Method of producing carbonylation products

FIELD: chemistry.

SUBSTANCE: invention relates to a novel catalyst for use in synthesis of aliphatic carboxylic acid containing (n+1) carbon atoms, where n denotes an integer of up to 6, and/or an ether derivative thereof by bringing an aliphatic alcohol containing n carbon atoms, and/or reactive derivative thereof, selected from dialkyl ether, ester of alcohol and alkyl halide, into contact with carbon monoxide, where said catalyst is prepared via ion exchange or saturation of the ammonium or hydrogen form of mordenite with silver, drying the saturated/ion exchange-treated mordenite and subsequent calcination of the dried silver-containing mordenite at temperature from 500 to 600°C. The invention also relates to a method of producing aliphatic carboxylic acid containing (n+1) carbon atoms, where n denotes an integer of up to 6, and/or an ether derivative thereof, which involves bringing the aliphatic alcohol containing n carbon atoms and/or reactive derivative thereof, selected from dialkyl ether, ester of alcohol and alkyl halide, into contact with carbon monoxide in the presence of said catalyst.

EFFECT: improved selectivity with respect to carbonylation products.

22 cl, 2 tbl, 16 ex

 

The object of the present invention is a method for carbonylation products, such as aliphatic carboxylic acids and/or derivatives thereof by reaction of the corresponding alcohol and/or its reactive derivative with carbon monoxide in the presence of metal-containing mordenite catalyst.

Obtaining acetic acid from methanol and carbon monoxide is well known by the carbonyl process, which is carried out on an industrial scale. The process of obtaining acetic acid on an industrial scale can be carried out as a homogeneous liquid phase process, in which the carbonylation reaction catalyze soluble radioiodine complex and alkylation, such as methyliodide.

The main disadvantages of this method are the use of iodide, which can lead to corrosion problems and difficulties associated with separation from one phase products and catalytic components. Both of these disadvantage could be eliminated if it would be possible to develop a heterogeneous gas-phase method using free iodides of the solid catalyst.

In GB 1185453 describes some of multiphase catalysts comprising a catalytically active metal, including, inter alia, copper, rhodium and iridium deposited on materials-a wide range of media, to cat the eye include silica, alumina, charcoal, zeolites, clays and polymers. These multiphase catalysts are presented as those that can be used in heterogeneous gas-phase carbonyliron of methanol to acetic acid in the presence of a halide promoter. A similar method is described in GB 1277242, although none of the patent examples of application are given in such a process of zeolites.

In the US 4612387 describes a method for monocarboxylic acids and esters, comprising the contacting of the carbon monoxide with a monohydroxy alcohol containing from 1 to 4 carbon atoms, in the presence of a crystalline aluminosilicate zeolite having a ratio of silica to alumina of at least about 6, and an index of permeability in the range of from 1 to 12 under pressure of at least 1 at. The most preferred zeolites in accordance with this definition are ZSM-5, ZSM-11, ZSM-12, ZSM-38 and ZSM-35, and particularly preferred ZSM-5.

In J.Catalysis, 71, 233-43 (1981) described the application of photoelectron spectroscopy (ASHA) for determining the activity of rhodium mordenite catalyst and other printed on the media rhodium catalysts in relation to the carbonylation of methanol to acetic acid.

In DE 3606169 describes a method for acetic acid, methyl acetate and/or dimethyl ether by carbonyliron besod the CSOs methanol, methyl acetate and/or dimethyl ether in the presence of cobalt containing zeolites or zeolites, mixed with cobalt salts. This carbonylation not necessarily hold in the presence of halide.

The preferred zeolites are described as belonging to Penthesilea type, pore sizes which are intermediate between the sizes of the pores of the zeolite And on the one hand, and zeolites X and Y, on the other.

In EP-A-0596632 describes a method for aliphatic carboxylic acid by the introduction of alcohol or its reactive derivative in contact with carbon monoxide essentially in the absence of Halogens or their derivative, in the presence of a catalyst consisting essentially of mordenite zeolite, in which a preliminary ion exchange or otherwise impose copper, Nickel, iridium, rhodium or cobalt, characterized in that the process is carried out at a temperature in the range from 300 to 600°C. and under a pressure in the range from 15 to 200 bar. From the work carried out in EP-A-0596632, it was found that the mordenite containing the included copper provides the best results in terms of selectivity.

In WO 01/07393 describes a method of catalytic conversion of starting material comprising carbon monoxide and hydrogen, to obtain the at least one alcohol, simple ester and mixtures thereof and the reaction of carbon monoxide with at measures is one of alcohol, simple ether and mixtures thereof in the presence of a catalyst selected from solid perkiset, heteropolyacids, clays, zeolites and molecular sieves, in the absence of a halide promoter, under conditions of temperature and pressure sufficient to obtain at least one of ester, acid, acid anhydride and mixtures thereof. However, examples of the application of zeolites to catalyze the carbonylation reaction is not given.

In WO 2005/105720 describes a method for carboxylic acids and their derivatives by carbonyliron alcohol or its derivative with mordenite catalyst, in which a preliminary ion exchange or otherwise impose copper, Nickel, iridium, rhodium or cobalt and which as modifying the frame elements contains one or more of gallium, boron and iron.

Taking into consideration the above-mentioned known technical solutions, a problem that must be solved is to develop a heterogeneous gas-phase method of obtaining carboxylic acids and/or derivatives of the alcohols or their derivatives and carbon monoxide using containing metal zeolite catalyst, surpassing the best ways carried out using the above-described mordenite zeolites.

