JP2001205089A - Catalyst for methanol synthesis and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst exhibiting high activity at 150 to 250 ° C. in producing methanol by reacting carbon oxide with hydrogen and a method for producing the same. The catalyst comprises copper oxide, zinc oxide, aluminum oxide and boron oxide, and has a boron oxide content of 2 to 12% by weight. One or more selected from the group consisting of silicon oxide, zirconium oxide and gallium oxide may be added. Gas containing methanol and 200-350
It is desirable to carry out a pretreatment of contacting at a temperature of ° C. 1
It is effective even at a relatively low temperature of 50 to 250 ° C.
It can be used in a temperature range of 350 ° C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a carbon oxide (CO)
₂ or CO) for the synthesis of methanol by catalytic hydrogenation.

[0002]

2. Description of the Related Art Conventionally, a synthesis reaction of methanol from a mixed gas in which a synthesis gas (a mixed gas of CO and H ₂ ) is used as a main material and a small amount of CO ₂ is added thereto is, for example, a reaction of copper / zinc / aluminum. Using a catalyst composed of an oxide or a catalyst composed of an oxide of copper / zinc / chromium, 250 to 3
It is carried out industrially under the conditions of 50 ° C. and 50 to 150 atm.
985)).

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, the above synthesis gas (mixed gas of CO and H ₂ ) is mainly used from the thermodynamic equilibrium of the reaction. It is necessary to carry out the reaction at a lower temperature, for example, 150 ° C. to 250 ° C. than that employed in the synthesis of methanol from a mixed gas as a raw material.

In addition, in the methanol synthesis reaction on a copper-based catalyst, the reaction is inhibited by water (steam) generated together with methanol from CO ₂ and hydrogen in the raw material gas (App.
lied Catalyst A: General
138 (1966) 311-318). The amount of water generated together with methanol increases with an increase in the CO ₂ / CO ratio in the raw material gas, and the above-described reaction inhibition is inevitable.

For these reasons, a catalyst for synthesizing methanol from a raw material gas having a high CO ₂ content is mainly composed of a synthetic gas (a mixed gas of CO and H ₂ ) and a mixed gas having a low CO ₂ content. There is a need for a catalyst that is even more active than the catalyst used in methanol synthesis from (source gas in current methanol synthesis).

There have been many attempts to improve the performance of catalysts by adding various compounds to catalysts comprising copper / zinc / aluminum oxides. Among them, the catalyst to which a boron compound is added has already been described in JP-B-51-44715, JP-B-59-10256, and JP-A-8-299796.

[0007] Japanese Patent Publication No. 51-47715 discloses copper,
A catalyst for methanol synthesis comprising an oxide of zinc, aluminum and boron and a method for producing the same are disclosed. In column 2, lines 33 to 34 of this publication, it is preferable that when boron is added to the catalyst, it is preferable that copper, zinc, aluminum and boron be coprecipitated, and that when only boron is added later, the activity decreases. Is stated. Also, column 2 of the publication
Lines 1 to 15 indicate that the content of boron in the catalyst is 0.3 to 5.3%, preferably 0.5 to 3.5% on an atomic basis.
It is shown that However, the examples only describe an example where the boron content in the catalyst is 1.97% on an atomic basis. Note that the atomic standard content is 5%
Is about 2.5% by weight as an oxide standard content.

[0008] JP-B-59-10256 discloses a catalyst production method similar to the catalyst production method described in JP-B-51-44715. Also in this publication, addition of boron to the catalyst (0.3 to 5.0 atomic%)
Precipitates a boron component from a water-soluble boron compound at the same time as copper, zinc, and aluminum (the same publication, column 1, 33-34).
Line).

JP-A-8-299796 discloses Japanese Patent Publication No. 51-47715 and Japanese Patent Publication No. 59-1025.
No. 6 discloses a catalyst production method similar to the catalyst production method described in Japanese Patent Publication No. Also in this publication, just as in the above-mentioned two publications, boron is added to the catalyst by adding a boron component (0.3 to 5 atomic%) from boric acid or borax to a copper source, a zinc source,
To the aluminum source (see the same publication, column 2, 48-49).
Row), by precipitation with copper, zinc, aluminum.

