CN112439437B - Iridium-containing solution used as catalyst for synthesizing acetic acid, and preparation method and application thereof - Google Patents
Iridium-containing solution used as catalyst for synthesizing acetic acid, and preparation method and application thereof Download PDFInfo
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- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
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Abstract
The invention discloses a preparation method of iridium-containing catalyst solution, which uses chloroiridium acid compound which is easier to purchase or prepare as raw material, so that the method has the possibility of industrial application. Meanwhile, the obtained solution is mutually soluble with compounds such as methyl acetate, methyl iodide and the like, so that the solution can be directly applied to a process for synthesizing acetic acid.
Description
Technical Field
The invention belongs to the field of catalysts, and relates to an iridium-containing solution used as a catalyst for synthesizing acetic acid, and a preparation method and application thereof.
Background
Iridium and iridium compounds are widely used as catalysts in a variety of chemical reactions, particularly in isomerization, hydroformylation and carbonylation reactions. Methods for preparing carboxylic acids by iridium-catalysed carbonylation reactions are becoming increasingly important and are described in patents DE1767150A1, EP0616997A1, etc. An iridium catalyst system is reported by BP company in patent EP0749948A1 and EP0752406A1, and is successfully applied to the industrial production of acetic acid, which is called a Cativa process. The process adopts a novel efficient iridium-based catalyst, and combines a novel accelerator, so that compared with rhodium-based catalysts, the process has the advantages of low price, less byproducts, reduced investment cost and operation cost, and greatly improved production capacity.
Although a process for synthesizing acetic acid using an iridium-based catalyst system has been studied and applied in a large amount in recent years, a study on a preparation method of an iridium catalyst has not been paid attention. Patent WO9623757A1 describes a process for the preparation of iridium carboxylates in which at least one chloride or bromide of iridium is reacted with an alkali or alkaline earth carboxylate in a medium containing a carboxylic acid to form a solution containing iridium carboxylate. In order to be able to use this solution for catalytic purposes, the alkali and alkaline earth metal chlorides and bromides obtained by the process are separated off as by-products using ion exchange columns, wherein alkali metal or alkaline earth metal ions are separated off using cation exchange resins and chlorine or bromine ions are separated off using anion exchange resins. This process takes a long time since both ion exchange and the regeneration of the column material are necessary, and at the same time ion exchange may lead to yield losses.
Patent EP1046629A1 describes a process for the preparation of iridium acetate by precipitation of iridium hydroxide from an aqueous chloride solution of iridium using an aqueous solution of an alkali metal hydroxide, carbonate or bicarbonate, reacting the separated iridium hydroxide with acetic acid or acetic anhydride mixture to form a solution containing iridium acetate, and evaporating the solvent to give solid iridium acetate. To reduce the chlorine content, it is preferable to reprecipitate iridium hydroxide prior to reaction with acetic acid. Iridium hydroxide is dissolved with nitric acid or a mixture of nitric acid and hydrogen peroxide, and an aqueous solution of an alkali metal hydroxide, carbonate or bicarbonate is added to reprecipitate iridium hydroxide. The method has more separation steps, the solvent is evaporated, time and energy are wasted, and the yield is still to be improved.
Patent CN101213165 describes a process for the preparation of iridium acetate by reacting an iridium compound with an alkaline substance to give an iridium-containing precipitate, separating the precipitate, and dissolving in acetic acid or acetic anhydride in the presence of oxalic acid or formic acid to give an iridium acetate solution. The solvent was evaporated to give iridium acetate as a solid. This process, despite the high yields, has the disadvantage of likewise a large number of separation steps, the solvent having to be evaporated in order to obtain solid iridium acetate, resulting in time and energy consumption.
Patent CN1043568C describes a process for the preparation of iridium-based solutions, using hydrated or unhydrated iridium oxide or hydroxide as starting material, in water, carboxylic acid or carboxylic acid ester, with hydroiodic acid or a compound capable of releasing hydroiodic acid, to obtain solutions containing iridium, at least 20% of the iridium being dissolved in the solution. Although the patent teaches that iridium is not completely dissolved and does not present any particular problem, the remaining solids can be recycled. In practice, however, separation of undissolved solids results in additional process steps and iridium losses.
