Method of producing ethyl acetate

FIELD: chemistry.

SUBSTANCE: catalyst further contains chromium oxide in amount of 5.0-20.0 wt % of the total amount of catalyst. Ethanol with water content of up to 15 wt % is used in the process. Use of the method enables to increase ethanol conversion to 58%, ethyl acetate selectivity to 95%, and use ethanol with water concentration of up to 15 wt %.

EFFECT: method does not require feeding an additional amount of hydrogen into the process.

2 cl, 10 ex, 1 tbl

 

The invention relates to the field of chemical technology, in particular to a method for producing ethyl acetate dehydrogenation of ethanol.

It is known that a large part of acetic acid ethyl ester obtained by the esterification of acetic acid with ethanol in the presence of sulfuric acid (Chashchin A.M., gloukhareva M.I. Production of acetate solvents in the forestry industry. M, Forestry, 1984).

The disadvantage of this method is the high corrosiveness of the reaction mass, resulting in a lot of the equipment must be made of high-alloy steel. In addition, to produce the required two main components - ethanol and acetic acid. To obtain high-quality acetate acetic acid should have a concentration of not lower than 99.5 wt.%.

A method of obtaining ethyl acetate dehydrogenation of ethanol in the presence of a copper-containing catalyst and hydrogen at a temperature 100-260°C and a pressure of 3-50 MPa. (WO 0020375, 2000; analogs: EP 0990638, 2000; US 6809217, 2004).

The disadvantage of this method is the use of dried ethanol. Technical ethanol is typically produced in the form of an azeotrope with water, the concentration in which the alcohol is at least 5 wt.%. Dehydration of ethanol is usually made with the help of a third component (e.g., benzene), forms a ternary azeotrope with the alcohol and the ode. To return to the third component in the process, it must be regenerated. Thus, dehydration of ethanol requires significant energy costs. Another disadvantage is the introduction of an additional quantity of hydrogen.

Closest to the claimed is a method of producing ethyl acetate dehydrogenation of ethanol in the presence of a copper-zinc catalyst at a temperature of 180-300°C at a feed rate of ethanol 250-700 l/l cat. hour. The concentration of water in ethanol is not specified (AV. St. USSR №362814, 1973).

The disadvantage of this method is the low conversion of ethanol upon receipt of ethyl acetate. For example, when using ethanol with a water content of 2-8 wt.% conversion of ethanol is only 25-25,7% (see comparative examples 1, 2).

The task of the invention is to develop a method of producing ethyl acetate dehydrogenation of ethanol to increase the conversion of ethanol and the selectivity for ethyl acetate, and to use ethanol with a concentration of water of up to 15 wt.%.

The problem is solved developed a method of producing ethyl acetate dehydrogenation of ethanol in the presence of a copper-zinc catalyst at elevated temperature and pressure, which differs in that the catalyst additionally contains chromium oxide in the amount of 5-20 wt.% from the total amount of catalyst, in which the process using ethanol with a water content up to 15 wt.%.

The process is carried out at a temperature of 250-290°C and a pressure of 7-20 ATM.

It should be noted that the method does not require the introduction of additional amounts of hydrogen. Formed in the process of acetaldehyde largely hereroense to ethanol, which is returned to the process. Thus, the loss of ethanol are mainly related to the education components of the lighter and heavier ethyl acetate.

Below are examples of specific implementations of the proposed method. Conditions and results of the process are presented in the table.

Example 1 (comparative)

Charged to the reactor copper-zinc catalyst in the form of particles with an average diameter of 4-6 mm, it serves ethanol with a water content of 2 wt.%, with the bulk velocity 0.8 1/h in the liquid phase. Dehydrogenation of ethanol is carried out at a temperature of 270°C and a pressure of 10 ATM.

The table shows the conditions and results of the process. Conversion of ethanol amounted to 25.7%, the selectivity for ethyl acetate amounted to 79.4 per cent.

Example 2 (comparative)

The process is carried out analogously to example 1, with the difference that the water content of ethanol is about 8 wt.% and volumetric flow rate of ethanol is 0.85 1/hour.

Conversion of ethanol amounted to 25.0%, the selectivity for ethyl acetate was 80.5 per cent.

