Method of carbonylation with application of mordenite catalyst, applied on inorganic oxides

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

 

The present invention relates to related mordenite zeolites and their use as catalysts for carbonylation capable carbonyliron reagent such as dimethyl ether and methanol.

The mordenite belongs to the class of materials called zeolites. Patterns of a large number of zeolites including mordenite, are well known and defined, for example, in The Atlas of Zeolite Framework Types (C.Baerlocher, W.M.Meier, D.H.Olson, 5 ed. Elsevier, Amsterdam, 2001). The Internet version (http://www.iza-structure.org/databases/) is a directory of topological and structural characteristics of zeolites including mordenite.

In General, zeolites are used for the catalysis of many different chemical processes, including the processes for conversion of hydrocarbons and carbonylation of alcohols and the corresponding ethers and carbon monoxide with obtaining carboxylic acids and/or esters.

It was shown that mordenite associated with a bonding material, suitable for use as catalysts in processes for the conversion of hydrocarbons, such as TRANS-alkylation of aromatic hydrocarbons, as described in patent US 6486372, and hydrocracking of hydrocarbons with a high boiling point, which is described in the patent WO 97/13826.

In the patent US 4612387 describes a method for monocarboxylic acids and esters, including contact and the Finance of carbon monoxide and monohydroxy alcohol, containing from 1 to 4 carbon atoms, in the presence of a crystalline aluminosilicate zeolite, in which the ratio of silica:alumina is at least about 6, and the difficulties approximately from 1 to 12, at a pressure of at least 1 ATM.

It was also described that the mordenite is a catalyst for gas-phase carbonylation processes, in which as carbonyliron reagent used dimethyl ether. For example, in patent WO 2006/121778 described a method of obtaining a lower alkyl complex ester of a lower aliphatic carboxylic acids by carbonylation, essentially anhydrous conditions, lower alkyl simple ether such as dimethyl ether, carbon monoxide in the presence of mordenite or ferrierite catalyst. In patent WO 2006/121778 does not describe the use of mordenite associated with a bonding material.

Inorganic oxide binder materials, such as oxides of aluminum, oxides of silicon, oxides of silicon, oxides of aluminum, titanium oxides and the oxides of zirconium, usually considered inert and, therefore, one would expect that a certain amount of a catalyst associated with a bonding material, would have a lower catalytic activity than the same amount of catalyst, in which the binder mA is Arial missing. Unexpectedly it was found that the catalyst for the carbonylation of dimethyl ether or methanol containing mordenite in acid form, coupled with a mesoporous inorganic oxide that acts as a binder, has an improved catalytic properties, mainly in relation to the catalytic activity and/or selectivity, compared with catalytic properties, which has mordantly catalyst not containing a binder material.

Accordingly, the present invention provides a method of producing acetate and/or acetic acid, comprising contacting carbonyliron reagent selected from dimethyl ether and methanol with carbon monoxide in the presence of a catalyst comprising a H-mordenite associated with mesoporous binder selected from oxides of silicon, oxides of aluminum, oxides of silicon oxides, aluminum silicates, magnesium and manuallyselected.

The present invention also provides a method for application of mesoporous binder to improve the catalytic properties of H-mordenite at carbonyliron carbonyliron reagent selected from dimethyl ether and methanol, carbon monoxide, and in the specified carbonyliron as the catalyst used H-mordenite associated with the specified binder, the rich binder selected from oxides of silicon, oxides of aluminum, oxides of silicon oxides, aluminum silicates, magnesium and manuallyselected.

The catalyst is designed for use in the present invention include N-mordenites zeolite associated with mesoporous binder selected from oxides of silicon, oxides of aluminum, oxides of silicon oxides, aluminum silicates, magnesium and manuallyselected.

H-mordenite (it is also called acid or protonated form of mordenite) is available. Also available other forms of mordenite, for example sodium form or ammonium form. Sodium and ammonium forms of mordenite can be transformed into H-mordenite using well known techniques. For example, the ammonium form can be transformed into H-form by calcination of ammonium form at high temperature. The sodium form can be transformed into H-form as follows: first, to turn it into the ammonium form by ion exchange with ammonium salts, such as ammonium nitrate and then calcined ammonium form at high temperatures.

Usually the mordenite has a silica: alumina comprising from 10:1 to 100:1, and such mordenite suitable for use in accordance with the present invention. However, preferably the ratio of silica: alumina in the H-mordenite, suitable for skin which has, in the present invention, is from 10:1 to 40:1, for example from 15:1 to 30:1.