Patent CN1070734C describes a process for the preparation of iridium-based solutions, using iridium carbonyl compounds as starting material, reacted with hydroiodic acid or its precursors in the liquid phase, the solvent being determined by the application of the solution obtained and being acetic acid or methyl acetate, adipic acid, 3-pentenoic acid or its esters, the total pressure being between 1 and 10bar, the temperature not exceeding the boiling temperature of the solvent under the conditions in which the reactants are subjected to contact. However, the iridium carbonyl compound is not a compound which can be industrially used on a large scale, and thus the industrial use of the present method is difficult.
Disclosure of Invention
The invention provides a preparation method of iridium-containing catalyst solution, which uses chloroiridium acid compound which is easier to purchase or prepare as raw material, so that the method has the possibility of industrial application. Meanwhile, the obtained solution is mutually soluble with compounds such as methyl acetate, methyl iodide and the like, so that the solution can be directly applied to a process for synthesizing acetic acid.
The first aspect of the present invention is to provide a method for preparing an iridium-containing solution as a catalyst for synthesizing acetic acid, comprising the steps of:
s1, preparing an iridium-containing aqueous solution by using an iridium-containing raw material to obtain an iridium-containing solution A;
s2, adding soluble carbonate or bicarbonate of alkali metal or alkaline earth metal into the iridium-containing solution A, and precipitating to obtain a precipitate A;
s3, separating the precipitate A, and washing until no chloride ions are detected to obtain a precipitate B;
and S4, dissolving the precipitate B in acid to obtain iridium-containing solution B serving as a catalyst for synthesizing acetic acid. .
The raw materials used in the invention are any commercially available iridium chloride, aqueous solution of chloroiridic acid or hydrochloric acid solution, and soluble chloroiridate, such as alkali metal chloroiridate, and the like. Compared with carbonyl iridium and hydrated or unhydrated iridium oxide, iridium chloride, chloroiridic acid and chloroiridate are easier to purchase, and at the same time, higher yields can be ensured.
According to some embodiments of the invention, the iridium-containing raw material containing iridium chloride, chloroiridic acid or soluble chloroiridate is selected from one or more of iridium chloride, chloroiridic acid, soluble chloroiridate, aqueous solution of iridium chloride, hydrochloric acid solution of iridium chloride, aqueous solution of chloroiridic acid, hydrochloric acid solution of chloroiridic acid, aqueous solution of soluble chloroiridate and hydrochloric acid solution of soluble chloroiridate.
According to some embodiments of the invention, the iridium-containing raw material containing iridium chloride, chloroiridic acid or soluble chloroiridate is selected from one or more of iridium chloride and sodium chloroiridate
According to some embodiments of the invention, the soluble chloroiridate salt is selected from one or more of sodium chloroiridate, potassium chloroiridate and ammonium chloroiridate.
According to some embodiments of the invention, the soluble chloroiridate salt is sodium chloroiridate;
according to some embodiments of the invention, the soluble carbonate or bicarbonate of an alkali or alkaline earth metal is selected from one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, calcium carbonate, magnesium carbonate, calcium bicarbonate, and magnesium bicarbonate.
According to some embodiments of the invention, the soluble carbonate or bicarbonate of an alkali or alkaline earth metal is selected from one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
According to some embodiments of the invention, the soluble carbonate or bicarbonate of an alkali metal or alkaline earth metal is sodium bicarbonate.
According to some embodiments of the invention, the iridium-containing solution A has a molar concentration of iridium of 0.01-1mol/L.
According to some embodiments of the invention, the iridium-containing solution A has a molar concentration of iridium of 0.1-0.5mol/L.
Slowly adding sodium bicarbonate aqueous solution into iridium-containing aqueous solution, and gradually increasing the pH value of the solution to obtain iridium-containing carbonate precipitate. The amount of sodium bicarbonate used depends on the end point pH of the precipitation process, which is suitably from 6 to 9, and preferably when the pH in the solution reaches 6 to 7, the addition of sodium bicarbonate is stopped, whereupon a large amount of precipitate is formed in the solution.
