JPH08108072A - Production of catalyst for hydrogenation reaction of aliphatic alkyl ester - Google Patents

Abstract

PURPOSE: To obtain a Cu-Mn-Al catalyst having high activity, producing a small amt. of a by-product and easily separable from a product by filtration. CONSTITUTION: When a catalyst contg. copper oxide, aluminum oxide and manganese oxide as constituent components is prepd. by coprecipitation, an aq. soln. of metallic salts and an alkali metallic compd. are continuously and simultaneously added to heated water under stirring at a constant pH. In this method, alumina hydrate is previously added to at least one of the aq. soln. and the heated water.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a catalyst for producing higher alcohols by hydrogenating aliphatic alkyl esters under high pressure.

[0002]

BACKGROUND OF THE INVENTION Higher fatty alcohols are important intermediate raw materials in the chemical industry, and fatty alcohol sulphates,
It is used as a raw material for surfactants such as polyglycol ether and is produced by catalytically hydrogenating fatty acids or fatty acid esters obtained from natural fats and oils under high pressure. Copper / chromium based catalysts have been used.

Copper / chromium-based catalysts can be produced by various methods, but copper / chromite-based catalysts known as Adkins catalysts have a high surface area and are not only highly active but also inexpensive hexavalent. Since it can be produced from chromium as a raw material, it has a history of being widely used.Chromates, dichromates or chromic anhydride are usually used as catalyst raw materials, and precipitates in the presence of metallic copper salts. It is manufactured and supplied according to the law.

The co-precipitation copper / chromite type catalyst using a chromate or a dichromate as a raw material cannot completely precipitate hexavalent chromium in the precipitation forming step due to the chemical nature of chromium. Since it is contained in wastewater etc. and discharged at the manufacturing stage, it is necessary to take measures to prevent environmental pollution.By treating with a reducing agent, etc., it will not be an insoluble precipitate and it will be prevented from flowing out of the system. Although it has been attempted, a final treatment method has not been established yet despite the fact that sludge containing chromium compounds is generated as a result and the disposal measures must be taken.

(3) Further, the copper-chromite type catalyst is usually used as a molded body or powder, and various handling must be carried out in the process of application from the production stage to the reaction, in which the catalyst is fine powder. It is necessary to take measures to prevent pulverization or dust collection, as it can be dispersed into the work environment and copper and chromite catalysts have excellent performance for hydrogenation reactions. However, there is a demand for the development of a chromium-free catalyst in consideration of the harmful effects of chromium.

It is generally said that chromium as a catalyst component imparts heat resistance to the catalyst and stabilizes the catalyst structure. Usually, a catalyst not containing chromium has low activity and tends to have poor activity durability. In order to make a catalyst that can be used industrially without any addition, it is necessary to improve these drawbacks, and aluminum oxide, silicon oxide, titanium oxide, zirconium oxide are components that are expected to have the same effect as chromium. , Magnesium oxide, etc. have been selected and used in combination with copper oxide for the development of chromium-free catalysts.

Among these oxides, aluminum oxide has been used as one of the main components in various industrial catalysts. For example, copper-zinc catalysts as low-temperature carbon monoxide conversion catalysts have been used for decades. It has a track record of being added and used as an essential third component, and is considered to be one of the effective components in the catalyst for hydrogenation belonging to the field of the present invention. Many attempts have been made to add aluminum.

These catalysts are usually produced by a coprecipitation method, but the precipitate containing aluminum is fine and has a high water retention property and is generally difficult to filter. Therefore, it is necessary to improve the filterability in industrial catalyst production. In many cases, the hydrogenation reaction is carried out under severe conditions, so the catalyst particles have a tendency to be pulverized during the reaction or during the operation thereof.
Since it is often difficult to separate the product and the catalyst by filtration in the subsequent product treatment process, a method for simultaneously solving these problems has been proposed. (4) For example, JP-A-55-55 In 8820, a catalyst is produced by forming a precipitate by simultaneously dropping an aqueous solution of copper, iron and aluminum salts and an aqueous solution of caustic soda at room temperature or under heating, and then aging, followed by washing with water, filtration, drying and firing. It is disclosed in Japanese Patent Laid-Open Nos. 4-59050 and 5-
In 31366, when a neutralization reaction of an aqueous solution of copper, iron, aluminum salts and an aqueous solution of an alkali metal compound is performed under heating, an aluminum compound, a metal compound containing copper and iron, and a metal compound containing copper and aluminum are alternately precipitated. It is disclosed that the catalyst is produced by aging, and then washing with water, filtration, drying, and calcination.
It is said that a catalyst having higher activity and better filterability than the conventional catalyst was obtained, but all of them contain iron as an essential component.

