JP5264083B2 - Methanol synthesis catalyst, method for producing the catalyst, and method for producing methanol - Google Patents

Abstract

Disclosed is a methanol synthesis catalyst for synthesis of methanol via a formic acid ester wherein a reaction is performed by using a raw material gas containing hydrogen and at least either of carbon monoxide and carbon dioxide in the presence of an alcohol as a solvent. The methanol synthesis catalyst contains a hydrocracking catalyst in addition to at least one of sodium formate, rubidium carbonate and caesium carbonate.

Description

  The present invention relates to a catalyst for methanol synthesis, a method for producing the catalyst, and a method for producing methanol. More specifically, the present invention relates to a highly active catalyst and a method for obtaining a product with high efficiency by using this catalyst when producing methanol from carbon source of either carbon monoxide or carbon dioxide and hydrogen.

  Generally, when industrially synthesizing methanol, carbon monoxide and hydrogen (synthetic gas) obtained by steam reforming natural gas mainly composed of methane are used as raw materials, and copper, zinc-based, etc. The catalyst is synthesized using a fixed bed gas phase method under severe conditions of 200 to 300 ° C. and 5 to 25 MPa (Non-patent Document 1). As shown below, the reaction mechanism is a sequential reaction in which methanol and water are produced by hydrogenation of carbon dioxide, and then the produced water reacts with carbon monoxide to produce carbon dioxide and hydrogen (water gas shift reaction). The theory is generally accepted.

CO ₂ + 3H ₂ → CH ₃ OH + H ₂ O (1)
H ₂ O + CO → CO ₂ + H ₂ (2)
CO + 2H ₂ → CH ₃ OH (3)
Although this reaction is an exothermic reaction, it is difficult to remove heat efficiently due to poor heat conduction in the gas phase method, so the conversion rate when passing through the reactor is kept low, and unreacted high-pressure raw material gas Recycling is a difficult process in terms of efficiency. However, taking advantage of the fact that reaction inhibition by water and carbon dioxide contained in synthesis gas is difficult, various plants are in operation.

  On the other hand, various methods for improving the heat removal rate by synthesizing methanol in a liquid phase have been studied. Among them, a method using a catalyst having high activity at a low temperature (about 100 to 180 ° C.) is thermodynamically advantageous for the production system, and has attracted attention (Non-patent Document 2, etc.). The catalyst used is an alkali metal alkoxide, but these methods have reported a decrease in activity due to water and carbon dioxide that are always contained in the synthesis gas, and none of them have been put into practical use (Non-patent Document 3). This is because a highly active alkali metal alkoxide is converted into a low activity and stable formate during the reaction. In order to prevent the decrease in activity, it is necessary to remove water and carbon dioxide in the raw material gas up to the ppb order. However, such pretreatment increases the cost and is not realistic.

The present inventors have so far made one or both of an alkali metal catalyst and an alkaline earth metal catalyst excluding alkali metal alkoxide coexist with a hydrocracking catalyst as a catalyst with a small decrease in activity due to water and carbon dioxide. A system to be used has been found (Patent Document 1). However, further improvement in catalytic activity makes it possible to synthesize product methanol with high efficiency.
JP2001-862701 JCJ Bart et al., Catal. Today, 2, 1 (1987) Seiichi Oyama, PETROTECH, 18 (1), 27 (1995) S. Ohyama, Applied Catalysis A: General, 180, 217 (1999)

  The present invention aims to solve the above-mentioned problems, and even if a small amount of carbon dioxide, water, etc. are mixed in the methanol synthesis raw material gas, the degree of catalyst activity decrease is low, and the temperature is low. The present invention provides a catalyst capable of synthesizing formate and methanol at low pressure, a method for producing the catalyst, and a method for synthesizing methanol in a liquid phase using the catalyst.