According to some embodiments of the invention, the soluble carbonate or bicarbonate of an alkali metal or alkaline earth metal is added to iridium-containing solution a in the form of a solid powder or an aqueous solution.
According to some embodiments of the invention, sodium bicarbonate or potassium bicarbonate formulated as an aqueous solution of 1% -10% by weight volume is added to iridium-containing solution a.
According to some embodiments of the present invention, sodium bicarbonate formulated as an aqueous solution of 5% -8% by weight volume is added to iridium-containing solution a;
according to some embodiments of the invention, the precipitation process is performed at ambient temperature or under heating.
According to some embodiments of the invention, the precipitation process is carried out under heating to 50-100 ℃.
According to some embodiments of the invention, the precipitation process is carried out under heating to 70-80 ℃.
According to some embodiments of the invention, the precipitation process is performed under any inert atmosphere.
According to some embodiments of the invention, the precipitation process is carried out under atmospheric conditions in air.
According to some embodiments of the invention, the soluble carbonate or bicarbonate salt of an alkali metal or alkaline earth metal is added in an amount to a pH of 6 to 9.
According to some embodiments of the invention, the soluble carbonate or bicarbonate salt of an alkali metal or alkaline earth metal is added in an amount to a pH of 6 to 7.
After the mixture containing the precipitate was cooled to room temperature, the precipitate was separated by filtration. And (3) repeatedly washing the precipitate by using hot water in the filtering process until the washing liquid is detected to have no chloridion reaction by using a silver nitrate solution, and ending the washing. The iridium-containing carbonate precipitate obtained was used for the subsequent synthesis.
According to some embodiments of the invention, after stopping the addition of the alkali or alkaline earth metal soluble carbonate or bicarbonate, the solution is heated to boiling, refluxed for 30min-1h, and then allowed to stand for cooling.
The dissolution process can be carried out under normal pressure or slightly more than atmospheric pressure in the flask, the iridium-containing precipitate begins to dissolve in the acetic acid solution only after being heated to a certain temperature, the black-green precipitate begins to slowly dissolve in the acetic acid solution after the solution is heated to more than 80 ℃, and the precipitate is basically completely dissolved after 20 hours, so that the solution turns to dark green.
According to some embodiments of the invention, the acid is acetic acid, which is glacial acetic acid or aqueous acetic acid.
According to some embodiments of the invention, precipitate B is dissolved in acetic acid, the aqueous acetic acid solution having a weight-volume concentration of 80-98%.
According to some embodiments of the invention, precipitate B is dissolved in acetic acid, the aqueous acetic acid solution having a concentration weight volume of 95% -96%.
According to some embodiments of the invention, precipitate B is dissolved in acetic acid, the aqueous acetic acid solution being used in an amount of 0.01 to 0.5mol of precipitate B per liter of aqueous acetic acid solution dissolved in iridium.
According to some embodiments of the invention, precipitate B is dissolved in acetic acid, the aqueous acetic acid solution being used in an amount of 0.05 to 0.1mol of precipitate B per liter of aqueous acetic acid solution dissolved in iridium.
According to some embodiments of the invention, precipitate B is dissolved in acetic acid, the dissolution being carried out at atmospheric or greater pressure.
According to some embodiments of the invention, precipitate B is dissolved in acetic acid and heated during the dissolution.
According to some embodiments of the invention, precipitate B is dissolved in acetic acid at a heating temperature of 80-130 ℃.
According to some embodiments of the invention, precipitate B is dissolved in acetic acid at a heating temperature of 80-110 ℃.
According to some embodiments of the invention, precipitate B is dissolved in acetic acid for a period of 5-48 hours.
According to some embodiments of the invention, precipitate B is dissolved in acetic acid for a period of 5-10 hours.
According to some embodiments of the invention, the acid is a mixed acid comprising glacial acetic acid and another acid.
According to some embodiments of the invention, the mixed acid is a mixed acid of glacial acetic acid and hydroiodic acid.
According to some embodiments of the invention, the hydroiodic acid is present in the mixed acid in an amount of 5% to 50% by weight.