Since natural fats and oils exist as triglycerides, they are usually used as a raw material for hydrogenation reaction after being esterified with methanol or the like. However, some free fatty acids remain in the reaction product, so that they are used as catalysts during the reaction. Is prone to acid erosion, which leads to activity deterioration due to elution of the active ingredient or catalyst particle disintegration and particle formation due to erosion, which results in deterioration of filterability between the product and catalyst after the completion of hydrogenation reaction Because the problem of
In order to overcome its catalytic drawbacks, eg German patent DE
-4028295 aims to improve the acid resistance of the catalyst by washing, filtering and drying the precipitate obtained by the neutralization reaction between the salt aqueous solution and the alkaline aqueous solution, followed by high temperature treatment in the catalyst containing copper and manganese as components. There is.

[0010]

[Problems to be Solved by the Invention] As a catalyst for hydrogenation of aliphatic alkyl esters, a conventional copper / chromite catalyst is being replaced by a catalyst system containing no chromium, and many catalysts mainly composed of copper are proposed. However, due to the fact that the reaction product contains some free acid and the reaction conditions are severe, the catalytic activity, durability of the activity, or the catalyst from the product after hydrogenation reaction A catalyst excellent in filterability and the like is required, and many researches and developments have been made to solve these problems, but there are still various problems to be improved.

(5)

[Means for Solving the Problems] The coprecipitation method is a catalyst production method based on the formation of a precipitate by a neutralization reaction between an aqueous metal salt solution and an aqueous alkali metal compound solution. Although it is effective as a means for producing, in the ordinary coprecipitation method, the production conditions change over time in the production of precipitates, so the precipitated particles become non-uniform and it is not possible to obtain a precipitate with a uniform particle size. On the other hand, if the aqueous solution of the metal salt and the aqueous solution of the alkali metal compound are continuously added simultaneously to the water under stirring while maintaining a constant pH, the precipitation generation environment will not change over time, and thus the particle size will be smaller than that of the conventional method. Since it is assumed that a catalyst powder having a small catalyst powder content and a large average particle diameter can be obtained, the present inventors have proposed that in order to solve the problems of the copper-based chromium-free catalyst, an aqueous solution of metal salts is used. Came studied alkali metal compound solution and at the same time precipitation method of adding.

Copper, aluminum and manganese are selected as main catalyst components, and a mixed aqueous solution of these metal salts and an aqueous alkali metal compound solution are continuously and simultaneously dropped into heated water under stirring to maintain a constant PH. While forming a precipitate by carrying out a neutralization reaction is the center of catalyst formation, alumina hydration is carried out in at least one part of a mixed aqueous solution of metal salts, an aqueous solution of an alkali metal compound, or heated water under stirring. The catalyst preparation method by adding a finely dispersed aluminum compound in advance as a catalyst constituent other than the precipitate was added, and the precipitate containing the alumina hydrate was then washed with water, filtered, dried and calcined. The catalyst for hydrogenation was obtained by carrying out the above, and the catalyst obtained by carrying out the precipitate formation under such limited conditions has a high surface area, Low content of particle size catalyst powder,
A catalyst with a large average particle size was obtained, and further hydrogenation reaction of aliphatic alkyl esters under high pressure with an autoclave device showed very high activity, good activity durability, and good catalyst elution. No coloring of the product was observed, and it was found that the product was an excellent catalyst in which the product and the catalyst could be easily separated by filtration after the completion of the hydrogenation reaction.

