Method for carbonylation with using bound argentous and/or cuprous modernite catalysts

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to an improved method for carbonylation of at least one carbonylating reagent specified in a group consisting of dimethyl ester and methanol, carbon monoxide in the presence of a catalyst to prepare at least one carbonylation product specified in a group consisting of methyl acetate and acetic acid, and the above catalyst is prepared by combining modernite comprising one of: silver and copper with an inorganic oxide binding agent.

EFFECT: improved method for carbonylation.

14 cl, 2 dwg, 2 tbl, 4 ex

 

The present invention relates to a method for containing metal related zeolites - mordenite and their application as catalysts for carbonylation.

It is shown that the associated mordenite suitable for use as catalysts in the way of the conversion of hydrocarbons, such as transalkylating aromatic hydrocarbon, described in US 6486372, and hydrocracking of high-boiling hydrocarbon, described in WO 97/13826.

The mordenite is also disclosed as a catalyst in the gas-phase methods carbonylation using dimethyl ether as Carboniferous reagent. For example, in WO 2006/121778 describes a method for NISS. Olkiluoto ether ness. aliphatic carbolic acid by carbonylation mainly in anhydrous environment NISS. Olkiluoto simple ether such as dimethyl ether, carbon monoxide in the presence of mordenite or ferrierite catalyst. In WO 2006/121778 not disclosed the use of the bound zeolite of the mordenite in the way carbonylation.

In EP-A-2000433 describes a method for acetic acid and/or methyl acetate by reacting methanol and/or its reactive derivative with catalyst decomposition with mixture of carbon monoxide and hydrogen and subsequent catalytic conversion monoxide is gerada and hydrogen in acetic acid and/or methyl acetate. Mordenite disclosed as suitable catalysts for the conversion of mixtures of carbon monoxide and hydrogen in acetic acid and/or methyl acetate.

WO 2007/128955 disclosed a method of obtaining a carboxylic acid and/or its ester by carbonylation of an alcohol and/or its reactive derivative with carbon monoxide in the presence containing silver mordenite catalyst.

In the article titled Heterogeneous Catalysts for the Direct, Halide-free Carbonylation of Methanol by Ellis et al, 11th International Congress on Catalysis - 40th Anniversary, Studies in Surface Science and Catalysis, Vol.101, pages 771-779, 1996, discloses the use of copper-containing of mordenite as heterogeneous catalysts for the carbonylation of methanol.

For example, from the above WO 2007/128955 known that containing metal mordenite can be used to catalyse the carbonylation of methanol. For ease of use and increase the strength of the zeolite catalysts compression zeolites usually combine with a binder and formed into beads, pellets or extrudates. However, the disadvantage of using a binder is that, because they are considered to be inert, it is necessary to minimize the amount of binder used, because it replaces the active component of the catalyst. Therefore, to ensure the same volume of catalyst with a binder and catalyst without connecting the first catalyst, in the o f must have greater catalytic activity. It is therefore desirable to obtain containing metal mordenite, which is included in the composite with a binder, but without a significant loss of catalytic activity.

According to the invention it was found that in ways carbonylation this can be achieved if the mordenite to include copper and/or silver to join with a binder. According to the invention it has been unexpectedly found that the catalysts that are obtained by the formation of mordenite composite with a binder and then adding copper and/or silver, are the worst catalysts.

In accordance with this present invention relates to a method for carbonylation of at least one Carboniferous reagent selected from the group comprising dimethyl ether and methanol, and carbon monoxide in the presence of a catalyst to obtain at least one carbonylation product selected from the group comprising methyl acetate and acetic acid, and the catalyst obtained by combining mordenite, which includes at least one of the following: silver and copper, with an inorganic oxide binder.

The catalyst is intended for use in the present invention, is a mordenite, which includes at least one of the following: copper andsilver, and which is combined with an inorganic oxide binder.

Mordenite is a zeolite and its structure is well known and described, for example, in the publication of The Atlas of Zeolite Framework Types (C.Baerlocher, W.M.Meier, D.H.Olson, 5thed. Elsevier, Amsterdam, 2001). See online version (http://www.iza-structure.org/databases/) is a summary of topological and structural characteristics of zeolites including mordenite.

The mordenite can be purchased or can be synthesized. Commercially available forms of mordenite include sodium form acidic form and ammonium form. For use in the present invention the preferred form of mordenite is the acid form (H-form mordenite. Sodium and ammonium forms can be turned into an acidic form of mordenite by well known methods. For example, the ammonium form can be converted into acid form by calcination of ammonium form at high temperature. The sodium form can be converted into acid form by the ongoing first transformation into the ammonium form by ion exchange with ammonium salts, such as ammonium nitrate, followed by calcination of the ammonium form at high temperatures.

Usually the mordenite has a ratio of silica: alumina in the range from 10 to 100:1, and such mordenite suitable for use in this image the shadow. However, preferably, if the ratio of silica: alumina in the mordenite, intended for use in the present invention, is in the range from 10 to 40:1.

Preferably, if the surface area of the mordenite determined by the method of brunauer-Emett-teller (BET) using nitrogen adsorption, is in the range from 100 to 500 m2/year Measurement of surface area by the BET method described in the publication of Charles N. Satterfield in Heterogeneous Catalysis in Practice, McGraw-Hill Book company, 1980, p.100-106.

In the context of the present invention in the mordenite include one or more of the following: copper and silver. The inclusion of metallic copper and/or silver in the mordenite can be performed by any method known in the art, for example according to the techniques of wet impregnation, the so called "impregnation on capacity and ion exchange. If you use ion exchange, then to 100% capable of exchanging cations centers of mordenite can be exchanged for metal ions of copper and/or silver. Preferably, all the cations remaining in subject to the exchange mordenite, was the protons, therefore, currency is convenient to begin with ammonium or acid form of mordenite.

Alternatively, ion exchange, ammonium or acid form of mordenite can be impregnated with a solution of salts of copper and/or silver, and then dried.

The inclusion of metal (metals)in the mordenite is preferably performed using ion exchange.

The following methods of ion exchange can be used to obtain mordenite containing copper and/or silver. The mordenite in a suitable form, such as H-mordenite or CN-mordenite, enter into contact with an aqueous solution of a metal salt selected from the group comprising salt of copper (I) or (II)salt of silver (I).

Suitable salts of copper (I) include copper halides such as copper chloride and copper acetate.

Suitable salts of copper (II) include copper nitrate, copper acetate, copper sulfate, oxalate, copper, copper halides such as copper chloride.

Suitable salts of silver (I) include silver nitrate, silver acetate, triflate silver.

When exposed to daylight of silver salts tend to be catalyzed by light recovery in metallic silver and therefore it is preferable that ion exchange was carried out almost in the absence of light.

