JP3163374B2 - Catalyst for methanol synthesis - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a technique for improving the performance of a copper-based catalyst used for synthesizing methanol by catalytic hydrogenation of carbon oxide (CO and / or CO ₂ ).

[0002]

2. Description of the Related Art Conventionally, a synthesis reaction of methanol using a synthesis gas (a mixed gas of CO and H ₂ ) as a main raw material is as follows.
For example, using a catalyst composed of an oxide of copper / zinc / aluminum or a catalyst composed of an oxide of copper / zinc / chromium, it is industrially carried out under the conditions of 250 to 350 ° C. and 50 to 150 atm. Catalyst Course, Volume 7, Catalysis Society,
Published by Kodansha (1985).

On the other hand, methanol synthesis using CO ₂ and hydrogen as main raw materials has recently attracted attention from the viewpoint of recycling and recycling of carbon resources and global environmental problems. When methanol is synthesized by reacting a gas containing CO ₂ as a main component with hydrogen on a catalyst, a temperature lower than that employed in methanol synthesis from the above-described synthesis gas is obtained from the thermodynamic equilibrium of the reaction. It is necessary to carry out the reaction. Therefore, there is a need for a catalyst with higher activity than that used in the synthesis of methanol from synthesis gas, but at present, there is no catalyst that exhibits sufficiently high activity at low temperatures.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a catalyst which exhibits high activity at a low temperature when methanol is synthesized by reacting carbon oxide with hydrogen.

[0005]

Means for Solving the Problems The present inventor has conducted research in view of the state of the art as described above, and as a result, by adding gallium to copper oxide and / or a catalyst containing copper as a main component, It has been found that the purpose can be achieved.

[0006]

That is, the present invention provides the following catalysts: A mixed gas containing carbon dioxide and hydrogen
Copper oxide and / or copper oxide
Or a catalyst containing copper or gallium. 2. Copper oxide and / or copper and gallium as active ingredients
The catalyst for methanol synthesis according to 1 above, wherein 3. In addition, zinc oxide, aluminum oxide, zirconium oxide
Selected from the group consisting of
The above 1 or 2 wherein at least one selected is an active ingredient
3. The catalyst for methanol synthesis according to 2.

[0008]

[0009] In the following, the present invention (hereinafter referred to as "the first feature of the present invention" Toi
Will be described in detail.

(1) First invention of the present application The catalyst according to the first invention of the present application contains 10 to 70% by weight of copper oxide and 0.1 to 70% by weight of gallium oxide. The activity of the catalyst according to the first aspect of the present invention can be further improved by adding components such as zinc oxide, aluminum oxide, zirconium oxide, chromium oxide and palladium, if necessary.

The catalyst according to the first invention of the present application can be produced by a known method such as a coprecipitation method, an impregnation method, a mixing method, a sequential precipitation method, or a combination of these methods.
That is, the obtained catalyst is copper oxide and / or
Alternatively, the production method is not particularly limited as long as it contains copper and gallium oxide.

For example, in the case of producing the catalyst of the first invention of the present application by a coprecipitation method, first, a water-soluble salt of copper as a catalytic metal component (nitrate, chloride, sulfate, acetate, etc.) ) And a water-soluble salt of gallium (a nitrate, chloride, sulfate, acetate, etc.) (solution A) is prepared. As the water-soluble salts of copper and gallium, nitrates are more preferred. The concentration of each catalyst metal component in such an aqueous solution may vary depending on the combination of the metal components, the conditions under which the catalyst is used, and the like, but is usually about 0.1 to 5 mol / l. The ratio between the two raw materials may be appropriately determined according to the ratio of the both materials required in the finally obtained catalyst. The mixing ratio of copper: gallium in the catalyst of the first invention of the present application can vary in a wide range, but is usually about 1: 0.00147 to 7 (weight ratio), preferably about 1: 0.016 to 3, and more preferably 1: about 0.05 to 2.

