Way to obtain the ester of formic acid or methanol and the catalyst of this method

 

(57) Abstract:

The invention relates to a method for producing ester of formic acid or methanol and the catalyst of this method. Obtaining a complex ester of formic acid is carried out by interaction of carbon monoxide with an alcohol in the presence of water and/or carbon dioxide, in the presence of a catalyst. A method of producing methanol includes the interaction of carbon monoxide with an alcohol in the presence of a catalyst to obtain a complex ester of formic acid in the presence of water and/or carbon dioxide. In the reaction system at the same time is the catalyst for the hydrogenolysis of ester of formic acid and hydrogen for hydrogenation of the formed complex ester of formic acid with methanol obtaining. The catalyst is a salt of an alkali metal other than alkali metal alkoxide. A method for production of methanol, which includes the interaction of alcohol with the reaction system containing carbon monoxide and hydrogen in the presence of a catalyst comprising a salt of an alkali metal other than alkali metal alkoxide, and a catalyst containing copper, together with manganese and/or resusage a salt of an alkali metal, other than alkoxide of an alkali metal, a solid catalyst for the hydrogenolysis of the ester of formic acid. Also, a catalyst for the production of methanol, which consists of a catalyst comprising a salt of an alkali metal other than alkali metal alkoxide and a catalyst containing copper, together with manganese and/or rhenium. The technical result is the synthesis of the product at low pressure and low temperature, the catalyst having a high resistance to deactivation. 6 N. and 3 C.p. f-crystals.

The technical field to which the invention relates

The invention relates to a method for producing ester of formic acid or methanol and the catalyst of this method. More specifically, the present invention relates to a method of producing methanol from carbon monoxide and hydrogen using a catalyst having high resistance against deactivation by water or carbon dioxide, which results in high efficiency of production of the product, and, in addition, refers to the catalyst of this method.

The level of technology

Usually in the industrial synthesis of methanol as raw materials use of manook is mainly methane, and the synthesis is carried out using the catalyst type copper/zinc or similar, in a fixed bed, gas-phase process, in harsh conditions - temperature 200-300C and a pressure of 5-25 MPa. Although this reaction is exothermic, it is hardly possible to achieve effective heat dissipation due to the poor thermal conductivity in the gas phase method, a reduction in the degree of conversion in a single pass and is used for recirculation of high pressure gas with the source material, which, however, creates significant difficulties for effective work. Despite this problem in the gas-phase process with a fixed bed there is almost no tendency to inhibition of the reaction with water or carbon dioxide contained in the synthesis gas, and at the present time, various plants are using this advantageous property.

On the other hand, explored different ways of synthesis of methanol in the liquid phase, which increases the degree of heat dissipation. Among these methods, the process using a catalyst having high activity at low temperature (approximately from 100 to 180C), is advantageous for synthesis system, especially from the point of view of thermodynamics, and this method deserves NR and carbon dioxide in many cases present in the synthesis gas, and therefore it is not applied in practice.

The invention

The aim of the present invention is to overcome the above problems and the development of a catalyst and method in which the catalyst remains active, even when carbon dioxide, water, etc. are part of the gaseous source materials and/or reaction mixture for the synthesis of the ester of formic acid or methanol, and ether formic acid or methanol can be synthesized at a low temperature and low pressure.

The present invention is characterized by the following features.

1. Way to obtain the ester of formic acid, including the interaction of carbon monoxide with an alcohol in the presence of a catalyst of the type of alkali metal and/or catalyst type alkaline-earth metal.

2. A method of producing methanol, comprising the interaction of carbon monoxide with an alcohol in the presence of a catalyst of the type of alkali metal and/or catalyst type alkaline-earth metal with the formation of the ester of formic acid, which is present in the reaction system at the same time there is a hydrogenolysis catalyst, ester S="ptx2">

3. A method of producing methanol, comprising the interaction of carbon monoxide with an alcohol in the presence of a catalyst of the type of alkali metal and/or catalyst type alkaline-earth metal with the formation of the ester of formic acid, separation of the formed ester of formic acid and hydrogenation of selected ester of formic acid when it contacts with a hydrogenolysis catalyst and hydrogen with a methanol obtaining.

4. A method of producing methanol, comprising the interaction of carbon monoxide with an alcohol in the presence of a catalyst of the type of alkali metal and/or catalyst type, alkaline earth metal catalyst containing copper, along with manganese and/or rhenium for the production of methanol from carbon monoxide and hydrogen.