Salt of the metal used in the form of an aqueous solution obtained by dissolving salt in any suitable solvent. Suitable solvents include deionized water and a solution of ammonium hydroxide in deionized water.

The mordenite enter into interaction with the metal salt solution, which is used in an amount corresponding to the level of impregnation of mordenite on capacity or exceeding it.

Mix, mordenite/water solution optional WMS is about to heat provided that supported the level of impregnation on capacity and the remaining solution of metal salt remains in solution. At atmospheric pressure, a suitable temperature may be in the range from 60 to 90°C. the Solution can be heated to provide the necessary degree of inclusion of metal.

Then optional hot solution is filtered to remove excess metal salt solution and extraction of the solid containing the metal mordenite.

After filtration of the solid containing metal mordenite was washed with a solvent in which to dissolve the metal salt solution and which does not remove from the mordenite metal, enabled through the exchange. Suitable solvents include deionized water.

Then rinsed containing metal mordenite is preferably dried to remove residual water and get a free flowing powder. Drying is preferably carried out by heating containing metal mordenite to a temperature of not lower than 90°C, for example from 90 to 120°C. the Heating can be done in still air or in a stream of air or inert gas, such as nitrogen.

Before use in the reaction of carbonyl containing metal mordenite can be calcined at a temperature in the range from 400 to 600°C. the Calcination can be carried out in still air or in a stream of air or inert gas, such as nitrogen.

The number is the proportion of metallic copper and/or silver, included in the mordenite can be expressed using the partial inclusion of metal in the form of a number of gram-atoms of metal per 1 gram-atom of aluminum contained in the mordenite. The inclusion of metals can also be expressed as a percentage molar content in terms of the content of aluminium in the mordenite with the formula:

mol. % metal = (number of gram-atoms of metal/number of gram-atoms of aluminum)×100

For example, the content of the mordenite average of 0.55 gram-atom of copper per 1 gram-atom of aluminum equivalent equal to 55 mol. % copper content, calculated on the content of aluminium in the mordenite.

For use in the present invention the degree of inclusion of the metal is not critical, but preferably, if it is in the range from 5 to 200 mol.% in terms of the content of aluminium in the mordenite.

In the context of the present invention, the copper and/or silver include mordenite to mix containing metal mordenite with an inorganic oxide binder.

Inorganic oxides which are suitable for use in the present invention as a binder include silica, aluminum oxide, aluminum silicates, magnesium silicates, magnesium silicates, titanium oxides, oxides of zirconium and clay. For use in the present invention in the quality of the ve particularly suitable binders are alumina or aluminosilicates. Examples of suitable oxides include aluminum oxide aluminum type boehmite and gamma-alumina. If you use the aluminosilicate, the contents of the silicate is preferably in the range from 5 to 40 wt.%. The silicate also preferably is amorphous.

It is preferable that the binder was not a zeolite.

Preferably, the binder was refractory inorganic oxide, so that binding was stable at high temperature and, in particular, stable at temperatures at which it is possible to carry out the calcination of the catalyst, such as temperature not lower than 400°C.

Preferably, if a binder is mesoporous. For the objectives of the present invention of mesopores mean pore having a diameter in the range from 2 to 50 nm, and the expression "misoprostol" means the sum of the total surface area of mesopores and the outer surface area inorganic oxide binder, measured by the BET method using nitrogen adsorption. Misoprostol binder preferably is in the range from 1 to 500 m2/year

Preferably, if the binder is characterized by low mikroporistogo. For the objectives of the present invention micropore mean pore with diameter less than 2 nm, and the expression "microporosity" means the total area of powerestimator inorganic oxide binder, measured by the BET method using nitrogen adsorption. Microporosity binder preferably is in the range from 1 to 100 m2/g, for example in the range from 1 to 10 m2/year

Binder is preferably contained in an amount in the range from 10% to 80 wt.% in terms of the catalyst, preferably in the range from 20% to 60 wt.% in terms of catalyst or in the range from 20 to 65 wt.% in terms of catalyst, such as from 35 to 65 wt.% in terms of the catalyst.

According to the invention it was found that binders, which contain little impurities of metals such as iron and metals of group 1 and group 2 of the Periodic system of elements, for example sodium, potassium, calcium and magnesium, are particularly suitable for use in the present invention. Thus, preferably, if the full amount of the metal impurities in the binder is in the range from more than 0 to 10 wt.% and more preferably in the range of from more than 0 to 7 wt.%.

The catalyst is intended for use in the present invention is prepared by obtaining a thoroughly mixed mixture (composite) inorganic oxide binder and containing copper and/or silver mordenite. Thoroughly mixed the mixture of binder and containing a metal of mordenite can be obtained, for example, by suspension is remesiana, dry mixing, mixing in shear mixer or mixing in a drum mixer binder and containing a metal of mordenite with obtaining a homogeneous dispersion of these two components with each other. After stirring associated containing metal mordenite can be ignited and preferably calcined. Typically, the calcination is carried out at a temperature in the range from 400 to 500°C. prior To use calcined catalyst can compress, grind and sift with the formation of aggregates.

One method of preparation of the catalyst suspension includes mixing containing metal mordenite with a binder. When the suspension stirring, a mordenite, a binder and deionized water is stirred for a period of time necessary to obtain a homogeneous wet paste or suspension. Then the suspension is dried, for example at a temperature in the range from 80 to 120°C for several hours to remove excess water, or all, or substantially all physically adsorbed water. Drying can be conducted at atmospheric pressure or under reduced pressure. Before drying the wet paste or suspension of its optional can be molded by pressing, extrusion or pelletizing to obtain pellets, extrudates or beads. Then dried or molded suspension can be ignited when the temperature is re in the range from 400 to 500°C over a period of time, approximately from 1 to 10 hours, to obtain the catalyst.

Alternatively, the catalyst can be prepared by thorough mixing of the powder containing the metal mordenite with a dry binder to obtain a composite material containing metal mordenite and a binder. Dry mixing can be performed by any suitable method, such as a drum or centrifugal mixing. Then the composite can be calcined. The annealing can be performed at a temperature in the range from 400 to 500°C over a period of time of about 1 to 10 hours, to obtain the catalyst.

Found that the composites obtained by the Association containing copper and/or silver mordenite with an inorganic oxide binder at carbonyliron dimethyl ether and/or methanol to obtain methyl acetate and/or acetic acid, possess catalytic ability, better than composites mordenite/binder that include copper and/or silver.

Carboniferous reagent may be dimethyl ether, methanol or mixtures thereof.