[0010]

However, in any of the production methods described in the above publications, since boron is added to the catalyst by the coprecipitation method, it is difficult to quantitatively add boron to the catalyst. Further, the content of boron in the catalyst is small, and the effect is not sufficiently obtained. Therefore, the performance of the catalyst cannot be sufficiently improved.

Accordingly, the present invention provides a method for producing methanol by reacting carbon oxide with hydrogen at 150 to 250 ° C.
It is an object of the present invention to provide a catalyst exhibiting high activity at a high temperature and a method for producing the same.

Another object of the present invention is to increase the content of boron oxide in a catalyst for methanol synthesis so as to sufficiently exert its effect.

[0013]

Means for Solving the Problems The present inventors have conducted intensive studies to improve the performance of a catalyst comprising copper oxide, zinc oxide and aluminum oxide. By producing a mixture of a precursor and a precursor of aluminum oxide by adding a boron compound to the mixture and calcining the mixture, copper oxide, zinc oxide, aluminum oxide and boron oxide are contained. In an amount of 2 to 12% by weight, preferably 3%
It has been found that the above-mentioned object can be achieved by obtaining a catalyst having a content of 〜12% by weight, more preferably 5-10% by weight. The boron compound is added as it is or in the form of a solution.

That is, the methanol synthesis catalyst of the present invention comprises copper oxide, zinc oxide, aluminum oxide and boron oxide, and has a boron oxide content of 2 to 12% by weight, preferably 3 to 12% by weight, more preferably. Is 5 to 10% by weight. Furthermore, copper oxide is 20 to 6
It is desirable that the content is 0% by weight, zinc oxide is 10 to 60% by weight, and aluminum oxide is 2 to 15% by weight. This catalyst is desirably brought into contact with a gas containing methanol at 200 to 400 ° C. This catalyst also has a
It is effective even at a relatively low temperature of
It can be used in a temperature range of 0 ° C.

Further, at least one selected from the group consisting of silicon oxide, zirconium oxide and gallium oxide may be added to the methanol synthesis catalyst. This allows
The durability and activity of the catalyst are improved.

The process for producing a catalyst for methanol synthesis according to the present invention is characterized in that a mixture of a precursor of copper oxide, a precursor of zinc oxide and a precursor of aluminum oxide, for example, a precipitate of a basic carbonate, a boron compound or The solution, for example, an aqueous boric acid solution is mixed, and the resulting mixture is dried and fired.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.

The catalyst for synthesizing methanol of the present embodiment comprises 20 to 60% by weight of copper oxide and 10 to 60% by weight of zinc oxide.
% By weight, 2 to 15% by weight as aluminum oxide and 2 to 12% by weight, preferably 3 to 12% by weight, more preferably 5 to 10% by weight as boron oxide. Further, it is effective to add silicon oxide, zirconium oxide, gallium oxide, or the like, for the purpose of improving the durability of the catalyst and the catalytic activity. As the addition amount, silicon oxide is preferably 0.3 to 2.0% by weight, and zirconium oxide and gallium oxide are each preferably 5 to 30% by weight.
These are substantial components, and it is possible to appropriately include any element that does not affect the catalytic action.

Further, the method for producing a catalyst for methanol synthesis according to the present embodiment is a method for preparing a mixture of a precursor of copper oxide, a precursor of zinc oxide and a precursor of aluminum oxide, for example, precipitation of a basic carbonate or hydroxide. A boron compound or a solution thereof, for example, an aqueous boric acid solution is added to the product, and the resulting mixture is dried and fired.

The precursors of copper oxide, zinc oxide and aluminum oxide can be prepared by a known precipitation method using water-soluble nitrates and sulfates as raw materials and sodium carbonate and sodium hydroxide as precipitants. It can be prepared by a coprecipitation method. The precursor mixture may be prepared simultaneously by a coprecipitation method, or may be prepared by preparing each precursor individually and mixing them. As a raw material of the boron compound, various boron compounds containing no alkali element such as sodium, such as boron oxide, metaboric acid and orthoboric acid, can be used.

