WO2006088253A1

WO2006088253A1 - Process for production of formic esters and methanol, catalysts for the production thereof, and process for production of the catalysts

Info

Publication number: WO2006088253A1
Application number: PCT/JP2006/303510
Authority: WO
Inventors: Noriyuki Yamane; Kenichiro Fujimoto; Kaoru Fujimoto
Original assignee: Nippon Steel Corporation; Nippon Steel Engineering Co., Ltd
Priority date: 2005-02-21
Filing date: 2006-02-20
Publication date: 2006-08-24
Also published as: JPWO2006088253A1; JP4990125B2

Abstract

Formic esters or methanol can be stably produced through a continuous reaction at low temperature under low pressure with reduced lowering in the activity even when the starting material contains water, carbon dioxide, or the like. A process for producing formic esters and methanol by reacting a starting material gas containing either carbon monoxide or carbon dioxide or both and hydrogen, characterized in that the reaction is carried out in the presence of an alkali metal formate, either an alkaline earth metal catalyst or an ether having an aromatic ring in the molecular structure or both, a hydrogenolysis catalyst, and an alcohol to thereby obtain methanol.

Description

Method for producing formate and methanol, catalyst for methanol production, and method for producing the catalyst

Technical field

The present invention relates to a method for producing formate and methanol. Akira

More specifically, the present invention relates to a method for obtaining a product with high efficiency by using a catalyst having high resistance to decrease in activity due to water, carbon dioxide, etc., when producing methanol from carbon monoxide and hydrogen, and the catalyst described therein.

Background art

In general, when synthesizing methanol industrially, carbon monoxide and hydrogen (synthetic gas) obtained by steam reforming natural gas mainly composed of methane are used as raw materials. (JC J. Bart et al., Catal. Today, 2, 1 (1987)) . As shown below, methanol and water are produced by hydrogenation of carbon dioxide, and then the sequential reaction in which the produced water reacts with carbon monoxide to produce carbon dioxide and hydrogen (water gas shift reaction). The theory that this is true is generally accepted.

C0 ₂ + 3H ₂ → CH ₃ 0H + H ₂ 0 (1)

H ₂ 0 + CO — → C0 _? _ + _H, (2)

CO I 2H ₂ → CH ₃ 0H (3)

Although this reaction is an exothermic reaction, heat transfer is poor in the gas phase method, so efficient heat removal is difficult.Therefore, the conversion rate when passing through the reactor is kept low, and the unreacted high-pressure raw material gas The efficiency of recycling It is a process. However, various plants are in operation, taking advantage of the fact that reaction inhibition by water and carbon dioxide contained in synthesis gas is difficult to receive.

On the other hand, various methods for improving the heat removal rate by synthesizing methanol in the liquid phase are being studied. Among them, the method using a highly active catalyst at low temperatures (about 100 to 180 ° C) is thermodynamically advantageous for the production system, and has attracted attention (for example, Sei Oyama, PETROTECH, 18 (1 ), 27 (1995)). The catalysts used are alkali metal alkoxides, 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 (S. Ohyama). , Applied Catalysis A: General, 180, 217 (1999)). This is because a highly active 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 costs and is not practical.

The present inventors have heretofore used a system in which one or both of an alkali metal catalyst and an alkaline earth metal catalyst excluding alkali metal alkoxide are used as a catalyst whose activity decrease due to water and carbon dioxide is small. Has been found in an evaluation using a batch reactor (Japanese Patent Application No. 2001-561711). However, in a subsequent study, in a continuous reaction using a semi-batch reactor, the charged Al-metal catalyst was changed to a low-activity, stable Al-metal formate, and the CO conversion rate over time It turned out to decrease with. An object of the present invention is to solve the above-mentioned problems. By improving the activity of a low activity and stable alkali metal formate, carbon dioxide is synthesized in a synthesis raw material gas of formate ester or methanol. Even if water etc. are mixed, the degree of catalyst activity decrease is low, and formate ester or methanol is stably synthesized even in continuous reaction at low temperature and low pressure The present invention provides a catalyst and a method that can be used. Disclosure of the invention

The features of the present invention are as described below.

