hydrolysis of Carboxylic Acid Ester] Using 2 g of the above catalyst, hydrogenolysis and analysis were carried out in the same manner as in Example 2. The results obtained are shown in Table 1.

Comparative Example 2 In Example 3, the basic carbonate containing copper and zinc (precursor of the hydrogenation catalyst) was reduced to 4 in air in advance before hydrogen reduction.
A catalyst was prepared and hydrocracked and analyzed in the same manner as in Example 3 except that it was calcined at 50 ° C. for 1 hour. Table 1 shows the catalyst preparation conditions and the obtained results.

Comparative Example 3 In Example 3, basic carbonate containing copper and zinc (precursor of hydrogenation catalyst) was only calcined in air at 450 ° C. for 1 hour, and subsequent hydrogen reduction and partial oxidation were carried out. A catalyst was prepared and hydrocracked and analyzed in the same manner as in Example 3 except that it was not performed. Table 1 shows the catalyst preparation conditions and the obtained results.

[0033]

[Table 1]

Example 4 [Preparation of catalyst] 200 ml of water was placed in a glass container (catalyst preparation tank) having an internal volume of 2 l and kept at 80 ° C., and 0.25 mol of copper nitrate and 0.25 mol of zinc nitrate were added to 500 of water.
A solution dissolved in ml and a 10 wt% sodium carbonate aqueous solution were simultaneously added dropwise with stirring. The dropping rate was 8 g / min for the aqueous sodium carbonate solution, and for the aqueous solutions of copper nitrate and zinc nitrate, the pH of the solution in the catalyst preparation tank was maintained at 8.0. When 650 ml of an aqueous sodium carbonate solution was added dropwise, the addition of both solutions was completed, and the mixture was then aged at 80 ° C. for 1.5 hours while stirring. At this time, the pH rose to 8.8. The precipitate formed is filtered and washed and then washed in air 12
After drying at 0 ° C, a basic carbonate containing copper and zinc was obtained through a 70-mesh sieve. Subsequently, hydrogen reduction and partial oxidation were carried out in the same manner as in Example 1, and the obtained catalyst was analyzed. Table 2 shows the catalyst preparation conditions and the obtained results. [Hydrolysis of Carboxylic Acid Ester] Using 2 g of the above catalyst, hydrogenolysis and analysis were carried out in the same manner as in Example 2. The obtained results are shown in Table 2.

Comparative Example 4 In Example 4, the basic carbonate containing copper and zinc (precursor of hydrogenation catalyst) was reduced to 4 in air in advance before hydrogen reduction.
A catalyst was prepared and hydrocracked and analyzed in the same manner as in Example 4 except that the catalyst was calcined at 50 ° C. for 1 hour. Table 2 shows the catalyst preparation conditions and the obtained results.

Example 5 In Example 4, the pH of the solution in the catalyst preparation tank was 6.5.
The catalyst was prepared and hydrocracked and analyzed as in Example 4, except that After the completion of dropping the aqueous solution of sodium carbonate, the p of the solution in the catalyst preparation tank was aged during aging.
H rose to 7.6. Table 2 shows the catalyst preparation conditions and the obtained results.

Example 6 In Example 4, the pH of the solution in the catalyst preparation tank was 9.0.
The catalyst was prepared in the same manner as in Example 4 except that the above conditions were maintained, and hydrocracking and analysis were conducted in the same manner. After the completion of dropping the aqueous solution of sodium carbonate, the p of the solution in the catalyst preparation tank was aged during aging.
H rose to 9.3. Table 2 shows the catalyst preparation conditions and the obtained results.

Example 7 In Example 4, an aqueous solution of copper nitrate and zinc nitrate was added to 0.10 mol of copper nitrate and 0.40 mol of zinc nitrate to 500 parts of water.
A catalyst was prepared and hydrocracked and analyzed in the same manner as in Example 4 except that the solution dissolved in ml was replaced. The pH of the solution in the catalyst preparation tank rose to 8.6 during aging after the completion of the dropwise addition of the sodium carbonate aqueous solution. Table 2 shows the catalyst preparation conditions and the obtained results.