The features of the present invention are as described below.
(1) A catalyst for synthesizing methanol via a formic acid ester that reacts in the presence of at least one of carbon monoxide and carbon dioxide, and hydrogen, and an alcohol as a solvent. In addition to at least one of rubidium and cesium carbonate (catalyst component 1) , a hydrocracking catalyst (catalyst component 2) containing Cu, Mg and Na, or Cu, Mg, Na and Pd is included, and the hydrogenation The decomposition catalyst Na (catalyst component 2) is supported on a solid catalyst of Cu / MgO as a carbonate or formate , and sodium formate (catalyst present) as at least one of the sodium formate, rubidium carbonate, and cesium carbonate. Component 1) is a catalyst for methanol synthesis, which is not supported on the solid catalyst.

(2) The methanol synthesis catalyst according to (1), wherein the Pd of the hydrocracking catalyst is supported on a Cu / MgO solid catalyst.

(3) A catalyst for synthesizing methanol via a formate ester that reacts in the presence of at least one of carbon monoxide and carbon dioxide, and hydrogen, and an alcohol as a solvent. In addition to at least one of rubidium and cesium carbonate (catalyst component 1) , the catalyst has a hydrocracking catalyst (catalyst component 2) containing Cu, Mg, Na and Pd, and the Pd (catalyst) of the hydrocracking catalyst Component 2) is supported on a solid catalyst of Cu / MgO, and sodium formate (catalyst component 1) present as at least one of sodium formate, rubidium carbonate, and cesium carbonate is not supported on the solid catalyst. A catalyst for synthesizing methanol.

( 4 ) The catalyst for methanol synthesis according to any one of (2) to ( 3 ), wherein the amount of Pd supported on the hydrocracking catalyst is 0.001 to 1 mass%.

( 5 ) The method for producing a catalyst for methanol synthesis according to ( 1 ) to ( 4 ), wherein Cu / MgO is prepared by a coprecipitation method, and then Cu / MgO is impregnated with Na and / or Pd. A method for producing a catalyst for methanol synthesis, characterized by being supported.

( 6 ) A method for producing a catalyst for methanol synthesis as described in ( 1 ) to ( 4 ), characterized in that the Cu / MgO is prepared while being kept constant in the range of pH = 8 to 11 in the coprecipitation method. A method for producing a catalyst for methanol synthesis.

(7) A method of producing methanol by reacting at least one of carbon monoxide and carbon dioxide, and hydrogen-containing source gas, wherein at least one of sodium formate, rubidium carbonate, and cesium carbonate (catalyst component 1) In addition to Cu, Mg and Na, or Cu, Mg, Na and Pd (catalyst component 2) , Pd and / or Na as a carbonate or formate (catalyst component 2) is a solid of Cu / MgO. Sodium hydroformate (catalyst component 1) present as at least one of sodium formate, rubidium carbonate, and cesium carbonate supported on the catalyst is present in the hydrocracking catalyst not supported on the solid catalyst, and alcohols The reaction below is performed to produce formate ester and methanol, and the produced formate ester is hydrogenated to produce methanol Method of manufacturing methanol according to claim Rukoto.

(8) At least one of carbon monoxide, carbon dioxide, and hydrogen-containing source gas is added to at least one of sodium formate, rubidium carbonate, cesium carbonate (catalyst component 1) , Cu, Mg and Na, or Cu Mg, Na and Pd (catalyst component 2) , and Pd and / or Na (catalyst component 2) as carbonate or formate are supported on a solid catalyst of Cu / MgO, and the sodium formate, Sodium formate (catalyst component 1) present as at least one of rubidium carbonate and cesium carbonate is a product obtained by reacting in the presence of a hydrocracking catalyst not supported on the solid catalyst and an alcohol. After the methanol is separated from the reaction system, methanol is produced by hydrogenating the formate in the product with a hydrocracking catalyst. Manufacturing method Le.

( 9 ) The method for producing methanol according to ( 7) or (8) , wherein the alcohol is a primary alcohol.

  In the present invention, in addition to at least one of sodium formate, rubidium carbonate, and cesium carbonate, a system containing a catalyst containing Cu, Mg, Na, and Pd, a synthetic raw material gas, carbon monoxide, carbon dioxide When formate and methanol were produced from at least one of the above and hydrogen in the presence of a solvent alcohol, it was possible to synthesize methanol stably and efficiently in a continuous reaction at low temperature and low pressure. In addition, even if a small amount of water, carbon dioxide, or the like is mixed in the synthetic raw material gas, it is possible to produce methanol at a low cost because the degree of decrease in the activity of the catalyst is low.

