JP2976716B2 - Catalyst for methanol synthesis and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst used for synthesizing methanol by catalytic hydrogenation of carbon oxides (carbon monoxide and carbon dioxide) and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, methanol synthesis (CO + 2H ₂ →) using synthesis gas (mixed gas of carbon monoxide and hydrogen) as a raw material.
CH ₃ OH) is, for example, as described in JP-A-3-68450, at 250 to 350 ° C. using a catalyst composed of an oxide of copper / zinc / aluminum or an oxide of copper / zinc / chromium. It is carried out industrially under the conditions of 50 to 150 atm. On the other hand, methanol synthesis using carbon dioxide as a raw material (CO ₂ + 3H ₂ → CH ₃ OH + H
_{2 O)} is from the point of view of circulation re-use and global environmental problems of carbon resource, it has been attracting attention recently. In this case, from the thermodynamic equilibrium of the reaction, when reacting a gas containing carbon dioxide as the main component with hydrogen on the catalyst to synthesize methanol, the temperature is lower than the reaction temperature in methanol synthesis from the aforementioned synthesis gas. It is necessary to do it at temperature. Therefore, a catalyst having higher activity than that used in the above-mentioned synthesis of methanol from synthesis gas is required, but no catalyst showing sufficient performance has been reported so far.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above points, and has a relatively low temperature of 250 ° C. or less.
In the case of synthesizing methanol by reacting carbon oxide with hydrogen , in particular, carbon dioxide or carbon dioxide as a main component
To react with the hydrogen to produce methanol
It is an object of the present invention to provide a high-performance catalyst exhibiting a high methanol yield when formed .

[0004]

According to the present invention, there is provided, according to the present invention, carbon dioxide or carbon dioxide containing carbon dioxide as a main component even at a relatively low temperature of 250 ° C. or less.
It can be used for methanol synthesis by hydrogenation of gas , containing copper oxide, zinc oxide and zirconium oxide,
Further, there is provided a catalyst containing at least one element selected from the group consisting of aluminum, chromium and palladium. The content of copper oxide in the catalyst is from 20 to 70
The catalyst performance is not sufficient even if the value is less than 20% by weight or more than 70% by weight. The content of zinc oxide is suitably from 5 to 75% by weight, and the content of zirconium oxide is from 5 to 29% by weight. The best catalyst performance can be obtained by appropriately determining the content of these components depending on the composition of the reaction gas. Even if the content of zinc oxide is less than 5% by weight or more than 75% by weight, the catalytic performance is not sufficient. Further, even if the content of zirconium oxide is less than 5% by weight or more than 29% by weight, the catalytic performance is not sufficient.

As described above, according to the present invention, copper oxide,
Carbon dioxide or carbon dioxide containing zinc oxide and zirconium oxide and containing at least one other element
Methanol synthesis by hydrogenation min to carbon oxide gas
A catalyst suitable for use is provided. As described above, aluminum, chromium, and palladium are effective as other elements to be added. And other metal elements to be added are
0.5 to 30% by weight is suitable. If the value is less than 0.5% by weight or exceeds 30% by weight, the catalyst performance is not improved.

[0006] The preparation of the catalyst, it is necessary to carry out in a way of following. The method how to copper, and the basic solution was added to a solution containing zinc and zirconium copper to precipitate zinc and zirconium, i.e. Ru coprecipitation der. The catalyst
Is prepared by first adding a basic solution to a solution containing one or two components to precipitate one or two components,
It can also be carried out by a method of precipitating the remaining components in a liquid containing the precipitate, that is, a sequential precipitation method. In either method, the main raw material for preparing the catalyst is a compound of copper, zinc, and zirconium, which is dissolved in a metal-free liquid such as water or methanol. Further, as a precipitant, sodium carbonate, urea, ammonia, sodium hydroxide, ammonium carbonate, potassium hydroxide,
A basic solution such as sodium bicarbonate can be used.

