JP4990125B2 - Method for producing formate and methanol, catalyst for producing methanol, and method for producing the catalyst - Google Patents

Description

  The present invention relates to a method for producing formate and methanol. 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 and the like when methanol is produced from carbon monoxide and hydrogen, and the catalyst.

In general, 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. Synthesized under severe conditions of 200 to 300 ° C. and 5 to 25 MPa by a fixed bed gas phase method using a catalyst (JCJ Bart et al., Catal. Today, 2, 1 (1987)) . 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 advantageous for a production system thermodynamically and attracts attention (for example, Seiichi Oyama, PETROTECH, 18 (1) , 27 (1995)). The catalyst used is an alkali metal alkoxide, but in these methods, it is reported that the activity is reduced by water and carbon dioxide which are always contained in the synthesis gas, and none of them has been put into practical use (S. Ohyama, Applied Catalysis). A: General, 180, 217 (1999)). 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 a 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 practical.

  In the past, the present inventors have used a batch reactor 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 with a small decrease in activity due to water and carbon dioxide. (Japanese Patent Application No. 2001-561711). However, in a subsequent study, in a continuous reaction using a semi-batch reactor, the charged alkali metal catalyst was changed to a low activity and stable alkali metal formate, and the CO conversion decreased with time. There was found.

  The present invention aims to solve the above problems, and by improving the activity of a low activity and stable alkali metal formate, carbon dioxide, The present invention provides a catalyst and a method capable of synthesizing formate ester or methanol stably even in continuous reaction at low temperature and low pressure even when water is mixed. is there.