Preferably, the surface area of H-mordenite, measured by adsorption of nitrogen Brunauer-Emmett-teller (BET), ranging from 100 to 500 m2/year Measurement of surface area by the BET described Charles N. Satterfield in Heterogeneous Catalysis in Practice, McGraw-Hill Book Company, 1980, p.100-106.

For use as a catalyst in the method according to the present invention, H-mordenite associated with mesoporous binder selected from oxides of silicon, oxides of aluminum, oxides of silicon oxides, aluminum silicates, magnesium and manuallyselected. Associated H-mordenite can be obtained by combining H-mordenite with a binder or, in the alternative, the mordenite in the ammonium form can be joined with a binder and to retrieve the associated H-mordenite by annealing the joined mixture of ammonium mordenite/binder.

Mesoporous binder designed for use in the present invention, are selected, at least one substance from the group comprising the oxides of silicon, oxides of aluminum, oxides of silicon, oxides of aluminum, magnesium silicates and maniamerica. Oxides of aluminum or silicon oxide - aluminum oxide are particularly suitable. Examples of suitable oxides include aluminum oxide aluminum belanoha type and gamma-alumina. If used, the silicon oxide - oxide of al is MINIA, the content of silicon oxide, preferably ranges from 5 to 40 wt. -%, appropriately, from 5 to 10% of the mass. Preferably, the silicon oxide - aluminum oxide is amorphous.

Preferably, the binder is a heat-resistant inorganic oxide, that is, the inorganic oxide is stable at high temperature, and, specifically, is stable at temperatures which may be used in the calcination of the catalyst, i.e. at a temperature of at least 400°C., for example, at the temperature of 400 to 550°C.

A binder used in the present invention, is mesoporous. For the purposes of the present invention, the mesopores defined as pores with a diameter ranging from 2 to 50 nm, and the phrase "misoprostol" means the aggregate of the total surface area of mesopores and surface area of the binder, measured by the BET method based on nitrogen adsorption. Appropriately, misoprostol binder is from 1 to 500 m2/year

Preferably, the binder has a low microporosity. For the purposes of this invention, the micropores are defined as pores whose diameter is less than 2 nm, and the phrase "microporosity" understand the total surface area of micropores binder, measured by the BET method based on nitrogen adsorption. Appropriately, ICRI is the porosity of the binder is from 1 to 100 m 2/g, preferably from 1 to 10 m2/year

The amount of binder that can be used in the catalyst may vary, but this amount, as appropriate, such that yields the highest rate of carbonylation reaction. Suitably, the binder content is from 10 to 80% (based on weight of catalyst, preferably from 20 to 60% per weight of catalyst, or from 20 to 65%, based on the weight of the catalyst. Specifically, the content of the binder and the catalyst comprises from 35 to 65%, based on the weight of the catalyst. Appropriately, if the binder is an alumina, for example, bemany alumina, the content of the binder in the catalyst is from 35 to 65%, based on the weight of the catalyst.

It was found that a binder with a low content of metallic impurities such as iron and metals of groups 1 and 2 of the Periodic table of elements, for example sodium, potassium, calcium and magnesium, are particularly suitable for use in the present invention. Thus, preferably, the total content of metal impurities in the binder is from more than 0 to 10 wt. -%, more preferably from more than 0 to 7% of the mass.

In a particularly preferred embodiment of the present invention, the binder is an alumina or oxide, PU glue, the I - aluminum oxide having mesoporosity constituting from 50 to 500 m2/g microporosity, constituting less than 10 m2/g, and comprising metals of groups 1 and 2 and of the iron group, the total content of which ranges from 0 to 1 wt. -%, preferably, from 0 to 0.2 wt. -%, moreover, the content of the binder in the catalyst is from 10 to 80%, based on the weight of the catalyst.

In General, the catalyst is designed for use in the present invention, can be obtained by forming a homogeneous mixture of a binder and N-form or ammonium form of mordenite by, for example, suspension or dry mixing the binder and mordenite components.

After mixing associated mordenite can be ignited. In General, the calcination is carried out at a temperature of from 400 to 500°C, but can be applied at higher temperatures, for example up to 550°C. Before use, the calcined catalyst can be compressed, grind and sift with receiving units.