5. Way to obtain the ester of formic acid, including the interaction of carbon monoxide with an alcohol in the presence of a catalyst containing copper, along with manganese and/or rhenium.

6. Method of production, which is described in any one of paragraphs 1-4, in which the catalyst of the type of alkali metal and catalyst type alkaline earth metal salt of an alkali metal and a catalyst containing salt deleteselection hydrogenolysis is solid, and the used catalyst of the type of alkali metal and/or catalyst type, alkaline earth metal deposited on a specified hard.

8. Method of production, which is described in any of items 1 to 5 in which the alcohol is a primary alcohol.

9. The catalyst for the production of methanol, which is obtained by applying a catalyst of the type of alkali metal and/or catalyst type, alkaline earth metal on a solid catalyst for the hydrogenolysis of the ester of formic acid.

10. The catalyst for the production of methanol, which consists of a catalyst of the type of alkali metal and/or catalyst type, alkaline earth metal, and a catalyst containing copper, together with manganese and/or rhenium.

11. Catalyst to obtain the ester of formic acid containing copper together with manganese and/or rhenium.

The present invention is described in detail below.

As a result of extensive studies, the authors of the present invention discovered that by using a catalyst of the type of alkali metal and/or catalyst type alkaline-earth metal which are not subject to poisoning by water and/or carbon dioxide, formic ether sour the carbon.

The present invention is carried out on the basis of this discovery. Examples of catalysts of the type of the alkali metal include metal compounds and simple substances, such as lithium, potassium, sodium and cesium. Examples of catalysts of the type of the alkali earth metal include metal compounds and simple substances, such as calcium, magnesium, barium and strontium. Metal compounds preferably are metal salts or metal oxides, more preferably alkali metal salts, such as carbonates, nitrates, phosphates, acetate and formate. In this case excluded the alkoxides of alkali metals (for example, methoxide, ethoxide), because they largely are poisoning the water and/or carbon dioxide. These catalysts can also be used as catalysts, applied to the primary carrier in the usual way. The alcohols used in this reaction are alcohols, formed as a result of the merger of the hydroxyl group to a branched or alicyclic hydrocarbon, and, in addition, can be a phenol or product replacement, or a thiol, or a product replacement. These alcohols can be primary, secondary or tertiary, but the tsya lower alcohols, such as methyl alcohol or ethyl alcohol. This reaction can be carried out or in the liquid or in the gas phase, but can be used in a system in which you can choose medium (more mild) conditions. To put it concretely, the temperature, pressure and reaction time is chosen in the interval correspondingly from 70 to 250C., of 0.3 to 7 MPa and from 5 minutes to 10 hours, but the conditions are not limited to the above. Alcohol may be enough, if its added amount is large enough to ensure that the course of the reaction, however, alcohol can also be used as a solvent and in larger quantities than stated above. In this reaction, in combination with the alcohols can be respectively used, and other organic solvents.

Upon receipt of the ester of formic acid can also be used a catalyst containing copper, together with manganese and/or rhenium.

The resulting ester of formic acid can be purified in the usual way, but also it can be used as such for the production of methanol. That is, the methanol can be obtained by hydrogenation of the ester of formic acid. When the hydrogenolysis is applied hydrogenolysis catalyst, and examples of the catalyst which can be used is to use catalysts of the type of copper, such as Cu/MnOx, Cu/ReOx(in which x is a chemically valid number), Cu/ZnO, Cu/DSA3and the Raney copper, and the type catalysts Nickel. Among them, Cu/MnOxand Cu/ReOxshow a very high activity in the reaction and provide a very high yield of methanol, even in the presence of water and/or carbon dioxide. The method of producing hydrogenolysis catalyst is not specifically limited, and can be applied by conventional methods such as impregnation method, deposition method, Sol-gel method, coprecipitation method, the method of ion exchange, the method of kneading and drying method. However, in accordance with the co-deposition can be obtained a catalyst having a high content of the active component, and you can easily get good results. In the present invention is based on the joint communication of the hydrogenolysis catalyst and hydrogen to the reaction system to obtain the ester of formic acid from carbon monoxide and alcohol, so you can get methanol in the so-called one-step process. The hydrogenolysis reaction may be carried out essentially in the same conditions of interaction, which are described above, however, the temperature and pressure can be is from 1 to 5. As described above, in the case of reactions in ensuring that the hydrogenolysis catalyst is present together with a catalyst of the type of alkaline metal, etc, these catalysts can be used in the form of a simple mixture, however, when a catalyst of the type of alkali metal applied to a solid catalyst for the hydrogenolysis, the selection of catalysts mainly facilitated. Regarding the actual method of loading, can be used conventional methods used in obtaining catalysts.