It was found that mordenites zeolite (hereinafter designated as mordenite), in which the pre-injected silver, provides superior selectivity for products of carbonylation (in relation to the carboxylic acid and/or its derivatives).

Accordingly, an object of the present invention is a method for aliphatic carboxylic acid containing (n+1) carbon atoms, where n denotes an integer up to 6, and/or its ether complex as a derivative, which comprises contacting an aliphatic alcohol containing n carbon atoms, and/or its reactive derivative with carbon monoxide in the presence of a catalyst which consists of a mordenite in which the ion exchange or otherwise introduced silver.

In the method according to the present invention using a modified silver mordantly catalyst to achieve good output values of carboxylic acids and their derivatives. It was determined that increased activity and/or selectivity with respect to the product can be achieved using mordenite, which is pre-modified silver.

In the method according to the present invention an aliphatic alcohol or its reactive derivative carbonylic carbon monoxide. The method is particularly applicable to aliphatic alcohols containing up to 6, in particular up to 3, carbon atoms. The preferred alcohol is methanol.

Reactive p is osvitnye such alcohol which can be used alternatively or in addition, alcohol include dialkyl ethers, esters of alcohol and alkylhalogenide. Acceptable reactive derivatives of methanol, for example, include methyl acetate, dimethyl ether and methyliodide. Can also be used a mixture of alcohol and its reactive derivative, for example a mixture of methanol and methyl acetate.

The product of such a process can be an aliphatic carboxylic acid and/or ester of aliphatic carboxylic acid. For example, when the alcohol is methanol, the product consists mainly of acetic acid, but it may also include some amount of acetate. When the reagent is used as a simple ether, the product is mainly ester. For example, when the reagent is dimethyl ether, the product is usually a mainly acetate.

The method in the preferred embodiment, is carried out in the presence of water. Source material, including alcohol, ester or ether, or any combination of them, may also include water. In a suitable embodiment, the molar ratio of alcohol/water, in particular methanol/water is in the range from 50:1 to 2:1, in particular from 10:1 to 3:1. When source material used slo is hydrated ether or a simple ester, such as methyl acetate or dimethyl ether, the molar ratio of water to ether complex or simple ether in a suitable embodiment is in the range from 1:1 to 1.5:1.

Water can be fed separately or jointly with alcohol and/or reactive derivative. Water can be in liquid or vaporous form.

Depending on the nature of the source material, water can be obtained in situ, for example by the reaction of an alcohol starting material to ethers or by esterification of the alcohol obtained with acetic acid. In a useful embodiment, the amount of water may be so, in which the ratio of alkyl groups, derivatizing from the spirit of the source material to water is less than or equal to 1.

The purity of the used carbon monoxide is particularly critical value, apparently, has not, although it is necessary to apply the gas mixture, in which the main component is carbon monoxide. The presence of small amounts of impurities such as nitrogen and inert gases, may be valid. Carbon monoxide can be used in a mixture with hydrogen. In a suitable embodiment, the ratio JI/N2is in the range from 1:3 to 15:1 in terms of molar basis, in particular from 1:1 to 10:1. For example, in the method according to the present invention may be the also used a mixture of carbon monoxide and hydrogen, produced by reforming or partial oxidation of hydrocarbons (synthesis gas).

The catalyst used in the method according to the present invention, is mordantly zeolite, in which a preliminary ion exchange or otherwise impose silver. The structure of mordenite is well known and defined, for example, in the work of the 'Atlas of Zeolite Structure Types' by W M Meier and D H Olson, published by the Structure Commission of the International Zeolite Association in 1978, It is, moreover, characterized by a permeability index of 0.4 and the ratio of silica to alumina in the range of from 8:1 to 20:1. Specialists in the art it is well known that the ratio of silicon dioxide to aluminum oxide can be increased using methods dealumination, for example, hydrothermal treatment or acid leached mordenite. The mordenite has a characteristic powder x-ray that specialists in this field of technology is well known.

Preferred for implementing the method of the present invention, the mordenite has a ratio of silicon dioxide to aluminum oxide in the range from 10:1 to 30:1, more preferably in the range from 15:1 to 25:1, and most preferably in the range from 18:1 to 22:1.

Before use as a catalyst in the mordenite by ion exchange or alternatively enter the silver. Put the e in the silver mordenite can be made by any method, such as the well known methods of ion exchange, impregnation and saturation to the initial moisture content. If the mordenite is necessary to saturate the ion exchange are 100% capable of casinoonline plots, the exchange with the cations Ag+the zeolite can be carried out using well known techniques. In the preferred embodiment, other cations in mordenite after ion exchange are the protons, resulting in the exchange process it is convenient to start with the ammonium or hydrogen form.

Alternatively, the ion exchange ammonium or hydrogen form of mordenite can be impregnated with a solution of silver salts and subsequently dried. In a preferred embodiment, after the introduction of metal or ion exchange mordenite calicivirus, for example in air at high temperature, in particular from 500 to 600°C.

The silver content can be expressed in terms of the degree of substitution on a molar basis, of atoms of aluminum (ion-exchange sites) of silver mordenite. In a preferred embodiment, the quantities used are to prepare a catalyst having a silver content of from 1 to 200 mol % in terms of unit volume of aluminum, in particular from 50 to 150 mol %, in particular from 50 to 120 mol%, and from 50 to 80 mol %. 100 mole % of silver equal to the content of silver 14,18 wt.%.