In the case where the catalyst of the first invention of the present application further contains the above-mentioned optional third component, a known method such as a coprecipitation method, an impregnation method, a mixing method, a sequential precipitation method, or these methods may be used. By combining these, a catalyst can be produced. In the case of the coprecipitation method, a water-soluble salt (nitrate, chloride, sulfate, acetate, etc.) of the metal as the third component of the catalyst metal is dissolved together with the aqueous solution A (aqueous solution B), Alternatively, a solution in which a water-soluble salt of these metals is dissolved (aqueous solution C) is separately prepared. As the water-soluble salt of the third component, nitrate is more preferable. The concentration of the third component in such an aqueous solution can also vary depending on the combination of components, conditions under which the catalyst is used, and the like, but is usually 0.1 to 5 mol / mol.
It is about l. The proportion of the third component of the catalytic metal used during the reaction may be appropriately determined according to the proportion of the third component required in the finally obtained catalyst. In the catalyst of the first invention of the present application, when the third component of the catalyst metal is used, the mixing ratio of copper: third component can also vary within a wide range, but usually is 1:
About 0.00147 to 7 (weight ratio), preferably 1:
About 0.016 to 3, more preferably 1: 0.05 to 2
It is about.

Next, the aqueous solution A or B is mixed with an alkaline solution with stirring to form a precipitate, or the aqueous solution A and the aqueous solution C are simultaneously or sequentially mixed with an alkaline solution to form a precipitate. The mixing of the aqueous solution of the catalytic metal component and the alkali solution can be performed by any method such as dripping the former into the latter, dripping the latter into the former, or dripping both into distilled water. The alkaline solution is used for precipitating a catalytic metal component, and includes Na ₂ CO ₃ , NaHCO ₃ , NaOH,
An aqueous solution of an alkaline substance such as K ₂ CO ₃ or NH ₃ can be used, but Na ₂ CO ₃ is more preferable. The concentration of the alkaline solution is not particularly limited, but is usually 0.1%.
About 5 mol / l.

The mixing of the aqueous solution of the catalytic metal component with the alkaline solution is preferably carried out at a temperature of about 0 to 90 ° C.
The conditions for mixing by dropping are not particularly limited as long as the catalyst metal components are precipitated in a state in which the catalyst metal components are uniformly dispersed as ions in each other. After the formation of a precipitate,
In order to stabilize the product, the product can be aged at a reaction temperature or a temperature close to the reaction temperature for about 1 to 24 hours according to a conventional method.

The resulting precipitate contains an alkali metal derived from an alkali substance, an anion derived from the alkali substance and a catalytic metal source, etc., and after washing and removing these, it is calcined at 300 to 600 ° C. in air. To form a composite oxide. If the firing temperature is lower or higher than this temperature range, the activity as a catalyst will be insufficient.

Thus, the catalyst for methanol synthesis according to the first aspect of the present invention, which contains copper and gallium as essential components, is obtained. This catalyst may be used as it is, and if necessary,
It may be used in the form of a molded article molded by a method such as pressure molding or extrusion molding according to a conventional method, or in the form of a granulated substance crushed after molding. The particle size and shape of the molded catalyst and the granular catalyst are not particularly limited, and can be appropriately selected according to the reaction method (gas phase or liquid phase), the shape of the reactor, and the like.

The above catalyst may be reduced with hydrogen before use. However, even when this reduction is not performed, prior reduction is not essential because hydrogen is naturally reduced during the methanol synthesis reaction using hydrogen as a part of the raw material.

The catalyst according to the first invention of the present application is useful both in a methanol synthesis reaction in the gas phase and in a methanol synthesis reaction carried out by suspending the catalyst in a liquid.

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

According to the present invention, a copper-based catalyst which exhibits high activity even at a low temperature of 250 ° C. or less when catalytically hydrogenating carbon oxide to synthesize methanol can be obtained.

More specifically, the catalyst according to the present invention is excellent in the conversion of methanol and the selectivity of methanol in a low temperature range in the synthesis of methanol by catalytic hydrogenation of carbon oxide. Can be greatly increased.

[0028]

EXAMPLES Examples are shown below to further clarify the features of the present invention.

Example 1 72.0 g of copper nitrate trihydrate, gallium nitrate hydrate
7 g was dissolved in distilled water to obtain 500 ml of an aqueous solution (aqueous solution a-1). On the other hand, 70.1 g of anhydrous sodium carbonate was dissolved in distilled water to obtain 500 ml of an aqueous solution (aqueous solution b).
-1).