(1) A method for producing a formate by reacting a raw material gas containing at least one of carbon monoxide and carbon dioxide, and hydrogen, wherein the alkaline earth metal catalyst is added to the alkali metal formate. And / or an ether having an aromatic ring in the molecular structure, and a reaction in the presence of an alcohol.

(2) A method of producing methanol by reacting a raw material gas containing at least one of carbon monoxide and carbon dioxide, and hydrogen, in addition to alkali metal formate, Reaction is carried out in the presence of one or both of the catalyst and ether having an aromatic ring in the molecular structure, a hydrocracking catalyst, and alcohols to produce formate ester and methanol, and the produced formate ester is hydrogenated to methanol. Manufacturing method of methanol characterized by manufacturing.

(3) A source gas containing at least one of carbon monoxide and carbon dioxide and hydrogen is added to the alkali metal formate, and one of the alkaline earth metal catalyst and the ether having an aromatic ring in the molecular structure. Alternatively, the product obtained by carrying out the reaction in the presence of both alcohols and alcohols is separated from the reaction system, and then the formate ester in the product is hydrogenated with a hydrogenolysis catalyst to produce methanol. A process for producing methanol characterized by

(4) The production according to any one of (1) to (3), wherein an alkali metal catalyst that can change into an alkali metal formate during the reaction is used instead of the alkali metal formate. Method.

(5) The alkali metal formate is potassium formate. The production method according to any one of (1) to (4).

(6) The production method according to (4), wherein the alkali metal catalyst which can be converted into an alkaline metal formate during the reaction is potassium carbonate.

(7) The production method according to any one of (1) to (6), wherein the alkaline earth metal catalyst is a catalyst containing a calcium salt.

(8) The production method according to any one of (1) to (7), wherein the aromatic ring of the ether having an aromatic ring in the molecular structure is a single ring.

(9) The method according to any one of (8) to (8), wherein the ether having an aromatic ring in the molecular structure is diphenyl ether.

(10) The production method according to any one of (1) to (8), wherein the ether having an aromatic ring in the molecular structure is benzyl ether.

(11) The methanol according to any one of (10) to (10), wherein the hydrocracking catalyst is a catalyst containing at least one of Mn and Re and an alkali metal element in addition to Cu. Manufacturing method.

(12) The method for producing methanol according to any one of (2) to (10), wherein the hydrocracking catalyst is a catalyst containing Cu, an alkaline earth metal element, and an alkali metal element. .

(13) The hydrocracking catalyst is a solid catalyst, and an alkali metal formate and an alkaline earth metal catalyst are supported on the solid catalyst and used for the reaction. (2) to (12 The method for producing methanol according to any one of the above.

(14) The production method according to any one of (1) to (13), wherein the alcohol is a primary alcohol.

(15) A methanol production catalyst comprising an alkali metal formate and an alkaline earth metal catalyst supported on a formate hydrocracking solid catalyst. (16) Hydrocracking containing Cu, alkaline earth metal elements, and alkaline metal elements in addition to one or both of alkali metal formate and alkaline earth metal catalysts and ethers having an aromatic ring in the molecular structure A catalyst for methanol production comprising a catalyst.

(17) Hydrogen containing at least one of Cu, Mn, Re, and an alkali metal element in addition to one or both of an alkali metal formate and alkaline earth metal catalyst and an ether having an aromatic ring in the molecular structure A catalyst for methanol production comprising a chemical decomposition catalyst.

(18) The catalyst for methanol production according to any one of (15) to (17), wherein the alkaline earth metal catalyst is a catalyst containing a calcium salt.

(19) The methanol according to any one of (15) to (18), which has an alkali metal catalyst capable of changing to an alkali metal formate during the reaction instead of the alkali metal formate. Catalyst for production.

(20) The catalyst for methanol production according to (16), (18) or (19), wherein the alkaline earth metal element contained in the hydrocracking catalyst is magnesium.