If Carboniferous reagent is dimethyl ether, it can be pure or may contain small amounts of inert impurities. In industry dimethyl ether produced by the catalytic conversion of synthesis gas (mixtures of hydrogen and carbon monoxide of plastics technology : turning & is Yes) over catalysts for methanol synthesis and dehydration of methanol. This catalytic transformation leads to a product which mainly contains dimethyl ether, but can contain some amount of methanol. For use in the method proposed in the present invention, downloadable dimethyl ether may contain a small amount of methanol, provided that the amount of methanol contained in the download, not so large as to inhibit the carbonylation of dimethyl ether with the formation of acetate. According to the invention it was found that in the downloadable dimethyl ether valid methanol content of 5 wt.% or less, such as 1 wt.% or less.

Alternatively, dimethyl ether can be obtained in situ from any suitable source, such as dimethylcarbonate. For example, liquid dimethylcarbonate you can enter into interaction with gamma-aluminum oxide by decomposition of dimethylcarbonate with the formation of dimethyl ether and carbon dioxide.

The concentration of dimethyl ether in the downloadable gases is preferably in the range from 0.1 to 20 mol.% in terms of the total number of downloadable gases (including recycled products).

The carbon monoxide can be a mostly pure carbon monoxide, for example carbon monoxide, usually purchased from suppliers of industrial gases, or he m which may contain impurities, which do not interfere with the turning Carboniferous reagent in the carbonylation product, such as nitrogen, helium, argon, methane and/or carbon dioxide.

The way carbonylation can be done in the presence of hydrogen. Thus, downloadable monoxide may also contain hydrogen. A mixture of hydrogen and carbon monoxide getting into the industry by steam reforming of hydrocarbons by partial oxidation of hydrocarbons. Such mixtures are commonly referred to as synthesis gas. The synthesis gas contains mainly carbon monoxide and hydrogen, but may also contain smaller amounts of carbon dioxide.

The molar ratio of carbon monoxide: hydrogen may preferably be in the range of from 1:3 to 15:1, such as from 1:1 to 10:1.

If the method is used the hydrogen, it can be a gauge of the partial pressure equal not below 0.1 bar, such as from 1 to 30 bar.

The molar ratio of carbon monoxide to the number Carboniferous reagent preferably is in the range from 1:1 to 99:1, such as from 2:1 to 60:1.

If Carboniferous reagent is methanol, the water formed in situ by the dimerization of methanol ethers, or by esterification of methanol produced acetic acid. If necessary, water may be added to the loaded methanol. the number of added water can be so that the molar ratio of methanol: water was in the range of from 50:1 to 2:1. Water can be downloaded separately or together with the download methanol. Water can be downloaded in the form of liquid or steam.

Carbonylation of dimethyl ether with the formation of acetate leads to the formation of water in situ. Since it is established that water suppresses the carbonylation of dimethyl ether with the formation of acetate, preferably, the carbonylation of dimethyl ether was carried out in a way that is carried out in an anhydrous environment. Therefore support as you lower the water content. To do this, dimethyl ether, carbon monoxide, optional hydrogen and the catalyst before use preferably dried. However, a small amount of water can be tolerated without harmful effects on the formation of acetate. Water may preferably be contained in the downloadable dimethyl ether in the amount of 2.5 wt.% or less, such as 0.5 wt.% or less.

The method can preferably be carried out at a temperature in the range from 100 to 400°C, such as from 150 to 350°C.

The method can be carried out at a gauge pressure in the range from 1 to 100 bar, such as from 10 to 100 bar.

Hourly space velocity of gas (COG) preferably is in the range from 500 to 40000 h-1such cacot 4000 to 10000 h -1.

Preferably, the catalyst was activated prior to use by heating the catalyst at an elevated temperature for at least 1 h in a flow of nitrogen, carbon monoxide, hydrogen or mixtures thereof.

The method preferably takes place practically in the absence of halides such as iodide. The term "almost" means that the content of the halide, such as iodide, reacting gases (carbonylbis reagent and carbon monoxide and the catalyst is less than 500 ppm million, preferably less than 100 ppm million

The method preferably takes place by passing vapors Carboniferous reagent, carbon monoxide and optionally hydrogen through a fixed bed, fluidized bed or moving bed of the catalyst, maintained at the required temperature and pressure.

If necessary carbonitrides reagent can be injected into the interaction of with a layer of aluminum oxide or corundum immediately before the interaction with the catalyst layer.

If Carboniferous reagent is methanol, the predominant product of the carbonylation is acetic acid, but depending on the degree of conversion of methanol can also produce small amounts of acetate.

If Carboniferous reagent is m is dimethyl ether, the predominant product of this method is the acetate, but can also produce a small amount of acetic acid.

The products of the method proposed in the present invention are acetate and/or acetic acid. If Carboniferous reagent is methanol, the predominant product of the carbonylation is acetic acid, but depending on the degree of conversion of methanol can also produce small amounts of acetate. If Carboniferous reagent is dimethyl ether, the predominant product of this method is the acetate, but can also produce a small amount of acetic acid. Acetic acid and/or methyl acetate formed in the method proposed in the present invention, can be extracted in the form of steam and then condense into a liquid.

In addition to acetic acid and methyl acetate stream products obtained by the method proposed in the present invention may also contain not affected by the conversion of dimethyl ether and/or not affected by the conversion of methanol.

The acetate and/or acetic acid can be extracted from a stream of product by conventional techniques such as distillation.

The acetate can be sold without processing or it can be used in other chemical processes. For example, at least h is here formed of acetate can hydrolyze with obtaining acetic acid.

Alternatively, at least a portion of the total flow of the product obtained by the method proposed in the present invention, which contains the acetate can be sent to stage hydrolysis and then to separate acetic acid.

The hydrolysis of methyl acetate can be performed by known techniques, such as reactive distillation, in the presence of an acid catalyst.

Acetic acid, which is extracted from the stream of product proposed in the present invention, or which is then obtained by hydrolysis of methyl acetate, can be cleaned by conventional cleaning methods, such as distillation.

The method can be carried out in a continuous or periodic manner, preferably in a continuous way.

The drawings show the following:

Figure 1 shows the dependence on time (in hours) of output of products of carbonylation in g/l/h in a single pass per unit of time (the website of altar servers) in the stream for various compositions containing copper mordenite with a binder Pural SB.

Figure 2 shows the dependence on time (in hours) of output of products of carbonylation in g/l/h in a single pass per unit of time (the website of altar servers) in the stream for various compositions containing copper mordenite with a binder Chinafill 200 and containing copper mordenite catalyst without binder.

Below the present invention is illustrated by the th following examples.