One way to obtain the catalyst of the present invention consists in a suspension mixing of mordenite and a binder. Suspension mixing can be accomplished by mixing mordenite, binder and deionized water over a period of time necessary to obtain wet homogeneous mass or suspe the Ziya. After that, the suspension is dried, for example at a temperature of from 80 to 120°C for several hours to remove excess water and all or essentially all physically adsorbed water. Drying can be performed at atmospheric pressure or under reduced pressure. Optionally, before drying the wet mass or suspension, it can be molded by pressing, extruding or pelletizing to obtain balls, extrudates or granules. The dried slurry or suspension in a molded form can then be calcined at a temperature of from 400 to 550°C., for from about 1 to about 10 hours to obtain a catalyst.

Alternatively, the catalyst can be obtained by dry mixing mordenite and binders. Dry mixing can be accomplished by thoroughly mixing mordenite powder and dry binder associated with the formation of mordenite. Dry mixing can be accomplished in any suitable way, for example, by processing in the drum or rotation. Then the associated mordenite can be ignited.

The calcination can be carried out at a temperature of from 400 to 550°C., for from about 1 to about 10 hours to obtain a catalyst.

The catalyst used in the method of producing methyl acetate and/or acetic acid way the carbonyl carbon monoxide carbonyliron reagent, selected from dimethyl ether and methanol.

If carbonyliron reagent is dimethyl ether, it can be essentially pure or may contain a small amount of inert impurities. In commercial scale dimethyl ether produced by the catalytic conversion of synthesis gas (mixtures of hydrogen and carbon monoxide) over catalysts for methanol synthesis and dehydrogenation of methanol. This catalytic transformation yields a product that represents mainly dimethyl ether, which, however, may contain some amount of methanol. When used in the method according to the present invention, the raw materials based on the dimethyl ether may contain a small amount of methanol, provided that the amount of methanol in the feedstock is insufficient to inhibit the carbonylation of dimethyl ether, which yields the final acetate. It was found that the permissible content of methanol in the feedstock on the basis of dimethyl ether is 5% of the mass. or less, for example, 1% of the mass. or less.

Alternatively, dimethyl ether can be obtained in situ from any suitable source, such as dimethylcarbonate. For example, it is possible to carry out the contacting liquid dimethylcarbonate with gamma-alumina with the purpose of decomposition of dimethylcarbonate on dimitrovi the ether and carbon dioxide.

Suitably, the concentration of dimethyl ether in the gaseous raw material is from 0.1 to 20 mol%. in calculating the total number of gaseous raw materials (including recycled substances).

The carbon monoxide can be an essentially pure carbon monoxide, for example carbon monoxide, usually supplied by the suppliers of industrial gases, or it may contain impurities that do not affect the transformation carbonyliron reagent in the carbonylation product, such as nitrogen, helium, argon, methane and/or carbon dioxide.

Optionally, the method carbonylation of the present invention can be performed in the presence of hydrogen. Consequently, as appropriate, raw materials based on carbon monoxide may also contain hydrogen. A mixture of hydrogen and carbon monoxide produced in commercial scale by steam reforming of hydrocarbons, partial oxidation of hydrocarbons. Such mixtures are commonly referred to as synthesis gas. The synthesis gas consists of mainly carbon monoxide and hydrogen, but it may also contain smaller amounts of carbon dioxide.

Suitably, the molar ratio of carbon monoxide:hydrogen can be from 1:3 to 15:1, for example from 1:1 to 10:1.

If the process is hydrogen, the partial pressure may be, at IU is e, 0.1 bar (Rel.), for example from 1 to 30 bar (Rel.).

The molar ratio of carbon monoxide to carbonyliron reagent, in a suitable manner, is from 1:1 to 99:1, such as from 2:1 to 60:1.

If carbonyliron reagent represents methanol, in situ will be generated water from the reaction of dimerization of methanol with the formation of ethers or by the esterification reaction of methanol end of acetic acid. If necessary, water can be added to a methanol feedstock. The amount of added water may be such that the molar ratio of methanol:water ranged from 50:1 to 2:1. Water can be fed separately or jointly with methanol feedstock. Water can be fed in liquid form or in the form of steam.

When carbonyliron dimethyl ether to obtain methyl acetate water in situ is not formed. It has been found that water inhibits carbonylation of dimethyl ether with the formation of acetate. Thus, the water content is maintained at the minimum possible level. Preferably, therefore, the carbonylation of dimethyl ether is carried out in anhydrous conditions. To achieve this, dimethyl ether, carbon monoxide and the catalyst is preferably dried before use in the method. However, it is possible to prevent the presence of water in small quantities without negative impact on education bromide is the Etat. Appropriately, the water content of the gaseous raw material fed to the process may be at least 2.5% of the mass. or less, for example 0.5% mass. or less based on the total weight of the gaseous raw materials (including recycled substances).