(2 1) The methanol production according to any one of (16) to (20), wherein the alkali metal element contained in the hydrocracking catalyst is sodium. Catalyst.

(22) The catalyst for methanol production according to any one of (16) to (2 1), wherein the aromatic ring of the ether having an aromatic ring in the molecular structure is a single ring.

(23) The methanol production catalyst according to any one of (16) to (22), wherein the ether having an aromatic ring in the molecular structure is diphenyl ether.

(24) The ether having an aromatic ring in the previous molecular structure is benzyl ether. (16) The catalyst for methanol production according to any one of (16) to (22).

(25) The methanol production according to any one of (15) to (24), wherein the hydrocracking catalyst is prepared while being kept constant in a pH = 8 to ll range in a coprecipitation method. For producing a catalyst for use. Brief Description of Drawings

FIG. 1 shows a reactor for carrying out the low-temperature liquid phase methanol synthesis of the present invention. In the figure, 1: synthesis gas, 2: semi-batch reactor, 3: product, mixture of unreacted gas, 4: cooler, 5: unreacted gas, 6: liquid mixture of formate ester and methanol, 7: Distillation tower, 8: formic acid ester, 9: methanol.

Figure 2 shows the relationship between pH and CO conversion controlled when Cu / MgO _x is prepared by coprecipitation. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

As a result of intensive studies, the present inventors have found that when one or both of an alkaline earth metal catalyst and an ether having an aromatic ring in the molecular structure are used in addition to the alkali metal formate in a semi-batch continuous reaction, In the production of formic acid ester or methanol from at least one of carbon oxide 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 produced continuously by the reaction process shown in Figure 1. In addition to alkali metal formate, semi-batch reactor 2 is charged with alkali earth metal catalyst, one or both of ethers having an aromatic ring in the molecular structure, and powdered hydrocracking catalyst with solvent alcohol. Syngas 1 is supplied. The product 3 at the outlet of the reactor (formate ester, methanol) and unreacted gas mixture 3 is cooled by cooler 4 and separated into unreacted gas 5 and 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. If the conversion rate is low, the unreacted gas 5 can be supplied again to the semi-batch reactor 2, but if it is obtained in high yield, the unreacted gas can be used as a heat source (fuel) for syngas production. Use.

In the case of obtaining a formate ester as a product, the semi-batch reactor 2 is charged with one or both of an alkali metal formate, an alkaline earth metal catalyst and an ether having an aromatic ring in the molecular structure together with a solvent alcohol. Syngas 1 is supplied. The formate ester thus obtained can be hydrocracked to obtain methanol, and the mixture of formate ester and unreacted gas is supplied to a tubular reactor filled with a hydrocracking catalyst, The formate is hydrocracked to produce methanol.

The highly active alkali metal alkoxide used in the conventional low-temperature liquid phase method gradually changes to alkali metal formate during the reaction, and the alkali metal formate is low in activity and stable. There was deterioration. The Al-rich metal formate of the present invention has low activity by itself, but its activity is significantly improved when it coexists with one or more of Al-earth metal catalysts or ethers having an aromatic ring in the molecular structure. Moreover, no deterioration in yield over time is confirmed.

Examples of the alkali metal formate include potassium formate, sodium formate, cesium formate, and rubidium formate. In particular, the use of potassium formate is preferred because the catalytic activity is increased.

Instead of alkali metal formate, an alkali metal catalyst that can take the form of formate during the reaction may be used. There is no particular limitation.

Examples of such an alkali metal catalyst include potassium carbonate and calcium methoxide. When using calcium carbonate, it is presumed that it changed to calcium formate by the reaction shown below. It is presumed that even when charged in other forms, it changes to a stable formate.