Example 1

This example demonstrates the effect on the carbonylation of dimethyl ether catalysts obtained by combining copper-containing mordenite with an inorganic oxide binder (catalysts 3-6), compared with catalysts obtained by mixing mordenite with a binder associated with the formation of mordenite with the subsequent inclusion of copper in the associated mordenite (catalysts 1 and 2). Pural SB alumina - boemite, Sasol) was used as a binder to obtain catalysts 1-6. Pural SB is characterized by metophorically, component 274 m2/g, mikroporistogo, component <10 m2/g, and a total content of metal impurities such as Na, K, CA, Mg and Fe, equal to 0.19 wt.%.

Each of the catalysts 1-6 had a copper content of 55 mol.% in terms of the content of aluminium in the mordenite, and for each catalyst, the mass ratio of catalyst: binder was 80:20.

Obtaining catalyst 1 (not in accordance with the present invention)

8 g of NH4-mordenite with a mass ratio of silicon dioxide by weight of aluminum oxide, equal to 20 (CBV21A ex Zeolyst) was mixed with 2 g of binder Pural SB. To the mixture was added deionized water and got a dense suspension and thoroughly mixed. Then the suspension was dried at 110°C for at least 20 hours a Dried mixture together with 1.48 g of hemipentahydrate nitrate copper(P) (98%ACS) were placed in a round bottom flask of 100 ml, equipped with a mixer. To the mixture was added 25 ml of deionized water and got a low viscosity slurry. On top of the flask was tightly closed and the contents were stirred overnight. Then mixed low-viscosity suspension was dried under reduced pressure using a rotary evaporator and then dried in a drying Cabinet at 110°C for at least 15 h and got the dry catalyst, catalyst 1. Then the catalyst 1 was progulivali by the method of annealing described below.

Obtaining catalyst 2 (not in accordance with the present invention)

Repeating the obtaining of the catalyst 1, except that 4.5 ml of deionized water to ensure complete impregnation of capacity) was added to the dried mixture binder/mordenite and 1.48 g of hemipentahydrate nitrate copper(II) (98% ACS). Then this mixture was vigorously stirred for 15 min to ensure uniform mixing and then dried according to the method described for the preparation of the catalyst 1. Then the dry catalyst was progulivali by the method of annealing described below.

Obtaining a copper-containing mordenite (for use in obtaining catalysts 3-6)

40 g of NH4-mordenite with a ratio of silica: alumina constituting 20 (CBV21A, Zeolyst) and 7.4 g of hemipentahydrate nitrate copper(II) (98% ACS) were placed in a round bottom flask with a volume of 500 ml, equipped with masakalli 100 ml of deionized water and got a low viscosity slurry. On top of the flask was tightly closed and the contents were stirred overnight. Then low viscosity slurry was dried under reduced pressure using a rotary evaporator and then dried in a drying Cabinet at 110°C for at least 15 h and got dry containing copper mordantly catalyst. The catalyst had a copper content of 55 mol.% in terms of the content of aluminium in the mordenite.

Obtaining catalyst 3

8 g of dry copper-containing mordenite (obtained as described above) was mixed with 2 g of binder Pural SB. To the mixture was added deionized water and got a dense suspension and thoroughly mixed. Then the suspension was dried in a drying Cabinet at 110°C for at least 20 h and got the dry catalyst. Then the dry catalyst was progulivali by the method of annealing described below.

Obtaining catalyst 4

Copper-containing mordenite (obtained as described above) was progulivali by the method of annealing described below to obtain the calcined copper containing mordenite. Then repeated the method of preparation of the catalyst 3 using 8 g of the thus obtained calcined copper containing mordenite.

Obtaining catalyst 5

8 g of dry copper-containing mordenite (obtained as described above) were grinded and got loose powder. Powder and 1 g of the binder Pural SB was placed in a flask Buch 500 ml, designed for drying of powder, and it was rotated at a speed of 100 rpm at normal temperature and pressure for 1 h and was received containing copper mordantly catalyst, mixed with a binder Pural SB. Then the catalyst was progulivali by the method of annealing described below.

Obtaining catalyst 6

Copper-containing mordenite (obtained as described above) was progulivali by the method of annealing described below to obtain the calcined copper containing mordenite. Then repeated the method of preparation of the catalyst 5 using 8 g of the thus obtained calcined copper containing mordenite.

Method of annealing

The calcination of the catalyst was carried out in an atmosphere of still air with increasing temperature from room temperature to 90°C at 3°C/min and kept at this temperature for 2 hours Then the temperature was linearly increased up to 110°C at a rate of about 0.6°C/min and kept at this temperature for 2 hours In conclusion, the temperature was linearly increased up to 500°C with a speed of about 3.3°C/min and kept at this temperature for 3 h and then it was allowed to cool to room temperature.

Carbonylation of dimethyl ether

Each of the catalysts 1-6 used for the carbonylation of dimethyl ether according to the following procedure. To use the cation in the reaction, carbonylation each catalyst was condensed under a pressure of 12 tons per press-fit size 33 mm using a Specac press Press and then crushed and sieved to obtain the fraction of pellets ranging in size from 250 to 500 microns.

The carbonylation reaction was carried out in the system flow reactors high pressure containing 16 reactors. In a tube reactor made of alloy Hastelloy with built-in electric heating casing was placed from 0.6 ml of catalyst and 0.2 g of gamma-alumina as a preliminary layer. The reactor and heating the casing was placed in the heating chamber. The temperature of the catalyst layer was controlled by using the built-in electric heating casing and the temperature of the preliminary layer was controlled by means of a heating chamber. The reactor was heated at atmospheric pressure in a stream of nitrogen to 130°C in the heating chamber and maintained at the same temperature. Then we load the gas was changed to 80 mol. % carbon monoxide and 20 mol. % hydrogen and gauge pressure in the system was increased to 20 bar. Gas flow rate (CASH) on this and subsequent stages was equal to 5,000 hours During this time, the reactor was heated to 300°C at 3°C/min using a heating casing and then the system was kept under these conditions for 2 hours Then the carbonylation reaction initiated by loading dimethylcarbonate at a given speed and got gas loading, containing 76 mol. % of carbon monoxide, 19 mol. % hydrogen and 5 mol. % dimethyl ether. From the high-pressure reactor system the volumes through the needle valve has released a steady stream of exhaust gases of the reaction and the pressure was reduced to atmospheric pressure at a temperature equal to not less than 130°C, and the flow was passed through a gas chromatograph for analysis of the acetylated products of carbonyl (methyl acetate and acetic acid). Information on the reactions of carbonyl is shown in figure 1.

From the data shown in figure 1, it can be seen that the catalysts 3-6 lead to better value the website of altar servers for the products of the carbonylation compared with catalysts 1 and 2, which are not obtained in accordance with the present invention.