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, and an ether having an aromatic ring in a molecular structure in addition to an alkali metal formate And a method for producing a formate ester, wherein the reaction is carried out in the presence of an alcohol.
(2) A method for producing methanol by reacting at least one of carbon monoxide and carbon dioxide and hydrogen, and an ether having an aromatic ring in the molecular structure in addition to the alkali metal formate, A process for producing methanol, wherein a reaction is carried out in the presence of a hydrocracking catalyst and an alcohol to produce a formate ester and methanol, and the produced formate ester is hydrogenated to produce methanol.
(3) A source gas containing at least one of carbon monoxide and carbon dioxide and hydrogen is added to an alkali metal formate, and the reaction is performed in the presence of an ether having an aromatic ring in the molecular structure and alcohols. A method for producing methanol, comprising separating the product obtained in (1) from a reaction system and then hydrogenating a formate in the product with a hydrocracking catalyst to produce methanol.
(4) A method for producing a formate by reacting a raw material 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, a molecule A method for producing a formate ester, wherein the reaction is carried out in the presence of both an ether having an aromatic ring in the structure and an alcohol.
(5) 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 an alkali metal formate, an alkaline earth metal catalyst, a molecular structure The reaction is carried out in the presence of both an ether having an aromatic ring, a hydrogenolysis catalyst, and an alcohol to produce a formate ester and methanol, and the produced formate ester is hydrogenated to produce methanol. A method for producing methanol.
(6) A source gas containing at least one of carbon monoxide, carbon dioxide, and hydrogen is added to an alkali metal formate, both an alkaline earth metal catalyst, an ether having an aromatic ring in the molecular structure, and an alcohol. The product obtained by carrying out the reaction in the presence of a kind is separated from the reaction system, and then the formic acid ester in the product is hydrogenated with a hydrocracking catalyst to produce methanol. Production method.
( 7 ) The production method according to any one of (1) to ( 6 ), wherein an alkali metal catalyst that can change into an alkali metal formate during the reaction is used instead of the alkali metal formate.
( 8 ) The method according to any one of (1) to ( 7 ), wherein the alkali metal formate is potassium formate.
( 9 ) The production method as described in ( 7 ), wherein the alkali metal catalyst capable of changing to an alkali metal formate during the reaction is potassium carbonate.
(1 0 ) The production method according to any one of (4) to (6), wherein the alkaline earth metal catalyst is a catalyst containing a calcium salt.
(1 1 ) The production method according to (1 0 ), wherein an alkali metal catalyst that can be converted into an alkali metal formate during the reaction is used instead of the alkali metal formate.
(1 2 ) The production method according to (1 1 ), wherein the alkali metal catalyst capable of changing to an alkali metal formate during the reaction is potassium carbonate.
(1 3 ) The production according to any one of (1) to (6), (1 0 ) to (1 2 ), wherein the aromatic ring of the ether having an aromatic ring in the molecular structure is a single ring Method.
(1 4 ) The production method according to any one of (1) to (6) and (1 0 ) to (1 2 ), wherein the ether having an aromatic ring in the molecular structure is diphenyl ether.
(1 5 ) The production method according to any one of (1) to (6) and (1 0 ) to (1 2 ), wherein the ether having an aromatic ring in the molecular structure is benzyl ether.
(1 6) in place of the alkali metal formate salt, which comprises using an alkali metal-based catalyst which can change into an alkali metal formate salt during the reaction (1 3) - according to any one of (1 5) Production method.
( 17 ) The production method according to any one of (1 3 ) to (1 5 ), wherein the alkali metal formate is potassium formate.
(18) the production method according to (1 6), wherein the alkali metal-based catalyst which can change into an alkali metal formate salt during the reaction is potassium carbonate.
( 19 ) (2), (3), (5), (6), wherein the hydrocracking catalyst is a catalyst containing at least one of Mn and Re and an alkali metal element in addition to Cu. The method for producing methanol according to any one of the above.
(2 0 ) Any one of (2), (3), (5), and (6 ), wherein the hydrocracking catalyst is a catalyst containing Cu, an alkaline earth metal element, and an alkali metal element A method for producing methanol according to claim 1.
(2 1 ) 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), (3) , (5), (6 ) The manufacturing method of methanol in any one of (6 ) .
(2 2 ) The production according to any one of ( 19 ) to (2 1 ), wherein an alkali metal catalyst capable of changing to an alkali metal formate during the reaction is used instead of the alkali metal formate. Method.
(2 3 ) The production method according to any one of ( 19 ) to (2 1 ), wherein the alkali metal formate is potassium formate.
(2 4 ) The production method as described in (2 2 ), wherein the alkali metal catalyst capable of changing to an alkali metal formate during the reaction is potassium carbonate.
(2 5 ) The production method according to any one of (1) to (2 4 ), wherein the alcohol is a primary alcohol.
( 26 ) From a hydrocracking catalyst containing Cu, an alkaline earth metal element, 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:
( 27 ) 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, hydrogenation containing Cu, at least one of Mn and Re, and an alkali metal element A catalyst for methanol production comprising a cracking catalyst.
( 28 ) The catalyst for methanol production according to ( 26 ) or ( 27 ), wherein the alkaline earth metal catalyst is a catalyst containing a calcium salt.
( 29 ) The methanol production according to any one of (2 6 ) to ( 28 ), which has an alkali metal catalyst that can be changed to an alkali metal formate during the reaction instead of the alkali metal formate. Catalyst.
(3 0) alkaline earth metal element contained in the hydrocracking catalyst is characterized in that it is a magnesium (26), (28) or (29) in methanol production catalyst described.
(3 1 ) The catalyst for methanol production according to any one of ( 26 ) to (3 0 ), wherein the alkali metal element contained in the hydrocracking catalyst is sodium.
(3 2 ) The catalyst for methanol production according to any one of ( 26 ) to (3 1 ), wherein the aromatic ring of the ether having an aromatic ring in the molecular structure is a single ring.
(3 3 ) The catalyst for methanol production according to any one of ( 26 ) to (3 2 ), wherein the ether having an aromatic ring in the molecular structure is diphenyl ether.
(3 4 ) The catalyst for producing methanol according to any one of ( 26 ) to (3 2 ), wherein the ether having an aromatic ring in the previous molecular structure is benzyl ether.
(3 5 ) The methanol according to any one of (2 6 ) to (3 4 ), wherein the hydrocracking catalyst 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 production.

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 an alkali metal formate in a semi-batch continuous reaction, In the production of formate 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 continuously produced by a reaction process as shown in FIG. In addition to alkali metal formate, semi-batch reactor 2 is charged with an alkaline earth metal catalyst, one or both ethers having an aromatic ring in the molecular structure, and a powdered hydrocracking catalyst together with solvent alcohol, and synthesized. 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 a high yield, the unreacted gas is used as a heat source (fuel) for syngas production. To do.

  When a formate ester is obtained as a product, a 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, and a synthesis gas. 1 is supplied. It is also possible to hydrocrack the formate ester thus obtained to obtain methanol. A mixture of formate ester and unreacted gas is supplied to a tubular reactor packed 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 into an alkali metal formate during the reaction, and the alkali metal formate is low in activity and stable. there were.