K ₂ C0 ₃ + H ₂ 0 → 2K0H + C0 ₂ (4)

K0H + C0 → HC00K (5)

Examples of the alkaline earth metal catalyst include metal compounds such as calcium, magnesium, barium, and strontium, or simple substances. These metal compounds are preferably metal salts or metal oxides, more preferably metal salts such as carbonates, nitrates, phosphates, acetates, and formates, more preferably carbonates. Salt, formate. Among them, when calcium salt is used, the catalytic activity becomes high and the molar ratio of the preferred Al-rich metal formate and the Al-rich earth-based metal catalyst is not particularly limited. Is sufficient if it is present in a small amount, and the (alkali metal formate mole number) / (alkali earth metal mole number) ratio is preferably in the range of 0.5 to 100, more preferably 1 to 50, More preferably, it is 2-20. For alkaline metal formates, alkaline earth metal catalysts have high yields of formate and methanol, even in trace amounts.

These alkali metal catalysts and alkaline earth metal catalysts do not have to be in one form each, but there are multiple types of alkali metal catalysts that can take the form of formate, and alkaline earth. Multiple types of metal-based catalysts may be mixed.

These catalysts can be used by being supported on a general carrier by a conventional method. You can also.

Examples of ethers having an aromatic ring in the molecular structure include compounds having a single ring such as anisole, compounds having two rings such as ethoxynaphthalene, and compounds having more than one ring. Further, compounds having a plurality of aromatic rings such as diphenyl ether and benzil ether are not limited thereto.

Of these, diphenyl ether, benzyl ether, and anisol are preferred because of high catalytic activity.

In addition, ethers having an aromatic ring in these molecular structures can be used in combination.

The molar ratio of the alkali metal formate to the ether having an aromatic ring in the molecular structure is not particularly limited, but a small amount of ether having an aromatic ring in the molecular structure may be present. Number) / (number of moles of ether having an aromatic ring in the molecular structure) is preferably in the range of 0.5 to 100, more preferably 1 to 50, and even more preferably 2 to 20. As with alkaline earth metal catalysts, the yield of formate and methanol increases even in the presence of trace amounts.

An alkaline earth metal catalyst and an ether having an aromatic ring in the molecular structure can be used at the same time.

The alcohol used in the reaction may be a chain or alicyclic hydrocarbon having a hydroxyl group, phenol and a substituted product thereof, and further 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 capable of selecting mild conditions can be employed. Specifically, temperature 70 ~ It is selected from about 250 ° C and a pressure of 3 to 70 atmospheres, and the liquid phase is preferable, but not limited thereto. Alcohols need only have such an amount that the reaction proceeds, for example, an amount enough to immerse the entire catalyst, but the reaction proceeds even below that amount. Further, a larger amount can be used as the solvent. In addition to the alcohols, an organic solvent can be appropriately used in the above reaction. The molar ratio of the solvent alcohol and the ether having an aromatic ring is not particularly limited, but a trace amount of the ether having an aromatic ring may be present, and (solvent alcohol mole number) / (ether having an aromatic ring). If the number of moles) = 50 or more, good results will be obtained.

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

Hydrocracking catalysts are used for hydrocracking. For example, Pt, i, Co, Ru, Pd common hydrocracking catalysts can be used. Specifically, Cu / MgO _x / NaY (X is a chemically acceptable value, Y is a chemically acceptable element or compound), Cu / MnO _x (X is a chemically acceptable value), Cu / ReO _x (X is a chemically acceptable value) Cu / ZnO, Cu / Cr ₂ 0 ₃ , copper catalysts such as Raney copper, and nickel catalysts are preferred.

Among them, a Cu / MgO _x prepared by co-precipitation method, this Cu / MgO _x / NaY was added pressure to the Na evaporation to dryness method has an extremely high activity in the reaction, one of water and carbon dioxide or Even if both are mixed, a high methanol yield can be obtained. As shown in Fig. 2, the CO conversion rate varies greatly depending on the pH controlled when preparing by the coprecipitation method, and the pH when preparing Cu / MgO _x by the coprecipitation method is preferably 8 to 11, more preferably Is 8.5 to 10.5, more preferably 9 to 10.5. In the range where pH exceeds 11, use of an alkaline compound used as a precipitating agent to maintain a high alkaline atmosphere It is not economical because the amount increases significantly. The amount of Na supported on Cu / MgO _x is not particularly limited, but is preferably in the range of 0.1 to 60 wt%, more preferably 1 to 40 wt%, more preferably 3 to 30wt%. NaY is preferably sodium formate or sodium carbonate.