Mordenite, in addition to the atom is silicon and aluminum, may contain zeolite framework additional elements. Such modifying the frame elements can be, for example, gallium and/or iron.

Modifying the frame elements can be introduced into the frame by any conventional means. For example, the mordenite may be synthesized using acceptable precursors of silicon, aluminum and modifying the frame elements. Thus, in particular, modified gallium mordenite can be prepared by reaction between the components of a mixture comprising white carbon, gallium nitrate and sodium aluminate. Acceptable methods of obtaining described, for example, in WO 05/105720.

When using the modifying the frame element, in a suitable embodiment, the mordenite may have a ratio of silica to oxide of modifying the frame element in the range from 10:1 to 50:1.

In a preferred variant of the method according to the present invention is carried out by passing vapors of methanol and gaseous carbon monoxide through a fixed or fluidized bed of catalyst maintained in the target conditions of temperature and pressure.

In an expedient embodiment, the method is carried out at a temperature in the range from 200 to 600°C., preferably from 250 to 400°C.

In an expedient embodiment, the method is carried out under a gauge pressure in the range from 10 to bar, preferably from 10 to 150 bar, in particular from 25 to 100 bar.

The molar ratio of carbon monoxide to alcohol, such as methanol or its reactive derivative in a suitable embodiment is in the range from 1:1 to 99:1, in particular from 1:1 to 30:1.

Hourly average gas flow rate (SPG) in a suitable embodiment is in the range from 500 to 15000 h-1in particular from 2000 to 10000 h-1.

Before applying mordantly the catalyst is activated by, for example, extracts mordenite catalyst for at least one hour at an elevated temperature in a stream of nitrogen, carbon monoxide or hydrogen.

If necessary, immediately before the layer mordenite catalyst alcohol and/or reactive derivative as the starting material can be introduced into contact with the layer of aluminum oxide or corundum.

In a preferred variant of the method according to the present invention is carried out essentially in the absence of halides such as iodide. The term "essentially" mean that the content of the halide, such as iodide, in the source gas and the catalyst is less than 500 ppm million, and preferably less than 100 ppm million

The process can be conducted either in a fixed bed, fluidized bed, or in the movable layer.

The process can be conducted Lieb is continuous, any periodic process, preferably as a continuous process.

Carbolic acid, obtained according to the method of the present invention, can be removed in the form of steam and then condensed to liquid. This carboxylic acid may be purified by conventional methods such as distillation.

When the product of the process is an ester such as methyl acetate, it can be isolated and used per se as the source material for other chemical processes or it can be hydrolyzed to the corresponding carboxylic acid using known techniques such as reactive distillation.

The invention is further illustrated with reference to the following examples.

Examples 1 to 3

Obtaining And preparation of H-mordenite

Mordenite with a ratio of silicon dioxide to aluminum oxide 20 (company Sud-chemie) was pressed under a pressure of 12 tons in a mortar with pestle and then sieved with the separation fraction with a particle size of from 125 to 160 microns. Next, 2.5 g of mordenite was caliciviral at a temperature of 600°C in air with a heating rate of 1°C/min to a temperature of 500°C, kept at 500°C for 30 min, the temperature was increased at a rate of 1°C/min up to 550°C, kept at 550°C for 30 min, then increased speed/min up to 600°C and kept at 600°is within 180 minutes

Getting B - preparation of mordenite Cu (55)

Mordenite with a ratio of silicon dioxide to aluminum oxide 20 (company Sud-Chemie) was treated with a solution of copper acetate to the molar content corresponding to replace 55% of the protons attached to the acid sites, the copper, with the copper content 4,88 wt.%. 1810 μl of a solution of 1.0 mol/l of copper acetate was mixed with 465 μl of water. To calculate the amount of water adsorbed on mordenite, in order to determine the number of solution of the metal required to achieve the target content of copper, has established a PPP (loss on ignition, 600°C), mordenite (usually from 10 to 20%, in this case 13%). The solution was well mixed using an automatic distribution system. Then the mordenite was impregnated with a solution of copper acetate. After impregnation, the mordenite was left in ambient conditions on a shaker for 2 hours After shaking containing copper mordenite was transferred into a drying oven with forced convection (air atmosphere) at 80°C and kept for 20 hours After the stage of drying the contained copper mordenite was caliciviral in air and heated at a rate of 1°C/min to a temperature of 500°C, kept at 500°C for 30 min, then the temperature was increased at a rate of 1°C/min up to 550°C, kept at 550°C for 30 min, then increased at a rate of 1 the C/min up to 600°C and kept at 600°C for 180 min and then cooled to ambient conditions in air flow. Further, the contained copper mordenite sieved to obtain particles with sizes in the range from 125 to 160 microns.

Getting In the preparation of mordenite Ag (55)

The process according to the method of preparation B was repeated, except that instead of copper acetate for the impregnation process used Ag nitrate in such quantities, which reached values of Ag content corresponding to the substitution of protons in the mordenite 55 mol %.

