Method of producing carboxylic acids and derivatives thereof

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 600C 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

 

The present invention relates to a method for producing aliphatic carboxylic acid and/or its derivatives by reaction of the corresponding alcohol or its reactive derivative with carbon monoxide in the presence containing metal mordenite catalyst.

Obtaining acetic acid from methanol and carbon monoxide is a well-known carbonyl process, which is carried out on an industrial scale. On an industrial scale obtaining acetic acid can be made in a homogeneous liquid phase process, in which the carbonylation reaction catalyze soluble complex of rhodium/iodide 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 the selection of products and catalytic components of a single phase. Both of these disadvantage could be eliminated if they could be developed in a heterogeneous gas-phase method using free of iodide solid catalyst.

In GB 1185453 describes some of multiphase catalysts comprising a catalytically active metal, which includes, inter alia, copper, rhodium and iridium deposited on materials-a wide range of media, including 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 way 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. Example VI the experiment 30, provides links to zeolites mordenite type, which have an index of the permeability of 0.4, and it is shown that the hydrogen form is catalytically effective. Preferred zeolites in a preferred embodiment, modified by the introduction of metals of groups IB, IIB, IVB or VIII, of which the most preferred copper.

In J.Catalysis, 71, 233-43 (1981) described the application of photoelectron spectroscopy (ES IS A) to determine the activity of the 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 anhydrous 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.

Work in Chemistry Letters, cc.2047-2050 (1984) refers to the vapor carbonyliron methanol in the absence of a halogen promoter. Table 1 of this article refers to three examples, experiments are carried out at 200C and under a pressure of 10 bar, where as catalysts using hydrogen mordenite and copper mordenite. In all three cases, the output values were relatively low output in similar experiments with the use of catalysts based on ZSM-5.

In EP 0596632 A1 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, which is an advanced ion the 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 600C. and under a pressure in the range from 15 to 200 bar.

Thus, there remains a need to develop improved heterogeneous gas-phase method of producing carboxylic acids and/or their derivatives from alcohols and/or their reactive derivatives and carbon monoxide using containing metal zeolite catalyst, which is carried out in the practical absence of Halogens or their derivatives.

It was found that mordenites zeolite (hereinafter designated as mordenite), which was previously modified by the inclusion in the framework of metals, in addition to silicon and aluminum, provides increased selectivity with respect to the product (in respect of acetic acid or its derivatives) and/or increased stability of the catalyst.

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 ester or anhydride which comprises contacting an aliphatic alcohol containing n carbon atoms, or its reactive derivative with carbon monoxide essentially in the absence of Halogens or their product is different and in the presence of a catalyst at a temperature in the range from 250 to 600C. and under a pressure in the range from 10 to 200 bar, characterized in that the catalyst consists essentially of a mordenite, which as frame elements include silicon, aluminum and one or more other elements selected from gallium, boron and iron, and in which prior to the ion exchange or otherwise introduced copper, Nickel, iridium, rhodium or cobalt.

In the method according to the present invention using a modified mordenites catalyst at high temperatures and pressures to achieve good output values of carboxylic acids and their derivatives. It was found that increased selectivity in respect of the product and the increased stability of the catalyst can be achieved with the use of mordenite, which was previously modified by adding as a frame element, one or more of gallium, boron and iron (modifying the frame elements), compared to mordenite, having as the only frame elements silicon and aluminum.

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.

A reactive derivative of this alcohol that m is should be used as an alternative or in addition to 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.

In one embodiment, where the alcohol is provided by the use of methanol, the methanol can be used as such, or it may be obtained from a source of carbon monoxide and hydrogen, such as is technically available synthesis gas, in the presence of an appropriate catalyst for the synthesis of alcohol. Acceptable catalysts for methanol synthesis are described, for example, in WO 99/38836 and WO 01/07393. A specific example of a suitable the methanol synthesis catalyst is a catalyst based on copper/zinc oxide together with or without aluminum promoter. The methanol synthesis can be performed in situ or in the reactor, separated from the carbonylation process of the present invention.

The product of the carbonylation process may be an aliphatic carboxylic acid, and may also include an ester of aliphatic carboxylic acid. For example, when the alcohol is methanol, the product comprises acetic acid and may also include the acetate. Ester can be converted into aliphatic carboxylic KIS the GTC by known methods. The method according to the present invention can also be implemented in the synthesis of propionic acid from ethanol and butyric acid from n-propanol.