Then, an aqueous solution a-1 and an aqueous solution b-1 were each added to 400 ml of distilled water with vigorous stirring at a rate of 3 ml / water.
Minutes, the resulting precipitate is washed with distilled water,
After drying at 110 ° C. and calcining at 350 ° C. for 2 hours in the air, pressure molding was performed at 200 kg / cm ² , and then the molded product was pulverized to obtain a 60-80 mesh granular catalyst.

The composition of the obtained molded catalyst is CuO 5
5.6% by weight and 44.4% by weight of Ga ₂ O ₃ .

3 ml of the obtained catalyst was filled in a reaction tube, and 2
After hydrogen reduction at 50 ° C. for 2 hours (catalyst volume after reduction 2.
4 ml), a mixed gas of 25% by volume of CO ₂ and 75% by volume of H ₂ was passed through the catalyst layer, and the pressure was 50 kg / cm ² · G.
Mixed gas flow rate 300ml / min, temperature 200 ℃ or 25
The mixed gas was reacted under the condition of 0 ° C.

The reaction product gas was analyzed by gas chromatography, and the CO ₂ conversion, methanol selectivity, and methanol space-time yield were examined. Table 1 shows the results.

The products other than methanol were mainly CO, and the production of trace amounts of methane, dimethyl ether and methyl formate was observed.

Comparative Example 1 120.8 g of copper nitrate trihydrate was dissolved in distilled water to obtain 500 ml of an aqueous solution (aqueous solution a-2). On the other hand, 58.3 g of anhydrous sodium carbonate was dissolved in distilled water to obtain an aqueous solution of 50%.
0 ml was obtained (aqueous solution b-2).

Next, an aqueous solution a-2 and an aqueous solution b-2 were each added to 400 ml of distilled water under vigorous stirring at 3 ml / water.
Minutes, the resulting precipitate is washed with distilled water,
After drying at 110 ° C. and calcining at 350 ° C. for 2 hours in the air, pressure molding was performed at 200 kg / cm ² , and then the molded product was pulverized to obtain a 60-80 mesh granular catalyst.

The composition of the obtained molded catalyst was CuO 1
00% by weight.

3 ml of the obtained catalyst was charged into a reaction tube, and 2
After hydrogen reduction at 50 ° C. for 2 hours (catalyst volume after reduction 1.
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, and the pressure was 50 kg / cm ² · G.
The mixed gas was reacted under the conditions of a mixed gas flow rate of 300 ml / min and a temperature of 250 ° C.

The reaction product gas was analyzed by gas chromatography, and the CO ₂ conversion, methanol selectivity, and methanol space-time yield were examined. Table 1 shows the results.

The products other than methanol were mainly CO, and the formation of trace amounts of methane, dimethyl ether and methyl formate was observed.

Example 2 69.9 g of copper nitrate trihydrate and 26.3 of zinc nitrate hexahydrate
g and 33.7 g of gallium nitrate hydrate were dissolved in distilled water to obtain 500 ml of an aqueous solution (aqueous solution a-3). On the other hand, 55.4 g of anhydrous sodium carbonate was dissolved in distilled water to obtain 500 ml of an aqueous solution (aqueous solution b-3).

Then, an aqueous solution a-3 and an aqueous solution b-3 were each added to 400 ml of distilled water under vigorous stirring at 3 ml / water.
Minutes, the resulting precipitate is washed with distilled water,
After drying at 110 ° C. and calcining at 350 ° C. for 2 hours in the air, pressure molding was performed at 200 kg / cm ² , and then the molded product was pulverized to obtain a 60-80 mesh granular catalyst.

The composition of the obtained granular catalyst was CuO 6
0.1% by weight, 18.9% by weight of ZnO and Ga ₂ O
₃ 21.0% by weight.

After reducing 3 ml of the obtained catalyst in the same manner as in Example 1, CO ₂ 25 was added under the same conditions as in Example 1.
A mixed gas containing 75% by volume of H _{2 and} 75% by volume of H ₂ was reacted.

The reaction product gas was analyzed by gas chromatography, and the CO ₂ conversion, methanol selectivity, and methanol space-time yield were examined. Table 1 shows the results.