The carbonylation reaction

Each of the samples mordenite catalyst with Ni, Cu and Ag, prepared as above, was used to obtain products of the carbonylation carbonyliron of methanol with carbon monoxide. These experiments were conducted in a pressure flow reactor, consisting of 16 identical reactors of this type, as described, for example, in WO 2005063372. Before loading the sample of catalyst in the reactor layer of corundum sieve fractions from 125 to 160 microns was placed in an appropriate container for the sample catalyst. 1-ml sample of the catalyst was placed over a layer of oxide. A sample of the catalyst is covered with a layer of oxide with a particle size of from 250 to 500 μm. Next above the sample catalyst with assistance FROM the pressure brought up to the target reaction level of 30 bar at a flow rate of 66,66 ml/min Then the catalyst was heated at a rate of 0.5°C/mi is up to temperature aging at 220°C, at which it was sustained during the period of exposure 3 hours later the temperature was increased to 300°C at a rate of 0.5°C/min with subsequent cooling-off period of 3 hours At this point, the activation of the catalyst is considered completed and included a gas mixture of carbon monoxide and hydrogen with the value of the ratio of CO/H24 at a flow rate of 66,66 ml/min and simultaneously in the form of steam was filed methanol at a flow rate of 40 ml/min to achieve the ratio of CO:H2:Meon all original material is approximately 80:20:1 in terms of molar basis. To balance the pressure fluctuations between the outputs of the 16 reactors were also introduced by the nitrogen with a variable speed from 0 to 50 ml/min Exited from the reactor stream is sent to a gas chromatograph to determine the concentration of the reactants and products of the carbonylation.

In example 1, the reaction was allowed to continue for 84,2 h under conditions of 300°C, 30 bar, an average hourly rate of gas supply (SSPG) 4000/h with a ratio of CO:H2:Meon in the source material 79,2:19,8:1. After 84,2 h supply Meon increased from 1 to 2 mol % with achievement of the ratio of CO:H2:Meon in the source material 78,4:19,6:2 and the reaction was continued for a total of 155, 2mm o'clock

In example 2, the reaction was allowed to continue for 164,4 h under conditions of 300°C, 30 bar, the hourly average speed of hearth and gas (SPG) 4000/h with a ratio of CO:H 2:Meon in the source material 79,2:19,8:1. After 164,4 h supply Meon increased from 1 to 2 mol % with achievement of the ratio of CO:H2:Meon in the source material 78,4:19,6:2 and the reaction was continued for a total of 233,3 PM

In example 3, the reaction was allowed to continue for 168,9 h under conditions of 300°C, 30 bar, an average hourly rate of gas supply (SSPG) 4000/h with a ratio of CO:H2:Meon in the source material 79,2:19,8:1. After 168,9 h supply Meon increased from 1 to 2 mol % with achievement of the ratio of CO:H2:Meon in the source material 78,4:19,6:2 and the reaction was continued for a total of 239,3 PM

The results of examples 1 to 3 (respectively, H-mordenite, the mordenite content C to 55 mol % and mordenite with Ag content of 55 mol %) are shown below in table 1.

Examples 4 to 16

Preparation of mordenite with Cu at values of 5 and 110 mol %

The experiment above, the method of preparation B was repeated, except that the impregnation process instead of copper acetate used copper nitrate, Cu(NO3)2·3H2O, in such quantities, which reached values of Cu content, equivalent substitution of protons in the mordenite 5 and 110 mol %.

Preparation of mordenite with Ag at values of 5 and 110 mol %

Experimental the above method of preparation B was repeated, except that the impregnation process instead of copper acetate used the silver nitrate in such quantities, which reached values of the content of Ag, equivalent substitution of protons in the mordenite 5 and 110 mol %.

Preparation of mordenite with Ir

The experiment above, the method of preparation B was repeated, except that the impregnation process instead of copper acetate was used hydrate trichloride iridium, IrCl3·hydrate, dissolved in water (treated by boiling under reflux for ~20 h), in such quantities, which reached values of Ir content, equivalent substitution of protons in the mordenite 5, 55 and 110 mol %.

Preparation of mordenite with Ni

The experiment above, the method of preparation B was repeated, except that the impregnation process instead of copper acetate used Nickel nitrate, Ni(NO3)2·6H2O, in such quantities, which reached values of Ni, equivalent substitution of protons in the mordenite 5, 55 and 110 mol %.

The receipt of the products of the carbonylation

Each of the samples mordenite catalyst with Cu, Ag, Ni and Ir, prepared as above, and H-mordenite and mordenite catalysts with Cu (55), Ag (55), prepared as described above in the preparation processes are appropriate to estwenno And, B and C, was used as a catalyst in carbonyliron of methanol with carbon monoxide. The carbonylation reaction was carried out using the above-described examples 1 to 3 of the method using a source material in a molar ratio of CO:H2:Meon 79,2:19,8:1. The results of examples 4 and 16 after approximately 40 h working cycle is presented below in table 2.

Table 2
ExamplePromotor metalThe metal content (%)Duty cycle (h)ODA on the Asón (g·kg-1·h-1))ODA in MeOAc (g·kg-1·h-1))ODA to aceticum (kg-1·h-1))
4no039,213,028,035,7
5Ag541,0to 43.131,668,8
6 Cu542,07,539,839,8
7Ir541,8to 47.2of 5.451,6
8Ni540,112,831,238,1
9Ag5540,691,524,2111,1
10Cu55of 40.938,145,575,0
11Ir5540,023,14,026,4
12Ni5540,6 60,9to 38.391,9
13Ag11040,786,125,0106,4
14Cu11041,775,016,388,2
15Ir11036,3a 21.514,7the 33.4
16Ni11039,854,646,492,2

ODA to aceticum is total ODA (volumetric capacity of catalyst) on MAOIs and Asón in Asón equivalents, i.e. ODA on acetyll equal ODA on Asón+{ODA, Meoac×(60,05/74,08)}.