Example 3 (comparative)

The process is carried out analogously to example 1, with the difference, Thu is as a catalyst using a copper-zinc catalyst with the addition of 13.7% chromium oxide, and ethanol contains 8 wt.% water. Process temperature 270°C, the pressure is 3 ATM. The conversion rate was only 38%, the selectivity for ethyl acetate amounted to 71.5%.

Examples 4-10

The process is carried out analogously to example 1, with the difference that the catalyst used copper-zinc catalyst with the addition of from 5.0 to 20.0% chromium oxide and ethyl alcohol contains from 2 to 15 wt.% water. Process temperature 250-290°C, the pressure is from 3 to 20 ATM.

Moreover, in examples 1, 2 (comparative), as well as 8, 9 catalyst was prepared by mixing the respective metal oxides pressing into pellets, drying at a temperature of 110-130°C and calcining at a temperature of 400-500°C. In examples 3 (comparative), 4-7 and 9 used industrial catalyst NTC-4, containing 13.7 wt.% chromium (TU 2171-004-52047005-2002).

This catalyst in industry are used in the process of low-temperature conversion of carbon monoxide.

The results of the experiments presented in the table.

From an analysis of the table shows that the conversion of ethanol amounted to 57%, the selectivity for ethyl acetate amounted to 95%.

1. The method of producing ethyl acetate dehydrogenation of ethanol in the presence of a copper-zinc catalyst at elevated temperature and pressure, wherein the catalyst further comprises an oxide of chromium in the amount of 5.0-20.0 wt.% from the General to whom icesta catalyst, in the process using ethanol with a water content up to 15 wt.%.

2. The method according to claim 1, characterized in that the process is carried out at a temperature of 250-290°C and a pressure of 7 to 20 ATM.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of reducing concentration of aldehyde in the crude stream of a carbonylation process, involving feeding a crude stream containing a carbonylatable agent selected from a group consisting of methanol, methyl acetate, methyl formate and dimethyl ether or mixture thereof, having primary concentration of aldehydes; and reaction thereof in gaseous phase with a deposited catalyst which contains at least one metal from group 8 to 11, in conditions which facilitate reduction of primary concentration of aldehydes to secondary concentration of aldehydes.

EFFECT: method improves degree of reduction of aldehyde.

28 cl, 3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved carbonylation method intended for producing a carbonylation product through reaction of carbon monoxide with raw material which contains alcohol and/or reactive derivative thereof, in vapour phase using a heterogeneous catalyst in form heteropoly acid which undergoes ion exchange with one or more metals selected from a group comprising rhodium, iridium, copper and palladium, and a group IA metal selected from lithium, sodium, potassium and rubidium, or in which these metals are included, where the heteropoly acid has formula H3M12XO40, where M denotes tungsten, molybdenum, chromium, vanadium, tantalum or niobium and X denotes phosphorus or silicon.

EFFECT: method provides high conversion of the methanol reagent and longer service life of the catalyst.

28 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to synthesis of esters from the alcohol fraction of caprolactam. The method of producing esters from caprolactam production wastes is realised via esterification of organic acid and alcohol in autocatalytic heat release conditions which support the esterification reaction at temperature 40-130°C using a catalyst in form of cation-exchange resin which is pre-treated with sulphuric acid in amount of 0.4-2 wt % of the weight of the loaded material with cooling down of the reaction mixture before separating the two phases.

EFFECT: high efficiency of the method.

2 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: method relates to production of acetic acid ether (methyl acetate) via carbonylation of dimethyl ether in gas phase in presence of catalyst and may be used in chemical industry. Invention covers catalyst for carbonylation of dimethyl ether that comprises acid cesium salt of phosphor-tungsten heteropoly acid CsxHyPW12O40, where 1.3≤x≤2.2, y=3-x with platinum additive in amount of 0.25-1.0 wt %. Catalyst in prepared on adding cesium soluble salt to mix of solutions of phosphor-tungsten heteropoly acid and platinum-hydrochloric acid, both taken in required ratio, evaporating, drying, tabletting and grinding to required size. Invention covers also production of methyl acetate in presence of above described catalyst.

EFFECT: higher catalytic activity.