In the present catalyst preparation method, aluminum is added as a precipitate to the catalyst component by adding the salt thereof to the mixed aqueous solution of the metal salt (6), and the mixed aqueous solution of the metal salt, the aqueous solution of the alkali metal compound, or It can also be added by adding alumina hydrate in advance to at least one place in the heated water under stirring to form a catalyst constituent component, but adding alumina hydrate in advance gives an excellent catalyst. Indispensable above, the alumina hydrate that can be used is usually commercially available gibbsite, boehmite, vialite, pseudo-boehmite gel, amorphous alumina hydrate and the like, but preferably gibbsite, and its average. The particle size is 7 to 30 μ, preferably 1
In the range of 0 to 20 μm, and aluminum salts added to the aqueous metal salt solution are aluminum nitrate, aluminum sulfate, aluminum chloride, etc., and when all the catalyst components are converted to oxides, the aluminum oxide content is 1
0.0 to 70.0% by weight, preferably 15 to 60% by weight
When the content is 10.0% by weight or less or 70.0% by weight or more, a highly active catalyst cannot be obtained. Particularly, in the case where the content is 70.0% by weight or more, there is a problem in the reducing property of the catalyst. Occurs.

The copper component is added by adding and dissolving the copper salt as one of the components in the aqueous metal salt solution, and the salts used are copper nitrate, copper sulfate, copper chloride, etc.,
The content of copper oxide in the catalyst is 20.0 to 80.0% by weight as copper oxide when all the catalyst components are converted to oxides.
The content is preferably in the range of 30.0 to 65.0% by weight, and when the content is 20.0% by weight or less or 80.0% or more, the activity is low and a catalyst that can be used practically cannot be obtained.

Further, in the catalyst of the present invention, manganese is added as the third component, but like the copper component, manganese nitrate, manganese sulfate, manganese chloride, etc. are added and dissolved in the aqueous metal salt solution as one of the salt components. The content of manganese oxide is 0.1 to 10.0% by weight, preferably 0.5 to 7.0% by weight, when all the catalyst components are converted into oxides. Is 0.
If it is less than 1% by weight, a highly active catalyst cannot be obtained, and if it is more than 10.0% by weight, the acid resistance of the catalyst becomes insufficient, and the activity and filterability upon repeated use of the catalyst are deteriorated. 7) Side reactions are likely to occur.

In the production of the catalyst of the present invention, the concentration of the aqueous metal salt solution used for forming the precipitate is 5 to 30 wt.% When the total content of metal salts in the aqueous solution is converted to metal. %, While the precipitating agent is an aqueous solution of a sodium or potassium compound in the alkali metal elements, and examples of these metal compounds include hydroxides, carbonates, bicarbonates or these compounds. However, carbonate is particularly preferable, and it is used as an aqueous solution of 5 to 30% by weight.

The aqueous solution of metal salt and the aqueous solution of alkali metal compound are continuously added simultaneously with stirring in heated water under constant pH to form a precipitate, and the obtained precipitate is a mixture of metal compounds. The properties of these metal compounds are largely dependent on the temperature of the aqueous solution or the PH value as the environment in which precipitation occurs. In order to obtain a precipitate having uniform physical and chemical properties and a large particle size, the temperature And it is important to control the PH value.

In the production of the catalyst of the present invention, the heating water temperature is 6
0 to 100 ° C, preferably 70 to 98 ° C,
When the temperature is 60 ° C or lower, a precipitate having preferable properties cannot be obtained, so that a catalyst showing stable activity and having durability against free acid cannot be obtained. The deterioration of the composite oxide precursor formed in 1) occurs, and a catalyst having high activity cannot be obtained.

On the other hand, P which is kept constant in the formation of precipitates
The H value is a value selected from the range of 5 to 11, preferably 6 to 10, and in order to obtain a precipitate having uniform properties, it is necessary to maintain a constant PH value during the dropping of the precipitating agent, and the value is If it is 5 or less, the metal salts cannot be sufficiently precipitated, and the catalyst yield decreases, and the composition becomes a catalyst that deviates from the designed value. If it is 11 or more, a part of aluminum begins to elute, so the catalyst yield or its A catalyst (8) having good performance cannot be obtained because it causes problems in composition and impairs the properties of the precipitate.