Suitably, the method according to the present invention can be carried out at the temperature of from 100 to 400°C., for example from 150 to 350°C.

The method according to the present invention can be performed at a pressure of from 1 to 100 bar (Rel.), for example from 10 to 100 bar (Rel.).

Hourly space velocity of gas (COG), as appropriate, is from 500 to 40000 h-1for example, from 2000 to 20000 h-1.

It is preferable to activate the catalyst prior to use by heating the catalyst at an elevated temperature for at least one hour in a stream of nitrogen, carbon monoxide, hydrogen or mixtures of the above.

Preferably, the method according to the present invention is carried out essentially in the absence of halides such as iodide. The term "essentially" is understood that the total content of the halide, such as iodide, in the gaseous reagents (carbonyliron the reagent and carbon monoxide and the catalyst is less than 500 hours per million, preferably less than 100 h/million

Suitably, the method according to the present invention done by the keys by passing a vaporous carbonyliron reagent, gaseous carbon monoxide and, optionally, gaseous hydrogen through a fixed bed, fluidized bed or moving bed of the catalyst, supported at the desired temperature and pressure.

If necessary, you can contact carbonyliron reagent with a layer of aluminum oxide, such as corundum, which is located immediately before the catalyst bed.

The products of the method according to the present invention are acetate and/or acetic acid. If carbonyliron reagent represents methanol, the main product of the carbonylation will be acetic acid, but can also produce small quantities of methyl acetate, depending on the degree of conversion of methanol. If carbonyliron reagent is dimethyl ether, the main product of the method is the acetate, but may form small amounts of acetic acid. Obtained by the method according to the present invention, acetic acid and/or acetate can be downloaded in the form of vapor, then condensing into liquid form.

In addition to acetic acid and methyl acetate, the product stream of the process according to the present invention may also include unreacted dimethyl ether and/or unreacted methanol.

The acetate and/or acetic acid can you elati from the stream of products using traditional techniques such as distillation.

The acetate can be sold as such or it can be used in other chemical processes. For example, at least a portion of the final acetate can be subjected to hydrolysis with the formation of acetic acid.

Alternatively, at least a portion of the total flow of the products of the method according to the present invention, including acetate, can be used for stage hydrolysis, which from him then emit acetic acid.

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

Acetic acid, isolated from the product stream of the present invention or obtained subsequently by hydrolysis of methyl acetate, can be cleaned using conventional cleaning methods, such as distillation.

The operation of the method according to the present invention can be performed in continuous or batch mode, preferably in a continuous mode.

Hereinafter the present invention will be illustrated with reference to the examples below.

Example 1

Obtaining catalyst

A series of catalysts, comprising 80% of the mass. H-mordenite and 20% of the mass. binder calculated on the total weight of the catalyst, prepared in accordance with method 1 to obtain a catalyst or ways is ω 2 preparation of the catalyst, described below.

Detailed information about the applied binder, the type and sources listed in the following table 1. Physical and chemical properties of the binder are shown in table 2.

Method 1 preparation of the catalyst

Mixing 8 g of ammonium forms of mordenite in which the ratio of silicon oxide to aluminum oxide was 20 (CBV21A set Zeolyst), and 2 g of binder. Added a sufficient amount of deionized water to obtain a thick slurry, and the mixture was thoroughly stirred. The suspension was dried in an oven at 110°C for at least 20 h, after which he progulivali in a furnace in air under static conditions. The calcination was carried out by increasing the temperature from room temperature up to 90°C at 3°C/min and held at this temperature for 2 hours and Then the temperature was increased to 110°C with a speed of approximately 0.6°C/min and held at this temperature for 2 hours Finally, the temperature was increased to 500°C with a speed of about 3.3°C/min and held at this temperature for 3 h, after which gave substance to cool to room temperature. Before using the calcined catalyst was pressed with a force of 12 tons using molds with a diameter of 33 mm on a Specac press, and then crushed and sieved to obtain fractions of particles with size from 250 to 500 microns.