Preparation of these hydrocracking catalysts may be carried out by ordinary methods such as impregnation method, precipitation method, sol-gel method, coprecipitation method, ion exchange method, kneading method, and evaporation to dryness method, and is not particularly limited. However, the coprecipitation method makes it possible to prepare a catalyst with a high loading rate, and it is easy to obtain good results.

In the present invention, by making these hydrocracking catalyst and hydrogen coexist in the reaction system for producing formate from carbon monoxide and alcohols, methanol can be produced in a so-called one-step process. This hydrocracking reaction can be basically performed under the above reaction conditions, but can be further optimized by appropriately changing the temperature and pressure. In this case, the hydrogen / carbon monoxide ratio is generally selected from about 0.2 to 5.

As mentioned above, when the reaction is carried out with the hydrocracking catalyst coexisting with the Al-rich metal catalyst, etc., it may be used as a simple mixture. When the catalyst is used, it becomes a heterogeneous system, and the separation of the catalyst from the reaction system is a solid-liquid separation. The supporting method itself can be a conventional method for preparing a catalyst as described above.

If it is difficult to produce methanol in a single stage using a catalyst with a high selectivity for formate ester, the product obtained in the reaction is separated from the reaction system by a distillation method, etc. It is possible to obtain methanol by hydrocracking the formate in the product in the presence of a hydrocracking catalyst and hydrogen. In the method using the catalyst of the present invention, the lower the concentration of C0 ₂ and H ₂₀ contained in the raw material gas, the higher the yield of methanol, but each contains about 1%. However, the CO conversion rate and methanol yield are almost unaffected. However, if the concentration is higher than that, CO conversion rate and methanol yield will decrease.

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

ROH + CO → HC00R (6)

HC00R + 2H ₂ → CH ₃ OH + ROH (7)

(Where R represents an alkyl group)

Therefore, the raw materials for producing methanol are carbon monoxide and hydrogen, and alcohols can be recovered and reused.

In addition, by using one or both of the alkali metal formate, the alkaline earth metal catalyst of the present invention and the ether having an aromatic ring in the molecular structure, water and carbon dioxide are present in a considerable amount in the raw material gas. In this case, formate and methanol can be obtained without losing the activity of the catalyst. Example

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

The CO conversion rate and methanol yield described in the following examples were calculated by the following formulas.

• CO conversion rate W = [1-(number of moles of CO recovered after reaction) / (number of moles of charged CO)] X 100 • Formic acid ester yield) = [(Moleic acid ester moles) / (Mole of CO charged)] X 100

• Methanol yield) = [(Mole moles produced) / ( ₂ moles charged CO + C0)] X 100

* Since the pathway for the production of methanol from co ₂ is thought to proceed in parallel, the number of co ₂ moles charged is also taken into account when co ₂ coexists. Example 1

Using an autoclave with an internal volume of 100 ml, add 5 匪 ol of potassium formate and 1 匪 ol of calcium formate to 15m1 of methanol as a solvent, and add synthetic gas (CO 48%, H ₂ 48%, Ar balance). The reaction was carried out at 150 ° C for 1 hour after filling with 3.0 MPa, and the reaction product was analyzed by gas chromatography. 5.57 mol of formate was obtained with a C0 conversion of 15.9%.

Example 2

The reaction was carried out by the method described in Example 1 except that calcium carbonate lmmo 1 was added instead of calcium formate lmmo 1. A methyl formate of 5.21% 01 was obtained with a C0 conversion of 13.5%.

Example 3

The reaction was carried out by the method described in Example 1 except that diphenyl ether 1 Dragon 01 was added instead of calcium formate lmmo 1. The C0 conversion was 31.8 and 11.55 mmol methyl formate was obtained.