Next, the aqueous solution containing the precipitate is aged by keeping it under stirring while continuing heating, and the holding time is 0.5 to 10.0 hours, preferably 1.0 to 5.0.
If the time is 1.0 or less, the aging is not sufficient, and if it is 10.0 or more, the effect on the catalyst in terms of performance or physical properties corresponding to the time taken for the aging cannot be expected. .

After the completion of aging, the precipitate is washed with water, filtered, dried and calcined. Washing with water is important for preventing impurities from being mixed into the catalyst. It is carried out by repeating washing and filtering several times, and the drying is carried out by the precipitation. It is an operation for removing free water contained in the product cake, and is performed in a temperature range of 50 to 200 ° C., preferably 80 to 150 ° C., while the baking removes bound water and the like in the dried product. It is performed to decompose and remove the catalyst component to form an oxide and to form a complex oxide between the catalyst components, which is important for imparting acid resistance or activity stability to the catalyst, and usually 300 to 1000.
It is necessary to perform calcination for several hours in a temperature range of 350 ° C, preferably 350 to 800 ° C. If the temperature is 300 ° C or lower, it is insufficient to form the catalyst component as an oxide, and 1000 ° C.
At the above temperature, crystal growth of oxide is promoted.

When the physical properties of the obtained catalyst powder were measured, an oxide powder having a high surface area, a small content of the catalyst powder having a small particle size, and a large average particle size was obtained. When hydrogenation reaction of methyl laurate was carried out under high pressure by an autoclave device to investigate, no coloration of the product showing high activity and relating to the elution of the catalyst was observed, and the product was obtained by filtration after completion of the reaction. It was confirmed that the catalyst was obtained in which the separation of the catalyst was easy and the generation of by-products was small.

By coprecipitating the catalyst component metals in one step, a catalyst exhibiting excellent hydrogenation of the fatty acid ester and excellent separability between the product and the catalyst was obtained (9). After obtaining co-precipitates by one more step, the inventors
A coprecipitate is formed in two steps by continuously and simultaneously adding another metal component salt aqueous solution and an alkali metal compound aqueous solution while continuously heating and stirring the slurry, and then aging the precipitate. After that, the catalyst oxide powder was obtained by washing with water, filtration, drying and calcination.Also in the preparation of this oxide, aluminum was precipitated by adding its salt to a mixed aqueous solution of metal salts to form a catalyst constituent component. The catalyst constituent was also prepared by adding alumina hydrate in advance to at least one of the mixed aqueous solution of metal salts, the aqueous solution of another metal salt, the aqueous solution of alkali metal compound, or the heated water under stirring.

The metal salts, alkali metal compound and alumina hydrate used in the two-step coprecipitation method are the same as in the one-step coprecipitation method, and the aging, washing with water, filtration and drying after the precipitation of the precipitate are carried out. The catalyst oxide powder was obtained by performing the treatment such as calcination exactly as in the one-step coprecipitation method.
When the physical properties of this oxide were measured, an oxide powder having a high surface area, a small content of catalyst powder having a small particle size, and a large average particle size was obtained in the same manner as in the one-step coprecipitation method. When the hydrogenation reaction of methyl laurate was carried out under high pressure by an autoclave device to investigate the performance, it showed a higher activity and the phenomenon of the product related to the elution of the catalyst was not observed, and the reaction was performed after filtration. It was confirmed that a catalyst was obtained in which the product and the catalyst were easily separated and the side reaction product was less produced, and the present invention was completed.