5 cl, 9 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to novel compounds of general formula (I)

, in which X denotes a CHO, CH2OH or CH2OC(O)R group, where R denotes a straight of branched C1-C5 alkyl chain; as well as to a synthesis method, particularly synthesis of 6,8-dimethylnon-7-enal (1) through hydroformylation of 5,7-dimethylocta-1,6-diene. The invention also relates to fragrant compositions containing formula (I) compounds. Owing to their fragrant properties, these compounds are of great interest in perfumery, particularly cosmetic products and household chemicals.

EFFECT: obtaining novel fragrant compositions.

12 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel compounds of general formula (I)

, in which X denotes a CHO, CH2OH or CH2OC(O)R group, where R denotes a straight of branched C1-C5 alkyl chain; as well as to a synthesis method, particularly synthesis of 6,8-dimethylnon-7-enal (1) through hydroformylation of 5,7-dimethylocta-1,6-diene. The invention also relates to fragrant compositions containing formula (I) compounds. Owing to their fragrant properties, these compounds are of great interest in perfumery, particularly cosmetic products and household chemicals.

EFFECT: obtaining novel fragrant compositions.

12 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing lower alkyl ether of lower aliphatic alcohol having formula R1-COO-R2, involving reaction of a pre-dried lower alkyl ether having formula R1-O-R2, in which R1 and R2 independently denote C1-C6alkyl groups, provided that the total number of carbon atoms in groups R1 and R2 ranges from 2 to 12, or R1 and R2 together form a C2-C6 alkenyl group, with material which contains carbon monoxide, in the presence of a catalyst which contains mordenite and/or ferrierites in anhydrous conditions. The invention also relates to a method of producing carboxylic acids through hydrolysis of esters obtained using the method given above.

EFFECT: high output and selectivity of end product.

29 cl, 3 tbl, 9 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method for synthesis of an ester through reaction of 1-olefin with a monobasic carboxylic acid and water in vapour phase in the presence of a heteropolyacid catalyst on silica gel, in which the silica gel support is in from of granules treated with water vapour at temperature between 100 and 300°C for a period of time between 0.1 to 200 hours, before or simultaneously with application of the heteropolyacid onto the support. The invention also relates to a heteropolyacid catalyst deposited on silica gel and to a method of preparing the catalyst, where the support is obtained by treating silica gel granules with water vapour at temperature between 100 and 300°C for a period of time between 0.1 and 200 hours, before or simultaneously with application of the heteropolyacid onto the support.

EFFECT: use of the said catalyst in the ester synthesis method through reaction of 1-olefin with a monobasic carboxylic acid and water in vapour phase enables to reduce content of methyl ethyl ketone in products.

43 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: method of producing acetic acid and its ester or anhydride involves bringing methanol and/or its reactive derivative selected from methyl acetate and dimethyl ether into contact with carbon monoxide in the presence of a catalyst at temperature ranging from 250 to 600°C and pressure ranging from 10 to 200 bars, and where content of iodide in the methanol and/or its reactive derivative, carbon monoxide and catalyst is less than 500 parts/million, where the catalyst essentially consists of mordenite which contains skeleton elements in form of silicon, aluminium and one or more of other elements selected from gallium and boron, and in which copper, nickel, iridium, rhodium or cobalt is added through ion exchange or some other method.

EFFECT: high selectivity with respect to the end product and high catalyst stability.

22 cl, 3 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: described is a carbonylation method for producing a carbonylation product by bringing carbon monoxide into contact with initial material containing alcohol and/or its reactive derivative, in vapour phase using a heterogeneous heteropolyacid catalyst containing one or more metal cations selected from Cu, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt. The initial material contains 0.5-20 wt % water and water in the initial material is fresh and/or recycled.

EFFECT: increased catalyst activity, increased degree of convertion of methanol into the desired product.

35 cl, 5 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of reducing concentration of aldehyde in the crude stream of a carbonylation process, involving feeding a crude stream containing a carbonylatable agent selected from a group consisting of methanol, methyl acetate, methyl formate and dimethyl ether or mixture thereof, having primary concentration of aldehydes; and reaction thereof in gaseous phase with a deposited catalyst which contains at least one metal from group 8 to 11, in conditions which facilitate reduction of primary concentration of aldehydes to secondary concentration of aldehydes.