  The alkali metal formate of the present invention has low activity by itself, but when it coexists with one or more of an alkaline earth metal catalyst or an ether having an aromatic ring in the molecular structure, the activity is remarkably improved, Yield deterioration over time is not confirmed.

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

  Moreover, it may replace with an alkali metal formate and may use the alkali metal catalyst which can take the form of a formate during reaction, and the form at the time of reaction preparation is not specifically limited.

Examples of such an alkali metal catalyst include potassium carbonate and potassium methoxide. When potassium carbonate is used, it is presumed that it has changed to potassium formate by the reaction shown below. When charged in other forms, it is presumed to change to a stable formate.
K ₂ CO ₃ + H ₂ O → ₂ KOH + CO ₂ (4)
KOH + CO → HCOOK (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, and even more preferably carbonates and formates. is there. Among these, use of a calcium salt is preferable because the catalytic activity is increased.

  The molar ratio of the alkali metal formate and the alkaline earth metal catalyst is not particularly limited, but it is sufficient that the alkaline earth metal catalyst is present in a small amount, and (alkaline metal formate moles) / ( The alkaline earth metal mole ratio) is preferably in the range of 0.5 to 100, more preferably 1 to 50, and even more preferably 2 to 20. The yield of formic acid ester and methanol is high even with a small amount of alkaline earth metal catalyst relative to alkali metal formate.

  These alkali metal catalysts and alkaline earth metal catalysts do not have to be in one form each, and there are a plurality of types of alkali metal catalysts that can take the form of formate and alkaline earth metal catalysts. A plurality of types of catalysts may be mixed.

These catalysts can be used by supporting them on a general carrier by a conventional method.
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. In addition, compounds having a plurality of aromatic rings, such as diphenyl ether and benzyl ether, are exemplified, but not limited thereto.

Of these, diphenyl ether, benzyl ether, and anisole are preferred because of high catalytic activity.
These ethers having an aromatic ring in the molecular structure can be used in combination of two or more.

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

The alkaline earth metal catalyst and the 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, 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 and the like, 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, conditions selected from a temperature of 70 to 250 ° C., a pressure of 3 to 70 atm, and a liquid phase are preferable, but not limited thereto. Alcohols may be in an amount sufficient for the reaction to proceed, for example, an amount sufficient to soak the entire catalyst, but the reaction proceeds even below that amount. Further, a larger amount can be used as the solvent. In the above reaction, in addition to alcohols, an organic solvent can be used as appropriate. The molar ratio of the solvent alcohol and the ether having an aromatic ring is not particularly limited, but a small amount of the ether having an aromatic ring may be present, and (solvent alcohol mole number) / (ether mole having an aromatic ring). Number) = 50 or more, good results are likely to be obtained.

  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, and 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) Acceptable values), copper-based catalysts such as Cu / ZnO, Cu / Cr ₂ O ₃ , Raney copper, and nickel-based catalysts are preferred.

Among them, a Cu / MgO _X was prepared in the coprecipitation method, Cu / MgO _X / NaY addition of Na evaporation to dryness method which has a very high activity in the reaction, one or both of water and carbon dioxide A high methanol yield can be obtained even if the mixture is mixed. 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 It is 8.5-10.5, More preferably, it is 9-10.5. About the range where pH exceeds 11, since the usage-amount of the alkaline compound used as a precipitating agent to maintain in a highly alkaline atmosphere increases remarkably, it is not economical. Loading amount of Na relative to Cu / MgO _X is not limited in particular, preferably in the range of 0.1～60Wt%, more preferably 1-40 wt%, more preferably from 3 to 30 wt% . NaY is preferably sodium formate, sodium carbonate or the like.

  The 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, evaporation to dryness method, and is not particularly limited. However, according to the coprecipitation method, it is possible to prepare a catalyst with a high loading rate, and good results are easily obtained.

  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 stage. 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 described above, when the reaction is carried out in the presence of a hydrocracking catalyst with an alkali metal catalyst or the like, it may be used as a simple mixture, but the hydrocracking solid catalyst is supported with an alkali metal catalyst or the like. Since the catalyst is separated from the reaction system by solid-liquid separation, recovery is easy, which is preferable. The supporting method itself can be a conventional method for preparing a catalyst as described above.

  In addition, when it is difficult to produce methanol in one step using a catalyst with a high selectivity for formate ester, the product obtained by the reaction is separated from the reaction system by distillation or the like, and then the product is produced. It is also 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 CO ₂ and H ₂ O contained in the raw material gas, the higher the yield of methanol can be obtained. Conversion and methanol yield are hardly affected. However, if it is contained at a concentration higher than that, the CO conversion rate and methanol yield decrease.