Hereinafter, the present invention will be described in detail.
As a result of diligent investigations, the present inventors have conducted a semi-batch continuous reaction in which a catalyst and a solvent are charged into a reactor and a raw material gas is supplied, in addition to at least one of sodium formate, rubidium carbonate, and cesium carbonate, Cu, Use a catalyst containing a hydrocracking catalyst containing Mg and Na, or Cu, Mg, Na and Pd, and Pd and / or Na as carbonate or formate supported on a Cu / MgO solid catalyst And in the manufacture of methanol from at least one of carbon monoxide and carbon dioxide, and hydrogen and alcohols, it was found that it can be produced in high yield, and the present invention has been achieved .

  For example, methanol can be continuously produced by a reaction process as shown in FIG. In addition to at least one of sodium formate, rubidium carbonate, and cesium carbonate, a semi-batch reactor 2 is charged with a solid catalyst containing Cu, Mg, Na, and Pd together with a solvent alcohol, and synthesis gas 1 is supplied. The product 3 at the outlet of the reactor (formate ester, methanol) and the unreacted gas mixture 3 are cooled by a cooler 4 and separated into an unreacted gas 5 and a liquid mixture 6 of formate ester and alcohol. The latter is separated into formate ester 8 and methanol 9 in distillation column 7 installed in the next stage. When the conversion rate is low, it is possible to supply the unreacted gas 5 to the semi-batch reactor 2 again, but when it is obtained in high yield, the unreacted gas is used as a heat source (fuel) for synthesis gas production. To do.

The solid catalyst containing Cu, Mg and Na, or Cu, Mg, Na and Pd is specifically Cu / MgO _x / Na / Pd (where X is a chemically acceptable value which may be 0), for example Cu / MgO _X / HCOONa / Pd (X is a chemically acceptable value). The preparation of Cu / MgO _X may be carried out by ordinary methods such as impregnation method, precipitation method, sol-gel method, coprecipitation method, ion exchange method, kneading method, evaporation to dryness method, and is not particularly limited. Good results are likely to be obtained by the coprecipitation method. The CO conversion varies greatly depending on the pH that is kept constant during preparation by the coprecipitation method. The pH for preparing Cu / MgO _X is preferably 8 to 11, more preferably 8.5 to 10.5, and still more preferably 9 to 10. When the pH exceeds 11, the amount of the alkaline compound used as the precipitating agent to maintain the high alkaline atmosphere is remarkably increased, which is not economical. The method for supporting Na salt on Cu / MgO _X may be the above-mentioned ordinary method, and is not particularly limited, but good results are easily obtained by the impregnation method or the evaporation to dryness method. The amount of Na supported on Cu / MgO _X is not less than the minimum amount that exhibits the effect, and is not particularly limited, but is preferably in the range of 0.1 to 60 mass%, more preferably 1 to 40 mass%, Preferably it is 3-30 mass%. Further, sodium formate, sodium carbonate and the like are preferable as the Na salt to be supported. Catalytic activity increases by loading these Na salts. Further, Cu / MgO _X / Na can be suppressed over time decrease in activity which is slightly observed in the Cu / MgO _X. Therefore, the addition effect of alkali metal carbonate is in activity improvement and activity reduction suppression.

The Pd loading method may be a normal method and is not particularly limited. Similarly, good results are easily obtained by the impregnation method and the evaporation to dryness method. The amount of Pd supported with respect to Cu / MgO _X / Na is not less than the minimum amount that exhibits an effect, and is not particularly limited, but is preferably in the range of 0.001 to 1 mass%, more preferably 0.005 to 0.5 mass%, More preferably, it is 0.01-0.1 mass%. By supporting Pd, the catalytic activity is improved.

Na and Pd are preferably supported sequentially on Cu / MgO _X as described above, but when the Na salt to be supported and the Pd precursor that is the precursor of Pd to be supported are dissolved in the same liquid, they may be supported simultaneously. Is possible. Alternatively, Cu / MgO _x / Pd can be prepared by loading Pd first, and then a Na salt can be loaded.