Example 2

This example demonstrates the effect on the carbonylation of dimethyl ether catalysts obtained by combining copper-containing mordenite with a binder (catalysts 9 and 10); catalysts obtained by mixing the mordenite with a binder associated with the formation of mordenite with the subsequent inclusion of copper in the associated mordenite (catalyst 7 and 8); and copper-containing mordenite catalyst without binder (catalyst 11).

Chinafill 200 (aluminosilicate clay, Amberge Kaolinwerke) used as a binder for receiving each of the catalysts 7-10. Chinafill 200 is characterized by metophorically, component <10 m2/g, mikroporistogo, component <10 m2/g, and a total content of metal impurities such as Na, K, CA, Mg and Fe, equal to 2.94 wt.%.

Each of the catalysts 9-11 had a copper content of 55 mol.% in terms of aluminum content in the IOE is Anita, for each catalyst, the mass ratio of catalyst: binder was 80:20.

Obtaining catalyst 7 (not in accordance with the present invention)

Repeating the obtaining of the catalyst 1 except that Chinafill 200 used as a binder instead of Pural SB.

Obtaining catalyst 8 (not in accordance with the present invention)

Repeating the obtaining of the catalyst 2, except that Chinafill 200 used as a binder instead of Pural SB.

Obtaining catalyst 9

Repeating the obtaining of the catalyst 3 with the exception that Chinafill 200 used as a binder instead of Pural SB.

Obtaining catalyst 10

Repeating the obtaining of the catalyst 5 with the exception that Chinafill 200 used as a binder instead of Pural SB.

Obtaining catalyst 11 (not in accordance with the present invention)

Copper-containing mordenite was obtained as described above, and then progulivali by the method of annealing described above. Upon receipt of this catalyst binder is not used.

Carbonylation of dimethyl ether

Each of the catalysts 7-11 used for the carbonylation of dimethyl ether according to the method of conducting the carbonylation reaction described in example 1.

Data for carbonylation reactions is shown in figure 2.

From the data given on IG, you can see that the catalysts obtained by the method proposed in the present invention (catalysts 9 and 10), for products of carbonylation lead to value the website of altar servers, significantly improved compared with catalysts containing a binder, but not obtained in accordance with the present invention (catalysts 7 and 8). The catalysts 9 and 10 also provide for acetylated products values the website of altar servers, improved compared with the binder-catalyst, the catalyst 11.

Example 3

Obtaining catalyst

The catalyst And is soaked in a suspension containing copper mordenite: a binder Pural SCF,

15 g of ammonium forms of mordenite silica: alumina ratio, equal to 20 (CBV21A, Zeolyst International) and C(NO3)2, 2,5H2O (2.67 g) was added to deionized water (40 ml) and was stirred for 12 h at room temperature. The solution/suspension was concentrated in vacuum at 80°C to remove most of the water, and then dried at 110°C for 20 h and got dry copper-containing mordenite. 8 g of dry copper-containing mordenite grinded and got loose powder. Powder and 2 g of binder Pural SCF (ex Sasol) was placed in a Buchi flask designed for drying of powder, and it was rotated in a rotary evaporator at a speed of 100 rpm at normal temperature and pressure for 1 h the ATEM contents of the flask were progulivali at 500°C for 3 h in an atmosphere of still air and received the catalyst A. The copper content in the catalyst And amounted to 55 mol.% in terms of aluminum content.

The catalyst is obtained by ion exchange of copper-containing mordenite: a binder Pural SCF

15 g ammonium form of mordenite with a ratio of silica: alumina constituting 20 (CBV21A, Zeolyst International)was added to aqueous solution of cu(NO3)2, 2,5H2O (1.07 g) in deionized water (150 ml) and stirred at 80°C for 2 hours and Then the resulting solution/suspension was filtered and the collected solid is washed with a large amount of deionized water (1.5 l per 10 g of catalyst). Then obtained using ion exchange copper containing mordenite was dried at 110°C for 20 h 8 g of dried copper-containing mordenite grinded and got loose powder. Powder and 2 g of Pural SCF (ex Sasol) was placed in a Buchi flask designed for drying of powder, and it was rotated in a rotary evaporator at a speed of 100 rpm at normal temperature and pressure for 1 h Then the contents of the flask were progulivali at 500°C for 3 h in an atmosphere of still air and received the catalyst Century, the copper Content in the catalyst was 55 mol.% in terms of aluminum content.

The catalyst is impregnated in the form of a suspension containing copper mordenite: a binder Chinafill 200

20 g ammonium form of mordenite with a ratio of silica:alumina, of 20 (CBV21A, Zeolyst International), and Cu(NO3)2, 2,5H2O (of 3.56 g) was added to deionized water (35 ml) and was stirred for 15 h at room temperature. The solution/suspension was concentrated in vacuum at 80°C to remove most of the water, and then dried at 110°C for 20 h and got dry copper-containing mordenite. 4 g of the dried copper-containing mordenite grinded and got loose powder. Powder and 1 g of the binder Chinafill 200 (ex Amberge Kaolinwerke) was placed in a Buchi flask designed for drying of powder, and it was rotated in a rotary evaporator at a speed of 100 rpm at normal temperature and pressure for 1 h Then the contents of the flask were progulivali at 500°C for 3 h in an atmosphere of still air and got catalyst C. the concentration of copper in the catalyst was 55 mol.% in terms of aluminum content.

Catalyst D obtained by ion exchange of copper-containing mordenite: Chinafill 200

4 g Ammonium form of mordenite with a ratio of silica: alumina constituting 20 (CBV21A, Zeolyst International)was added to aqueous solution of cu(NO3)2, 2,5H2O (0,286 g) in deionized water (40 ml) in an autoclave and stirred at 80°C for 2 hours, the Autoclave was placed in an oven for autoclave was rotated at high speed for 2 h at 80°C. Then, the autoclave was cooled to ambient temperature with the food. The resulting solution/suspension was filtered through a funnel with a porous filter and the collected solid is washed with a large amount of deionized water (1.5 l per 10 g of catalyst). Then the catalyst was dried at 110°C for 20 h and then was progulivali at 500°C for 3 h in an atmosphere of still air and got catalyst D. the copper Content in the catalyst D was 55 mol.% in terms of aluminum content.

Carbonylation of dimethyl ether

Each of the catalysts A - D were used to catalyse the carbonylation of dimethyl ether and carbon monoxide, as described below. Before using each of the catalysts was condensed under a pressure of 10 t in the mold size 13 mm using a pneumatic press, and crushed and sieved to obtain the fraction of particles ranging in size from 125 to 160 microns.