After preparation, the catalyst is prepared in air at 300-600.
It is necessary to bake at a temperature of ° C. to form an oxide. By doing so, a stable catalyst can be obtained. Whether it is not fired or fired at a temperature below 300 ° C.
Alternatively, firing at a temperature exceeding 600 ° C. lowers the performance. From the above, the method for producing a catalyst for methanol synthesis of the present invention includes a basic solution in a solution containing copper, zinc and zirconium, and containing at least one selected from the group consisting of aluminum, chromium and palladium. In addition, copper, zinc and zirconium and aluminum,
After precipitating at least one selected from the group consisting of chromium and palladium,
Calcination at 20 ° C., the content of copper oxide being 20 to 70% by weight,
The content ratio of zinc oxide is 5 to 75% by weight, the content ratio of zirconium oxide is 5 to 29% by weight, and the content of at least one element selected from the group consisting of aluminum, chromium and palladium is 0.1%. 5 to 30% by weight
At a reaction temperature of 250 ° C or less
By hydrogenation of carbon oxide gas containing silicon as the main component
It is characterized by obtaining a catalyst suitable for use in the synthesis of toluene .

When the catalyst of the present invention is used in a methanol synthesis reaction, the catalyst may be used as it is, or the catalyst may be treated in advance with hydrogen to reduce copper oxide in the catalyst. The point is that the copper in the catalyst only needs to be active during the reaction. The catalyst may be molded by a known method, or may be used as it is. The particle size and shape of the catalyst can be arbitrarily selected depending on the type of reaction and the shape of the reactor.

[0009]

The present invention will be described in more detail with reference to the following examples. A contact made of CuO, ZnO and ZrO ₂
Experimental examples in which the medium was prepared by the coprecipitation method and the sequential precipitation method were also explained.
I will tell. Experiment Example 1 Copper nitrate trihydrate 61.2g and zinc nitrate hexahydrate 44.
3 g and 26.2 g of zirconium oxynitrate were dissolved in distilled water to prepare a 500 ml aqueous solution, which was used as solution A. Separately, 74.2 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 500 ml aqueous solution, which was used as solution B. Solution A and Solution B were mixed in 400 ml of distilled water with vigorous stirring.
The solution was dropped at a rate of ml / min (this method is called a coprecipitation method). After washing the obtained precipitate with distilled water,
And calcined at 400 ° C. in air for 2 hours. The composition of this catalyst was 43.6 wt% CuO, 26.1 ZnO.
wt% and ZrO ₂ 26.1 wt%. This catalyst 3
After filling the reaction tube with hydrogen at 250 ° C. for 2 hours with hydrogen (reduced catalyst volume 2.5 ml), a mixed gas of 25% by volume of CO ₂ and 75% by volume of H ₂ was passed through the catalyst layer. Pressure = 50 kg / cm ² G, raw material flow rate = 300 ml / mi
The reaction was performed under the conditions of n, temperature = 200 ° C., 250 ° C.
When the reaction product gas was analyzed by gas chromatography,
The CO ₂ conversion, methanol selectivity and methanol space-time yield were as shown in Table 1. Other products are mainly CO, methane, dimethyl ether,
Only trace amounts of methyl formate were formed.

[0010]

[Table 1]

Comparative Example 1 Copper nitrate trihydrate 48.0 g, zinc nitrate hexahydrate 34.7
g and 69.4 g of aluminum nitrate nonahydrate were dissolved in distilled water to prepare a 500 ml aqueous solution, which was used as solution A. Separately, 87.9 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 500 ml aqueous solution, which was used as solution B. Solution A and Solution B were mixed in 400 ml of distilled water with vigorous stirring.
The solution was dropped at a rate of ml / min. The obtained precipitate was washed with distilled water, dried at 110 ° C., and calcined at 400 ° C. in air for 2 hours. The composition of this catalyst is CuO43.
6 wt%, ZnO 26.1 wt%, Al ₂ O ₃ 26.1
wt%. Using this catalyst, reaction was performed in the same manner as Experiment Example 1. When the reaction product gas was analyzed by gas chromatography, the CO ₂ conversion, methanol selectivity, and methanol space-time yield were as shown in Table 2. The other products were mainly CO, and only trace amounts of methane, dimethyl ether and methyl formate were formed.

[0012]

[Table 2]

[0013] was dissolved Experiment Example 2 of copper nitrate trihydrate 72.5g of distilled water 300m
1 aqueous solution was prepared and used as solution A. Zinc nitrate hexahydrate 5
3.8 g and 31.8 g of zirconium oxynitrate were dissolved in distilled water to prepare a 500 ml aqueous solution, which was used as solution B.
Separately, 53.0 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 500 ml aqueous solution, which was used as solution C. First, 94 ml of both solution B and solution C were dropped at a rate of 3 ml / min into 400 ml of distilled water which was vigorously stirred to obtain a precipitate of zinc and zirconium (this method is referred to as a sequential precipitation method). Next, 96 ml of the solution A and the solution C were added dropwise at a rate of 3 ml / min while containing the precipitate to obtain a copper precipitate. After washing the obtained precipitate with distilled water,
And calcined at 400 ° C. in air for 2 hours. The composition of this catalyst was 43.6 wt% CuO, 26.1 ZnO.
wt% and ZrO ₂ 26.1 wt%. Using this catalyst, reaction was performed in the same manner as Experiment Example 1. When the reaction product gas was analyzed by gas chromatography, the CO ₂ conversion, methanol selectivity, and methanol space-time yield were as shown in Table 1. The other products were mainly CO, and only trace amounts of methane, dimethyl ether and methyl formate were formed.