[0025]

According to the present invention, a catalyst composed of copper oxide, aluminum oxide, and manganese oxide is continuously and simultaneously added to an aqueous solution of a metal salt and an aqueous solution of an alkali metal compound under stirring while maintaining a constant PH. 1 stage, or 2
In a method for preparing a catalyst, which produces a precipitate by performing coprecipitation operation over steps, aluminum as a catalyst component is added to an aqueous solution of a metal salt, and at the same time alumina hydrate is added to the aqueous solution of a metal salt, a two-step coprecipitation method. The catalyst prepared by previously adding it to another metal salt aqueous solution used in accordance with the method, an alkali metal compound aqueous solution (10), or heated water under stirring has a high surface area and has a small particle size catalyst powder. It is a catalyst oxide powder with low content and large average particle size, which shows high activity for the hydrogenation reaction of aliphatic alkyl esters and does not elute the catalyst component, and in the filtration step after the reaction is completed. The product and the catalyst can be easily separated, and the catalyst is practically excellent for the hydrogenation of aliphatic alkyl esters.

[0026]

EXAMPLES The present invention will now be described in detail by way of examples. The performance evaluation described therein is carried out under the following equipment and conditions, and the surface area is measured by nitrogen adsorption at liquid nitrogen temperature. The particle size was measured by a laser diffraction type measuring device. Performance measuring device Vertical stirring type autoclave (internal volume 100 ml) Performance evaluation conditions Reactant Methyl laurate Charge amount (g) 40 Catalyst amount (g) 2.0 Reaction pressure [kg / cm ² (G)] 280 Reaction temperature (° C) ) 250 Filtration test conditions Filtration pressure [kg / cm ² (G)] 1.0 Filtration temperature (° C) 55

Catalyst Performance Evaluation Method 40 g of methyl laurate (purity 98 wt.%) And 2.0 g of catalyst oxide powder were weighed in a 100 ml vertical stirring autoclave, and the temperature was 200 ° C. and the hydrogen pressure was 10 kg / cm.
² (G), after hydrogen reduction of the catalyst for 60 minutes at a stirring rate of 60 times / min, the temperature and pressure were set to 280 ° C. and 2
The hydrogenation reaction was carried out by changing to 50 kg / cm ² (G) and maintaining it under the same conditions for 10 (11) 0 minutes, and the obtained product was separated from the catalyst by a pressure filter after cooling,
Then, the composition was analyzed by gas chromatography to evaluate the catalytic activity and selectivity. The conversion rate of methyl laurate as the catalytic activity was obtained by the following formula, and the catalytic selectivity was determined as the formation of hydrocarbon as a side reaction product. It depends on the quantity.

Catalytic Filtration Test After the hydrogenation reaction was completed, the product taken out from the autoclave was cooled, then diluted by adding 80 ml of lauryl alcohol, and then transferred to an external heating type temperature controller added pressure filter to obtain a filtration pressure of 1 kg / cm 2. ² (G), the filterability of the catalyst was determined by determining the time required to filter a given amount (50-100 ml) of product at a temperature of 55 ° C.

Example 1-1 After adding 24 L of pure water to a reactor equipped with a reflux condenser, the mixture was heated to 95 ° C. under stirring and heated to a temperature of A (solution A), and in parallel with this, copper sulfate ( _{CuSO 4 · 5H 2 O) 3.8kg} ,
Manganese Sulfate (MnSO ₄・ 4-5H ₂ O) 0.4k
An aqueous solution prepared by adding 1.4 kg of aluminum hydroxide (gibbsite-based) to an aqueous solution prepared by dissolving 24 g of pure water in 24 L of pure water (referred to as solution B), and sodium carbonate (Na ₂ CO ₃ ).
Prepare and prepare an aqueous solution (referred to as liquid C) in which 2.7 kg of pure water is dissolved in 9 L of pure water, and while keeping liquid A at 95 ° C. under stirring,
Solution B and solution C were simultaneously added dropwise to solution A under a constant pH (8.0), and a precipitate was generated by completing the addition in 60 minutes.