How 2 get catalysis of the ora

4 g ammonium form of mordenite in which the ratio of silicon oxide to aluminum oxide was 20 (CBV21A set Zeolyst), in powder form was mixed with 2 g of the binder in the test tube for drying powder Buchi 500 ml and was rotated at a speed of 100 rpm at room temperature and pressure for 1 h Then the mixture was progulivali in accordance with the methodology described above for method 1 to obtain a catalyst. Before using the calcined catalyst was pressed with a force of 12 tons using molds with a diameter of 33 mm on a Specac press, and then crushed and sieved to obtain fractions of particles with size from 250 to 500 microns.

*impurity metals are Na, K, CA, Mg and Fe. It should be noted that for the binder constituting the silicates of magnesium or maniamerica, magnesium is not considered a metal impurity.

The carbonylation reaction

Each of the N-mordenite catalysts obtained using each of the binders listed above in table 1, was used to catalyse the carbonylation reaction of dimethyl ether, described next. Also experienced H-mordenite (calcined CBV21A set Zeolyst), not containing the binder. The carbonylation reaction was carried out in a flow reactor under pressure, including 16 react the ditch. The reaction pipe, made of alloy and Hastelloy equipped with built-in electric heating jacket, was filled with 0.6 ml of the catalyst and 0.2 g of the preliminary layer of gamma-alumina. The reactor and the heating jacket mounted on the unit, placed in a heated enclosure. The temperature of the catalyst layer was controlled by means of internal heating jacket, and the temperature of the preliminary layer was controlled by means of the heated enclosure. The reactor, located in a heated enclosure was heated at atmospheric pressure in a stream of nitrogen to 130°C and maintained at this temperature. The composition of the gaseous raw material was changed so that it included 80 mol%. of carbon monoxide and 20 mol%. hydrogen, and the system pressure was set at 20 bar (Rel.). Gas flow rate (CASH) in these and all subsequent stages was 5000 h-1. The reactor was heated up to 300°C with a heating rate of 3°C per minute, and the reactor was maintained in these conditions for two hours, after which began the implementation of the carbonylation reaction by introducing into the reactor a gaseous feedstock comprising 76% mole. carbon monoxide, 19 mol%. hydrogen and 5 mol%. dimethylcarbonate. From the reactor at high pressure, unloaded a steady stream of effluent gases, reducing the pressure to atmospheric when the fact is the temperature value, at least 130°C and direct the flow into the gas chromatograph for analysis of acetyl products (acetate and acetic acid).

The results of carbonylation reactions listed in the following table 3. Hour volume output (COV) acetyl products was calculated as follows:

COW acetyl products =COV Asón+60/74 * COW Meoac

COW acetyl products (g·kgcat-1·h-1) represents COV calculated on the total weight of H-mordenite and a binder.

COW acetyl products (g·kgMor-1·h-1dstanley COW in calculating the masses of H-mordenite, part of the combined mixture of H-mordenite and a binder.

Table 3
BinderThe method of producing catalystCOW acetyl products (g·kgcat-1·h-1) after 20 hCOW acetyl products (g·kgMor-1·h-1)after 20 h
No (only H-mordenite)181181
Actigel1 206258
Pural SB1346 (a)433 (a)
M 970151206257
Chinafill 2001253 (b)317(b)
Chinafill 1001186232
Pural SB2357446
Chinafill 1002186233
Kaolin (Aldrich)2210262
Kaolin (Zeochem)2258322
Siral 52412515
Siral 102375469

BinderThe method of producing catalystCOW acetyl products (g·kgcat-1·h-1)after 20 hCOW acetyl products (g·kgMor-1·h-1)after 20 h
Siral 202292365
Siral 402318397
Puralox THl00/1502338422
Puralox SCFa-1402342427
Catalox HTFa-1012367459
Montmorillonite K-102317396
Pansil 4002370463
Bentonite 2277346
Ludox2310387

(a) the Result is the arithmetic mean based on two trials in carbonyliron;

(b) the Result is the arithmetic mean based on three tests in carbonyliron.

In addition, he carried out a series of the above carbonylation reactions, which were carried out in the presence of a binding, but in the absence of H-mordenite. When testing any of the binding reaction of carbonyl was observed. Tested binder was a Pural SB, Siral 5, Siral 10, Siral 40, Chinafill 200, Puralox SCFa-140, kaolin, montmorillonite K-10 and Pansil 400.

From the results listed in the above table 3, it is seen that N-mordenite catalysts containing a binder, have a higher catalytic activity compared to N-mordenite catalyst not containing the binder.

Example 2

Preparation of catalyst

Catalyst A - H-mordenite

10 g ammonium form of mordenite with respect to the silica:alumina constituting 20 (CBV21A, Zeolyst International)was progulivali at 500°C for 3 h in air under static conditions with obtaining H-mordenite.