The carbonylation reaction was carried out in the system flow reactors high pressure, consisting of 16 identical reactors of the type described in WO 2005/063372. Prior to the introduction of catalyst into the reactor in the appropriate holder of the catalyst was placed a layer of steatite sieve fractions of 100-350 μm thickness of about 5 cm Top layer of steatite were placed area corundum sieve fraction 125-160 μm thickness of about 5 cm and Then on top of the layer of oxide was placed 0.625 g of catalyst based on the weight in the dry state(determined by loss of the catalyst during calcination by heating the catalyst from room temperature to 600°C at a constant speed, equal to approximately 30°C/min). The catalyst was covered with a layer of oxide with a thickness of approximately 5 cm with particle size 125-160 μm. On top of the layer of oxide was placed area of steatite sieve fractions of 100-350 μm thickness of about 5 cm Each zone to summarize, hitting or shaking, and have a stable layer and the zone of catalyst a certain initial height. Then, using a mixture of CO/H24/1 at a flow rate equal to 4.0 l/h, over a catalyst created a pressure of 70 bar, required for the reaction. Then the catalyst was heated to a constant temperature equal to 220°C at a rate of 0.5°C/min and this temperature was kept for 3 hours Then the temperature was linearly increased up to 300°C at a rate of 0.5°C/min, then maintained for 3 hours After the end of withstanding the load of the gas was replaced with a mixture of carbon monoxide, hydrogen and dimethyl ether WITH/N2/dimethyl ether comprising 72/18/10, at a flow rate equal to 4,275 l/h, and the download speed vapors of dimethyl ether was equal 0,4275 l/h, and received a mixture of CO/H2/dimethyl ether in a molar ratio of average 72/18/10. In addition, variable rate equal to 0-50 ml/min, injected nitrogen for equalization of pressure fluctuations in the output channels 16 reactors. From the test reactor output stream was passed through the gas chromatographs determine the concentrations of the reactants and products of the carbonylation. The reaction was carried out for 150 hours (for 148 hours for catalysts C and D) at a temperature of 300°C, a pressure of 70 bar, hour flow rate of gas (COG)equal 4275 h-1. The product of the carbonylation were mostly the acetate and formed only a small quantity of acetic acid. Table 1 shows the data for catalysts A - D after the reaction for 140 hours

Table 1
CatalystBinderBinder/wt.%Method for producing copper-containing mordeniteThe selectivity of the formation of Meoac/% (a)
AndPural SCF20The impregnation suspension88
InPural SCF20Ion exchange96
Chinafill20020The impregnation suspension89
DChinafill 200 20Ion exchange95

(a) the Selectivity of the formation of acetate in terms of the number affected by the conversion of dimethyl ether.

Comparison of catalysts b and D with catalysts a and C, respectively, shows that catalysts b and D, which are obtained through ion exchange, upon receipt of the acetate provide improved selectivity in comparison with the catalysts a and C, which are obtained by the impregnation suspension.

Example 4

Catalyst E containing copper mordenite

20 g ammonium form of mordenite with a ratio of silica: alumina constituting 20 (CBV21A, Zeolyst International), and Cu(NO3)2, 2,5H2O (of 3.56 g) was added to deionized water (50 ml) and was stirred for 12 h at room temperature. The solution was concentrated in vacuum at 80°C and then dried at 110°C for 20 h and then was progulivali at 500°C for 3 h in an atmosphere of still air. The mordenite had a copper content of approximately 55 mol. % in terms of Al contained in the mordenite.

Catalyst F - Containing copper mordenite: Pural SCF

15 g ammonium form of mordenite with a ratio of silica: alumina constituting 20 (CBV21A, Zeolyst International), and C(NR2)2, 2,5H2O (2.67 g) was added to deionized water (40 is l) and stirred for 12 h at room temperature. The solution was concentrated in vacuum at 80°C and then dried at 110°C for 20 h Mordenite had a copper content of approximately 55 mol. % in terms of aluminum contained in the mordenite. 8 g of the dried copper-containing mordenite carefully grinded and got loose powder. Powder and 2 g of Pural SCF (Sasol) was placed in a Buchi flask designed for drying of powder, and it was rotated in a rotary evaporator at a speed of 100 rpm at normal temperature and pressure for 1 h Then the contents of the flask were progulivali at 500°C for 3 h in an atmosphere of still air.

Carbonylation of dimethyl ether

Each of the catalysts E and F were used to catalyse the carbonylation of dimethyl ether using the method carbonyl described above in example 3. The results obtained after the reaction for 140 h are presented below in table 2.

Table 2
CatalystBinderBinder/wt.%Mordantly catalystThe website of altar servers for products acetylation/g·kg-1mordenite·h-1(a)
ENo 0C-mordenite805
FPural SCF20C-mordenite805
(a) the website of altar servers is expressed in the number of kilograms of mordenite in 1 h, excluding binder.

From table 2 one can see that the inclusion of a binder in copper-containing mordenite does not result in adverse modification of catalytic activity compared to containing copper mordenite without binder.

1. The way carbonylation of at least one Carboniferous reagent selected from the group comprising dimethyl ether and methanol, and carbon monoxide in the presence of a catalyst to obtain at least one carbonylation product selected from the group comprising methyl acetate and acetic acid, and the catalyst was prepared by combining mordenite, which includes at least one of the following: silver and copper, with an inorganic oxide binder.

2. The method according to claim 1, in which the Association containing the metal mordenite with a binder carried out using a slurry mixing or using dry mixing.

3. The method according to claim 1, wherein the mordenite, which includes at least oneof the following: silver and copper, calcined prior to mixing with the binder.

4. The method according to claim 1, wherein the catalyst is calcined.

5. The method according to claim 1, in which the binder is selected from the group comprising silica, aluminum oxide, aluminum silicates, magnesium silicates, magnesium silicates, titanium oxides, oxides of zirconium and clay.

6. The method according to claim 5, in which the binder is selected from the group including aluminum oxide and aluminum silicate.

7. The method according to claim 1, in which the binder is characterized by metophorically, measured by the BET method using nitrogen adsorption in the range from 1 to 500 m2/year

8. The method according to claim 1, in which the binder is characterized by mikroporistogo, measured by the BET method using nitrogen adsorption in the range from 1 to 100 m2/year

9. The method according to claim 1, in which the binder contains metals of group 1 and group 2 of the Periodic system of elements and iron in the full amount in the range from more than 0 to 10 wt.%.

10. The method according to claim 1, in which the binder is contained in the catalyst in amounts in the range from 10 to 80 wt.% in terms of the weight of the catalyst.

11. The method according to claim 1, wherein at least one of the following: copper, silver include mordenite using ion exchange.

12. The method according to claim 1, which is also used hydrogen.

13. The method according to claim 1, in which Carboniferous reage the fact is dimethyl ether and the method is carried out in an anhydrous environment.