Example 8 In Example 4, 0.15 mol of copper nitrate and zinc nitrate aqueous solution and 0.35 mol of zinc nitrate were added to 500 parts of water.
A catalyst was prepared and hydrocracked and analyzed in the same manner as in Example 4 except that the solution dissolved in ml was replaced. Note that the pH of the solution in the catalyst preparation tank rose to 8.5 during aging after the completion of dropping the aqueous sodium carbonate solution. Table 2 shows the catalyst preparation conditions and the obtained results.

Example 9 In Example 4, 0.20 mol of copper nitrate and zinc nitrate aqueous solution and 0.30 mol of zinc nitrate were added to 500 parts of water.
A catalyst was prepared and hydrocracked and analyzed in the same manner as in Example 4 except that the solution dissolved in ml was replaced. Note that the pH of the solution in the catalyst preparation tank rose to 8.7 during aging after the completion of dropping the aqueous sodium carbonate solution. Table 2 shows the catalyst preparation conditions and the obtained results.

Example 10 In Example 4, an aqueous solution of copper nitrate and zinc nitrate was added to 0.30 mol of copper nitrate and 0.20 mol of zinc nitrate to 500 parts of water.
A catalyst was prepared and hydrocracked and analyzed in the same manner as in Example 4 except that the solution dissolved in ml was replaced. Note that the pH of the solution in the catalyst preparation tank rose to 8.9 during the aging after the completion of the dropwise addition of the aqueous sodium carbonate solution. Table 2 shows the catalyst preparation conditions and the obtained results.

Example 11 A catalyst was prepared and hydrocracked and analyzed in the same manner as in Example 4 except that the temperature of the catalyst preparation tank was changed to 60 ° C. The pH of the solution in the catalyst preparation tank was 8.8 during the aging after the completion of the dropwise addition of the sodium carbonate aqueous solution.
Rose to. The catalyst preparation conditions and the results obtained are shown in Table 2.
Shown in.

Example 12 A catalyst was prepared and hydrocracked and analyzed in the same manner as in Example 4 except that the temperature of the catalyst preparation tank was changed to the reflux temperature. After the completion of dropping the aqueous solution of sodium carbonate, the p of the solution in the catalyst preparation tank was aged during aging.
H rose to 9.5. Table 2 shows the catalyst preparation conditions and the obtained results.

Example 13 In Example 4, an aqueous solution of copper nitrate and zinc nitrate was added to 0.25 mol of copper sulfate and 0.25 mol of zinc sulfate to 500 parts of water.
A catalyst was prepared and hydrocracked and analyzed in the same manner as in Example 4 except that the solution dissolved in ml was replaced. The pH of the solution in the catalyst preparation tank rose to 8.8 during the aging after the completion of the dropping of the sodium carbonate aqueous solution. Table 2 shows the catalyst preparation conditions and the obtained results.

[0045]

[Table 2]

Example 14 [Preparation of catalyst] In Example 1, hydrogen reduction of a basic carbonate containing copper and zinc (precursor of hydrogenation catalyst) with hydrogen gas diluted with nitrogen gas (hydrogen concentration: 2) Capacity%) 12
2 at a rate of 30 ° C / hr while flowing at a flow rate of 1 / hr
A catalyst was prepared and analyzed in the same manner as in Example 1 except that the temperature was raised to 80 ° C., the temperature was maintained for 1 hour to reduce the temperature, and then the temperature was cooled to room temperature in a nitrogen stream. Table 3 shows the catalyst preparation conditions and the obtained results. [Hydrolysis of Carboxylic Acid Ester] Using 2 g of the above catalyst, hydrogenolysis and analysis were carried out in the same manner as in Example 2. The results obtained are shown in Table 3.

Examples 15 to 19 In Example 14, hydrogen reduction of a basic carbonate (precursor of hydrogenation catalyst) containing copper and zinc was carried out by using hydrogen gas having a hydrogen concentration shown in Table 2 and a heating rate and A catalyst was prepared and hydrocracked and analyzed as in Example 14, except that it was carried out at temperature. Table 3 shows the catalyst preparation conditions and the obtained results.