According to some embodiments of the invention, the hydroiodic acid is present in the mixed acid in an amount of 20% to 30% by weight.
According to some embodiments of the invention, precipitate B is dissolved in a mixed acid at a temperature of 80-100 ℃ for a time of 0.5-6 hours.
According to some embodiments of the invention, precipitate B is dissolved in a mixed acid at a temperature of 80-100 ℃ for a time of 0.5-5 hours.
The addition of a certain proportion of hydriodic acid into glacial acetic acid can accelerate the dissolution of iridium-containing precipitate, shorten the dissolution time and reduce the dissolution temperature. When the dissolution is carried out using a mixed solution of glacial acetic acid and hydroiodic acid, the temperature is preferably 80-10 ℃, the precipitation begins to dissolve when heated for 30min, and after 5h the precipitation is substantially completely dissolved.
In a second aspect, the invention provides a catalyst obtained by the preparation method according to the first aspect, which is used for synthesizing acetic acid by methanol carbonylation.
According to some embodiments of the invention, in the reaction of synthesizing acetic acid by methanol carbonylation, iridium-containing solution C as a catalyst is mixed with methyl acetate, methyl iodide, water and a promoter, wherein the weight volume of iridium in the system is 500-3000ppm, the weight volume of methyl acetate is 10-20% in concentration, the weight volume of water is 3-10% in concentration, the weight volume of methyl iodide is 5-15% in concentration, and the weight volume of the promoter is 500-3000ppm in concentration.
According to some embodiments of the invention, the reaction conditions for synthesizing acetic acid from methanol carbonyl are: the partial pressure of carbon monoxide is 0.5-10MPa, and the reaction temperature is 140-250 ℃.
According to some embodiments of the invention, the reaction conditions for synthesizing acetic acid from methanol carbonyl are: the partial pressure of carbon monoxide is 1-5MPa, and the reaction temperature is 170-210 ℃.
According to some embodiments of the invention, the methanol oxo acetic acid reaction is performed in a batch mode or a continuous mode.
According to some embodiments of the invention, the methanol oxo-acetic acid reaction is performed in a continuous manner.
The invention has the beneficial effects that:
the method has simple process, simple and easily obtained raw materials and high product yield, and the iridium-containing catalyst solution is subjected to elemental analysis, and the calculated yield of the iridium metal is more than 95%. The iridium-containing catalyst solution prepared by the method has low impurity content, and elemental analysis shows that the chloride ion content in the iridium-containing catalyst solution is lower than 50ppm. The solution is completely mutually soluble with substances such as methyl acetate, methyl iodide, a cocatalyst and the like, so that the solution can be directly used in the reaction of synthesizing acetic acid by methanol carbonyl without removing a solvent, and is separated to obtain solid, thereby reducing energy consumption and being more beneficial to industrial application.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
Example 1
4.888g of chloroiridium acid solution (weight volume ratio, 35wt% of iridium) was weighed into a three-necked flask, and 50ml of deionized water was added for dilution. The solution was heated to 80 ℃, 10% aqueous sodium bicarbonate was slowly added to the solution, and the addition was stopped when the pH of the solution was 8. The solution was heated to boiling and refluxed for 30min. The solution was then cooled to room temperature and the precipitate was filtered. And washing the precipitate by using hot water until no chloridion reaction is detected by using a silver nitrate solution in the washing solution, and ending the washing to obtain the iridium-containing carbonate precipitate.
200ml of 95% acetic acid aqueous solution was used to dissolve the iridium-containing carbonate precipitate, the mixture was heated to 100℃and after 40 hours of reaction, the precipitate was completely dissolved to obtain a dark greenish black solution. ICP analysis showed that the chlorine content in the solution was 35ppm and the yield was 95% based on iridium.
The catalyst solution was used for methanol carbonylation reaction and its catalytic performance was tested. The solution is mixed with substances such as methyl acetate, methyl iodide, water, a promoter and the like, the content of iridium in the system is 1000ppm, the concentration of methyl acetate is 15%, the water content is 5%, the concentration of methyl iodide is 8%, and the content of the promoter is 2000ppm. The solution was charged into a 300ml autoclave, and after pressure test and slow substitution of nitrogen, CO was introduced at 0.6MPa, and after heating to 185℃under stirring at 750 rpm, CO was introduced at about 2.5MPa to start the reaction. The carbonylation rate was measured to be 13.7 mol/(L.hr). A liquid sample after the reaction was taken for testing, and the selectivity of acetic acid in the product was 99.9%.