The production method of formate ester and methanol in the present invention is presumed to be based on the following reaction formula (an example in which the alcohol is a chain or alicyclic hydrocarbon having a hydroxyl group attached thereto) ).
ROH + CO → HCOOR (6)
HCOOR + 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.

  Further, 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. Formic acid ester and methanol can be obtained without losing the activity of the catalyst.

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 (%) = [1− (number of CO moles recovered after reaction) / (number of charged CO moles)] × 100
Formate ester yield (%) = [(number of moles of formate ester produced) / (number of moles of charged CO)] × 100
Methanol yield (%) = [(number of moles of methanol produced) / (number of moles of charged CO + CO ₂ )] × 100
* Since the pathway for the production of methanol from CO ₂ is thought to proceed in parallel, the number of moles of CO ₂ charged is also considered in the case of a CO ₂ coexisting system.

Reference example 1
Using an autoclave with an internal volume of 100 ml, 5 mmol of potassium formate and 1 mmol of calcium formate were added to 15 ml of methanol as a solvent, and synthesis gas (CO 48%, H ₂ 48%, Ar balance) was charged at 3.0 MPa, and 150 ° C. The reaction was performed for 1 hour, and the reaction product was analyzed by gas chromatography. With a CO conversion of 15.9%, 5.57 mmol of methyl formate was obtained.

Reference example 2
The reaction was carried out by the method described in Reference Example 1 except that 1 mmol of calcium carbonate was added instead of 1 mmol of calcium formate. A CO conversion of 13.5% gave 5.21 mmol of methyl formate.

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

Example 2
The reaction was carried out by the method described in Reference Example 1 except that 1 mmol of benzyl ether was added instead of 1 mmol of calcium formate. With a CO conversion of 30.1%, 10.91 mmol of methyl formate was obtained.

Reference example 3
The reaction was carried out by the method described in Reference Example 1 except that anisole was added instead of 1 mmol of calcium formate. 9.98 mmol of methyl formate was obtained with a CO conversion of 27.5%.

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

Reference example 4
The reaction was carried out by the method described in Reference Example 1 except that 10 mmol of calcium carbonate was added instead of 1 mmol of calcium formate. 3.55 mmol methyl formate was obtained with a CO conversion of 7.4%.

Reference Example 5
The reaction was carried out by the method described in Reference Example 1 except that 0.5 mmol of calcium carbonate was added instead of 1 mmol of calcium formate. With a CO conversion of 12.2%, 5.18 mmol of methyl formate was obtained.

Reference Example 6
Using an autoclave with an internal volume of 100 ml, adding 2 mmol of potassium formate and 2 mmol of calcium carbonate to 27.8 ml of methanol as a solvent, and supplying synthesis gas (CO 48%, H ₂ 48%, Ar balance) at 60 ml / min, The continuous reaction was performed for 20 hours under the condition of 150 ° C.-5.0 MPa. The reaction product was analyzed by gas chromatography. Only methyl formate was obtained with a CO conversion of 1.98%.

Example 3
The reaction was carried out by the method described in Reference Example 5 except that 2 mmol of diphenyl ether was added instead of 2 mmol of calcium carbonate. Only methyl formate was obtained with a CO conversion of 3.95%.

Comparative Example 2
The reaction was performed by the method described in Reference Example 3 except that only 10 mmol of potassium formate was added. Only methyl formate was obtained with a CO conversion of 1.45%.

Reference Example 7
Using an autoclave with an internal volume of 100 ml, 27.8 ml of methanol as a solvent, 10 mmol of potassium formate and 2 mmol of calcium carbonate, Cu (NO ₃ ) ₂ .3H ₂ O, Mg (NO ₃ ) ₂ .6H ₂ O as hydrocracking catalysts As a raw material, Cu / MgO _x (X is a chemically acceptable value) is prepared by a coprecipitation method while maintaining pH = 10.0, and Na ₂ CO ₃ is used as a raw material to prepare Na / CO3 by evaporation to dryness. 3 g of Cu / MgO _x / Na ₂ CO ₃ supporting _X (X is a chemically acceptable value) is added, and synthesis gas (CO 48%, H ₂ 48%, Ar balance) is supplied at 60 ml / min. The continuous reaction was performed for 20 hours under the condition of 170 ° C.-5.0 MPa. The reaction product was analyzed by gas chromatography. The CO conversion was 32.9%, and the methanol yield was 32.7%.