As shown by the data in table 2, the use of mordenite with Ag provides results superior to the results achieved with the use of mordenite containing Cu, Ir and Ni, and N-Mord is Nita.

1. The catalyst for use in preparation of aliphatic carboxylic acids containing (n+1) carbon atoms, where n denotes an integer up to 6, and/or its ether derived by introduction of aliphatic alcohol containing n carbon atoms, and/or its reactive derivative, selected from dealkiller ester, complex ester alcohol and alkylhalogenide, in contact with carbon monoxide, where the said catalyst is prepared by ion exchange or by impregnation with ammonium or hydrogen form of mordenite silver, drying the impregnated/treated by ion exchange of mordenite and subsequent calcining the dried containing silver mordenite at a temperature of from 500 to 600°C.

2. The catalyst according to claim 1, wherein the mordenite has a molar ratio of silica/alumina from 10 to 30:1 and a silver content of from 50 to 150 mol.% per unit volume of aluminum.

3. The method of obtaining aliphatic carboxylic acid containing (n+1) carbon atoms, where n denotes an integer up to 6, and/or its ether derivative, which comprises contacting an aliphatic alcohol containing n carbon atoms, and/or its reactive derivative, selected from dealkiller ester, complex ester alcohol and alkylhalogenide, with carbon monoxide in the presence of a catalyst according to claim 1 or 2.

4. The method according to P3, in which the mordenite is characterized by a silver content of from 1 to 200 mol.% per unit volume of aluminum.

5. The method according to claim 4, in which the mordenite is characterized by a silver content of from 50 to 150 mol.% per unit volume of aluminum.

6. The method according to claim 3, in which the mordenite has a molar ratio of silica/alumina from 10:1 to 30:1.

7. The method according to claim 3, in which the mordenite contains modifying the frame element selected from at least one of gallium and iron.

8. The method according to claim 7, in which the mordenite has a molar ratio of silica/oxide modifying the frame element from 10:1 to 50:1.

9. The method according to claim 3, in which the alcohol is a methanol.

10. The method according to claim 3, in which alcohol and/or reactive derivative immediately before the layer mordenite catalyst is introduced into contact with the layer of aluminum oxide or corundum.

11. The method according to claim 3, in which carbon monoxide is used in a mixture with hydrogen.

12. The method according to claim 3, in which in the process also enter the water.

13. The method according to claim 3, in which the process is carried out essentially in the absence of halides.

14. The method according to claim 3, in which the process is carried out at a temperature of from 200 to 600°C.

15. The method according to 14, in which the process is carried out at a temperature of from 250 to 400°C.

16. The method according to claim 3, in which the process is performed under a pressure of from 10 to 200 bar.

17. The method according to clause 16, in which the process is performed under a pressure of 25 to 100 bar.

18. The method according to claim 3, in which the hourly average gas flow rate ranges from 2000 to 10000 h-1.

19. The method according to claim 3, in which the process is conducted as a continuous process.

20. The method according to claim 3, in which the process is performed as the process in a fixed bed, fluidized bed or a moving layer.

21. The method according to claim 3, in which the carboxylic acid is an acetic acid.

22. The method according to claim 3, in which the process is a process of obtaining acetic acid by the introduction of methanol into contact with carbon monoxide in the presence of hydrogen at a temperature of from 250 to 400°C. and under a pressure of 25 to 100 bar and in which the mordenite contains from 50 to 150 mol.% silver per unit volume of aluminum.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing acetic acid comprising the following steps: (a) carbonylation of methanol and/or reactive derivative thereof with carbon monoxide in a first reaction zone containing a liquid reaction mixture which contains a carbonylation catalyst and a promoter metal for the carbonylation catalyst, methyl iodide, methyl acetate, acetic acid and optionally water, where the liquid reaction mixture contains, in equilibrium, at least a first soluble catalytic material with a promoter metal and a second soluble catalytic material with a promoter metal, wherein among the materials which are in equilibrium, the first catalytic material with a promoter metal is the least promoter active; (b) outputting from said first reaction zone the liquid reaction mixture together with dissolved and/or trapped carbon monoxide and other gases; (c) optionally passing said output liquid reaction mixture through one or more successive reaction zones for using up at least a portion of the dissolved and/or trapped carbon monoxide; (d) directing said liquid reaction mixture from step (b) and optional step (c) to one or more steps for separation through single equilibrium evaporation to obtain a vapour fraction which contains condensable components and a low-pressure exhaust gas, where the condensable components contain the obtained acetic acid, methyl iodide, methyl acetate and optionally water, and the low-pressure exhaust gas contains carbon monoxide and other gases which are dissolved and/or trapped by the output liquid reaction mixture; and a liquid fraction which contains the carbonylation catalyst, the promoter metal for the carbonylation catalyst and acetic acid as a solvent; (e) returning the liquid fraction from the step for separation through single equilibrium evaporation to the first reaction zone; (f) determining (I) concentration of the first catalytic material with a promoter metal and/or (II) the ratio of concentration of the first catalytic material with a promoter metal to concentration of the second catalytic material with a promoter metal which are in equilibrium with each other, contained in the liquid reaction mixture at any of steps (a) to (d) and/or contained in the liquid fraction at step (e); and (g) maintaining (I) and/or (II) lower than a predetermined value.