The products other than methanol were mainly CO, and the formation of trace amounts of methane, dimethyl ether and methyl formate was observed.

Comparative Example 2 67.8 g of copper nitrate trihydrate and zinc nitrate hexahydrate 6
5.2 g was dissolved in distilled water to obtain 500 ml of an aqueous solution (aqueous solution a-4). On the other hand, anhydrous sodium carbonate 55.4
g was dissolved in distilled water to obtain 500 ml of an aqueous solution (aqueous solution b-4).

Next, the aqueous solution a-4 and the aqueous solution b-4 were each added to 400 ml of distilled water under vigorous stirring at 3 ml / water.
Minutes, the resulting precipitate is washed with distilled water,
After drying at 110 ° C. and calcining at 350 ° C. for 2 hours in the air, pressure molding was performed at 200 kg / cm ² , and then the molded product was pulverized to obtain a 60-80 mesh granular catalyst.

The composition of the obtained granular catalyst was CuO 5
It was 5.6% by weight and 44.4% by weight of ZnO.

After 3 ml of the obtained catalyst was filled in a reaction tube and reduced in the same manner as in Example 1, a mixed gas of 25% by volume of CO ₂ and 75% by volume of H ₂ was added under the same conditions as in Example 1. Reacted.

The reaction product gas was analyzed by gas chromatography, and the CO ₂ conversion, methanol selectivity, and methanol space-time yield were examined. Table 1 shows the results.

The products other than methanol were mainly CO, and the production of trace amounts of methane, dimethyl ether and methyl formate was observed.

Example 3 72.6 g of copper nitrate trihydrate, 34.8 g of zinc nitrate hexahydrate
g, 16.6 g of zirconium oxynitrate and 8.1 g of gallium nitrate hydrate were dissolved in distilled water to obtain an aqueous solution of 500 g.
ml was obtained (aqueous solution a-5). On the other hand, 55.9 g of anhydrous sodium carbonate was dissolved in distilled water to obtain 500 ml of an aqueous solution (aqueous solution b-5).

Then, an aqueous solution a-5 and an aqueous solution b-5 were each added to 400 ml of distilled water with vigorous stirring at a rate of 3 ml / water.
Minutes, the resulting precipitate is washed with distilled water,
After drying at 110 ° C. and calcining at 350 ° C. for 2 hours in the air, pressure molding was performed at 200 kg / cm ² , and then the molded product was pulverized to obtain a 60-80 mesh granular catalyst.

The composition of the obtained granular catalyst was CuO 5
5.6% by weight, ZnO 22.2% by weight, ZrO ₂ 1
7.8% by weight and 4.4% by weight of Ga ₂ O ₃ .

After reducing 3 ml of the obtained catalyst in the same manner as in Example 1, CO ₂ 25 was added under the same conditions as in Example 1.
A mixed gas containing 75% by volume of H _{2 and} 75% by volume of H ₂ was reacted.

The reaction product gas was analyzed by gas chromatography, and the CO ₂ conversion, methanol selectivity, and methanol space-time yield were examined. Table 1 shows the results.

The products other than methanol were mainly CO, and the production of trace amounts of methane, dimethyl ether and methyl formate was observed.

COMPARATIVE EXAMPLE 3 146.6 g of copper nitrate trihydrate, zinc nitrate hexahydrate
4 g and 41.9 g of zirconium oxynitrate were dissolved in distilled water to obtain 1000 ml of an aqueous solution (aqueous solution a-
6). On the other hand, 116.6 g of anhydrous sodium carbonate was dissolved in distilled water to obtain 1000 ml of an aqueous solution (aqueous solution b-
6).

Next, the aqueous solution a-6 and the aqueous solution b-6 were each added to 400 ml of distilled water under vigorous stirring at 3 ml / water.
Minutes, the resulting precipitate is washed with distilled water,
After drying at 110 ° C. and calcining at 350 ° C. for 2 hours in the air, pressure molding was performed at 200 kg / cm ² , and then the molded product was pulverized to obtain a 60-80 mesh granular catalyst.

The composition of the obtained granular catalyst was CuO 5
5.6% by weight, 22.2% by weight of ZnO and ZrO ₂
22.2% by weight.