Example 4
The reaction was carried out by the method described in Reference Example 7 except that diphenyl ether was used instead of 2 mmol of calcium carbonate. The CO conversion was 55.6% and the methanol yield was 54.3%.

Comparative Example 3
The reaction was carried out by the method described in Reference Example 4 except that Cu / Cr ₂ O ₃ (ENGELHARD, Cu-1987T 1/8) was added instead of Cu / MgO _x / NaY. The CO conversion was 27.7%, and the methanol yield was 27.5%.

Comparative Example 4
The reaction was carried out by the method described in Reference Example 4 except that Cu / SiO ₂ (ENGELHARD, Cu-0860 E 1/8) was added instead of Cu / MgO _x / NaY. The CO conversion was 11.1% and the methanol yield was 10.9%.

Reference Example 8
The reaction was carried out by the method described in Reference Example 4 except that the supply amount of synthesis gas was 30 ml / min. The CO conversion was 60.9%, and the methanol yield was 60.1%.

Reference Example 9
The reaction was carried out by the method described in Reference Example 4 except that the supply amount of synthesis gas was 90 ml / min. The CO conversion was 28.0% and the methanol yield was 27.9%.

Reference Example 10
The reaction was carried out by the method described in Reference Example 4 except that synthesis gas having a different composition (CO 48%, H ₂ 48%, CO ₂ 1%, Ar balance) was used. The CO conversion was 28.5%, and the methanol yield was 27.9%.

Reference Example 11
The reaction was carried out by the method described in Reference Example 4 except that 1% of H ₂ O was continuously added by bubbling the source gas to H ₂ O with temperature control. The CO conversion was 29.3%, and the methanol yield was 28.6%.

  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 alkaline earth metal system in addition to the alkali metal formate Catalyst, one or both of ethers having an aromatic ring in the molecular structure, and a system using a hydrocracking catalyst, among them, a catalyst containing Cu, an alkaline earth metal element, and an alkali metal element as a hydrocracking catalyst, or Formic acid in the presence of solvent alcohol from at least one of carbon monoxide and carbon dioxide, which is a synthesis raw material gas, in a system in which a catalyst containing at least one of Cu, Mn, and Re and an alkali metal element coexists. When ester and methanol are produced, formate or methanol is stably synthesized with high efficiency in a continuous reaction at low temperature and low pressure. Theft has become possible. In addition, even if water, carbon dioxide, or the like is mixed in the synthetic 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.

1 is 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: formate, 9: methanol. It is the relationship between pH and CO conversion controlled when Cu / MgO _x is prepared by coprecipitation.

Claims (35)