An embodiment of the method for producing a catalyst for methanol synthesis according to the present invention will be described as follows.

First, nitrates and sulfates of copper, zinc and aluminum are dissolved in water to prepare a mixed aqueous solution.
On the other hand, a basic compound such as sodium carbonate, sodium hydrogen carbonate, sodium hydroxide or the like is dissolved in water to obtain an aqueous precipitant solution. By mixing these two solutions,
A co-precipitate forms. This is filtered and washed to obtain a precursor mixture of copper oxide, zinc oxide and aluminum oxide. A predetermined amount of boric acid aqueous solution is mixed with the obtained precursor mixture, and then dried. Further, by calcining at a predetermined temperature, a catalyst for methanol synthesis is produced.

The firing temperature is 350 ° C. to 650 ° C.
In particular, 400 ° C to 600 ° C is preferable.

When the thus obtained catalyst for methanol synthesis is used for methanol synthesis, the methanol synthesis activity of the catalyst continues to increase for several days after the start of the reaction and eventually reaches the maximum activity.

The catalyst for methanol synthesis may be reduced with hydrogen prior to use. Thereby, an effect that the catalyst is activated is obtained. However, even when this reduction is not performed, a prior reduction operation is not essential because hydrogen is naturally reduced during a methanol synthesis reaction using hydrogen as a part of the raw material.

If necessary, the catalyst for methanol synthesis of the present invention may be treated with methanol-containing hydrogen or an inert gas at around the reaction temperature of methanol synthesis, that is, within a temperature range of 200 to 400 ° C. By the treatment, the highest activity can be obtained immediately after the start of the reaction.

Furthermore, the catalyst for methanol synthesis according to the present invention can be used in a methanol synthesis reaction in the gas phase or in a methanol synthesis reaction performed by suspending the catalyst in a liquid.
Useful.

The reaction conditions for synthesizing methanol using the catalyst for methanol synthesis according to the present invention vary depending on the concentrations of carbon oxides and hydrogen in the raw material gas, the contents of the catalyst components, and the like. 150-350 ° C., reaction pressure 10-300 kg / cm ² , space velocity 500-1
A range of 00000 is suitable.

[0029]

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

Example 1 Copper nitrate hexahydrate 32.5 g,
43.0 g of zinc nitrate hexahydrate and 7.9 g of aluminum nitrate nonahydrate were dissolved in distilled water to prepare a 300 mL aqueous solution, which was used as solution A. On the other hand, anhydrous sodium carbonate 3
6.2 g was dissolved in distilled water to prepare a 300 mL aqueous solution, which was designated as solution B.

While stirring 800 mL of room temperature distilled water well, Liquid A and Liquid B were simultaneously dropped at a rate of 8 mL / min, respectively, to obtain a precipitate. After aging this precipitate at room temperature for 3 days, sodium in the precipitate was removed by filtration and washing with distilled water.

The resulting precipitate was mixed with diboron trioxide 1.25.
g of a solution of boric acid dissolved in 30 mL of distilled water was added and mixed well.

Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours to obtain a catalyst. The composition of this catalyst was 44.6% by weight of copper oxide, 45.5% by weight of zinc oxide, 4.2% by weight of aluminum oxide, and 5.7% of boron oxide.
% By weight.

1 mL of the obtained catalyst was filled in a reaction tube to form a catalyst layer, and a reduction treatment was performed at 250 ° C. for 2 hours using a mixed gas of 90% by volume of helium and 10% by volume of hydrogen. .

Thereafter, a mixed gas consisting of 22% by volume of CO ₂ , 3% by volume of CO and 75% by volume of H ₂ was supplied at a pressure of 5 MPa, a mixed gas flow rate of 167 mL / min, and a temperature of 250 ° C.
Was passed through the catalyst layer to carry out a methanol synthesis reaction.