EFFECT: present invention enables to optimise the process of producing acetic acid through carbonylation of methanol and/or a reactive derivative by maintaining concentration of the first catalytic material and/or the ratio of concentration of the first to the second catalytic material lower than a value where the negative effect could have been on one or more of such parameters as rate of reaction, selectivity, stability or service life of the catalyst.

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28 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing acetic acid, which is conversion of methanol and its reactive derivative in the presence of carbon monoxide and a rhodium-based catalyst system consisting of: (i) rhodium; (ii) a halogen promoter; (iii) an iodide salt as a co-promoter in concentration which ensures concentration of the iodide ion higher than 3 wt % of the reaction mixture; and (iv) a metal salt as a stabiliser, selected from a group consisting of ruthenium salts, tin salts and mixtures thereof; wherein the reaction mixture contains 0.1-14 wt % water; and wherein the ruthenium salt, tin salt or mixtures thereof are present in the reaction mixture in molar ratio of combined ruthenium and tin to rhodium between 0.1:1 and 20:1. The metal salt as a stabiliser minimises deposition of rhodium metal when extracting the product - acetic acid - particularly in an evaporation apparatus in the acetic acid separation process. Stability of rhodium metal is achieved even when producing acetic acid in a reaction mixture with low content of water in the presence of an iodide salt as a co-promoter in a concentration which ensures concentration of the iodide ion higher than approximately 3 wt % of the reaction mixture.

EFFECT: improved method of producing acetic acid via a catalytic carbonylation reaction.

8 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: method involves carbonylation of methanol and/or its reactive derivative with carbon monoxide in at least one carbonylation reaction zone, containing al liquid reaction composition which contains an iridium carbonylation catalyst, acetic acid, methyl acetate, ruthenium - promoter, and indium - catalyst system stabiliser, selected from indium, where the molar ratio iridium/promoter/stabiliser in the liquid reaction composition is kept in the interval 1:(from >2 to 15):(from 0.25 to 12).

EFFECT: using of indium as a catalyst system stabiliser in a method of producing acetic acid.

1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing ethylene, and ethylene and acetic acid from initial gas containing ethane and oxygen when said gas gets into contact with a MoaVvTaxTeyOz catalyst, in which a equals 1.0, v ranges from approximately 0.01 to approximately 1.0, x ranges from approximately 0.01 to approximately 1.0, y ranges from approximately 0.01 to approximately 1.0 and z is the number of oxygen atoms required to transform the catalyst into an electrically neutral state.

EFFECT: use of the methods enables to obtain said products with high selectivity and high output in a single step in unit time under reaction conditions.

30 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: method involves the following steps: (a) separation of a carbonylation product to obtain a gaseous overhead fraction containing acetic acid, methanol, methyl iodide, water, methyl acetate and at least one permanganate reducing compound, including acetaldehyde and less volatile fractions of catalyst; (b) distillation of the gaseous overhead fraction to obtain purified acetic acid and a low-boiling gaseous overhead fraction containing methanol, methyl iodide, water, acetic acid, methyl acetate and at least one permanganate reducing compound, including acetaldehyde; (c) condensation of the low-boiling gaseous overhead fraction and its separation into a condensed heavy liquid fraction which contains methyl iodide and methyl acetate and a condensed light liquid fraction containing water, acetic acid and at least one permanganate reducing compound, including acetaldehyde; (d) distillation of the light liquid fraction in a separate distillation column to obtain a second gaseous overhead fraction containing methyl iodide and at least one permanganate reducing compound, including acetaldehyde, and residue containing a fraction of high-boiling liquid containing methyl acetate, water and acetic acid, where the second gaseous overhead fraction is rich in permanganate reducing compounds relative the light liquid fraction; (e) condensation of the second gaseous overhead fraction containing methyl iodide and at least one permanganate reducing compound, including acetaldehyde, and aqueous extraction of the condensed stream to obtain a stream of an aqueous solution containing permanganate reducing compounds, including acetaldehyde, and a raffinate containing methyl iodide.

EFFECT: selective extraction and reduced amount of permanganate reducing compounds.

20 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to improved combined methods of producing acetic acid and vinyl acetate involving the following steps: (a) obtaining a first stream of product from the first reaction zone containing acetic acid, where the acetic acid is obtained via an exothermic carbonylation reaction, and where at least part of the heat obtained from the acetic acid is tapped from the first reaction zone and at least part of the heat tapped during production of acetic acid is transferred to a heat exchange system; (b) bringing the reaction stream of acetic acid containing at least a portion of acetic acid from the first stream of product into contact an oxygen-containing gas in a second reaction zone in the presence of a catalyst to obtain a second stream of product which contains vinyl acetate monomer; (c) directing at least a portion of the second stream of product to purification section for purification of at least a portion of vinyl acetate in the second stream of product; and either (d) tapping at least part of heat transferred to the heat exchange system, and delivering at least part of the heat tapped from the heat exchange system to at least one reaction stream of acetic acid and the vinyl acetate purification section, and where the heat exchange system contains a stream of a steam condensate, and where at least part of the heat tapped during production of acetic acid is delivered to the stream of steam condensate which is used to provide at least one reaction stream of acetic acid and the vinyl acetate purification section with heat tapped during production of acetic acid, where the stream of steam condensate containing heat from production of acetic acid is directed to a low-pressure evaporation vessel kept at pressure between 4.0 kg/cm2 and 5.3 kg/cm2, or (d) tapping at least part of the heat transferred to the heat exchange system, and delivering at least part of heat tapped from the heat exchange system to at least one reaction stream of acetic acid and the vinyl acetate purification section, in which a loop is used to cycle the condensate in order to remove most of the heat from production of acetic acid by directing a stream of a hot reaction solution through the heat exchanger for transferring heat to the stream of steam condensate, where the stream of steam condensate which contains heat from production of acetic acid is directed to the low-pressure evaporation vessel kept at pressure between 4.0 kg/cm2 and 5.3 kg/cm2.