Example 4

The reaction was carried out by the method described in Example 1, except that 1 mmol of benzyl ether was added instead of 1 mmol of calcium formate. 10.9 lmmo 1 methyl formate was obtained with a C0 conversion of 30.1%.

Example 5

Calcium formate Other than adding anisole instead of lmmol, The reaction was carried out by the method described in Example 1. With a CO conversion of 27.5¾, 9.98 ol of methyl formate was obtained.

Comparative Example 1

The reaction was carried out by the method described in Example 1, except that only 5 mmol of potassium formate was added. With a CO conversion of 10.7%, 3.00 ol of methyl formate was obtained.

Example 6

The reaction was performed by the method described in Example 1 except that calcium carbonate lOmmol was added instead of calcium formate lmmol. A CO conversion of 7.4% and 3.55 mmo methyl formate were obtained.

Example 7

The reaction was carried out by the method described in Example 1 except that 0.5 mmol of calcium carbonate was added instead of 1 mmol of calcium formate. A C18 conversion of 12.2% gave 5.18 ol of methyl formate.

Example 8

Using an autoclave with an internal volume of 100 ml, adding 2Ool of calcium formate and 2 ol of calcium carbonate to 27.8 ml of methanol as a solvent, 60 ml of synthesis gas (CO 48%, H ₂ 48%, Ar balance) The reaction was continued for 20 hours at 150 ° C-5. OMPa. The reaction product was analyzed by gas chromatography. Only methyl formate was obtained with a C0 conversion of 1.98%.

Example 9

The reaction was carried out by the method described in Example 7 except that 2 nimol of diphenyl ether was added instead of 2 mmol of calcium carbonate. Only methyl formate was obtained at a C0 conversion of 3.95%.

Comparative Example 2

The method described in Example 5, except that only lOmmol potassium formate is added. The reaction was done. Only methyl formate was obtained with a CO conversion of 1.45%. Example 10

Using an autoclave with an internal volume of 100 ml, methanol 27.8 ml as solvent, calcium formate lOmmol and calcium carbonate 2 mmol, hydrocracking catalyst Cu (N0 ₃ ) 2 3H ₂ 0, Mg (N0 ₃ ) Using 2 · 6H ₂ 0 as raw material, Cu / MgO _x (X is a chemically acceptable value) was prepared by co-precipitation while maintaining ρΗ = 10 · 0, and Na ₂ C0 ₃ was used as the raw material. Add 3g of Cu / MgO _x / Na ₂ C0 ₃ (X is a chemically acceptable value) with Na supported by evaporation to dryness, synthesis gas (CO 4 8%, H ₂ 48%, Ar balance) Was fed at a rate of 60 ml / min, and a continuous reaction was carried out for 20 hours under the conditions of 170 ° C-5.0 MPa. The reaction product was analyzed by gas chromatography. The C0 conversion was 32.9%, and the methanol yield was 32.7%. Example 11

The reaction was carried out by the method described in Example 10 except that diphenyl ether was used instead of calcium carbonate 2 mmo 1. The C0 conversion was 55.6% and the methanol yield was 54.3%.

Comparative Example 3

The reaction was carried out by the method described in Example 6 except that Cu / Cr ₂ 0 ₃ (ENGELHARD, Cu-1987T 1/8) was added instead of Cu / Mg0 _x / NaY. The C0 conversion was 27.7%, and the methanol yield was 27.5.

Comparative Example 4

Cu / MgO _x / NaY in place of _{Cu / Si0 2 (ENGELHARD, Cu} - 0860 E 1/8) addition to added pressure to Reaction was conducted in the procedure described in Example 6. The C0 conversion was 11.1% and the methanol yield was 10.9%.