When methanol is difficult to obtain in the one-stage process, it is also possible the obtaining of methanol by separating the formed ester of formic acid, followed by hydrogenolysis of the selected ester of formic acid in the presence of a hydrogenolysis catalyst and hydrogen.

I believe that the process of obtaining the ester of formic acid or methanol in accordance with the present invention proceeds according to the following reaction scheme (as the example shows a case of using an alcohol formed by the joining of the hydroxyl group to a branched or alicyclic hydrocarbon -):

(where R represents aboutreal for the production of methanol, moreover, alcohol can be isolated and reused. In accordance with the present invention, even if there are large quantities of water and carbon dioxide in gaseous source material (e.g., even more than 5% of carbon dioxide) and/or in the reaction system, the catalyst does not lose its activity, and the ester of formic acid or methanol can be obtained. Moreover, even if in the reaction system, there is an admixture of sulfur-containing compounds or chlorine-containing compounds, such as H2S and Hcl, ether formic acid and methanol can be obtained in the same way without any problems.

The best option of carrying out the invention

The present invention is described in more detail with reference to the following examples, although the present invention is not limited to these examples.

In the examples, the degree of conversion of CO (%) and yield of methanol (%) calculated in accordance with the following formula:

the degree of transformation WITH a=[1-(number of moles of CO+CO2after reaction)/(number of moles of CO+CO2at the entrance)]100

the yield of methanol=((number of moles of the formed methanol)/(number of moles of CO+CO2input))100.

Example 1

In the autoclave, the ima solvent, and fill it to a pressure of 3 MPa synthesis gas mixed with carbon dioxide (32%; 4.7% OF CO2; else H2), and at a temperature of 170To carry out the reaction for 2 hours the reaction Product is analyzed by gas chromatography; the result is that it turns out only the ethyl formate when the degree of conversion, equal to 3.0%.

Example 2

The reaction is carried out according to the method described in example 1, except that the reaction time is reduced to 20 minutes. Receive the same results as in Example 1, therefore, concluded that the reaction reaches equilibrium in about 20 minutes.

Example 3

The reaction is carried out according to the method described in example 1, except that add potassium bicarbonate instead of potassium carbonate. The result is ethyl formate when the degree of conversion, equal to 3.1%.

Example 4

The reaction is carried out according to the method described in example 1, except that the added cesium carbonate instead of potassium carbonate. The degree of transformation FROM 3.2%.

Example 5

The reaction is carried out according to the method described in example 1, except that add sodium carbonate instead of potassium carbonate. Stepi example 1 except that add lithium carbonate instead of potassium carbonate. The degree of transformation FROM 0.4%.

Example 7

The reaction is carried out according to the method described in example 1, except that add potassium nitrate instead of potassium carbonate. The degree of transformation WITH is 1.0%.

Example 8

The reaction is carried out according to the method described in example 1, except that add sodium nitrate instead of potassium carbonate. The degree of transformation FROM 0.9%.

Example 9

The reaction is carried out according to the method described in example 1, except that add potassium phosphate instead of potassium carbonate. The degree of transformation FROM 1.7%.

Example 10

The reaction is carried out according to the method described in example 1, except that add potassium acetate instead of potassium carbonate. The degree of transformation WITH is 1.51 percent.

Example 11

The reaction is carried out according to the method described in example 1, except that add potassium formate instead of potassium carbonate. The degree of transformation is WITH 3,44%.

Example 12

The reaction is carried out according to the method described in example 1 for isclosed 4,0%.

Example 13

The reaction is carried out according to the method described in example 1, except that use of n-propanol instead of ethanol. The degree of conversion of CO in n-propyl-formate is 3.4%.

Example 14

The reaction is carried out according to the method described in example 1, except using n-butanol instead of ethanol. The degree of reaction WITH n-butyl formate is 3.4%.

Example 15

The reaction is carried out according to the method described in example 1, except that the use of isopropanol instead of ethanol. The degree of conversion of CO in isopropylpalmitate is 1.1%.