The above-mentioned solid catalyst containing Cu, Mg and Na, or Cu, Mg, Na and Pd mainly shows a catalytic action in the hydrocracking of the produced formate, but also catalyses the CO insertion reaction into the solvent alcohol. Indicates.

  Sodium metal formate, rubidium carbonate, and alkali metal salts of cesium carbonate show high activity in the CO insertion reaction into solvent alcohol.

  The alcohol used in the reaction may be a chain or alicyclic hydrocarbon having a hydroxyl group, a phenol and a substituted product thereof, or a thiol and a substituted product thereof. These alcohols may be any of primary, secondary and tertiary, but primary alcohols are preferred from the viewpoint of reaction efficiency, etc., and lower alcohols such as methyl alcohol and ethyl alcohol are the most common. is there.

  The reaction can be carried out in either the liquid phase or the gas phase, but a system in which mild conditions can be selected can be employed. Specifically, a temperature of 70 to 250 ° C. and a pressure of 3 to 100 atmospheres are preferable conditions, and a temperature of 120 to 200 ° C. and a pressure of 15 to 80 atmospheres are more preferable, but not limited thereto. Alcohols only need to have such an amount that the reaction proceeds, but more than that can be used as a solvent. In the above reaction, in addition to alcohols, an organic solvent can be used as appropriate.

  The resulting formic acid ester can be purified by conventional methods such as distillation, but can also be used for the production of methanol as it is. That is, methanol can be produced by hydrogenolysis of formate.

For hydrocracking, a hydrocracking catalyst is used. For example, a general hydrocracking catalyst of Cu, Pt, Ni, Co, Ru, Pd can be used, but the Cu / MgO _x / Na of the present invention can be used. You can also use / Pd. By making these general hydrocracking catalysts coexist in the reaction system for producing formate and methanol from the raw material gas and alcohol, it is possible to increase methanol selectivity and efficiently produce methanol. is there.

  In addition, when it is difficult to produce methanol in one step under the reaction conditions with high formate ester selectivity, the product obtained in the reaction is separated from the reaction system by distillation or the like, It is also possible to obtain methanol by hydrocracking formate in the presence of a hydrocracking catalyst and hydrogen.

In the method using the catalyst of the present invention, methanol can be obtained even with only CO ₂ as the carbon source in the raw material gas, but the activity is lower than in the case of using only CO. Moreover, the lower the concentration of CO ₂ and H ₂ O contained in the source gas containing CO as a main component as a carbon source, the higher the yield of methanol can be obtained. CO conversion and methanol yield are hardly affected. However, if it is contained at a concentration higher than that, the CO conversion rate and the methanol yield decrease.

  The method for producing methanol in the present invention is presumed to be based on the following reaction formula (shown as an example where the alcohol is a chain or alicyclic hydrocarbon having a hydroxyl group attached thereto).

ROH + CO → HCOOR (4)
HCOOR + 2H ₂ → CH ₃ OH + ROH (5)
(Where R represents an alkyl group)

  Therefore, the raw material for producing methanol is at least one of carbon monoxide and hydrogen, carbon dioxide and hydrogen, and alcohols can be recovered and reused. According to the method of the present invention, even if a small amount of water and carbon dioxide are present in the raw material gas, the decrease in the activity of the catalyst is small.