The obtained precipitate is further aged by continuing stirring for 60 minutes while maintaining the temperature at 95 ° C., and then filtration and washing with water are repeated several times, and the electric conductivity of the filtrate is 100.
The precipitate cake obtained by terminating the washing with water at the point of time when μS (12) dropped below and then filtering off was dried at 110 ° C. for 12 hours, then transferred to an electric furnace and calcined at 750 ° C. for 1 hour to obtain a catalyst oxide. A powder was obtained. This catalyst had the following composition, and its surface area, small particle (particle size 3 μm or less) catalyst powder content, and average particle size measurement results are shown in Table 1, and catalyst performance evaluation and filtration. The test results were as shown in Table-2. Catalyst composition CuO 54.8 wt. % Mn ₂ O ₃ 6.1 wt. % Al ₂ O ₃ 39.1 wt. %

Example 1-2 In addition to copper sulfate and manganese sulfate in Example 1-1, aluminum sulfate [Al ₂ (SO ₄ ) ₃ · 16H ₂ O) was used.
Example 1-except that 3.7 kg was added and dissolved in solution B
The catalyst of Example 1-2 was prepared by exactly the same treatment method as in Example 1. The catalyst had the following composition, the average particle size measurement results thereof are shown in Table 1, and the catalyst performance evaluation and filtration test results are shown. It was as shown in Table-2. Catalyst composition CuO 43.5 wt. % Mn ₂ O ₃ 5.2 wt. % Al ₂ O ₃ 51.3 wt. %

Comparative Example 1 Copper sulfate (CuSO ₄ .5H ₂ ) was added to a reactor equipped with a reflux condenser.
O) 3.8 kg, manganese sulphate (MnSO ₄・ 4-5H
₂ O) 0.4 kg is weighed, and 24 L of pure water is added with stirring to dissolve, and then aluminum hydroxide (gibbsite type)
1.4 kg was added and dispersed, and the temperature was raised to 95 ° C. while continuing stirring (precipitation mother liquor). In parallel with this, 2.7 kg of sodium carbonate (Na ₂ CO ₃ ) was dissolved in 9 L of pure water. Prepare the prepared aqueous solution and drop it into the mother liquor of the precipitation prepared in advance while maintaining the temperature at 95 ° C (13). After the precipitation is generated in about 60 minutes, adjust the PH value to 8. The precipitation generation operation is completed by.

The obtained precipitate is further aged by continuing stirring for 60 minutes while maintaining the temperature at 95 ° C., and then filtration and washing with water are repeated several times, and the electric conductivity of the filtrate is 100.
The precipitate cake obtained by terminating the washing with water at the time when the temperature dropped to μS or less and then filtering off was dried at 110 ° C. for 12 hours, then transferred to an electric furnace and calcined at 750 ° C. for 1 hour to obtain a catalyst oxide powder. This catalyst had the following composition, and its surface area, small particle size (particle size 3 μm or less) catalyst powder content, and average particle size measurement results are shown in Table 1, and the results of catalyst performance evaluation and filtration test are shown. The results were as shown in Table-2. Catalyst composition CuO 54.3 wt. % Mn ₂ O ₃ 7.8 wt. % Al ₂ O ₃ 37.9 wt. %

Example 2-1 After adding 24 L of deionized water to a reactor equipped with a reflux condenser, the mixture was heated to 95 ° C. under stirring and heated to a temperature of A (solution A), and in parallel with this, copper sulfate ( _{CuSO 4 · 5H 2 O) 3.8kg} ,
Manganese Sulfate (MnSO ₄・ 4-5H ₂ O) 0.4k
An aqueous solution prepared by adding 1.4 kg of aluminum hydroxide (gibbsite-based) to an aqueous solution prepared by dissolving 24 g of pure water in 24 L of pure water (referred to as solution B), and sodium carbonate (Na ₂ CO ₃ ).
Prepare and prepare an aqueous solution (referred to as liquid C) in which 2.7 kg of pure water is dissolved in 9 L of pure water, and while keeping liquid A at 95 ° C. under stirring,
The solution B and the solution C are simultaneously added dropwise to the solution A under a constant pH (8.0), and the addition of the solution is completed in 60 minutes, thereby completing the first-stage precipitation formation.

[0035] On the other hand Apart from copper sulfate from this (CuSO ₄ · 5
H ₂ O) 0.4 kg, aluminum sulfate [Al ₂ (S
O ₄ ) ₃ · 16H ₂ O] 3.7 kg dissolved in 8.7 L of pure water to prepare water solution (Solution D) and sodium carbonate (Na ₂ C).
An aqueous solution (referred to as liquid E) in which 2.0 kg of O ₃ ) was dissolved in 7.1 L of pure water (14) was prepared, and the precipitation temperature was set to 95 ° C. in the slur after completion of the first-stage precipitation formation.
The solution D and the solution E were simultaneously added dropwise while maintaining the above condition and continuous stirring, and the addition of the solution was completed in 60 minutes under a constant pH (8.0) to complete the second-stage precipitation formation.