Example 16

The reaction is carried out according to the method described in example 1, except that the use of isobutyl alcohol instead of ethanol. The degree of conversion of CO in isobutylparaben is 1.8%.

Example 17

The reaction is carried out according to the method described in example 1, except using tert-butanol instead of ethanol. The degree of reaction WITH tert-bodyformat is 0.7%.

Example 18

The reaction is carried out according to the method described in example 1, except that additionally add 0.2 g soosazhdenie copper/Tinkov is to be placed, equal to 2.9%, and the yield of methanol equal to 0.3%.

Example 19

In an autoclave having a net volume of 85 ml, add 1.4 mmol of potassium carbonate to 20 ml of ethanol containing 0,010% by weight of water, as a solvent, and fill it to a pressure of 3 MPa synthesis gas mixed with carbon dioxide (32%, 4,7% CO2the rest of H2) and at a temperature of 170To carry out the reaction for 2 hours the reaction Product is analyzed by gas chromatography; the result is that it turns out only the ethyl formate when the degree of conversion, equal to 16%.

Example 20

The reaction is carried out according to the method described in example 19, except that additionally add 4.0 g soosazhdenie copper/zinc catalyst as a catalyst for hydrogenolysis. The result is methanol when the degree of conversion WITH 25% and the yield of methanol equal to 1.2%.

Example 21

The reaction is carried out according to the method described in example 19, except that additionally add 4.0 g soosazhdenie copper/manganese catalyst as a catalyst for hydrogenolysis. The result is methanol when the degree of conversion WITH 90% and the yield of methanol equal to 27%.

Example add 2.0 g soosazhdenie copper/manganese catalyst as a catalyst for hydrogenolysis. The result is methanol when the degree of conversion WITH 79% and the yield of methanol equal to 27%.

Example 23

The reaction is carried out according to the method described in example 19, except that additionally add 1.0 g soosazhdenie copper/manganese catalyst as a catalyst for hydrogenolysis. The result is methanol when the degree of conversion WITH 33% and the yield of methanol equal to 1.1%.

Example 24

The reaction is carried out according to the method described in example 22, except that a mixed synthesis gas does not contain carbon dioxide. The result is methanol, the extent of transformation WITH equal to 92% and the yield of methanol equal to 41%.

1. A method of obtaining a complex ester of formic acid, including the interaction of carbon monoxide with an alcohol in the presence of water and/or carbon dioxide, according to which interact in the presence of a catalyst comprising a salt of an alkali metal other than alkali metal alkoxide.

2. A method of producing methanol, comprising the interaction of carbon monoxide with an alcohol in the presence of a catalyst comprising a salt of an alkali metal, otlichnaya carbon wherein in the reaction system simultaneously a catalyst for hydrogenolysis of ester of formic acid and hydrogen for hydrogenation of the formed complex ester of formic acid with methanol obtaining.

3. A method of producing methanol, comprising the interaction of carbon monoxide with an alcohol in the presence of a catalyst comprising a salt of an alkali metal other than the alkali metal alkoxide to obtain a complex ester of formic acid, in the presence of water and/or carbon dioxide, the Department received a complex ester of formic acid and its hydrogenation in the presence in the reaction system of the hydrogenolysis catalyst and hydrogen simultaneously with water and/or carbon dioxide with methanol obtaining.

4. A method of producing methanol, comprising the interaction of alcohol with the reaction system containing carbon monoxide and hydrogen in the presence of a catalyst comprising a salt of an alkali metal other than alkali metal alkoxide, and a catalyst containing copper, together with manganese and/or rhenium.

5. The method of receiving according to any one of paragraphs.1-4, in which a catalyst comprising a salt of alkaline metal is as strong acids.

6. A method of producing methanol under item 2 or 4, wherein the hydrogenolysis catalyst is a solid catalyst, the catalyst comprising a salt of an alkali metal other than alkoxide of an alkali metal deposited on a specified solid catalyst.

7. The method according to any of paragraphs.1-5, in which the alcohol is a primary alcohol.

8. The catalyst for the production of methanol, which is produced by applying a catalyst comprising a salt of an alkali metal other than alkali metal alkoxide, a solid catalyst for the hydrogenolysis of the ester of formic acid.

9. The catalyst for the production of methanol, which consists of a catalyst comprising a salt of an alkali metal other than alkali metal alkoxide and a catalyst containing copper, together with manganese and/or rhenium.

 

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