EFFECT: proposed methods are useful for lowering expenses and reducing power consumption during vinyl acetate production.

10 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing acetic acid comprising the following steps: (a) carbonylation of methanol and/or reactive derivative thereof with carbon monoxide in a first reaction zone containing a liquid reaction mixture which contains a carbonylation catalyst and a promoter metal for the carbonylation catalyst, methyl iodide, methyl acetate, acetic acid and optionally water, where the liquid reaction mixture contains, in equilibrium, at least a first soluble catalytic material with a promoter metal and a second soluble catalytic material with a promoter metal, wherein among the materials which are in equilibrium, the first catalytic material with a promoter metal is the least promoter active; (b) outputting from said first reaction zone the liquid reaction mixture together with dissolved and/or trapped carbon monoxide and other gases; (c) optionally passing said output liquid reaction mixture through one or more successive reaction zones for using up at least a portion of the dissolved and/or trapped carbon monoxide; (d) directing said liquid reaction mixture from step (b) and optional step (c) to one or more steps for separation through single equilibrium evaporation to obtain a vapour fraction which contains condensable components and a low-pressure exhaust gas, where the condensable components contain the obtained acetic acid, methyl iodide, methyl acetate and optionally water, and the low-pressure exhaust gas contains carbon monoxide and other gases which are dissolved and/or trapped by the output liquid reaction mixture; and a liquid fraction which contains the carbonylation catalyst, the promoter metal for the carbonylation catalyst and acetic acid as a solvent; (e) returning the liquid fraction from the step for separation through single equilibrium evaporation to the first reaction zone; (f) determining (I) concentration of the first catalytic material with a promoter metal and/or (II) the ratio of concentration of the first catalytic material with a promoter metal to concentration of the second catalytic material with a promoter metal which are in equilibrium with each other, contained in the liquid reaction mixture at any of steps (a) to (d) and/or contained in the liquid fraction at step (e); and (g) maintaining (I) and/or (II) lower than a predetermined value.

EFFECT: present invention enables to optimise the process of producing acetic acid through carbonylation of methanol and/or a reactive derivative by maintaining concentration of the first catalytic material and/or the ratio of concentration of the first to the second catalytic material lower than a value where the negative effect could have been on one or more of such parameters as rate of reaction, selectivity, stability or service life of the catalyst.

13 cl 1 dwg, 2 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: method of carbonylating an alcohol and/or reactive derivative thereof includes the following steps: (a) feeding one or more streams of starting materials into a reaction zone, where at least one stream of starting materials of the reaction zone includes an alcohol and/or reactive derivative thereof and at least one stream of starting materials of the reaction zone includes carbon monoxide; (b) maintaining temperature and pressure in the reaction zone which is sufficient to enable flow of an exothermic carbonylation reaction to obtain a carboxylic acid and/or carboxylic acid anhydride; (c) removal from the reaction zone of one or more product streams containing carboxylic acid and/or carboxylic acid anhydride; (d) transferring heat contained in at least part of one or more product streams to a first heat-exchange stream. Heat is transferred from a second heat-exchange stream to the stream of starting materials of the reaction zone at step (a) before directing said stream of initial materials of the reaction zone into the reaction zone where temperature of the second heat-exchange stream before heat transfer is lower than the temperature of one or more product streams. That way, heat coming from the second heat-exchange stream can be transferred to the first heat-exchange stream.

EFFECT: low heat loss and high efficiency of the process.

17 cl, 3 dwg

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 producing acetic acid, which is conversion of methanol and its reactive derivative in the presence of carbon monoxide and a rhodium-based catalyst system consisting of: (i) rhodium; (ii) a halogen promoter; (iii) an iodide salt as a co-promoter in concentration which ensures concentration of the iodide ion higher than 3 wt % of the reaction mixture; and (iv) a metal salt as a stabiliser, selected from a group consisting of ruthenium salts, tin salts and mixtures thereof; wherein the reaction mixture contains 0.1-14 wt % water; and wherein the ruthenium salt, tin salt or mixtures thereof are present in the reaction mixture in molar ratio of combined ruthenium and tin to rhodium between 0.1:1 and 20:1. The metal salt as a stabiliser minimises deposition of rhodium metal when extracting the product - acetic acid - particularly in an evaporation apparatus in the acetic acid separation process. Stability of rhodium metal is achieved even when producing acetic acid in a reaction mixture with low content of water in the presence of an iodide salt as a co-promoter in a concentration which ensures concentration of the iodide ion higher than approximately 3 wt % of the reaction mixture.

EFFECT: improved method of producing acetic acid via a catalytic carbonylation reaction.

8 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: method involves carbonylation of methanol and/or its reactive derivative with carbon monoxide in at least one carbonylation reaction zone, containing al liquid reaction composition which contains an iridium carbonylation catalyst, acetic acid, methyl acetate, ruthenium - promoter, and indium - catalyst system stabiliser, selected from indium, where the molar ratio iridium/promoter/stabiliser in the liquid reaction composition is kept in the interval 1:(from >2 to 15):(from 0.25 to 12).