[0048]

[Table 3]

Example 20 [Preparation of catalyst] In Example 4, hydrogen reduction of a basic carbonate containing copper and zinc (precursor of hydrogenation catalyst) with hydrogen was diluted with nitrogen (hydrogen concentration: 2 vol. %) 12 l /
350 at a rate of 30 ° C / hr while flowing at a flow rate of hr
After heating up to ℃ and holding at this temperature for 1 hour to reduce,
Example 4 except that it was cooled to room temperature in a nitrogen stream.
A catalyst was prepared and analyzed in the same manner as in. Table 4 shows the catalyst preparation conditions and the obtained results. [Hydrolysis of Carboxylic Acid Ester] Using 2 g of the above catalyst, hydrogenolysis and analysis were carried out in the same manner as in Example 2. The results obtained are shown in Table 4.

Examples 21 to 25 In Example 20, hydrogen reduction of a basic carbonate (precursor of hydrogenation catalyst) containing copper and zinc was carried out by using hydrogen gas having a hydrogen concentration shown in Table 4, a heating rate and A catalyst was prepared and hydrocracked and analyzed as in Example 21, except that it was carried out at temperature. Table 4 shows the catalyst preparation conditions and the obtained results.

[0051]

[Table 4]

Example 26 [Preparation of catalyst] In Example 23, a catalyst was prepared in the same manner as in Example 23 except that the hydrogenolysis of the carboxylic acid ester was carried out as follows. Analysis was carried out. That is, 100 g of ethyl laurate as a carboxylic acid ester and 2 g of the catalyst prepared in Example 23 were charged into an SUS autoclave having an internal volume of 500 ml, and hydrogen gas was injected at 25 ° C. to 180 kg / cm ² (gauge pressure). The mixture was heated to 240 ° C. with stirring, and hydrogenolysis was carried out for 1 hour at a hydrogen pressure of 250 kg / cm ² (gauge pressure) at the start of the reaction. As a result, the hydrogen absorption rate is 1.50 m
The filtration time was 0.4 minutes at ol / hr. Further, when the reaction solution was analyzed, it was found that the reaction solution contained 79.1% by weight of lauryl alcohol, 18.5% by weight of ethanol, and 1.4% by weight of ethyl laurate. The results obtained are shown in Table 5.

Comparative Example 5 In Example 26, the catalyst was a commercially available copper-chromium catalyst (N
203: manufactured by JGC Chemical Co., Ltd.), the temperature of hydrocracking was changed to 260 ° C. (hence the hydrogen pressure at the start of the reaction was 260 kg / cm ^{2 in} gauge pressure), and the time was changed to 2 hours. Otherwise, hydrogenolysis and analysis were performed in the same manner as in Example 26. As a result, the hydrogen absorption rate was 0.45 mol /
At hr, the filtration time was 0.7 minutes. Further, when the reaction solution was analyzed, it was found that the reaction solution contained 79.3% by weight of lauryl alcohol, 18.3% by weight of ethanol and 1.1% by weight of ethyl laurate. The results obtained are shown in Table 5.

[0054]

[Table 5]

[0055]

According to the present invention, it is possible to obtain a chromium-free hydrogenation catalyst for alcohol production which simultaneously overcomes the problems of the conventional hydrogenation catalyst for alcohol production, which are related to activity, filterability and handling. While you can
A corresponding alcohol can be easily produced at a high reaction rate by hydrogenolysis of a carboxylic acid ester with hydrogen. INDUSTRIAL APPLICABILITY The hydrogenation catalyst for alcohol production of the present invention is particularly useful in a method of industrially producing a diol such as 1,6-hexanediol using an esterified product of a carboxylic acid mixture separated from a cyclohexane oxidation reaction solution as a raw material. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location // C07B 61/00 300 (72) Inventor Shinichi Furusaki 10 Ube, 1978, Kobegushi, Ube City, Yamaguchi Prefecture Kosan Co., Ltd.Ube Integrated Office

Claims (1)

[Claims] 1. A basic carbonate containing copper and zinc obtained by mixing an aqueous solution containing a soluble copper salt and a soluble zinc salt with an aqueous solution containing an alkali carbonate or an alkali hydrogen carbonate is reduced with hydrogen, and then, A method for producing a hydrogenation catalyst for alcohol production, which comprises partial oxidation with an oxygen-containing gas.