Catalyst B - H-mordenite: PuralSCF (80:20)

8 g ammonium form of mordenite with respect to the silica:alumina constituting 20 (CBV21A, Zeolyst International), and 2 g of binder Pural SCF (Sasol) were placed in a test tube for drying powder Buchi. These two powder was mixed using a rotary evaporator at 100 rpm for 1 h at the temperature and pressure environment. A mixture of ammonium form of mordenite with a binder then progulivali for 3 h at 500°C in air under static conditions with obtaining the catalyst. Pural SCF is bemany aluminum oxide, mesoporosity which is 237 m2/g microporosity is less than 10 m2/g, and the total content of metal impurities is 0.02% of the mass.

The catalyst Is H-mordenite: Pural SCF (50:50)

Repeating the method of preparation of the catalyst B, with the difference that used 10 g of ammonium form of mordenite with respect to the silica:alumina constituting 20 (CBV21A, Zeolyst International)and 10 g of Pural SCF (Sasol).

Catalyst G - H-mordenite: Siral 5 (50:50)

Repeating the method of preparation of the catalyst B, with the difference that used 10 g of ammonium form of mordenite with respect to the silica:alumina constituting 20 (CBV21A, Zeolyst International)and 10 g of binder Siral 5 (Sasol).

Catalyst D - H-mordenite: Siral 5 (20:80)

Repeating the method of preparation of the catalyst B, with the difference that applied 2 g ammo the applications form of mordenite with respect to the silicon oxide:aluminum oxide, components 20 (CBV21A, Zeolyst International), and 8 g of binder Siral 5 (Sasol).

Carbonylation of dimethyl ether

Each of the catalysts a to D were used to catalyse the carbonylation of dimethyl ether with carbon monoxide in the presence of hydrogen using the device and method described below. Before using 0.75 g of each catalyst was pressed with a pressure of 10 tons using a 13 mm of the mold for a pneumatic press, and then crushed and sieved to obtain the fraction with a particle size of from 125 to 160 microns.

The carbonylation reaction was carried out in a flow reactor under pressure, including 16 of the same reactors of this type, which is described in the patent WO 2005063372. Before loading the catalyst into the reactor, in the appropriate holder of the catalyst was placed a layer of steatite 5 cm thick with a particle size of from 100 to 350 μm. The top layer of steatite were placed area oxide thickness of 5 cm with a particle size of from 125 to 160 microns. Then on top of the layer of oxide was placed a sample of the catalyst mass 0.625 g dry matter (determined on the basis of weight loss during calcination of the corresponding sample, measured by heating the catalyst from room temperature to 600°C at 30°C per minute). The catalyst was covered with a layer of oxide with a thickness of 5 cm with the size of the part is from 125 to 160 microns. On top of the layer of oxide was placed a layer of steatite 5 cm thick with a particle size of from 100 to 350 μm. Each zone was condensed by tapping or vibration with the aim of obtaining a stable layer and a specific initial height of the area of the catalyst. The pressure in the reactor in the zone of the catalyst was increased to the reaction average of 70 bar, serving WITH/N2when the molar ratio of 4:1 and flow rate 4 l/H. Then the catalyst was heated at a rate of 0.5°C/min to 220°C, and this temperature was maintained for 3 h, and then increased to 300°C at a rate of 0.5°C/min and kept catalyst for 3 hours After that, the feed gas was changed to a mixture of carbon monoxide, hydrogen and dimethyl ether at a molar ratio of 72:18:10 at a flow rate of component 4,275 l/h nitrogen Gas was introduced at a variable speed component from 0 to 50 ml/min, with the purpose of equalization of pressure fluctuations in the 16 outputs of the reactors. The exit stream of the reactor is sent to a gas chromatograph to determine the concentration of the reactants and products of the carbonylation. The reaction was continued for 169 h at 300°C, 70 bar, and time flow rate of gas (COG), component 4275 h-1. On the basis of gas chromatographic analysis of the exit stream of the reactor contents acetate (Meoac), time volumetric output (COV) methyl end is Zetta was determined in grams of acetate per kilogram of catalyst per hour. The carbonylation product, mainly represented acetate, formed only a small amount of acetic acid. The results of carbonylation reactions are shown below in table 4.