Example 12

The reaction was carried out by the method described in Example 6 except that the amount of synthesis gas supplied was 30 ml / iniii. The C0 conversion was 60.9%, and the methanol yield was 60.1%. Example 13 The reaction was carried out by the method described in Example 6 except that the synthesis gas supply rate was 90 ml / min. The CO conversion was 28.0%, and the methanol yield was 27.9%. Example 14

The reaction was carried out by the method described in Example 6 except that synthesis gas having different composition (CO 48%, H ₂ 48%, C0 ₂ 1¾, Ar balance) was used. The CO conversion was 28.5%, and the methanol yield was 27.9%.

Example 15

The reaction was carried out by the method described in Example 6 except that H ₂ 01 was continuously added by bubbling the source gas to temperature-controlled H ₂₀ . The CO conversion was 29.3% and the methanol yield was 28.6%.

table 1

CO conversion rate Methyl formate Methyl formate Methanol Experimental features

(¾) Yield (匪 ol) Yield (%) Yield (¾) Example 1 Base Experiment 15. 9 5. 57

Example 2 Addition of Ca salt change 13. 5 5. 21

Diphenyl A

Example 3 31. 8 11. 55

Tell addition

Benzylate

Example 4 30. 1 10. 91

Added

Example 5 Anisol addition 27. 5 9. 98

Added Ca salt change,

Example 6 7. 4 3. 55

Addition change

Added Ca salt change,

Example 7 12. 2 5. 18

Addition change

Continuous reaction, carbonic acid

Example 8 1.98 1.98

Calcium addition

Anti-M, M

Example 9 phenyl ether 3.95 3.95

Addition

Continuous reaction, carbonic acid

Calcium addition

Example 10 32. 9 32.7, hydrocracking catalyst

Coexistence

Continuous rumination, gif

Enyl ether

Example 11 55. 6 54.3 Addition, hydrogenation content

Co-catalyst coexistence,

Continuous reaction, hydrogen

Pyrolysis catalyst coexistence

Example 12 60. 9 60.1, continuous change of gas supply, hydrogen

Pyrolysis catalyst coexistence

Example 13 28. 0 27.9, Gas supply amount change Continuous reaction, Hydrogen

Pyrolysis catalyst coexistence

Example 14 28. 5 27. 9, Gas composition change

(co ₂ added)

Continuous reaction, hydrogen

Example 15 Co-decomposition catalyst 29. 3 28. 6

, ¾0 addition Table 2

Industrial applicability

In the present invention, in addition to the alkali metal formate, an alkaline earth metal catalyst, a system using one or both of ethers having an aromatic ring in the molecular structure, or an alkali metal formate, A system using a metal earth catalyst, one or both of ethers having an aromatic ring in the molecular structure, and a hydrocracking catalyst. Among them, Cu, an alkaline earth metal element, and an alkali as a hydrocracking catalyst. A system that contains a catalyst containing a lithium metal element, or at least one of Mn and Re, and a catalyst containing an alkaline metal element, and at least carbon monoxide and carbon dioxide that are synthetic raw material gases. When formate and methanol are produced from any of them and hydrogen in the presence of solvent alcohol, the formate or methanol is stably increased in a continuous reaction at low temperature and low pressure. It became possible to synthesize with efficiency. In addition, even if water, carbon dioxide, etc. are mixed in the synthesis raw material gas, it is possible to produce formate or methanol at a low cost because the degree of decrease in the activity of the catalyst is low.

Claims

1. A method for producing a formate by reacting a source gas containing at least one of carbon monoxide and carbon dioxide, and hydrogen, in addition to an alkali metal formate, an alkaline earth metal catalyst, One or both of ethers having an aromatic ring in the molecular structure and the presence of alcohols

Bite

A method for producing a formate ester, characterized by carrying out the reaction in the presence.

2. A method for producing methanol by reacting a source gas containing at least one of carbon monoxide and carbon dioxide, and hydrogen, in addition to alkali metal formate, an alkaline earth metal catalyst, One or both ethers having an aromatic ring in the molecular structure, hydrocracking catalyst, and

A method for producing methanol, comprising reacting in the presence of alcohol to produce formate ester and methanol, and hydrogenating the produced formate ester to produce methanol.