After reducing 3 ml of the obtained catalyst in the same manner as in Example 1, CO ₂ 25 was added under the same conditions as in Example 1.
A mixed gas of volume% and 75 volume% of H ₂ was reacted.

The reaction product gas was analyzed by gas chromatography to examine the CO ₂ conversion, methanol selectivity, and methanol space-time yield. Table 1 shows the results.

The products other than methanol were mainly CO, and the production of trace amounts of methane, dimethyl ether and methyl formate was observed.

[0065]

[Table 1]

From the results shown in Table 1, in the copper oxide and / or copper-containing catalyst used in the synthesis of methanol by hydrogenation of CO ₂ , the presence of Ga ₂ O ₃ indicates that CO ₂ is present.
It is evident that the conversion and methanol conversion were increased, resulting in a significant increase in methanol yield.

[0067] charged to the reaction tube the same catalyst 1ml and obtained in Example 3, was 2 hours hydrogen reduction at 250 ° C. (catalyst volume 2.4ml after reduction), CO ₂ 25% by volume, A mixed gas of 6.2% by volume of CO and 68.8% by volume of H ₂ was passed through the catalyst layer, and the pressure was 50 kg / cm ² · G, and the mixed gas flow rate was 300.
The mixed gas was reacted under the conditions of ml / min and a temperature of 250 ° C.

The reaction product gas was analyzed by gas chromatography, and the (CO ₂ + CO) conversion, methanol selectivity, and methanol space-time yield were examined. Table 2 shows the results.

The products other than methanol were traces of methane, dimethyl ether and methyl formate.

COMPARATIVE EXAMPLE 4 1 ml of the same catalyst as obtained in Comparative Example 3 was reduced in the same manner as in Example 4, and CO 2 was reduced under the same conditions as in Example 4.
25% by volume, 6.2% by volume of CO ₂ and 68.8 of H ₂
A volume% of the mixed gas was reacted.

The reaction product gas was analyzed by gas chromatography, and the (CO ₂ + CO) conversion, methanol selectivity and methanol space-time yield were examined. Table 2 shows the results.

The products other than methanol were traces of methane, dimethyl ether and methyl formate.

[0073]

[Table 2]

Further, methanol is synthesized by hydrogenation of CO ₂ (KC Waugh, Catalysis Today 15, 51 (19)
As a matter of course from 92)), in the synthesis of methanol by hydrogenation of a mixed gas containing CO, the presence of Ga ₂ O _{3 in} the catalyst containing copper oxide and / or copper shows the (CO + CO ₂ ) conversion and It is evident that the methanol conversion has been increased, thereby significantly increasing the methanol yield.

Reference Example 1 146.6 g of copper nitrate trihydrate, zinc nitrate hexahydrate
4 g and 41.9 g of zirconium oxynitrate were dissolved in distilled water to obtain 1000 ml of an aqueous solution (aqueous solution a-
7). On the other hand, 116.6 g of anhydrous sodium carbonate was dissolved in distilled water to obtain 1000 ml of an aqueous solution (aqueous solution b-
7).

Then, an aqueous solution a-7 and an aqueous solution b-7 were each added to 400 ml of distilled water under vigorous stirring at 3 ml / water.
Minutes, the resulting precipitate is washed with distilled water,
It was dried at 110 ° C. and calcined in air at 350 ° C. for 2 hours.

Then, 2 g of the fired product thus obtained was obtained.
Then, 5 ml of an aqueous solution in which 0.08 g of ammonium metavanadate was dissolved was added, dried, and calcined at 350 ° C. for 2 hours in the air.

The composition of the obtained granular catalyst was CuO 5
3.9% by weight, ZnO 21.5% by weight, ZrO ₂ 2
1.5% by weight and 3.0% by weight of V ₂ O ₅ .

After filling 1 ml of the obtained catalyst in a tubular reactor and reducing it with hydrogen at 250 ° C. for 2 hours, a mixed gas of 25% by volume of CO ₂ and 75% by volume of H ₂ was passed through the catalyst layer.
Pressure 50kg / cm ² · G, mixed gas flow rate 300ml /
The reaction was carried out at a temperature of 200 ° C. or 250 ° C. for one minute.