This process can be carried out in the presence or essentially in the absence of water. When source material using a reactive derivative such as an ester or ether, in the preferred embodiment, the reaction of the injected water. For example, in the reaction of the injected water as source material using dimethyl ether, in particular when the molar ratio of water:dimethyl ether from more than 0 to less than or equal to 1.

Suppose that the degree of purity of the used carbon monoxide is especially critical to have, although you should use a gas mixture in which carbon monoxide is a major component. It may be acceptable to the presence of small amounts of impurities such as nitrogen and noble gases. In addition, in the method according to the present invention can also be used a mixture of carbon monoxide and hydrogen in the form as they are received by reforming or partial oxidation of hydrocarbons (synthesis gas).

The catalyst used in the method according to the present invention is a modified mordenites zeolite, in which a preliminary ion exchange or otherwise impose m is d', Nickel, iridium, rhodium or cobalt. 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 in General 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 8:1 to 50:1, more preferably in the range from 10:1 to 30:1, and most preferably in the range from 15:1 to 25:1.

Modifying the frame elements (gallium, boron and/or iron) can be introduced into the frame by any conventional means. For example, the mordenite may be synthesized using acceptable precursors for silicon, aluminum and gallium, iron and/or boron components of the framework, such as modified for what Allium mordenite, joint reaction in a mixture comprising white carbon, gallium nitrate and sodium aluminate.

For implementing the method of the present invention in a preferred embodiment, the mordenite has a ratio of silica to oxide of modifying the frame elements (i.e. in the aggregate to the gallium oxide, boron oxide and iron oxide) in the range from 10:1 to 50:1, preferably in the range from 20:1 to 50:1, and more preferably in the range from 30:1 to 40:1.

Preferred modifying the frame element is gallium. Thus, in a preferred embodiment, the mordenite has a ratio of silicon oxide to gallium oxide in the range from 10:1 to 50:1, preferably in the range from 20:1 to 50:1, and more preferably in the range from 30:1 to 40:1.

Before use as a catalyst mordenite is subjected to ion exchange or otherwise it is injected copper, Nickel, rhodium, iridium or cobalt. If the mordenite must be subjected to ion exchange, up to 80% capable of nationalen sites on the zeolite can be subjected to ion exchange with the substitution, for example, ions of Cu2+Ir3+or Rh3+using well known techniques. In a preferred embodiment, the remaining cations in subjected to the ion exchange mordenite are protons, resulting in a process of ion exchange, it is advisable to start with ammonium or water the native form.

Alternatively, the ion exchange ammonium or hydrogen form of mordenite can be impregnated with a solution of metal salt and subsequently dried. When using ammonium form, then after saturation or ion exchange mordenite in the preferred embodiment, calicivirus. We prefer the quantities used when preparing the catalyst, the metal content of which ranges from 0.5 to 10 wt.% in terms of the entire catalyst.

In a preferred embodiment, 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.

The method according to the present invention in a preferred embodiment, carried out by passing vapors of methanol and gaseous carbon monoxide through a fixed or fluidized bed of catalyst maintained in the conditions required temperature and pressure. This process is carried out essentially in the absence of iodide. The term "essentially" mean that the content of iodide in the source gases and the catalyst is less than 500 ppm million, and preferably less than 100 ppm million

This process is carried out at a temperature in the range from 250 to 600C., preferably from 250 to 400C. and under a pressure in the range from 10 d is 200 bar, preferably from 10 to 150 bar, in particular from 25 to 100 bar.

The molar ratio of carbon monoxide to methanol in a suitable embodiment is in the range from 1:1 to 60:1, preferably from 1:1 to 30:1, most preferably from 2:1 to 10:1. If it is served in a catalytic layer in liquid form, average hourly feed rate of the liquid (SCSI) in the case of methanol in the preferred embodiment, should be in the range from 0.5 to 2.

Carboxylic acid, produced according to the method of the present invention, can be removed in the form of steam and then condensed into a liquid. Further carboxylic acid may be purified by conventional methods such as distillation.