The reaction product gas was analyzed by gas chromatography, and the space-time yield of methanol, which is a measure of the catalytic activity, was examined. The methanol space-time yield gradually increased to about 10
After 0 hour, the maximum value was 634 (g-methanol / l-catalyst.
h).

Thereafter, a methanol synthesis reaction was carried out for a long time under the same reaction conditions. The methanol space-time yield gradually decreased, and the methanol space-time yield at 500 hours after the start of the reaction was 450 (g-methanol / l-catalyst · h).

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 1 Copper nitrate hexahydrate 32.5 g,
43.0 g of zinc nitrate hexahydrate and 7.9 g of aluminum nitrate nonahydrate were dissolved in distilled water to prepare a 300 mL aqueous solution, which was used as solution A. On the other hand, anhydrous sodium carbonate 3
6.2 g was dissolved in distilled water to prepare a 300 mL aqueous solution, which was designated as solution B.

While thoroughly stirring 800 mL of room temperature distilled water, Solution A and Solution B were simultaneously added dropwise at a rate of 8 mL / min to obtain a precipitate. After aging this precipitate at room temperature for 3 days, sodium in the precipitate was removed by filtration and washing with distilled water.

Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours to obtain a catalyst. The composition of the catalyst was 47.3% by weight of copper oxide, 48.2% by weight of zinc oxide, and 4.5% by weight of aluminum oxide.

After 1 mL of the obtained catalyst was filled in a reaction tube to form a catalyst layer, the catalyst was reduced in the same manner as in Example 1, and then a methanol synthesis reaction was performed under the same reaction conditions as in Example 1. Was.

The reaction product gas was analyzed by gas chromatography, and the space-time yield of methanol was examined. The methanol space-time yield was highest for one hour after the start of the reaction (552 (g-
Methanol / l-catalyst · h)) and then gradually decreased to 405 (g-methanol / l-catalyst · h) after 500 hours.

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

From the results of Example 1 and Comparative Example 1, it is clear that the activity of the catalyst without boron was significantly lower than that of the catalyst with boron added.

Comparative Example 2 Copper nitrate hexahydrate 32.5 g,
43.0 g of zinc nitrate hexahydrate, 7.9 g of aluminum nitrate nonahydrate and 11.2 g of diboron trioxide were dissolved in distilled water to prepare a 300 mL aqueous solution, which was used as solution A. On the other hand, 39.5 g of anhydrous sodium carbonate was dissolved in distilled water,
A 300 mL aqueous solution was prepared and used as solution B.

While thoroughly stirring 800 mL of room temperature distilled water, the solution A and the solution B were simultaneously dropped at a rate of 8 mL / min, respectively, to obtain a precipitate. After aging this precipitate at room temperature for 3 days, sodium in the precipitate was removed by filtration and washing with distilled water.

Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours to obtain a catalyst. The composition of this catalyst was 47.3% by weight of copper oxide, 46.2% by weight of zinc oxide, 4.4% by weight of aluminum oxide and 2.1% by weight of boron oxide.

After 1 mL of the obtained catalyst was filled in a reaction tube to form a catalyst layer, the catalyst was reduced in the same manner as in Example 1, and a methanol synthesis reaction was performed under the same reaction conditions as in Example 1. Was.

The reaction product gas was analyzed by gas chromatography, and the space-time yield of methanol was examined. The methanol space-time yield increased gradually and reached a maximum (about 5 hours) after about 24 hours.
59 (g-methanol / l-catalyst · h)).

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

From the results of Example 1 and Comparative Example 2, it was found that if boron was added to the catalyst by the coprecipitation method, boron was dissolved and removed, or a large amount of boron was required, and the catalytic activity of boron was improved. It is clear that little effect is seen.

(Example 2) In the same manner as in Example 1, copper,
A precipitate containing zinc and aluminum was prepared.
0.5 g of diboron trioxide was added to the obtained precipitate by adding 20 g of distilled water.
An aqueous solution of boric acid dissolved in mL was added and mixed well.

Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours to obtain a catalyst. The composition of this catalyst was 46.2% by weight of copper oxide, 47.1% by weight of zinc oxide, 4.4% by weight of aluminum oxide, 2.3% of boron oxide.
% By weight.

1 mL of the obtained catalyst was filled in a reaction tube to form a catalyst layer, and a reduction treatment of the catalyst was performed in the same manner as in Example 1. Then, a methanol synthesis reaction was performed under the same reaction conditions as in Example 1. Was.

The reaction product gas was analyzed by gas chromatography, and the space-time yield of methanol was examined. The methanol space-time yield increased gradually and reached its highest value (5
89 (g-methanol / l-catalyst.h)).

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) In the same manner as in Example 1, copper,
A precipitate containing zinc and aluminum was prepared.
2.5 g of diboron trioxide was added to the obtained precipitate in 30 portions of distilled water.
An aqueous solution of boric acid dissolved in mL was added and mixed well.

Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours to obtain a catalyst. The composition of this catalyst was 42.2% by weight of copper oxide, 43.1% by weight of zinc oxide, 4.0% by weight of aluminum oxide, and 10% by weight of boron oxide.
7% by weight.

1 mL of the obtained catalyst was filled in a reaction tube to form a catalyst layer, and a reduction treatment of the catalyst was performed in the same manner as in Example 1. Then, a methanol synthesis reaction was performed under the same reaction conditions as in Example 1. Was.

The reaction product gas was analyzed by gas chromatography, and the space-time yield of methanol was examined. The methanol space-time yield gradually increased and reached a maximum value (586 (g-methanol / l-catalyst · h)) after about 170 hours.

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) In the same manner as in Example 1, copper,
A precipitate containing zinc and aluminum was prepared.
3.75 g of diboron trioxide was added to the obtained precipitate in distilled water 4.
An aqueous solution of boric acid dissolved in 0 mL was added and mixed well.

Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours to obtain a catalyst. The composition of this catalyst was 40.0% by weight of copper oxide, 40.8% by weight of zinc oxide, 3.8% by weight of aluminum oxide, and 15% of boron oxide.
It was 5% by weight.

After 1 mL of the obtained catalyst was filled in a reaction tube to form a catalyst layer, the catalyst was reduced in the same manner as in Example 1, and a methanol synthesis reaction was carried out under the same reaction conditions as in Example 1. Was.

The reaction product gas was analyzed by gas chromatography to examine the methanol space-time yield. The methanol space-time yield gradually increased and reached a maximum (478 (g-methanol / l-catalyst-h)) after about 216 hours.

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

Table 1 shows the boron oxide content and the highest catalytic activity of Examples 1 to 3 and Comparative Examples 1 to 3. From Example 2, the lower limit of the boron oxide content is considered to be 2% by weight.

From the results of Example 3 and Comparative Example 3, it is clear that adding too much boron reduces the catalytic activity. Therefore, it is considered that 12% by weight is the upper limit.

[0070]

[Table 1]

(Example 4: Pretreatment with methanol-containing hydrogen gas) 1 mL of the catalyst produced by the method of Example 1 was filled in a reaction tube to form a catalyst layer. Next, a mixed gas of 90% by volume of helium and 10% by volume of hydrogen was passed through a methanol saturation tank, and then supplied to the reaction tube to pretreat the catalyst layer at 250 ° C.

Thereafter, a methanol synthesis reaction was carried out in the same manner as in Example 1.

The reaction product gas was analyzed by gas chromatography, and the space-time yield of methanol was examined. In this example, the methanol space-time yield showed almost the same maximum value as in Example 1 immediately after the start of the reaction. After showing the highest value, the methanol space-time yield showed the same change as in Example 1.

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

In Example 1, 150 minutes were required to obtain the highest activity.
Although it took time, as can be seen from Example 4, the highest activity was obtained after the start of the reaction by pretreatment in which a helium-hydrogen mixed gas containing methanol was brought into contact.