Table 4 shows the results for catalysts a to D after 140 hours

Siral 5
Table 4
CatalystBinderBinder, % of the mass.COW Meoac, g·kg-1catalyst·h-1(a)COW Meoac, g·kg-1mordenite·h-1(b)
AndNo0199199
BPural SCF20753941
InPural SCF507801560
GSiral 5506401280
D802841420

(a) COV expressed per kilogram of catalyst, including H-mordenite and a binder;

(b) COV expressed per kilogram of H-mordenite in an hour, not counting the binder.

From table 4 it is seen that the use of H-mordenite together with a binder Pural SCF or Siral 5 significantly improves the activity of H-mordenite, compared with H-mordenite, containing no binder.

Example 3

Catalyst E - copper-containing mordenite

20 g ammonium form of mordenite with respect to the silica:alumina constituting 20 (CBV21A, Zeolyst International), and C(BUT3)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 under vacuum at 80°C and then dried at 110°C for 20 h, after which he progulivali at 500°C for 3 h in air under static conditions. The copper content in the mordenite was about 55 mol%. in the calculation contained in the mordenite A1.

Catalyst W - copper-containing mordenite: Pural SCF (80:20)

15 g ammonium form of mordenite with respect to the silica:alumina constituting 20 (CBV21A, Zeolyst International), and C(BUT3)2·2,5H2O (2.67 g) was added to deionized water (40 ml) and was stirred for 12 h at to matnog temperature. The solution was concentrated under vacuum at 80°C and then dried at 110°C for 20 hours, the copper Content in the mordenite was about 55 mol%. in the calculation contained in the mordenite A1. 8 g of dry copper-containing mordenite gently crushed with obtaining free flowing powder and then placed in a test tube for drying powder Buchi together with 2 g of Pural SCF (Sasol), and then rotated on a rotary evaporator at a rate of 100 rpm for 1 h at the temperature and pressure environment. Then a mixture of copper-containing mordenite and binder progulivali at 500°C for 3 h in air under static conditions.

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 2. The results for catalysts E and F compared with catalysts a and B after 140 h of the reaction is shown below in table 5.

(a) COV expressed per kilogram of catalyst, including mordenite and a binder;

(b) COV expressed per kilogram of mordenite in an hour, not counting the binder;

(C) the Selectivity of the formation of acetate is given in the calculation into dimethyl ether.

When considering table 5 shows that the compound N-morden is the one with the bonding agent (catalyst B) markedly improves the activity of H-mordenite (catalyst A), while the introduction of the binder in the copper-containing mordenite (catalyst G) reduces the activity of copper-containing mordenite.

When connecting H-mordenite (catalyst A) with a binder (catalyst B) high selectivity of the formation of acetate is saved, however, when connecting a copper-containing mordenite (catalyst E) with a binder (catalyst G) the selectivity of the formation of acetate is reduced.

Moreover, comparison of catalyst B (linked H-mordenite) with catalyst W (associated copper-containing mordenite) shows that these catalysts have similar activity, but the catalyst B is significantly more selective in respect of acetate.

Example 4

To determine the effect of the amount of binding at the catalytic properties of H-mordenite at carbonyliron was conducted several experiments. In accordance with the method of preparation of catalyst B (in the above example 2) was prepared by several catalysts containing from 10 to 80% of the mass. binder Pural SCF (Sasol) and screened them to produce a fraction with a particle size of from 125 to 160 microns. The catalytic properties of these catalysts, and catalyst A (H-mordenite prepared in accordance with the above-described example 2) was tested in carbonyliron dimethyl ether. The carbonylation reaction carried out the AK, as described in example 1 with the use of 1.95 g of the catalyst and a gaseous raw material containing 6 mol%. dimethyl ether is 0.5 mol%. methyl acetate and carbon monoxide and hydrogen at a molar ratio of 4:1. Reaction conditions carbonylation were as follows: 300°C, 70 bar and CASH, component 4000 h-1. Results after 140 h of the reaction is shown below in table 6.

(a) COV expressed per kilogram of catalyst, including H-mordenite and a binder;

(b) COV expressed per kilogram of N-mordenite per hour, not counting the binder;

(C) the Selectivity of the formation of Meoac given in the calculation of transformed DME.

From table 6 it is seen that with the increasing content of the binder in the catalyst activity mordenite catalytic component also increases, until it reaches the maximum when the binder content of about 65% of the mass.