The reaction product gas was analyzed by gas chromatography, and the CO ₂ conversion, methanol selectivity, and methanol space-time yield were examined. Table 3 shows the results.

The products other than methanol were mainly CO, and the production of trace amounts of methane, dimethyl ether and methyl formate was observed.

Comparative Example 5 146.6 g of copper nitrate trihydrate, zinc nitrate hexahydrate
4 g and 41.9 g of zirconium oxynitrate were dissolved in distilled water to obtain 1000 ml of an aqueous solution (aqueous solution a-
8). On the other hand, 116.6 g of anhydrous sodium carbonate was dissolved in distilled water to obtain 1000 ml of an aqueous solution (aqueous solution b-
8).

Next, an aqueous solution a-8 and an aqueous solution b-8 were added to 400 ml of distilled water under vigorous stirring at a rate of 3 ml / water.
Minutes, the resulting precipitate is washed with distilled water,
It was dried at 110 ° C. and calcined in air at 350 ° C. for 2 hours.

The composition of the obtained granular catalyst was CuO 5
5.6% by weight, 22.2% by weight of ZnO and ZrO ₂
22.2% by weight.

After 1 ml of the obtained catalyst was reduced in the same manner as in Example 5, CO ₂ 25 was added under the same conditions as in Example 5.
A mixed gas of volume% and 75 volume% of H ₂ was reacted.

The reaction product gas was analyzed by gas chromatography, and the CO ₂ conversion, methanol selectivity, and methanol space-time yield were examined. Table 3 shows the results.

The products other than methanol were mainly CO, and the production of trace amounts of methane, dimethyl ether and methyl formate was observed.

Reference Example 2 146.6 g of copper nitrate trihydrate, zinc nitrate hexahydrate
4 g and 41.9 g of zirconium oxynitrate were dissolved in distilled water to obtain 1000 ml of an aqueous solution (aqueous solution a-
9). On the other hand, 116.6 g of anhydrous sodium carbonate was dissolved in distilled water to obtain 1000 ml of an aqueous solution (aqueous solution b-
9).

Next, an aqueous solution a-9 and an aqueous solution b-9 were added to 400 ml of distilled water with vigorous stirring at a rate of 3 ml / water.
Minutes, the resulting precipitate is washed with distilled water,
It was dried at 110 ° C. and calcined in air at 350 ° C. for 2 hours.

Next, 2 g of the fired product thus obtained was obtained.
Then, 5 ml of an aqueous solution in which 0.075 g of ammonium molybdate was dissolved was added, dried, and calcined at 350 ° C. for 2 hours in the air.

The composition of the obtained granular catalyst was CuO 5
3.9% by weight, ZnO 21.5% by weight, ZrO ₂ 2
1.5% by weight and 3.0% by weight of MoO ₃ .

After 1 ml of the obtained catalyst was reduced in the same manner as in Example 5, CO ₂ 25 was reduced under the same conditions as in Example 5.
A mixed gas containing 75% by volume of H _{2 and} 75% by volume of H ₂ was reacted.

The reaction product gas was analyzed by gas chromatography to examine the CO ₂ conversion, methanol selectivity, and methanol space-time yield. Table 3 shows the results.

The products other than methanol were mainly CO, and the production of trace amounts of methane, dimethyl ether and methyl formate was observed.

Reference Example 3 146.6 g of copper nitrate trihydrate, zinc nitrate hexahydrate
4 g and 41.9 g of zirconium oxynitrate were dissolved in distilled water to obtain 1000 ml of an aqueous solution (aqueous solution a-1).
0). On the other hand, 116.6 g of anhydrous sodium carbonate was dissolved in distilled water to obtain 1000 ml of an aqueous solution (aqueous solution b-1).
0).

Next, the aqueous solution a-10 and the aqueous solution b-10 were each mixed with 400 ml of distilled water under vigorous stirring for 3 m.
The resulting precipitate was washed with distilled water, dried at 110 ° C., and calcined in air at 350 ° C. for 2 hours.

Next, 2 g of the fired product thus obtained was obtained.
Was added with 5 ml of an aqueous solution in which 0.068 g of ammonium paratungstate was dissolved, and the mixture was dried.
Fired for hours.