Example 5: Containing silicon oxide 32.5 g of copper nitrate hexahydrate, 43.0 g of zinc nitrate hexahydrate, 7.9 g of aluminum nitrate nonahydrate and colloidal silica (Nissan Chemical Industries, Ltd. ), Snowtex O, silica concentration 2
(0% by weight) was dissolved in distilled water to prepare a 300 mL aqueous solution, which was designated as solution A. On the other hand, 36.2 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 300 mL aqueous solution, which was used as solution B.

While 800 mL of room temperature distilled water was well stirred, the solution A and the solution B were simultaneously dropped at a rate of 8 mL / min, respectively, to obtain a precipitate. After aging this precipitate at room temperature for 3 days, sodium in the precipitate was removed by filtration and washing with distilled water.
To the obtained precipitate, 1.25 g of diboron trioxide was added to 3 parts of distilled water.
An aqueous solution of boric acid dissolved in 0 mL was added and mixed well.

Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours to obtain a catalyst. The composition of this catalyst was 44.2% by weight of copper oxide, 45.0% by weight of zinc oxide, 4.2% by weight of aluminum oxide, 1.0% by weight of silicon oxide.
% By weight and 5.6% by weight of boron oxide.

[0079] 1 mL of the obtained catalyst was filled in a reaction tube to form a catalyst layer, and a reduction treatment of the catalyst was performed in the same manner as in Example 1. Then, a methanol synthesis reaction was performed under the same reaction conditions as in Example 1. Was.

The reaction product gas was analyzed by gas chromatography to examine the methanol space-time yield. 5 after the start of the reaction
The space-time yield of methanol at 00 hours was 560 (g-
Methanol / l-catalyst · h).

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

(Example 6: containing zirconium oxide) 35.1 g of copper nitrate hexahydrate, 25.3 g of zinc nitrate hexahydrate,
8.5 g of aluminum nitrate nonahydrate and 12.5 g of zirconium oxynitrate were dissolved in distilled water to prepare a 300 mL aqueous solution, which was used as solution A. On the other hand, 36.3 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 300 mL aqueous solution, which was used as solution B.

While stirring 800 mL of room temperature distilled water well, Liquid A and Liquid B were simultaneously dropped at a rate of 8 mL / min, respectively, to obtain a precipitate. After aging this precipitate at room temperature for 3 days, sodium in the precipitate was removed by filtration and washing with distilled water.
To the obtained precipitate, 1.25 g of diboron trioxide was added to 3 parts of distilled water.
An aqueous solution of boric acid dissolved in 0 mL was added and mixed well.

Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours to obtain a catalyst. The composition of this catalyst was 43.0% by weight of copper oxide, 25.7% by weight of zinc oxide, 4.3% by weight of aluminum oxide, 21.4% by weight of zirconium oxide and 5.6% by weight of boron oxide.

After 1 mL of the obtained catalyst was filled in a reaction tube to form a catalyst layer, the catalyst was reduced in the same manner as in Example 1, and then a methanol synthesis reaction was performed under the same reaction conditions as in Example 1. Was.

The reaction product gas was analyzed by gas chromatography, and the space-time yield of methanol was examined. 5 after the start of the reaction
The space-time yield of methanol at 00 hours is 510 (g-
Methanol / l-catalyst · h).

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

Example 7: Contains gallium oxide 32.7 g of copper nitrate hexahydrate, 39.3 g of zinc nitrate hexahydrate, 7.9 g of aluminum nitrate nonahydrate and 3.0 g of gallium nitrate
9 g is dissolved in distilled water to prepare a 300 mL aqueous solution,
Solution A was used. On the other hand, 36.9 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 300 mL aqueous solution, which was used as solution B.

While stirring 800 mL of room temperature distilled water well, the solution A and the solution B were simultaneously dropped at a rate of 8 mL / min, respectively, to obtain a precipitate. After aging this precipitate at room temperature for 3 days, sodium in the precipitate was removed by filtration and washing with distilled water.
To the obtained precipitate, 1.25 g of diboron trioxide was added to 3 parts of distilled water.
An aqueous solution of boric acid dissolved in 0 mL was added and mixed well.

Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours to obtain a catalyst. The composition of this catalyst was 44.2% by weight of copper oxide, 42.0% by weight of zinc oxide, 4.2% by weight of aluminum oxide, 4.0% by weight of gallium oxide and 5.6% by weight of boron oxide.

A 1 mL of the obtained catalyst was filled in a reaction tube to form a catalyst layer, and a reduction treatment of the catalyst was performed in the same manner as in Example 1. Then, a methanol synthesis reaction was performed under the same reaction conditions as in Example 1. Was.

The reaction product gas was analyzed by gas chromatography, and the space-time yield of methanol was examined. 5 after the start of the reaction
The methanol space-time yield at 00 hours was 520 (g-
Methanol / l-catalyst · h).

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

By adding silicon oxide as in Example 5, containing zirconium oxide as in Example 6, or containing gallium oxide as in Example 7, compared to Example 1, The space-time yield of methanol at 500 hours after the start of the reaction can be improved.

As described above, it is clear that the catalyst produced by the method of the present invention exhibits very high performance in the methanol synthesis reaction.

[0096]

Industrial Applicability The catalyst for methanol synthesis of the present invention exhibits high activity at 150 to 250 ° C. in a methanol synthesis reaction.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masaki Takeuchi 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo 7th Oriental Maritime Building 8F CO2 Fixation Project, etc. Indoor Environment (72) Invention Watanabe Daiki 2-8-11, Nishi-Shimbashi, Minato-ku, Tokyo 7th Oriental Maritime Building 8F CO2 Fixation Project, etc. The Institute for Global Environmental Research, Japan (72) Inventor Kenji Ushikoshi 2 Nishi-Shimbashi, Minato-ku, Tokyo -8-11 7th Oriental Maritime Building 8F 7th Oriental Maritime Building 8F, Innovative Researcher, Institute for Global Environmental Technology, CO2 Fixation Project, etc. Room (72) Inventor Itaru Hayakawa 2-8-11 Nishishinbashi, Minato-ku, Tokyo Research Institute of Innovative Technology for the Earth, CO2 Fixation Project, etc. Room (72) Inventor Kubo Takeshi 2-8-11, Nishi-Shimbashi, Minato-ku, Tokyo 7th Oriental Maritime Building 8F CO2 Fixation Project, The Institute for Research on Global Environment, Japan (72) Inventor Kozo Mori 2-8- Nishi-Shimbashi, Minato-ku, Tokyo 11 7th Oriental Maritime Building 8F Foundation for Global Environmental Technology, CO2 Fixation Project, etc. Indoor F-term (reference) 4G069 AA01 AA08 AA15 BB12B BB16B BC16A BC16B BC16C BC17A BC17B BC17C BC31A BC31B BC31C BC35A BC35B BC51CBCA BC31B BD03C BD05A BD05B BD05C CB02 FB30 FB44 FB77 4H006 AA02 AA05 AC41 BA05 BA07 BA09 BA10 BA30 BA31 BA33 BE20 BE40 BE41 4H039 CA60 CL35

Claims (5)

[Claims] 1. 20 to 60% by weight of copper oxide, 10 of zinc oxide
1 to 60% by weight, 2 to 15% by weight of aluminum oxide and 2 to 12% by weight of boron oxide. 2. The catalyst for methanol synthesis according to claim 1, comprising at least one member selected from the group consisting of silicon oxide, zirconium oxide and gallium oxide. 3. A gas containing methanol at a temperature of 200 ° C. to 40 ° C.
The catalyst for methanol synthesis according to claim 1 or 2, wherein the catalyst has been subjected to a pretreatment of contacting at a temperature in the range of 0 ° C. 4. A step of preparing a mixture of a precursor of copper oxide, a precursor of zinc oxide and a precursor of aluminum oxide, a step of adding a boron compound to the mixture, and firing the mixture to which the boron compound is added. A method for producing a catalyst for methanol synthesis comprising the steps of: 5. After the calcination, a gas containing methanol is added to the gas.
The method for producing a catalyst for methanol synthesis according to claim 4, comprising a step of contacting at a temperature in the range of 00C to 400C.