The obtained precipitate is further aged by continuing stirring for 60 minutes while maintaining the temperature at 95 ° C., and then filtration and washing with water are repeated several times so that the filtrate has an electric conductivity of 100.
The precipitate cake obtained by terminating the washing with water at the time when the temperature dropped to μS or less and then filtering off was dried at 110 ° C. for 12 hours, then transferred to an electric furnace and calcined at 750 ° C. for 1 hour to obtain a catalyst oxide powder. This catalyst had the following composition, and its surface area, small particle (particle size 3 μm or less) catalyst powder content, and average particle size measurement results are shown in Table 1, and the results of catalyst performance evaluation and filtration test. Was as shown in Table-2. Catalyst composition CuO 44.1 wt. % Mn ₂ O ₃ 4.7 wt. % Al ₂ O ₃ 51.2 wt. %

Examples 2-2, 2-3 In Example 2-1, the amount of copper sulfate charged to solution B was 1.
6 kg or 8.3 kg, and the amount of copper sulfate charged to the liquid D was set to 0.
Example 2 except that the amount of sodium carbonate charged to the liquid E was 17 kg or 0.92 kg and 1.9 kg or 2.2 kg.
The catalysts of Examples 2-2 and 2-3 were prepared by exactly the same treatment method as in -1, but these catalysts had the following compositions, and the average particle size measurement results are shown in Table 1 and the catalyst performance evaluation and The results of the filtration test were as shown in Table-2. (15)

Examples 2-4 and 2-5 In the precipitation formation in the first stage in Example 2-1, the manganese sulfate charge amount to the solution B was 0.3 kg, respectively.
Alternatively, the catalysts of Examples 2-4 and 2-5 were prepared by the same treatment method as that of Example 2-1, except that the amount was 0.2 kg. The measurement results are shown in Table-1, and the results of the catalyst performance evaluation and filtration test are shown in Table-2.

Examples 2-6 and 2-7 In Example 2-1, the amount of aluminum hydroxide charged to the liquid B was 0.7 kg or 2.1 kg, and the amount of aluminum sulfate charged to the liquid D was 1.9 kg or. 5, 7 kg, the amount of sodium carbonate charged to the liquid E is the same as in Example 2-1, or 3.0
The catalysts of Examples 2-6 and 2-7 were prepared by exactly the same treatment method as in Example 2-1, except that the amount was kg. The catalysts have the following compositions, and the average particle size measurement results are shown in the table. −
The results of the catalyst performance evaluation and the filtration test are shown in Table 1.

Comparative Example 2-1 (16) In Example 2-1, the charged amounts of copper sulfate, manganese sulfate and aluminum hydroxide to the solution B were 8.3 kg and 0.
12 kg and 0.41 kg, the amounts of copper sulfate and aluminum sulfate charged to the D liquid are 0.9 kg and 1.1 kg, and the amounts of sodium carbonate charged to the C liquid and the E liquid are 5.3 kg and 0.
Catalysts of Comparative Example 2-1 were prepared by the same treatment method as in Example 2-1, except that the amount was 9 kg. These catalysts have the following compositions, and the average particle size measurement results are shown in Table-1.
The results of the catalyst performance evaluation and the filtration test are shown in Table 2. Catalyst composition CuO 85.8 wt. % Mn ₂ O ₃ 1.2 wt. % Al ₂ O ₃ 13.0 wt. %

Comparative Examples 2-2, 2-3 In Example 2-1, the amount of manganese sulfate charged to the liquid B was 0 kg or 3.02 kg, and the amount of sodium carbonate charged to the liquid C was 2.4 kg or 4. Comparative Examples 2-2, 2-3 by the same treatment method as in Example 2-1 except that the amount was 5 kg.
Were prepared, which had the following composition:
The average particle diameter measurement results are shown in Table-1, and the catalyst performance evaluation and filtration test results are shown in Table-2.