[0014] Experimental Example 3 copper nitrate trihydrate 146.6g and zinc nitrate hexahydrate 7
0.4 g and 41.9 g of zirconium oxynitrate were dissolved in distilled water to prepare 11 aqueous solutions, which were designated as solution A. Also,
116.6 g of anhydrous sodium carbonate was dissolved in distilled water to obtain 1
The aqueous solution of No. 1 was prepared and used as solution B. 400 with vigorous stirring
Solution A and Solution B in 3 ml of distilled water
At a speed of. The obtained precipitate was washed with distilled water, dried at 110 ° C., and calcined at 350 ° C. in air for 2 hours. After calcination, the catalyst was molded under pressure at 200 kg / cm ² . The composition of the catalyst was 55.6 wt% CuO, Zn
O was 22.2 wt% and ZrO _{2 was} 22.2 wt%.
The catalyst 3ml was filled in the reaction tube, after reduction with 2 hours hydrogen at 250 ° C. (catalyst volume 2.4ml after reduction), reaction was performed in the same manner as Experiment <br/> Example 1. When the reaction product gas was analyzed by gas chromatography, the CO ₂ conversion, methanol selectivity, and methanol space-time yield were as shown in Table 1. The other products were mainly CO, and only trace amounts of methane, dimethyl ether and methyl formate were formed.

Comparative Example 2 61.2 g of copper nitrate trihydrate and zinc nitrate hexahydrate
3 g was dissolved in distilled water to prepare a 500 ml aqueous solution.
Liquid. 59.7 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 500 ml aqueous solution, which was used as solution B. The solution A and the solution B were added dropwise at a rate of 3 ml / min to 400 ml of distilled water which was vigorously stirred to obtain a precipitate of copper and zinc.
The obtained precipitate was washed with distilled water to obtain precipitate C. next,
26.2 g of zirconium nitrate is dissolved in distilled water and 500
An aqueous solution (ml) was prepared and used as solution D. Solution E was prepared by diluting 13.1 g of 28% aqueous ammonia to 500 ml. Solution D and E were mixed in 400 ml of distilled water with vigorous stirring.
It was dropped at a rate of ml / min to obtain a zirconium precipitate. The obtained precipitate was washed with distilled water to obtain precipitate F. The precipitate C and the precipitate F were mixed well (this method is called a mixing method). The mixed precipitate was dried at 110 ° C. and calcined at 400 ° C. in air for 2 hours. The composition of this catalyst is CuO
43.6 wt%, ZnO 26.1 wt%, ZrO ₂ 2
It was 6.1% by weight. Using this catalyst, reaction was performed in the same manner as Experiment Example 1. When the reaction product gas was analyzed by gas chromatography, the CO ₂ conversion, methanol selectivity, and methanol space-time yield were as shown in Table 2. Other products are mainly CO,
Only trace amounts of methane, dimethyl ether and methyl formate were produced.

Comparative Example 3 First, 89.4 g of zinc nitrate hexahydrate and 53.3 g of zirconium oxynitrate were dissolved in distilled water to obtain 500 ml.
An aqueous solution was prepared and used as solution A. Anhydrous sodium carbonate 5
3.0 g was dissolved in distilled water to prepare a 500 ml aqueous solution, which was used as solution B. The solution A and the solution B were dripped at a rate of 3 ml / min into 400 ml of distilled water which was vigorously stirred to obtain a precipitate of zinc and zirconium. The obtained precipitate was washed with distilled water, dried at 110 ° C, and calcined at 350 ° C. 6 g of this calcined product is impregnated with 15.2 g of copper nitrate trihydrate dissolved in 100 ml of distilled water (this method is referred to as impregnation method), dried at 110 ° C., and dried at 400 ° C. in air. It was baked for 2 hours. The composition of this catalyst is CuO4
3.6 wt%, ZnO 26.1 wt%, ZrO ₂ 26.
It was 1 wt%. Using this catalyst, reaction was performed in the same manner as Experiment Example 1. When the reaction product gas was analyzed by gas chromatography, the CO ₂ conversion, methanol selectivity, and methanol space-time yield were as shown in Table 2. The other products were mainly CO, and only trace amounts of methane, dimethyl ether and methyl formate were formed.