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

Examples

Synthesis of mordenite

Comparative example A: synthesis of Ga mordenite

Tetraethylammonium (tea-Br) (for 9.47 g) was dissolved in 30 g of distilled water and then added to the suspension 22,26 g of white carbon black (Cab-O-Sil) in 150 g of distilled water. The resulting mixture was thoroughly stirred. To this suspension was added a solution of sodium hydroxide (6.75 g) in 30 g of distilled water and then the mixture was stirred for one hour. After this period, the dissolution 7,53 g of gallium nitrate in 70 g of distilled water was prepared a solution of gallium nitrate. The dal is a solution of gallium nitrate was added to a suspension of silicon dioxide and the resulting gel was stirred for another 1 h On stoichiometric calculations this gel was a

25,2SiO21,0Ga2O35,7Na2O3,TEA-BrN2About

Next, the gel was transferred into a stainless steel autoclave and kept at 150C for 16 days. After this period, the autoclave was cooled and the contents were filtered and washed with copious quantities of distilled water. Then the white solid product was dried at 120C during the night.

Radiographic analysis showed that the material was vysokochastotnom and had mordenite structure. Chemical analysis showed that the material had the carcass composition of SiO2/Ga2O3=31,1.

Example 1: synthesis of Ga/Al mordenite "low Al"

Mordantly a synthesis gel was prepared in accordance with the method of comparative example A, except that the reaction mixture was added a mixture of gallium nitrate and sodium aluminate. This was achieved by adding silica gel with intensive stirring solution of gallium nitrate (6,02 g, dissolved in 35 g of distilled water) and sodium aluminate solution (0.50 g, dissolved in 35 g of distilled water). After stirring for one hour the resulting gel was transferred into a stainless steel autoclave and kept at 150C for 11 days. On stoichiometric calculations this gel was the FDS is th

126,4SiO24,0Ga2O31.0Al2O329,6Na2O15,TEA-Br5276H2O

After this period, the autoclave was cooled and the contents were filtered and washed with copious quantities of distilled water. Then the white solid product was dried at 120C during the night.

Radiographic analysis showed that the material was vysokochastotnom and had mordenite structure. Chemical analysis showed that mordenites zeolite contained frame as gallium and aluminum and had the carcass composition of SiO2/Ga2O3=32,6 and SiO2/Al2O3=102,4.

Example 2: synthesis of Ga/Al mordenite with high Al content"

In this example, the Ga/Al mordantly zeolite synthesized with an increased amount of aluminum frame. Repeated the experiment of example 1, except that the amount of added sodium aluminate was increased from 0.50 to 2,88, stoichiometric calculations, this gel was a

48,5SiO21,5Ga2O31,0Al2O329,6Na2O15,TEA-Br5276H2O

The formed gel was kept at 150C for 14 days. The resulting crystalline solid product was filtered, washed with copious quantities of water and dried at 120C during the night. Radiographic analysis showed that the material was vysokochastotnom and the region is al mordenite structure. Chemical analysis showed that mordenites zeolite contained frame as gallium and aluminum and had the carcass composition of SiO2/Ga2O3=39,2 and SiO2/Al2O3=19,4.

Comparative example B: synthesis of mordenite with low Al content"

The mordenite with low Al content was prepared by acid leaching. 30 g of technically available mordenite zeolite (ex. PQ, CBV20A, SiO2/Al2O3=19,4) was boiled under reflux for 2 h in a solution of hydrochloric acid, prepared by diluting 24 ml of concentrated hydrochloric acid 76 ml of distilled water. After this period, the solid product was filtered and washed with copious quantities of distilled water.

Radiographic analysis showed that the material was, however, vysokochastotnom and had mordenite structure. Chemical analysis showed that the material had the carcass composition of SiO2/Al2O3=36,0.

Comparative example: Al mordenite

As a further comparative example used technically available mordantly zeolite (ex. PQ, CBV20A, SiO2/Al2O3=19,4).

Preparation of catalyst

Synthesized mordenite comparative example a and examples 1 and 2 were caliciviral extract solids at 550C for 6 h for UDA is possible organic template. Mordenite comparative examples a to b and examples 1 and 2 was converted into the ammonium form by contacting solid particles with a 1.5 M solution of ammonium nitrate at 80C for 3 h followed by filtration and drying. The mass ratio of 1.5 M solution of ammonium nitrate to the mordenite used in ionoobmennyh, was 25:1. The process of noobman for each mordenite was repeated three times.