Example 2
5.007g of chloroiridium acid solution (weight-volume ratio, 35wt% of iridium-containing solution) was weighed into a three-necked flask, and 50ml of deionized water was added for dilution. The solution was heated to 70 ℃, 5% aqueous sodium bicarbonate was slowly added to the solution, and the addition was stopped when the pH of the solution was 6. The solution was heated to boiling and refluxed for 1h. The solution was then cooled to room temperature and the precipitate was filtered. And washing the precipitate by using hot water until no chloridion reaction is detected by using a silver nitrate solution in the washing solution, and ending the washing to obtain the iridium-containing carbonate precipitate.
200ml of 80% acetic acid and 20% hydriodic acid solution is used for dissolving iridium-containing carbonate precipitate, the mixture is heated to 80 ℃ and reacted for 5 hours, and the precipitate is completely dissolved, so that dark green solution is obtained. ICP analysis showed that the chlorine content in the solution was 33ppm and the yield was 96% based on iridium.
The catalyst solution was used for methanol carbonylation reaction and its catalytic performance was tested. The solution is mixed with substances such as methyl acetate, methyl iodide, water, a promoter and the like, the content of iridium in the system is 2000ppm, the concentration of methyl acetate is 12%, the water content is 3%, the concentration of methyl iodide is 10%, and the content of the promoter is 1000ppm. The solution was charged into a 300ml autoclave, and after pressure test and slow substitution of nitrogen, CO was introduced at 0.6MPa, and after heating to 185℃under stirring at 750 rpm, CO was introduced at about 2.5MPa to start the reaction. The carbonylation rate was found to be 16.2 mol/(L.hr). A liquid sample after the reaction was taken for testing, and the selectivity of acetic acid in the product was 99.9%.
Example 3
3.015g of iridium chloride (weight/volume ratio, 35wt% iridium content) was weighed into a three-necked flask and dissolved by adding 50ml of deionized water. The solution was heated to 80 ℃, 5% aqueous sodium bicarbonate was slowly added to the solution, and the addition was stopped when the pH of the solution was 7. The solution was heated to boiling and refluxed for 30min. The solution was then cooled to room temperature and the precipitate was filtered. And washing the precipitate by using hot water until no chloridion reaction is detected by using a silver nitrate solution in the washing solution, and ending the washing to obtain the iridium-containing carbonate precipitate.
200ml of 70% by volume acetic acid (glacial acetic acid) +30% by volume hydriodic acid solution (weight/volume concentration, 47%) was used to dissolve the iridium-containing carbonate precipitate, and the mixture was heated to 80℃and after 5h of reaction the precipitate was completely dissolved, giving a dark greenish solution. ICP analysis showed that the chlorine content in the solution was 40ppm and the yield was 95.5% based on iridium.
The catalyst solution was used for methanol carbonylation reaction and its catalytic performance was tested. The solution is mixed with substances such as methyl acetate, methyl iodide, water, a promoter and the like, the content of iridium in the system is 2000ppm, the concentration of methyl acetate is 12%, the water content is 5%, the concentration of methyl iodide is 5%, and the content of the promoter is 2000ppm. The solution was charged into a 300ml autoclave, and after pressure test and slow substitution of nitrogen, CO was introduced at 0.6MPa, and after heating to 185℃under stirring at 750 rpm, CO was introduced at about 2.5MPa to start the reaction. The carbonylation rate was found to be 17.9 mol/(L.hr). A liquid sample after the reaction was taken for testing, and the selectivity of acetic acid in the product was 99.9%.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (17)
1. A method for preparing iridium-containing solution used as a catalyst for synthesizing acetic acid, comprising the following steps:
s1, preparing an iridium-containing aqueous solution from an iridium-containing raw material to obtain an iridium-containing solution A, wherein the iridium-containing raw material is selected from one or more of an iridium chloride aqueous solution, an iridium chloride hydrochloric acid solution, a soluble chloroiridate aqueous solution and a soluble chloroiridate hydrochloric acid solution; the molar concentration of iridium in the iridium-containing solution A is 0.01-1mol/L;
s2, adding alkali metal or alkaline earth metal soluble carbonate or bicarbonate into the iridium-containing solution A, wherein the amount of the alkali metal or alkaline earth metal soluble carbonate or bicarbonate added is 6-9 of the pH value added into the mixed system, and precipitating to obtain a precipitate A;
s3, separating the precipitate A, and washing away chloride ions to obtain a precipitate B;
s4, dissolving the precipitate B in acid, wherein the acid is a mixed acid of glacial acetic acid and hydroiodic acid, heating in the dissolving process, wherein the heating temperature is 80-100 ℃, and the dissolving time is 0.5-6h, so as to obtain iridium-containing solution B serving as a catalyst for synthesizing acetic acid.