[0017] filled with the same catalyst 3ml reaction tube as used in Experiment Example 4 Experiment Example 3,
After hydrogen reduction at 250 ° C. for 2 hours (reduced catalyst volume 2.4 ml), a mixed gas of 16.7% by volume of CO ₂ , 11.1% by volume of CO, and 72.2% by volume of H ₂ was passed through the catalyst layer. Pressure = 50 kg / cm ² G, raw material flow rate = 300 ml
The reaction was carried out under the following conditions: / min, temperature = 200 ° C., 250 ° C. When the reaction product gas was analyzed by gas chromatography, (CO ₂ + CO) conversion, methanol selectivity, and methanol space-time yield were as shown in Table 3. In addition,
Other products include methane, dimethyl ether,
Only trace amounts of methyl formate and ethanol were produced.

[0018]

[Table 3]

[0019] After filling the 3ml the same catalyst as that used in Experimental Example 5 Experimental Example 3 in the reaction tube was reduced by 2 h of hydrogen at 250 ° _C., CO 2 8.3
% Of CO, 22.2% by volume of CO, and 69.4% by volume of H ₂ were passed through the catalyst layer to obtain a pressure of 50 kg / cm.
² G, raw material flow rate = 300 ml / min, temperature = 200
The reaction was performed under the conditions of 250C and 250C. When the reaction product gas was analyzed by gas chromatography, (CO ₂ + CO)
The conversion, methanol selectivity, and methanol space-time yield were as shown in Table 3. As other products, only trace amounts of methane, dimethyl ether, methyl formate, and ethanol were produced.

The following is a description of a preferred embodiment of the present invention.
You. Example 1 Copper nitrate trihydrate 42.1 g, zinc nitrate hexahydrate 20.2
g, 9.7 g of zirconium oxynitrate and 8.0 g of aluminum nitrate nonahydrate were dissolved in distilled water to prepare a 300 ml aqueous solution, which was designated as solution A. Further, 32.9 g of anhydrous sodium carbonate was dissolved in distilled water to prepare 300 ml of an aqueous solution, which was used as solution B. The solution A and the solution B were dripped at a rate of 3 ml / min into 400 ml of vigorously stirred distilled water. After washing the obtained precipitate with distilled water,
And calcined in air at 350 ° C. for 2 hours. The composition of this catalyst was 55.6 wt% CuO, 22.2 ZnO.
_{wt%, ZrO 2 17.8wt%,} Al 2 O 3 4.4w
t%. This catalyst was molded under pressure at 200 kg / cm ² and then pulverized to a particle size of 60 to 80 mesh.
3 ml of this catalyst was filled in a reaction tube, and hydrogen reduction was performed at 250 ° C. for 2 hours (at this time, the catalyst volume was 2.4 ml).
₂ 25 volume% and H275 volume% of the mixed gas was passed through the catalyst layer, the pressure = 50 kg / ^cm 2 G, the raw material gas flow rate = 30
The reaction was performed under the conditions of 0 ml / min, temperature = 200 ° C. and 250 ° C. When the product thus obtained was analyzed by gas chromatography, the CO ₂ conversion, methanol selectivity, and methanol space-time yield were as shown in Table 4. The other products were mainly CO, and only trace amounts of methane, dimethyl ether and methyl formate were formed.

[0021]

[Table 4]

Example 2 43.6 g of copper nitrate trihydrate, 21.0 g of zinc nitrate hexahydrate
g, 11.5 g of zirconium oxynitrate and 2.5 g of chromium nitrate nonahydrate were dissolved in distilled water to prepare 300 ml of an aqueous solution, which was used as solution A. Also, anhydrous sodium carbonate 3
A solution B was prepared by dissolving 2.1 g in distilled water to prepare a 300 ml aqueous solution. The solution A and the solution B were dripped at a rate of 3 ml / min into 400 ml of vigorously stirred distilled water. After washing the obtained precipitate with distilled water,
And calcined in air at 350 ° C. for 2 hours. The composition of this catalyst was 55.6 wt% CuO, 22.2 ZnO.
wt%, ZrO ₂ 20.4 wt%, Cr ₂ O ₃ 1.8 w
t%. This catalyst was molded under pressure at 200 kg / cm ² and then pulverized to a particle size of 60 to 80 mesh.
Using this catalyst, a reaction was carried out in the same manner as in Example 1 .
When the product thus obtained was analyzed by gas chromatography, the CO ₂ conversion, methanol selectivity and methanol space-time yield were as shown in Table 4. The other products were mainly CO, and only trace amounts of methane, dimethyl ether and methyl formate were formed.