14. The method according to claim 1, wherein the carbonylation product is acetate and at least a portion of the methyl acetate is hydrolyzed with the formation of acetic acid.



 

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FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of reducing formation of byproducts when producing methyl acetate, which involves carbonylation of dimethyl ether with carbon monoxide in one or more carbonylation reaction zones in the presence of a mordenite catalyst to obtain a methyl acetate product, characterised by that at least one of methyl acetate and acetic acid is fed into at least one of said reaction zones.

EFFECT: improved method of reducing formation of byproducts when producing methyl acetate.

17 cl, 5 dwg, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to improved method of increasing catalytic activity and/or selectivity in the process of obtaining product of methylacetate and/or acetic acid, which includes contact of carbonylated reagent, selected from dimethyl ether and methanol, with carbon monoxide in presence of catalyst, representing H-mordenite, bound with mesoporous binding agent, selected from silicon oxides, aluminium oxides, silicon oxides-aluminium oxides, magnesium silicates and magnesium-alumosilicates.

EFFECT: increased catalytic activity and/or selectivity.

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FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining acylated alkoxylate of secondary alcohol of formula R1-C(O)-(OA)n-OR2(I), in which R1 is linear or branched alkyl group, including from 1 to 30 carbon atoms, optionally substituted cycloalkyl group, which includes from 5 to 30 carbon atoms, or optionally substituted aryl group, including from 6 to 30 carbon atoms, OA stands for one or several oxyalkylene fragments, which can be similar or different, n stands for integer number in the range from 0 to 70, and R2 is linear or branched alkyl group, including from 4 to 32 carbon atoms, optionally substituted cycloalkyl group, including from 5 to 32 carbon atoms, or optionally substituted bicycloalkyl group, including from 7 to 32 carbon atoms, where claimed method includes: (i) interaction of one or several olefins with internal double bond with one or several carboxylic acids in presence of catalytic composition with obtaining one or several ethers of carboxylic acid; (ii) interaction of one or several ethers of carboxylic acid, obtained at stage (i), with one or several alkylene oxide reagents in presence of catalytically efficient quantity of catalytic composition, which includes: (a) one or several salts of alkali earth metals and carboxylic acids and/or hydroxycarboxylic acids, which include 1-18 carbon atoms, and/or hydrates of the former; (b) oxygen-containing acid, selected from sulfuric acid and orthophosphoric acid; (c) alcohol, containing from 2 to 39 carbon atoms; and/or products of (a), (b) and/or (c) interactions with obtaining one or several acylated alkoxylates of secondary alcohols.

EFFECT: invention also relates to methods of obtaining alkoxylates of secondary alcohols and alkoxy sulfates of secondary alcohols, including the claimed method.

10 cl, 4 ex, 1 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of increasing efficiency and catalyst stability when producing methyl acetate, involving carbonylation of dimethyl ether based material with carbon monoxide in virtually anhydrous conditions in the presence of a zeolite catalyst which is efficient in said carbonylation, wherein the reaction is carried out at temperature ranging from 275°C to 350°C, and in the presence of hydrogen.

EFFECT: high efficiency and catalyst stability.

14 cl, 9 ex, 4 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of increasing efficiency and selectivity when producing methyl acetate, involving carbonylation of material based on dimethyl ether with carbon monoxide in virtually anhydrous conditions in the presence of a zeolite catalyst which is efficient in said carbonylation, wherein the reaction is carried out at temperature ranging from higher than 250 to 350°C, and at pressure ranging from higher than 10 to 100 bar (isobar).

EFFECT: high efficiency and selectivity when producing methyl acetate.

15 cl, 11 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to chemical engineering and specifically to processing fusel oil, which is a large-tonnage waste in the alcohol industry. Fusel oil from production of ethyl alcohol is processed by esterification with glacial acetic acid in the presence of a sulphuric acid catalyst, and neutralisation, wherein esterification is carried out while boiling the reaction mixture and continuously separating water using a separating flask. The obtained product is separated from the catalyst under a vacuum at temperature not higher than 110°C. The obtained product and the catalyst are separately neutralised and the obtained product is additionally dried.

EFFECT: method enables to process fusel oil into a highly efficient component of mixed solvents of high quality with low cost of production and high output of the product.

4 cl

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of increasing catalytic activity when producing methyl acetate, involving carbonylation of dimethyl ether-based material with carbon monoxide in the presence of hydrogen in virtually anhydrous conditions at temperature ranging from more than 250°C to 350°C, in the presence of a zeolite catalyst which is efficient in said carbonylation, wherein concentration of dimethyl ether is at least 1 mol % with respect to the total amount of material.

EFFECT: improved method of increasing catalytic activity when producing methyl acetate.

13 cl, 4 ex, 3 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing C1-C3 aliphatic carboxylic acid and/or the corresponding ester, by carbonylating the corresponding C1-C3 aliphatic alcohol and/or an ester or ether derivative thereof with carbon monoxide material containing hydrogen, in the presence of a catalyst containing a zeolite having at least one 8-member ring channel, said 8-member ring channel being connected with a channel formed by a ring with greater than or equal to 8 members, said 8-member ring having a window size of at least 2.5 Å × at least 3.6 Å and at least one Bronsted acid site and that zeolite has a silicon dioxide: X2O3 molar ratio of not less than 5, where X is selected from aluminium, boron, iron, gallium and mixtures thereof with the condition that the zeolite is not mordenite or ferrierite. The catalysts demonstrate considerable carbonylation activity compared to other zeolite catalysts.

EFFECT: improved method of producing C1-C3 aliphatic carboxylic acid.

41 cl, 2 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts for producing methyl acetate and a method of producing methyl acetate. Described is a method of producing methyl acetate, involving carbonylation of dimethyl ether-based material with carbon monoxide with almost no water in the presence of a mordenite catalyst in which at least one of the following elements is introduced using an ion exchange or some other method: silver and copper, and in which platinum is also introduced into the mordenite via an ion exchange or some other method in amount of 0.05-10 mol % with respect to aluminium. Described is a catalyst for producing methyl acetate via carbonylation of dimethyl ether-based material with carbon monoxide in virtually anhydrous conditions, which is prepared via simultaneous ion exchange or saturation of the ammonium or hydrogen form of mordenite with platinum and at least one of the metals - silver and copper, drying and/or calcination of the mordenite which has been saturated or subjected to ion exchange, wherein the catalyst contains platinum in amount of 0.05-10 mol % with respect to aluminium and a catalyst prepared via ion exchange or saturation of the ammonium or hydrogen form of mordenite with at least one of the metals - silver and copper, drying and/or calcination of the mordenite which has been saturated or subjected to ion exchange to obtain copper- and/or silver-containing mordenite, followed by ion exchange or saturation of the copper- and/or silver-containing mordenite with platinum, wherein the catalyst contains platinum in amount of 0.05-10 mol % with respect to aluminium.