1. The way to increase catalytic activity and/or selectivity upon receipt of the product methyl acetate and/or acetic acid, comprising contacting carbonyliron reagent selected from dimethyl ether and methanol with carbon monoxide in the presence of a catalyst comprising a H-mordenite associated with mesoporous binder selected from oxides of silicon, oxides of aluminum, is of xadow silicon - oxides of aluminum, magnesium silicates and manuallyselected.

2. The method according to claim 1, in which the binder is selected from oxides of aluminium and silicon oxides - oxides of aluminum.

3. The method according to claim 2, in which the aluminum oxide is bemany aluminum oxide.

4. The method according to claim 2, in which the content of silicon oxide in the silicon oxide - aluminum oxide is from 5 to 40 wt. -%

5. The method according to claim 1 or 2, in which misoprostol binding, determined by the BET method based on nitrogen adsorption, is from 1 to 500 m2/year

6. The method according to claim 1 or 2, in which microporosity binding, determined by the BET method based on nitrogen adsorption, is from 1 to 100 m2/year

7. The method according to claim 1 or 2, in which the binder contains metals of groups 1 and 2 of the Periodic table of elements and iron, total number of which is from more than 0 to 10 wt. -%

8. The method according to claim 1 or 2, wherein a content of the binder in the catalyst is from 10 to 80% of the mass. based on the weight of the catalyst.

9. The method according to claim 1, in which H-mordenite associated with the alumina, the content of which is from 35 to 65% of the mass. calculated on the total weight of H-mordenite and a binder.

10. The method according to claim 1, in which H-mordenite bound with a binder based on alumina or silica - alumina, mesoporosity which ranges from 50 to 500 m2 /g microporosity which is less than 10 m2/g, it contains a total of from 0 to 1% of the mass. metals of group 1, group 2, and iron, and the content of the binder in the catalyst is from 10 to 80% of the mass. based on the weight of the catalyst.

11. The method according to claim 10, in which the binder contains a total of from 0 to 0.2% of the mass. iron, metals of group 1 and group 2 of the Periodic table of elements.

12. The method according to claim 1 or 2, in which carbonyliron reagent is a dimethyl ether.

13. The method according to item 12, in which the process is carried out in anhydrous conditions.

14. The method according to claim 1 or 2, in which in the process also contains hydrogen.

15. The method according to claim 1 or 2, in which the product of the method comprises acetate and at least a portion of the final acetate is subjected to hydrolysis to obtain acetic acid.



 

Same patents:

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 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 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 method of obtaining acetic acid, which includes: (a) carbonylation of methanol in presence of catalyst to form reaction mixture; (b) instant evaporation and distillation of reaction mixture in evaporator, equipped with distillation column to form liquid flow, including catalyst, from evaporator boiler, and steam flow from upper part of distillation column, and (c) return of liquid flow into the cycle to stage (a), with steam flow being distilled in stripping column to form bottom flow of raw acetic acid and flow of distillate steam, which is condensed and separated into light phase and heavy phase, part of light phase is introduced into the top part of evaporator distillation column, and liquid flow is withdrawn from the bottom of evaporator distillation column and directed to the top of stripping column to obtain practically pure acetic acid.

EFFECT: increased method efficiency.

11 cl, 2 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: method includes the following stages: a) bringing methanol and/or its reaction-capable derivative and carbon momoxide into first reaction zone, containing liquid reaction composition, which includes carbonylation catalyst, optionally, promoter of carbonylation catalyst, methyl iodide, methyl acetate, acetic acid and water; b) removal of, at least, part of liquid reaction composition together with dissolved and caught carbon monoxide and other gases from first reaction zone; c) supply of, at least, part of removed liquid reaction composition into second reaction zone, in which, at least, part of dissolved and/or caught carbon monoxide is consumed; d) supply of, at least, part of liquid reaction composition from second reaction zone into zone of evaporative separation with formation of: vapour fraction, which includes acetic acid, methyl iodide, methyl acetate and low-pressure waste gas, including carbon monoxide; and liquid fraction, which includes carbonylation catalyst and, optionally, carbonylation catalyst promoter; e) supply of vapour fraction from zone of evaporative separation into one or more distillation zones for removal of final acetic acid, with temperature of liquid reaction composition, removed from first reaction zone, constituting from 170 to 195°C; and temperature of liquid reaction composition, supplied from second reaction zone into zone of evaporative separation, is, at least, 8°C higher than temperature of liquid reaction composition, removed from first reaction zone.

EFFECT: improvement of method of acetic acid obtaining with improved output.

21 cl, 1 dwg, 1 tbl, 5 ex

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