2. The method of claim 1, wherein the soluble chloroiridium acid salt is selected from one or more of sodium chloroiridium acid salt, potassium chloroiridium acid salt, and ammonium chloroiridium acid salt;
and/or the soluble carbonate or bicarbonate of alkali metal or alkaline earth metal is selected from one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, calcium carbonate, magnesium carbonate, calcium bicarbonate and magnesium bicarbonate.
3. The method according to claim 1, wherein the molar concentration of iridium in the iridium-containing solution a is 0.1 to 0.5mol/L.
4. A process according to any one of claims 1 to 3, characterized in that the soluble carbonate or bicarbonate of an alkali or alkaline earth metal is added to iridium-containing solution a in the form of a solid powder or an aqueous solution;
and/or the precipitation process is performed under heating;
and/or the precipitation process is carried out under any inert atmosphere;
and/or the amount of soluble carbonate or bicarbonate added to the alkali metal or alkaline earth metal is such that the pH added to the mixed system is from 6 to 7;
and/or after stopping adding the soluble carbonate or bicarbonate of alkali metal or alkaline earth metal, heating the mixed system to boiling, refluxing for 30min-1h, and then standing for cooling.
5. The method according to claim 4, wherein in step S2, sodium bicarbonate or potassium bicarbonate is added in an aqueous solution of 1-10% by weight.
6. The method according to claim 4, wherein sodium bicarbonate is added in the form of a 5% -8% aqueous solution in step S2.
7. The method according to claim 4, wherein the precipitation is carried out under heating to 50-100 ℃.
8. The method according to claim 4, wherein the precipitation is carried out under heating to 70-80 ℃.
9. The method according to claim 4, wherein the precipitation process is carried out under atmospheric pressure conditions in air.
10. A process according to any one of claims 1 to 3, characterized in that the hydroiodic acid is present in the mixed acid in an amount of 5% to 50% by weight and volume.
11. The method of claim 10, wherein the hydroiodic acid is present in the mixed acid in an amount of 20% to 30% by weight.
12. A method according to any one of claims 1-3, characterized in that the dissolution time is 0.5-5h.
13. Use of a catalyst prepared according to the method of any one of claims 1-12 in a reaction for synthesizing acetic acid from methanol.
14. The use according to claim 13, wherein in the methanol oxo acetic acid reaction, iridium-containing solution B as a catalyst is mixed with methyl acetate, methyl iodide, water and a promoter, wherein the weight volume content of iridium in the system is 500-3000ppm, the weight volume content of methyl acetate is 10% -20%, the weight volume content of water is 3% -10%, the weight volume content of methyl iodide is 5% -15%, and the weight volume content of promoter is 500-3000ppm.
15. The use according to claim 14, wherein the methanol oxo acetic acid reaction conditions are: the partial pressure of carbon monoxide is 0.5-10MPa, and the reaction temperature is 140-250 ℃.
16. The use according to claim 14, wherein the methanol oxo acetic acid reaction is carried out in a continuous manner.
17. Use according to claim 15, wherein the carbon monoxide partial pressure is between 1 and 5MPa and the reaction temperature is between 170 and 210 ℃.
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