Mordenite in ammonium form was turned in containing introduced copper acid form by impregnation of mordenite copper-containing solution, followed by calcination. All received mordenite had a nominal copper content of approx. 7 wt.%.

The following process with reference to comparative example B is an example of the process of introduction of copper. 23,04 g ammonium form of mordenite with low Al content obtained in comparative example B was added to solution of three-hydrate of copper nitrate (6,33 g) in 140 g of distilled water, and intensively stirred. The solution is evaporated to dryness exposure at 80C. the Blue solid product was caliciviral at 500C for 2 h Chemical analysis showed that the material contained 6.6 wt.% Cu. Further catalysts alloy preformed by crushing entered contained copper zeolites under a pressure of 10 ton press in the infrared, the resulting tablet was destroyed and the material sieved emitting particles is the sizes in the range from 250 to 850 microns.

Carbonylation of methanol

Each of the catalysts of comparative examples a to b and examples 1 and 2 were used to catalyse the reaction of methanol and carbon monoxide in the single high-pressure microreactor. The amount used of the catalyst, as a rule, was 10 ml in order to ensure effective preheating of the reactants prior to contacting with the catalyst used is a preliminary layer of granules of silicon carbide. The catalyst was activated in a stream of nitrogen (100 ml/min) at 350C for 16 h, and then restored in a stream of carbon monoxide (200 ml/min) at 350C for 2 hours Then use the slider to back pressure the system pressure was brought to 25 at. The flow rate of carbon monoxide brought up to 800 ml/min and using a pump to the reactor filed methanol (at a rate of 0.15 ml/min). Liquid and solid products were collected in a cooled trap, while the gaseous products and reactants were selected after the back pressure regulator.

Every three hours, samples were taken of the reaction mixture. All samples were analyzed using provided outside the process line gas chromatography. The content of carbon dioxide formed as a by-product resulting from the concurrent reaction of changes in the ratio of carbon monoxide and hydrogen in the water gas, in all cases which was relatively low, ranged from 1 to 10 mol % of the total number of moles of the formed product.

The results of the experiments with carbonyliron presented in tables 1 through 3.

Table 1
Catalytic performance properties of Cu/N-(Ga) of mordenite and Cu/N-(Ga, Al) mordenite when carbonyliron methanol
CatalystThe catalyst SiO2/Ga2O3The catalyst SiO2/Al2O3Reaction time, hThe transformation of the Meon, %The selectivity in respect of the product (mol %)
DMEHC(I)MeoacAsn
Comparative example a30,6-392,548,54,8 31,615,1
788,782,71,113,5of 5.4
Example 132,6102,4399,50,022,86,968,2
6of 98.21,27,534,852,6
Example 239,219,4396,82,044,823,429,8
697,04,23,149,242,9

Reaction temperature: 350C, gauge pressure: 25 bar, SPH: 4400, WITH/Meon: 9, SCSI: 0,9 (I), hydrocarbon (HC) means the hydrocarbon.

The results in table 1 show that the catalyst with mordenite structure containing gallium (comparative example A), capable of catalyzing residenoe carbonylation of methanol to acetic acid. However, the catalysts of examples 1 and 2, which mordenite structure contains both aluminum and gallium can be postign is you're much higher level of activity and selectivity in respect of the resulting acetic acid and methyl acetate. Beneficial impact in mordenite frame as aluminum and gallium on the selectivity in respect of the product is additionally shown in table 2.

Table 2
Comparison of values of the selectivity in respect of the product in cases of Cu/H-(Al) mordenite and Cu/H-(Ga, Al) mordenite catalysts
CatalystThe catalyst SiO2/Ga2O3Catalyst
SiO2/Al2O3
The selectivity in respect of the product (mol %)
DMEHCMeoacAsn
Example 239,219,44,23,149,2 42,9
Comparative example B-36,060,41,128,96,0
Comparative example-20,06,734,7of 17.539,3

Reaction time: 6 hours the Reaction temperature: 350C, gauge pressure: 25 bar, SPH: 4400, WITH/Meon: 9, SCSI: 0,9. From table 2 we can see that with containing Ga and Al mordenite catalyst (example 2) can be achieved with high activity, as evidenced by the low selectivity for DME and high selectivity for the resulting acetic acid and acetate when compared with the system only aluminum is observed which provides relatively high values of selectivity in respect of the hydrocarbon by-product with a high content of aluminum frame and low activity (as evidenced by a large number of the received DME) with low content of aluminum frame.