  In the present invention, in addition to at least one of sodium formate, rubidium carbonate, and cesium carbonate, a catalyst having a hydrocracking catalyst, when used in a liquid phase, is at least one of sodium formate, rubidium carbonate, and cesium carbonate. Even if they are partially or completely dissolved depending on the conditions, and they are separated from the hydrocracking catalyst, they can act as catalysts, so when preparing the catalyst, sodium formate, rubidium carbonate, cesium carbonate At least one of the above and a hydrocracking catalyst may be added to the reaction system, or a mixture of both may be input to the reaction system and used as the catalyst of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples 1 to 19 and Comparative Examples 1 and 2, but the present invention is not limited to these Examples. These results are listed in Tables 1 and 2.
Example 1
Using an autoclave with an internal volume of 50 ml, in addition to 2.5 mmol of rubidium carbonate in 10 ml of ethanol containing 1% by mass of water as a solvent, Cu (NO ₃ ) ₂ · 3H ₂ O, Mg (NO ₃ ) ₂ · 6H ₂ O Cu / MgO _X was prepared as a raw material while maintaining pH = 10.0 by the coprecipitation method, and Cu / MgO _X was sequentially impregnated and supported with Na ₂ CO ₃ (18.7 mass%) and Pd (0.25 mass%). / MgO _X / Na ₂ CO ₃ (18.7 mass%) / Pd (0.25 mass%) 1 g of catalyst was added, and synthesis gas (CO 32.40 vol%, hydrogen 64.58 vol%, Ar 3.02 vol%) was charged at 5 MPa, The reaction was performed at 160 ° C. for 5 hours, and the reaction product was analyzed by gas chromatography. The amount of methanol produced was 84.6 mmol, and the amount of ethyl formate produced was 2.1 mmol.

Example 2
The reaction was carried out by the method described in Example 1, except that 2.5 mmol of sodium formate was added instead of 2.5 mmol of rubidium carbonate. The amount of methanol produced was 109.1 mmol, and the amount of ethyl formate produced was 2.7 mmol.

Example 3
The reaction was carried out by the method described in Example 1, except that 2.5 mmol of cesium carbonate was added instead of 2.5 mmol of rubidium carbonate. The amount of methanol produced was 77.8 mmol, and the amount of ethyl formate produced was 2.2 mmol.

Comparative Example 1
The reaction was carried out by the method described in Example 1 except that 2.5 mmol of potassium formate was added instead of 2.5 mmol of rubidium carbonate. The amount of methanol produced was 55.3 mmol, and the amount of ethyl formate produced was 2.1 mmol.

Example 4
The reaction was carried out by the method described in Example 1 except that the amount of rubidium carbonate added was 1.25 mmol. The amount of methanol produced was 55.6 mmol and the amount of ethyl formate produced was 1.9 mmol.

Example 5
The reaction was carried out by the method described in Example 1 except that 1.0 mmol of sodium formate was added instead of 2.5 mmol of rubidium carbonate. The amount of methanol produced was 79.4 mmol, and the amount of ethyl formate produced was 1.8 mmol.

Example 6
The reaction was carried out by the method described in Example 1 except that 1.25 mmol of cesium carbonate was added instead of 2.5 mmol of rubidium carbonate. The amount of methanol produced was 38.7 mmol and the amount of ethyl formate produced was 1.7 mmol.

Example 7
_{Cu / MgO X / Na 2 CO} 3 (18.7mass%) / Pd a (0.25 mass%) instead of _{Cu / MgO X / Na 2 CO} 3 catalyst 1g (18.7mass%) / Pd ( 0.001mass%) catalyst 1g The reaction was carried out by the method described in Example 2 except for the addition. The amount of methanol produced was 61.2 mmol, and the amount of ethyl formate produced was 2.1 mmol.

Example 8
_{Cu / MgO X / Na 2 CO} 3 (18.7mass%) / Pd a (0.25 mass%) instead of _{Cu / MgO X / Na 2 CO} 3 catalyst 1g (18.7mass%) / Pd ( 0.005mass%) catalyst 1g The reaction was carried out by the method described in Example 2 except for the addition. The amount of methanol produced was 85.3 mmol, and the amount of ethyl formate produced was 2.2 mmol.

Example 9
_{Cu / MgO X / Na 2 CO} 3 (18.7mass%) / Pd a (0.25 mass%) instead of _{Cu / MgO X / Na 2 CO} 3 catalyst 1g (18.7mass%) / Pd ( 0.01mass%) catalyst 1g The reaction was carried out by the method described in Example 2 except for the addition. The amount of methanol produced was 127.1 mmol, and the amount of ethyl formate produced was 2.5 mmol.