The composition of the obtained granular catalyst was CuO 5
3.9% by weight, ZnO 21.5% by weight, ZrO ₂ 2
It was 1.5% by weight and WO ₃ 3.0% by weight.

After reducing 1 ml of the obtained catalyst in the same manner as in Example 5, CO ₂ 25 was added under the same conditions as in Example 5.
A mixed gas containing 75% by volume of H _{2 and} 75% by volume of H ₂ was reacted.

The reaction product gas was analyzed by gas chromatography to examine the CO ₂ conversion, methanol selectivity, and methanol space-time yield. Table 3 shows the results.

The products other than methanol were mainly CO, and the production of trace amounts of methane, dimethyl ether and methyl formate was observed.

[0102]

[Table 3]

From the results shown in Table 3, at least one of V ₂ O ₅ , MoO ₃ and WO _{3 was found to be present in} the catalyst containing methanol and copper oxide and / or copper and zinc oxide for the catalytic hydrogenation of CO _2. It is evident that the presence of the species increases the CO ₂ conversion and the methanol conversion, thereby greatly increasing the methanol yield.

Continuation of the front page (73) Patent holder 000000974 Kawasaki Heavy Industries, Ltd. 3-1-1, Higashikawasaki-cho, Chuo-ku, Kobe-shi, Hyogo (73) Patent holder 000156961 Kansai Thermochemical Co., Ltd. 2-23 Ohamacho, Amagasaki-shi, Hyogo Address (73) Patent holder 000001199 Kobe Steel, Ltd. 1-3-18, Wakihama-cho, Chuo-ku, Kobe-shi, Hyogo (73) Patent holder 000183303 Sumitomo Metal Mining Co., Ltd. 5-113, Shimbashi, Minato-ku, Tokyo, Japan (73) Patent holder 000005887 Mitsui Chemicals, Inc. 3-5-2 Kasumigaseki, Chiyoda-ku, Tokyo (74) The above six agents 100065215 Patent Attorney Eiji Saegusa (four others) (72) Inventor Masahiro Saito Ibaraki 16-3 Onogawa, Tsukuba City, National Institute of Advanced Industrial Science and Technology (72) Inventor Tadahiro Fujitani 16-3, Onogawa, Tsukuba City, Ibaraki Prefecture Inside the National Institute of Advanced Industrial Science and Technology (72) Inventor Yoshiyuki Sasaki Tsukuba, Ibaraki 16-3 Onogawa Research Institute of Industrial Technology In-house (72) Inventor Kenichi Tominaga 16-3 Onogawa, Tsukuba, Ibaraki Pref. National Institute of Advanced Industrial Science and Technology (72) Inventor Daiki Watanabe 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo Global Environmental Industrial Technology Within the Research Organization (72) Inventor Motoi Kawai 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo Within the National Institute for Global Environmental Technology (72) Inventor Masami Takeuchi 2-8-11, Nishi-Shimbashi, Minato-ku, Tokyo Foundation Inside the Research Institute of Innovative Technology for the Earth (72) Inventor Yuki Kanai 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo Inside the Research Institute for Innovative Technology for the Earth (72) Keiko Moriya 2--Nishi-Shimbashi, Minato-ku, Tokyo 8-11 Inside the Research Institute of Innovative Technology for the Earth (72) Inventor Terumitsu Kadomoto 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo Examiner in the Research Institute of Innovative Technology for the Environment Yoshihisa Seki (56) References JP-A-57-130547 (JP, A) JP-A-64-27645 (JP, A) JP-A-59-9924 (JP, A) 60-197633 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) B01J 21/00-38/74 C07B 61/00 300

Claims (3)

(57) [Claims] 1. A catalyst for methanol synthesis using a mixed gas containing carbon dioxide and hydrogen as a reaction raw material, wherein copper oxide and / or copper and gallium are blended. 2. The catalyst for methanol synthesis according to claim 1, comprising copper oxide and / or copper and gallium as active components. 3. The catalyst for methanol synthesis according to claim 1, further comprising at least one selected from the group consisting of zinc oxide, aluminum oxide, zirconium oxide, chromium oxide and palladium as an active ingredient.