EFFECT: method improves degree of reduction of aldehyde.

28 cl, 3 tbl, 3 ex

The invention relates to an improved process for the preparation of ethyl acetate, widely used mainly in organic synthesis

The invention relates to a method of automatic control of technological processes and can be used in the chemical industry to automate the process of synthesis of ethyl acetate from acetaldehyde and several similar processes

FIELD: chemistry.

SUBSTANCE: invention relates to zeolite-containing catalysts. Described is a zeolite-containing catalyst for converting a straight-run gasoline fraction to a high-octane gasoline component with low benzene content, which contains high-silica zeolite with H-ZSM-5 type high-silica zeolite structure with silica modulus SiO2/Al2O3=30-50, in amount of 97.0-99.0 wt % and a modifying component which is at least one metal from the group: copper, tungsten, molybdenum, which is introduced into the high-silica zeolite in form of nanopowder of said metals in amount of 1.0-3.0 wt %; the catalyst is formed during thermal treatment. Described is a method of producing said catalyst, characterised by that the H-ZSM-5 type high-silica zeolite with silica modulus SiO2/Al2O3=30-50 is obtained via hydrothermal crystallisation of the reaction mixture at 120-180°C for 1-6 days, which contains sources of silicon oxide, aluminium oxide, alkali metal oxide, hexamethylene diamine and water, with further mixing of a high-silica zeolite with metal nanopowder obtained by electric blasting the wire of the metal in a medium of argon, followed by mechanochemical treatment, moulding the catalyst mass, drying and calcination. Described is a method of converting a straight-run gasoline fraction to a high-octane gasoline component with low content of benzene in the presence of the catalyst described above, wherein the conversion process is carried out at 350-425°C, volume rate of 1.0-2.0 h-1 and pressure 0.1-1.0 MPa.

EFFECT: high activity and selectivity of the catalyst.

4 cl, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts for synthesis of carboxylic esters. Described is a catalyst for synthesis of a carboxylic ester through reaction of (a) an aldehyde and alcohol, or (b) one or more types of alcohols in the presence of oxygen, the catalyst containing: nickel oxide; and X, where X is at least one element selected from a group comprising palladium, platinum, ruthenium, gold, silver and copper, deposited on a carrier in atomic ratio Ni/(Ni+X) from 0.20 to 0.99. Described is a method of preparing a catalyst for synthesis of a carboxylic ester, involving a first step for producing a catalyst precursor by depositing nickel and component X, where X is at least one element selected from a group comprising palladium, platinum, ruthenium, gold, silver and copper on a carrier through neutralisation of an acidic solution of a soluble metal salt containing nickel and X; and a second step for oxidising nickel via thermal treatment of the obtained catalyst precursor, where the atomic ratio Ni/(Ni+X) ranges from 0.20 to 0.99. Described also is a method for synthesis of a carboxylic ester, involving a step for reaction of the described catalyst with (a) an aldehyde and alcohol, or (b) one or more types of alcohols, in the presence of oxygen.

EFFECT: active catalyst for synthesis of a carboxylic ester is obtained.

17 cl, 5 tbl, 5 dwg, 48 ex

FIELD: shift reaction catalysts.

SUBSTANCE: invention relates to iron oxide-containing catalysts generally used for high-temperature shift reactions wherein gas stream containing water steam and carbon monoxide is passed over catalyst at temperature within a range of 350 to 550°C to convert carbon monoxide into carbon dioxide with simultaneous formation of hydrogen. Catalyst is prepared via precipitation of composition containing ferrous and ferric iron and chromium(III) with a base, ferrous iron being partly oxidized by an oxidant into ferric iron. Further formation of resulting precipitate into formed catalyst blocks is effected at temperature above 200°C. Invention also provides a high-temperature shift reaction process using above catalyst blocks.

EFFECT: avoided need of catalyst restoration stage resulting in improved catalyst strength and activity.

10 cl, 2 tbl, 2 ex

The invention relates to the refining and petrochemical industries, in particular to catalysts for Hydrotreating of petroleum distillates

The invention relates to a process for the preparation of catalysts used for chemical transformations in the gas phase, and can be used for the conversion of carbon monoxide with water vapor
Up!