Example 10
_{Cu / MgO X / Na 2 CO} 3 (18.7mass%) / Pd a (0.25 mass%) instead of _{Cu / MgO X / Na 2 CO} 3 catalyst 1g (18.7mass%) / Pd ( 0.025mass%) catalyst 1g The reaction was carried out by the method described in Example 2 except for the addition. The amount of methanol produced was 129.2 mmol and the amount of ethyl formate produced was 2.4 mmol.

Example 11
_{Cu / MgO X / Na 2 CO} 3 (18.7mass%) / Pd a (0.25 mass%) instead of _{Cu / MgO X / Na 2 CO} 3 catalyst 1g (18.7mass%) / Pd ( 0.05mass%) catalyst 1g The reaction was carried out by the method described in Example 2 except for the addition. The amount of methanol produced was 116.0 mmol, and the amount of ethyl formate produced was 2.1 mmol.

Example 12
_{Cu / MgO X / Na 2 CO} 3 (18.7mass%) / Pd a (0.25 mass%) instead of _{Cu / MgO X / Na 2 CO} 3 catalyst 1g (18.7mass%) / Pd ( 0.1mass%) catalyst 1g The reaction was carried out by the method described in Example 2 except for the addition. The amount of methanol produced was 104.1 mmol and the amount of ethyl formate produced was 2.0 mmol.

Example 13
Using an autoclave with an internal volume of 50 ml, in addition to 2.5 mmol of rubidium carbonate in 10 ml of ethanol containing 1% by weight of water as a solvent, Cu (NO ₃ ) ₂ · 3H ₂ O, Mg (NO ₃ ) ₂ · 6H ₂ O the Cu / MgO _X was prepared while maintaining the pH = 10.0 by co-precipitation method as a starting material, Na ₂ CO ₃ Cu / MgO impregnated carrying _{(18.7mass%) X / Na 2} CO 3 (18.7mass%) catalyst 1g Was charged with 5 MPa of synthesis gas (CO 32.40%, hydrogen 64.58%, Ar 3.02%), the reaction was performed at 160 ° C. for 5 hours, and the reaction product was analyzed by gas chromatography. The amount of methanol produced was 75.6 mmol, and the amount of ethyl formate produced was 1.6 mmol.

Example 14
The reaction was performed by the method described in Example 13, except that the amount of rubidium carbonate added was 1.25 mmol. The amount of methanol produced was 46.8 mmol and the amount of ethyl formate produced was 1.9 mmol.

Example 15
The reaction was conducted by the method described in Example 13 except that the reaction temperature was 140 ° C. The amount of methanol produced was 30.5 mmol, and the amount of ethyl formate produced was 3.6 mmol.

Example 16
The reaction was performed by the method described in Example 13 except that the reaction pressure was 3.5 MPa. The amount of methanol produced was 29.4 mmol and the amount of ethyl formate produced was 1.7 mmol.

Example 17
The reaction was performed by the method described in Example 13, except that 2.5 mmol of cesium carbonate was added instead of 2.5 mmol of rubidium carbonate. The amount of methanol produced was 55.8 mmol, and the amount of ethyl formate produced was 2.3 mmol.

Example 18
The reaction was performed by the method described in Example 13, except that 1.25 mmol of cesium carbonate was added instead of 2.5 mmol of rubidium carbonate. The amount of methanol produced was 42.7 mmol and the amount of ethyl formate produced was 1.9 mmol.

Example 19
The reaction was performed by the method described in Example 13, except that 2.5 mmol of sodium formate was added instead of 2.5 mmol of rubidium carbonate. The amount of methanol produced was 34.1 mmol, and the amount of ethyl formate produced was 1.9 mmol.

Comparative Example 2
The reaction was performed by the method described in Example 8, except that 2.5 mmol of potassium formate was added instead of 2.5 mmol of rubidium carbonate. The amount of methanol produced was 20.0 mmol, and the amount of ethyl formate produced was 2.3 mmol.

From the above Examples and Comparative Examples, sodium formate, rubidium carbonate, and cesium carbonate significantly increase the amount of methanol produced compared to other alkali metal salts such as potassium formate , and Cu, Mg and hydrocracking catalysts. It is clear that good results are obtained when using catalysts containing Na or Cu, Mg, Na and Pd.