EFFECT: high catalytic activity.

15 cl, 1 tbl, 2 dwg, 2 ex

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

FIELD: chemistry.

SUBSTANCE: invention relates to improved method of increasing catalytic activity and/or selectivity in the process of obtaining product of methylacetate and/or acetic acid, which includes contact of carbonylated reagent, selected from dimethyl ether and methanol, with carbon monoxide in presence of catalyst, representing H-mordenite, bound with mesoporous binding agent, selected from silicon oxides, aluminium oxides, silicon oxides-aluminium oxides, magnesium silicates and magnesium-alumosilicates.

EFFECT: increased catalytic activity and/or selectivity.

15 cl, 6 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of increasing efficiency and catalyst stability when producing methyl acetate, involving carbonylation of dimethyl ether based material with carbon monoxide in virtually anhydrous conditions in the presence of a zeolite catalyst which is efficient in said carbonylation, wherein the reaction is carried out at temperature ranging from 275°C to 350°C, and in the presence of hydrogen.

EFFECT: high efficiency and catalyst stability.

14 cl, 9 ex, 4 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of increasing efficiency and selectivity when producing methyl acetate, involving carbonylation of material based on dimethyl ether with carbon monoxide in virtually anhydrous conditions in the presence of a zeolite catalyst which is efficient in said carbonylation, wherein the reaction is carried out at temperature ranging from higher than 250 to 350°C, and at pressure ranging from higher than 10 to 100 bar (isobar).

EFFECT: high efficiency and selectivity when producing methyl acetate.

15 cl, 11 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of increasing catalytic activity when producing methyl acetate, involving carbonylation of dimethyl ether-based material with carbon monoxide in the presence of hydrogen in virtually anhydrous conditions at temperature ranging from more than 250°C to 350°C, in the presence of a zeolite catalyst which is efficient in said carbonylation, wherein concentration of dimethyl ether is at least 1 mol % with respect to the total amount of material.

EFFECT: improved method of increasing catalytic activity when producing methyl acetate.

13 cl, 4 ex, 3 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing C1-C3 aliphatic carboxylic acid and/or the corresponding ester, by carbonylating the corresponding C1-C3 aliphatic alcohol and/or an ester or ether derivative thereof with carbon monoxide material containing hydrogen, in the presence of a catalyst containing a zeolite having at least one 8-member ring channel, said 8-member ring channel being connected with a channel formed by a ring with greater than or equal to 8 members, said 8-member ring having a window size of at least 2.5 Å × at least 3.6 Å and at least one Bronsted acid site and that zeolite has a silicon dioxide: X2O3 molar ratio of not less than 5, where X is selected from aluminium, boron, iron, gallium and mixtures thereof with the condition that the zeolite is not mordenite or ferrierite. The catalysts demonstrate considerable carbonylation activity compared to other zeolite catalysts.

EFFECT: improved method of producing C1-C3 aliphatic carboxylic acid.

41 cl, 2 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts for producing methyl acetate and a method of producing methyl acetate. Described is a method of producing methyl acetate, involving carbonylation of dimethyl ether-based material with carbon monoxide with almost no water in the presence of a mordenite catalyst in which at least one of the following elements is introduced using an ion exchange or some other method: silver and copper, and in which platinum is also introduced into the mordenite via an ion exchange or some other method in amount of 0.05-10 mol % with respect to aluminium. Described is a catalyst for producing methyl acetate via carbonylation of dimethyl ether-based material with carbon monoxide in virtually anhydrous conditions, which is prepared via simultaneous ion exchange or saturation of the ammonium or hydrogen form of mordenite with platinum and at least one of the metals - silver and copper, drying and/or calcination of the mordenite which has been saturated or subjected to ion exchange, wherein the catalyst contains platinum in amount of 0.05-10 mol % with respect to aluminium and a catalyst prepared via ion exchange or saturation of the ammonium or hydrogen form of mordenite with at least one of the metals - silver and copper, drying and/or calcination of the mordenite which has been saturated or subjected to ion exchange to obtain copper- and/or silver-containing mordenite, followed by ion exchange or saturation of the copper- and/or silver-containing mordenite with platinum, wherein the catalyst contains platinum in amount of 0.05-10 mol % with respect to aluminium.

EFFECT: high catalytic activity.

15 cl, 1 tbl, 2 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method for selective production of acetic acid and/or methyl acetate, with formation of small amounts of hydrocarbon by-products, involving bringing methanol and/or reactive derivative thereof, selected from dimethyl ether and methyl acetate, into contact with carbon monoxide in aqueous conditions in the presence of a ferrierite catalyst.

EFFECT: improved method for selective production of acetic acid and/or methyl acetate.

23 cl, 1 tbl, 15 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: 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 removing hydrocarbon impurities from an intermediate product of production of acetic acid, which includes extracting the intermediate product with a hydrocarbon extracting agent to form a light phase containing the hydrocarbon impurity and the extracting agent, and a heavy phase containing acetic acid, where the intermediate product contains methyl iodide, acetic acid, methyl acetate and the hydrocarbon impurity. The invention also relates to a method of producing acetic acid, which includes a) reacting methanol and carbon monoxide in the presence of a carbonylation catalyst, a catalyst stabiliser, methyl iodide, water and methyl acetate to obtain an acetic acid stream containing a hydrocarbon impurity; b) dividing, by flash evaporation, the acetic acid stream into a vapour stream containing acetic acid, water, methanol, methyl acetate, methyl iodide and the hydrocarbon impurity, and a liquid stream containing the catalyst and the catalyst stabiliser; c) dividing the vapour stream from step b) by distillation into a product stream containing acetic acid and water, and an overhead product containing methyl iodide, water, methyl acetate, acetic acid and the hydrocarbon impurity; d) condensing the overhead product from step c) to form a light aqueous phase containing water and acetic acid, methyl acetate and a heavy organic phase containing methyl iodide, acetic acid, water and the hydrocarbon impurity; e) distilling the heavy organic phase from step d) into a vapour stream containing methyl iodide, and a lower stream containing acetic acid, methyl iodide, water and the hydrocarbon impurity; and f) extracting the lower stream from step e) with a hydrocarbon extracting agent and forming a light phase containing the hydrocarbon impurity and the extracting agent, and a heavy phase containing methyl iodide, water and acetic acid.

EFFECT: improved method of removing hydrocarbon impurities from an acetic acid production intermediate product.

13 cl, 6 ex

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