EFFECT: using of indium as a catalyst system stabiliser in a method of producing acetic acid.

1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: method involves the following steps: (a) separation of a carbonylation product to obtain a gaseous overhead fraction containing acetic acid, methanol, methyl iodide, water, methyl acetate and at least one permanganate reducing compound, including acetaldehyde and less volatile fractions of catalyst; (b) distillation of the gaseous overhead fraction to obtain purified acetic acid and a low-boiling gaseous overhead fraction containing methanol, methyl iodide, water, acetic acid, methyl acetate and at least one permanganate reducing compound, including acetaldehyde; (c) condensation of the low-boiling gaseous overhead fraction and its separation into a condensed heavy liquid fraction which contains methyl iodide and methyl acetate and a condensed light liquid fraction containing water, acetic acid and at least one permanganate reducing compound, including acetaldehyde; (d) distillation of the light liquid fraction in a separate distillation column to obtain a second gaseous overhead fraction containing methyl iodide and at least one permanganate reducing compound, including acetaldehyde, and residue containing a fraction of high-boiling liquid containing methyl acetate, water and acetic acid, where the second gaseous overhead fraction is rich in permanganate reducing compounds relative the light liquid fraction; (e) condensation of the second gaseous overhead fraction containing methyl iodide and at least one permanganate reducing compound, including acetaldehyde, and aqueous extraction of the condensed stream to obtain a stream of an aqueous solution containing permanganate reducing compounds, including acetaldehyde, and a raffinate containing methyl iodide.

EFFECT: selective extraction and reduced amount of permanganate reducing compounds.

20 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing acetic acid and specifically to a method of producing acetic acid via carbonylation in the presence of a rhodium catalyst system. Described is a catalyst system for producing acetic acid, which includes a carbonylation rhodium catalyst, methyl iodide, at least one heteropolyacidic promoter and a method of producing acetic acid through carbonylation of methanol and/or its reactive derivative with carbon monoxide in a liquid reaction mixture which contains methyl acetate, limited concentration of water, acetic acid and the catalyst system mentioned above.

EFFECT: faster carbonylation.

21 cl, 6 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry. stream of methanol material reacts with oxygen and optionally a temperature regulator in a partial oxidation reactor to obtain a stream of synthetic gas. The partial oxidation reactor has a burner in an open uncatalysed gas generator with free flow and works in the 1100-2000 °C temperature interval. The synthetic gas stream is divided into a stream with high carbon dioxide content and a mixed stream containing hydrogen and carbon oxide which is then divided into a stream with high hydrogen content and a stream with high carbon oxide content. Re-equipment of the initial installation for producing methanol to an installation for synthesis of acetic acid involves the following steps: provision for the initial installation for producing methanol, having at least one partial oxidation reactor for converting hydrocarbon into a synthetic gas stream and a methanol synthesis loop for converting hydrogen and carbon oxide from the synthetic gas stream to methanol, supply of at least one portion of methanol material stream, oxygen from an air separation unit and, optionally, a temperature regulator, into at least one partial oxidation reactor, mounting the first separation unit for separating a stream with carbon dioxide content and a mixed stream of hydrogen and carbon oxide from the outgoing synthetic gas stream, mounting the second separation unit for separating a stream with high hydrogen content and a stream with high carbon oxide content from the mixed stream, mounting the acetic acid synthesis installation, supplying a stream with high carbon oxide content from the second separation unit and a portion of methanol material stream into the acetic acid synthesis installation and fitting isolation valves for isolation of the methanol synthesis loop from the remaining part of the reconstructed installation.

EFFECT: invention increases cost-effectiveness of the process.

18 cl, 10 dwg

FIELD: chemistry.

SUBSTANCE: method involves impulse evaporation of flow discharged from reactor to form upper distillate; further treatment of upper distillate by distillation in standard operational conditions, obtaining acetic acid; running control of acetic acid formation rate by regulation of at least one independent process parametre; running control of acetic acid formation rate by regulation of at least one dependent process parametre; acetic acid formation rate reduction in response to changes in the process course of process equipment state; process control at reduced acetic acid formation rate by regulation of at least one of independent and/or dependent parametre during return of process equipment system to original state of standard operational process before the said change; increase of acetic acid formation rate until the system returns to original state of standard operational process by regulation of at least one of independent and/or dependent parametre, where non-linear multivariant regulation is based on the process model.

EFFECT: improved cost efficiency.

3 cl, 2 ex, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing catalysts for oxidising carbon monoxide. Described is a method of producing a porous granular catalyst for oxidising carbon monoxide, involving mixing functional oxides, including manganese dioxide, obtained from chemical reaction of reactants, wherein the mixture is put into a porous frame having the shape of granules, wherein the porous frame used is silica gel granules saturated with iron, cobalt and manganese oxides via step-by-step impregnation with aqueous solutions of metal salts with inter-operation drying in the following sequence: first step - separate impregnation with iron sulphate and cobalt nitrate, each conjugated with the last impregnation of porous granules with potassium hydroxide solution in ethyl alcohol, and the formed metal hydroxides are then thermally decomposed to end iron and cobalt oxides; second step - separate impregnation with potassium permanganate and sodium hyposulphite, thereby saturating porous granules of the formed manganese dioxide; the obtained mixture of said metal oxides then undergoes final washing and the ready powdered product is then dried.

EFFECT: efficient, highly stable carbon monoxide oxidation catalyst is obtained.

3 cl, 1 ex

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