3. — A source gas containing at least one of carbon oxide, carbon dioxide, and hydrogen is added to the alkali metal formate, and one or both of an alkaline earth metal catalyst and an ether having an aromatic ring in the molecular structure. The product obtained by carrying out the reaction in the presence of alcohol and alcohol is separated from the reaction system, and then the formate ester in the product is hydrogenated with a hydrocracking catalyst to produce methanol. A method for producing methanol.

4. The alkali metal formate according to any one of claims 1 to 3, wherein an alkali metal-based catalyst capable of changing to an alkali metal formate during the reaction is used instead of the alkali metal formate. Production method.

5. The production method according to any one of claims 1 to 4, wherein the alkali metal formate is potassium formate.

6. Al force Li metal that can be converted to Li metal formate during the reaction 5. The production method according to claim 4, wherein the system catalyst is calcium carbonate.

7. The production method according to any one of claims 1 to 6, wherein the alkaline earth metal catalyst is a catalyst containing a calcium salt.

8. The production method according to any one of claims 1 to 7, wherein the aromatic ring of the ether having an aromatic ring in the molecular structure is a single ring.

9. The production method according to any one of claims 1 to 8, wherein the ether having an aromatic ring in the molecular structure is diphenyl ether.

10. The production method according to any one of claims 1 to 8, wherein the ether having an aromatic ring in the molecular structure is benzyl ether.

11. The hydrocracking catalyst is a catalyst containing at least one of Mn and Re, and an alkali metal element in addition to. A method for producing methanol as described in 1. above.

1 2. The methanol according to any one of claims 2 to 10, wherein the hydrocracking catalyst is a catalyst containing Cu, an alkaline earth metal element, and an alkali metal element. Manufacturing method.

13. The hydrocracking catalyst is a solid catalyst, and an alkali metal formate and an alkaline earth metal catalyst are supported on the solid catalyst for use in the reaction. [1] The method for producing a methanol according to any one of [1].

14. The production method according to any one of claims 1 to 13, wherein the alcohol is a primary alcohol.

15. A mesomorphic acid hydrocracking solid catalyst carrying an alkali metal formate salt and an alkaline earth metal catalyst. Catalyst for the production of Yunol.

1 6. In addition to one or both of alkali metal formate and alkaline earth metal catalyst and ether having an aromatic ring in the molecular structure, Cu, alkaline earth metal element, and alkaline metal element are contained. A catalyst for methanol production, comprising a hydrocracking catalyst.

1 7. In addition to one or both of alkali metal formate and alkaline earth metal catalyst and ether having an aromatic ring in the molecular structure, at least one of Cu, Mn and Re, and alkali metal element A catalyst for producing methanol, comprising a hydrogenolysis catalyst containing

18. The catalyst for methanol production according to any one of claims 15 to 17, wherein the alkaline earth metal catalyst is a catalyst containing a calcium salt.

1 9. The method according to any one of claims 15 to 18, characterized by having an alkali metal-based catalyst capable of changing to an alkali metal formate during the reaction instead of the alkali metal formate. The catalyst for methanol production as described.

20. The catalyst for producing methanol according to claim 16, wherein the alkaline earth metal element contained in the hydrocracking catalyst is magnesium.

21. The methanol production catalyst according to any one of claims 16 to 20, wherein the alkali metal element contained in the hydrocracking catalyst is sodium.

2 2. The catalyst for methanol production according to any one of claims 16 to 21, wherein the aromatic ring of the ether having an aromatic ring in the molecular structure is a single ring.

23. The catalyst for producing methanol according to any one of claims 16 to 22, wherein the ether having an aromatic ring in the molecular structure is diphenyl ether.

2 4. The catalyst for methanol production according to any one of claims 16 to 22, wherein the ether having an aromatic ring in the molecular structure is benzyl ether.

25. The catalyst for methanol production according to any one of claims 15 to 24, wherein the hydrocracking catalyst is prepared while being kept constant in a pH range of 8 to ll in a coprecipitation method. Manufacturing method.