Example 3 Copper nitrate trihydrate 40.5 g, zinc nitrate hexahydrate 21.6
g and 12.9 g of zirconium oxynitrate and 1.2 g of a 10% aqueous solution of palladium nitrate were dissolved in distilled water to give 300 g.
An aqueous solution (ml) was prepared and used as solution A. In addition, 32.7 g of anhydrous sodium carbonate was dissolved in distilled water to prepare 300 ml of an aqueous solution, which was used as solution B. Vigorously stirred distilled water 400
The solution A and the solution B were added dropwise at a rate of 3 ml / min. After washing the obtained precipitate with distilled water, 1
It was dried at 10 ° C and calcined at 350 ° C in air for 2 hours. The composition of this catalyst is 50.3 wt% of CuO, ZnO
22.3 wt%, ZrO ₂ 22.3 wt%, PdO5.
It was 1 wt%. This catalyst was molded under pressure at 200 kg / cm ² and then pulverized to a particle size of 60 to 80 mesh. Using this catalyst, a reaction was carried out in the same manner as in Example 1 . When the product thus obtained was analyzed by gas chromatography, the CO ₂ conversion, methanol selectivity and methanol space-time yield were as shown in Table 4. Other products are mainly CO,
Only trace amounts of methane, dimethyl ether and methyl formate were produced.

Example 4 Copper nitrate trihydrate 38.8 g, zinc nitrate hexahydrate 20.7
g, 9.9 g of zirconium oxynitrate, 8.2 g of aluminum nitrate nonahydrate and 1.1 g of a 10% aqueous solution of palladium nitrate were dissolved in distilled water to prepare 300 ml of an aqueous solution, which was used as solution A. In addition, 33.8 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 300 ml aqueous solution, which was used as solution B. The solution A and the solution B were dripped at a rate of 3 ml / min into 400 ml of vigorously stirred distilled water. The obtained precipitate was washed with distilled water, dried at 110 ° C.
Calcination was performed in air at 50 ° C. for 2 hours. The composition of this catalyst was 50.3 wt% of CuO, 22.3 wt% of ZnO, Z
rO ₂ 17.8 wt%, Al ₂ O ₃ 4.5 wt%, Pd
O was 5.1 wt%. 200 kg / cm
After being press-molded in ² , it was pulverized to a particle size of 60 to 80 mesh. Using this catalyst, a reaction was carried out in the same manner as in Example 1 . When the product thus obtained was analyzed by gas chromatography, the CO ₂ conversion, methanol selectivity and methanol space-time yield were as shown in Table 4. The other products were mainly CO, and only trace amounts of methane, dimethyl ether and methyl formate were formed.

Example 5 A reaction was carried out in the same manner as in Example 4 except that the hydrogen reduction temperature of the catalyst was changed to 300 ° C. The conversion of CO ₂ , the selectivity of methanol and the space-time yield of methanol are also shown in Table 4. It was right. The other products are mainly CO 2
And only trace amounts of methane, dimethyl ether and methyl formate were formed.

Example 6 A reaction tube was charged with 3 ml of the same catalyst as used in Example 1 ,
After hydrogen reduction at 250 ° C. for 2 hours, a mixed gas of 16.7% by volume of CO ₂ , 11.1% by volume of CO, and 72.2% by volume of H ₂ was passed through the catalyst layer, and the pressure = 50 kg / cm ² G, raw material Gas flow rate = 300 ml / min, temperature = 200 ° C., 2
The reaction was carried out at 50 ° C. When the product thus obtained was analyzed by gas chromatography, (CO 2
₂ + CO) conversion, methanol selectivity, and methanol space-time yield were as shown in Table 5. In addition, as other products, methane, dimethyl ether, methyl formate,
Only traces of ethanol were produced.