1 is a reactor for carrying out the low-temperature liquid phase methanol synthesis of the present invention.

Explanation of symbols

1 Syngas
2 Semi-batch reactor
3 Mixture of product and unreacted gas
4 Cooler
5 Unreacted gas
6 Liquid mixture of formate and methanol
7 Distillation tower
8 Formate
9 Methanol

Claims (9)

A catalyst for synthesizing methanol via a formic acid ester that reacts in the presence of at least one of carbon monoxide and carbon dioxide and hydrogen and an alcohol as a solvent, comprising sodium formate, rubidium carbonate, carbonic acid In addition to at least one of cesium (catalyst component 1) , a hydrocracking catalyst (catalyst component 2) containing Cu, Mg and Na, or Cu, Mg, Na and Pd is used. The Na (catalyst component 2) is supported on a Cu / MgO solid catalyst as a carbonate or formate , and is present as sodium formate (catalyst component 1) present as at least one of the sodium formate, rubidium carbonate, and cesium carbonate. Is a catalyst for methanol synthesis, which is not supported on the solid catalyst.   The catalyst for methanol synthesis according to claim 1, wherein the Pd of the hydrocracking catalyst is supported on a Cu / MgO solid catalyst. A catalyst for synthesizing methanol via a formic acid ester that reacts in the presence of at least one of carbon monoxide and carbon dioxide and hydrogen and an alcohol as a solvent, comprising sodium formate, rubidium carbonate, carbonic acid At least one of cesium, in addition to (catalyst component 1) have Cu, Mg, a hydrocracking catalyst containing Na and Pd (catalyst component 2), the Pd of hydrogenation cracking catalyst (catalyst component 2) Is supported on a solid catalyst of Cu / MgO, and sodium formate (catalyst component 1) present as at least one of sodium formate, rubidium carbonate, and cesium carbonate is not supported on the solid catalyst. A catalyst for methanol synthesis.   The catalyst for methanol synthesis according to claim 2 or 3, wherein the supported amount of Pd in the hydrocracking catalyst is 0.001 to 1 mass%.   The method for producing a catalyst for methanol synthesis according to any one of claims 1 to 4, wherein the Cu / MgO is prepared by a coprecipitation method and then Cu / MgO is impregnated with Na and / or Pd. A method for producing a catalyst for methanol synthesis, characterized by being supported.   It is a manufacturing method of the catalyst for methanol synthesis | combination of any one of Claims 1-4, Comprising: Said Cu / MgO is prepared while keeping constant in the range of pH = 8-11 in a coprecipitation method. A method for producing a catalyst for methanol production. A method of producing methanol by reacting at least one of carbon monoxide, carbon dioxide, and hydrogen, and adding methanol to at least one of sodium formate, rubidium carbonate, and cesium carbonate (catalyst component 1) , Cu, Mg and Na, or Cu, Mg, Na and Pd (catalyst component 2) , Pd and / or Na as a carbonate or formate (catalyst component 2) supported on a solid catalyst of Cu / MgO Sodium formate (catalyst component 1) present as at least one of sodium formate, rubidium carbonate, and cesium carbonate is reacted in the presence of a hydrocracking catalyst not supported on the solid catalyst and alcohols. To produce formate and methanol, and to produce methanol by hydrogenating the formate produced A process for producing methanol characterized by A source gas containing at least one of carbon monoxide, carbon dioxide, and hydrogen is added to at least one of sodium formate, rubidium carbonate, and cesium carbonate (catalyst component 1), and then Cu, Mg, and Na, or Cu, Mg , Na and Pd (catalyst component 2) , and Pd and / or Na (catalyst component 2) as carbonate or formate is supported on a Cu / MgO solid catalyst, and the above-mentioned sodium formate, rubidium carbonate Sodium formate (catalyst component 1) present as at least one of cesium carbonate reacts with the product obtained by carrying out the reaction in the presence of a hydrocracking catalyst not supported on the solid catalyst and an alcohol. After separation from the system, methanol is produced by hydrogenating the formate in the product with a hydrocracking catalyst. Production method.   The method for producing methanol according to claim 7 or 8, wherein the alcohol is a primary alcohol.