  A method for producing a formate by reacting a raw material gas containing at least one of carbon monoxide and carbon dioxide, and hydrogen, an ether having an aromatic ring in the molecular structure in addition to an alkali metal formate, and an alcohol A method for producing a formate ester, characterized in that the reaction is carried out in the presence of an alcohol.   A method for producing methanol by reacting at least one of carbon monoxide and carbon dioxide, and hydrogen-containing source gas, in addition to alkali metal formate, an ether having an aromatic ring in the molecular structure, hydrocracking A method for producing methanol, comprising reacting in the presence of a catalyst and alcohols to produce formate ester and methanol, and producing methanol by hydrogenating the produced formate ester.   It is obtained by adding a source gas containing carbon monoxide, carbon dioxide, and hydrogen to an alkali metal formate in the presence of an ether having an aromatic ring in the molecular structure and an alcohol. A method for producing methanol, comprising separating the product from the reaction system and then hydrogenating the formic acid ester in the product with a hydrocracking catalyst to produce methanol.   A method of producing a formate by reacting a raw material gas containing at least one of carbon monoxide and carbon dioxide and hydrogen, and in addition to an alkali metal formate, an alkaline earth metal catalyst, and an aromatic structure. A method for producing a formate ester, wherein the reaction is carried out in the presence of both an ether having a ring and an alcohol.   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 an alkali metal formate, an alkaline earth metal catalyst, an aromatic ring in the molecular structure The reaction is carried out in the presence of both an ether having a hydrocracking catalyst and an alcohol to produce a formate ester and methanol, and the produced formate ester is hydrogenated to produce methanol. Production method.   Add source gas containing at least one of carbon monoxide, carbon dioxide, and hydrogen to alkali metal formate, and both alkaline earth metal catalyst, ether having aromatic ring in molecular structure, and presence of alcohol A method for producing methanol, comprising separating a product obtained by carrying out the reaction below from a reaction system and then hydrogenating a formate in the product with a hydrocracking catalyst to produce methanol. The production method according to any one of claims 1 to 6 , wherein an alkali metal catalyst that can change into an alkali metal formate during the reaction is used instead of the alkali metal formate. The process according to any one of claims 1 to 7, wherein the alkali metal formate salt is characterized in that it is a potassium formate. 8. The production method according to claim 7 , wherein the alkali metal catalyst capable of changing to an alkali metal formate during the reaction is potassium carbonate.   The production method according to claim 4, wherein the alkaline earth metal catalyst is a catalyst containing a calcium salt. The process according to claim 1 0, wherein in place of the alkali metal formate salt, which comprises using an alkali metal-based catalyst which can change into an alkali metal formate salt during the reaction. The process according to claim 1 1, the alkali metal-based catalyst which can change into an alkali metal formate salt during the reaction is characterized by a potassium carbonate. The method according to any one of claims 1 to 6, 10 to 12 , wherein an aromatic ring of an ether having an aromatic ring in the molecular structure is a single ring. The production method according to any one of claims 1 to 6, 10 to 12 , wherein the ether having an aromatic ring in the molecular structure is diphenyl ether. The manufacturing method according to any one of claims 1 to 6, 10 to 12 , wherein the ether having an aromatic ring in the molecular structure is benzyl ether. Instead of the alkali metal formate salt A process according to any one of claims 1 3 to 1 5, which comprises using an alkali metal-based catalyst which can change into an alkali metal formate salt during the reaction. The process according to any one of claims 1 3 to 1 5, wherein the alkali metal formate salt is characterized in that it is a potassium formate. The production method according to claim 16 , wherein the alkali metal catalyst capable of changing to an alkali metal formate during the reaction is potassium carbonate. Said hydrocracking catalyst is added to Cu, Mn, at least one of Re, and claims 2, 3 and 5, characterized in that a catalyst containing an alkali metal element, according to any one of the 6 A method for producing methanol. The method for producing methanol according to any one of claims 2, 3, 5, and 6, wherein the hydrocracking catalyst is a catalyst containing Cu, an alkaline earth metal element, and an alkali metal element. . Is said hydrocracking catalyst is a solid catalyst, either the solid catalyst carries an alkali metal formate salt and alkaline earth metal-based catalyst, according to claim 2, 3, 5, characterized in that for the reaction, 6 The method for producing methanol according to claim 1. The method according to any one of claims 19 to 21 , wherein an alkali metal catalyst that can change into an alkali metal formate during the reaction is used instead of the alkali metal formate. The method according to any one of claims 19 to 21, wherein the alkali metal formate is potassium formate. The method according to claim 2 2, alkali metal-based catalyst which can change into an alkali metal formate salt during the reaction is characterized by a potassium carbonate. The process according to any one of claims 1-2 4, characterized in that the alcohol is a primary alcohol.   Consists of a hydrocracking catalyst containing Cu, an alkaline earth metal element, 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.   From a hydrocracking catalyst 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: 28. The catalyst for methanol production according to claim 26 or 27 , wherein the alkaline earth metal catalyst is a catalyst containing a calcium salt. 29. The catalyst for methanol production according to any one of claims 26 to 28 , comprising an alkali metal catalyst that can be changed to an alkali metal formate during the reaction instead of the alkali metal formate. 30. The methanol production catalyst according to claim 26 , 28 or 29 , wherein the alkaline earth metal element contained in the hydrocracking catalyst is magnesium. Methanol production catalyst according to any one of claims 26 to 3 0 wherein the alkali metal element contained in the hydrocracking catalyst is sodium. The catalyst for methanol production according to any one of claims 26 to 31, wherein the aromatic ring of the ether having an aromatic ring in the molecular structure is a single ring. Methanol production catalyst according to any one of claims 26 to 3 2, wherein the ether having an aromatic ring in the molecular structure is diphenyl ether. Methanol production catalyst according to any one of claims 26 to 3 2, wherein the ether having an aromatic ring in the molecular structure is benzyl ether. The hydrocracking catalyst, methanol production catalyst according to any one of claims 2 6-3 4, characterized in that the preparation being kept constant in the range of pH = 8 to 11 in a co-precipitation method Production method.

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