[0027]

[Table 5]

Example 7 A reaction tube was filled with 3 ml of the same catalyst as used in Example 1 ,
After hydrogen reduction at 250 ° C. for 2 hours, a mixed gas of 4.2% by volume of CO ₂ , 27.8% by volume of CO, and 68.0% by volume of H ₂ was passed through the catalyst layer, and pressure = 50 kg / cm ² G, raw material Gas flow rate = 300 ml / min, temperature = 200 ° C., 2
The reaction was carried out at 50 ° C. When the product thus obtained was analyzed by gas chromatography, (CO 2
₂ + CO) conversion, methanol selectivity and methanol space-time yield were as shown in Table 5. As other products, only trace amounts of methane, dimethyl ether, methyl formate, and ethanol were produced.

[0029]

As described above, when the catalyst of the present invention is used, carbon oxide can be reacted with hydrogen even at a relatively low temperature of 250 ° C. or less, and methanol can be synthesized at a high rate. Therefore, carbon dioxide or diacid
Carbon oxide gas containing carbonized carbon as the main component reacts with hydrogen on the catalyst.
High methanol, even when synthesizing methanol
The performance can be obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (73) Patent holder 999999999 Kobe Steel, Ltd. 1 Nishinokyo Kuwaharacho, Nakagyo-ku, Kyoto-shi, Kyoto (73) Patent holder 000000974 Kawasaki Heavy Industries, Ltd. 3-chome, Higashikawasaki-cho, Chuo-ku, Kobe-shi, Hyogo No. 1 No. 1 (73) Patent holder 000005887 Mitsui Chemicals, Inc. 3-5-2 Kasumigaseki, Chiyoda-ku, Tokyo (73) Patent holder 999999999 Osaka Gas Co., Ltd. 2-2-1 Otemachi, Chiyoda-ku, Tokyo ( 72) Inventor Masahiro Saito 16-3 Onogawa, Tsukuba, Ibaraki Pref., National Institute for Natural Resources and Environment (72) Inventor Yuki Kanai 2-8-11 Nishishinbashi, Minato-ku, Tokyo 7th Toyo Maritime Building 8F Global Environmental Industry Technology Within the Research Organization (72) Inventor Masaki Takeuchi 2-8-11 Nishishinbashi, Minato-ku, Tokyo 7th Oriental Maritime Building 8F Foundation Inside the Global Environmental Technology Research Institute (72) Keiko Moriya 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo 7th Oriental Maritime Building 8F Inside the Global Environmental Technology Institute (72) Inventor Daiki Watanabe Tokyo 2-8-11 Nishi-Shimbashi, Minato-ku 7th Oriental Maritime Building 8F Inside the Research Institute of Innovative Technology for the Earth (72) Inventor Motoi Kawai 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo 7th Oriental Maritime Building 8F Foundation (72) Inventor Terumitsu Kadomoto 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo 7th Oriental Maritime Building 8F Judge, Yukio Numazawa, Judge, Councilor, Global Environmental Industry Research Institute Tomoyasu Nomi, Judge Tomoo Niida (56) References JP-A-60-106534 (JP, A) JP-A-60-209255 (JP, A)

Claims (2)

(57) [Claims] 1. A catalyst containing copper oxide, zinc oxide and zirconium oxide and further containing at least one element selected from the group consisting of aluminum, chromium and palladium, wherein the content of copper oxide is 20 to 70% by weight, a content of zinc oxide of 5 to 75% by weight, a content of zirconium oxide of 5 to 29% by weight, and at least one element selected from the group consisting of aluminum, chromium and palladium. Content is 0.5 to 30% by weight
Der Ri, 250 ° C. carbon dioxide or diacid in the following reaction temperature
By hydrogenation of carbon oxide gas containing carbon fluoride as a main component
A catalyst for methanol synthesis characterized by being suitable for use in the synthesis of phenol. 2. A solution containing copper, zinc and zirconium and containing at least one selected from the group consisting of aluminum, chromium and palladium, and adding a basic solution to the solution to form copper, zinc and zirconium and aluminum;
After precipitating at least one selected from the group consisting of chromium and palladium,
Calcination at 20 ° C., the content of copper oxide being 20 to 70% by weight,
The content ratio of zinc oxide is 5 to 75% by weight, the content ratio of zirconium oxide is 5 to 29% by weight, and the content of at least one element selected from the group consisting of aluminum, chromium and palladium is 0.1%. 5 to 30% by weight
At a reaction temperature of 250 ° C or less
By hydrogenation of carbon oxide gas containing silicon as the main component
A method for producing a catalyst for methanol synthesis, comprising obtaining a catalyst suitable for use in methanol synthesis.