Comparative Examples 2-4 and 2-5 In Example 2-1, the amount of aluminum hydroxide charged to solution B was 0 kg or 3.5 kg, and the amount of aluminum sulfate charged to solution D was 0 kg or 9.5 kg, respectively. Also, it was carried out except that the amount of sodium carbonate charged into the E liquid was 0.17 kg or 4.9 kg. (17) Comparative Examples 2-4, 2-by the same treatment method as in Example 2-1.
The catalyst of No. 5 was prepared. These catalysts had the following compositions, and the average particle diameter measurement results were as shown in Table-1, and the catalyst performance evaluation and filtration test results were as shown in Table-2.

Example 3 The catalyst of Example 3 was prepared in the same manner as in Example 2-1, except that the precipitation in the first step and the precipitation in the second step were both carried out at 80 ° C. This catalyst had the following composition. The average particle size measurement results were as shown in Table-1, and the catalyst performance evaluation and filtration test results were as shown in Table-2. Catalyst composition CuO 45.2 wt. % Mn ₂ O ₃ 5.0 wt. % Al ₂ O ₃ 49.8 wt. %

Comparative Example 3 The catalyst of Example 3 was prepared in the same manner as in Example 2-1, except that the precipitation in the first step and the precipitation in the second step were both carried out at 50 ° C. This catalyst had the following composition. The average particle size measurement results were as shown in Table-1, and the catalyst performance evaluation and filtration test results were as shown in Table-2. Catalyst composition CuO 45.1 wt. % Mn ₂ O ₃ 4.6 wt. % Al ₂ O ₃ 50.3 wt. % (18)

[0045]

[Table 1] * Small particle size (particle size 3μ or less) catalyst powder content (19)

[0046]

[Table 2]

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C07C 69/22 9546-4H // C07B 61/00 300

Claims (6)

[Claims] 1. A catalyst prepared by simultaneously adding an aqueous metal salt solution of copper, aluminum and manganese and an aqueous alkali metal compound solution to heated water under stirring at a constant pH and then aging, followed by washing with water, filtration, drying and firing. A method for producing a catalyst for hydrogenation reaction of an aliphatic alkyl ester, wherein an alumina hydrate is added in advance to at least one location in an aqueous solution of a metal salt, an aqueous solution of an alkali metal compound, or heated water under stirring. 2. An aqueous solution of another metal salt of copper and aluminum in a slurry obtained by simultaneously adding an aqueous metal salt solution of copper and manganese and an aqueous solution of an alkali metal compound to heated water under stirring at a constant pH. And the alkali metal compound aqueous solution is heated to a constant P while continuing stirring.
In a method for producing a catalyst by simultaneous addition under H, aging, and then washing with water, filtration, drying, and calcination, at least one of a metal salt aqueous solution, another metal salt aqueous solution, an alkali metal compound aqueous solution, or heated water under stirring is used. A method for producing a catalyst for hydrogenation reaction of aliphatic alkyl esters, in which hydrated alumina is added in advance to several places. 3. The temperature of the heated water under stirring is 60 to 10
It is 0 degreeC, The manufacturing method of the catalyst for hydrogenation reaction of aliphatic alkylesters of Claim 1 or 2. 4. The method for producing a catalyst for hydrogenation reaction of an aliphatic alkyl ester according to claim 1, wherein the constant PH value is a value selected from the range of 5 to 11. 5. When all the catalyst components are converted into oxides, the copper oxide content is 20.0 to 80.0% by weight, the aluminum oxide content is 10.0 to 70.0% by weight, and the manganese oxide content is Is 0.10 to 10.0% by weight, and the method for producing a catalyst for hydrogenation reaction of aliphatic alkyl esters according to claim 1 or 2. 6. The catalyst for hydrogenation reaction of aliphatic alkyl esters according to claim 1 or 2, wherein the alumina hydrate added in advance is at least one of gibbsite, boehmite, bayerite and pseudo-boehmite gel. Manufacturing method. (2)