Table 3 shows that significant selectivity for acetic acid and methyl acetate in the catalysts of the present invention is maintained even after 70 h of the application process.

Table 3
The study of life, for example 1
Reaction time, hThe transformation of the Meon, %The selectivity in respect of the product (mol %)
DMEHCMeoacAsn
399,50,0 22,86,968,2
6of 98.21,27,534,852,6
26br93.141,21,239,9of 17.5
5986,461,10,330,48,1
6888,777,40,715,26,6

Reaction temperature: 350C, gauge pressure: 25 bar, SPH: 4400, WITH/Meon: 9, SCSI: 0,9.

1. The method of obtaining acetic acid and/or its ester or anhydride which comprises contacting methanol and/or reactive derivative selected from methyl acetate and dimethyl ether with carbon monoxide in the presence of a catalyst at a temperature in the range from 250 to 600C. and under a pressure in the range from 10 to 200 bar, and where the concentration of the iodide in methanol and/or its reactive derivative,carbon monoxide and the catalyst is less than 500 million -1, characterized in that the catalyst consists essentially of a mordenite, which as frame elements include silicon, aluminum and one or more of other elements selected from gallium and boron, and in which the ion exchange or otherwise introduced copper, Nickel, iridium, rhodium or cobalt.

2. The method according to claim 1, in which the frame elements are silicon, aluminum, and gallium.

3. The method according to claim 1 or 2, in which the mordenite ion exchange or otherwise impose copper.

4. The method according to claim 1 or 2, wherein the mordenite has a ratio of silicon dioxide to aluminum oxide in the range from 10:1 to 30:1.

5. The method according to claim 1 or 2, wherein the mordenite has a ratio of silicon dioxide to the oxides of gallium and boron in the range from 20:1 to 50:1.

6. The method according to claim 5, in which the ratio of silicon oxide to gallium oxide is in the range from 20:1 to 50:1.

7. The method according to claim 1 or 2, wherein the mordenite is subjected to ion exchange with copper, Nickel, iridium, rhodium or cobalt.

8. The method according to claim 1 or 2, in which the mordenite includes up to 80% of its capable of currency areas, subjected to ion exchange with copper, Nickel, iridium, rhodium or cobalt.

9. The method according to claim 1 or 2, wherein the catalyst has a metal content of from 0.5 to 10 wt.% in terms of the total weight of the catalyst.

10. The method according to claim 1 or 2, in which the catalyst before applying kiviruut.

11. The method according to claim 10, in which the catalyst is activated by contacting the catalyst with a stream of nitrogen, carbon monoxide or hydrogen for at least one hour at an elevated temperature.

12. The method according to claim 1 or 2, in which the carbon monoxide and steam to methanol is fed through a fixed or fluidized bed of catalyst, and where the concentration of the iodide in methanol, carbon monoxide and the catalyst is less than 500 million-1.

13. The method according to claim 1 or 2, in which methanol is prepared from a mixture of carbon monoxide and hydrogen.

14. The method according to claim 1 or 2, in which the methanol receive in situ.

15. The method according to claim 1 or 2, in which the reactive derivative use of dimethyl ether.

16. The method according to item 15, in which a mixture of methanol and dimethyl ether.

17. The method according to item 15, in which the starting material for process water use.

18. The method according to 17, in which the molar ratio of water: dimethyl ether is in the range from greater than 0 to less than or equal to 1.

19. The method according to claim 1 or 2, in which the process is carried out in the practical absence of water.

20. The method according to claim 1 or 2, in which the process is carried out at a temperature in the range from 250 to 400C. and under a pressure in the range from 10 to 150 bar.

21. The method according to claim 1 or 2, in which the molar ratio of carbon monoxide to methanol finds the I in the range from 1:1 to 30:1.

22. The method according to claim 1 or 2, in which the average hourly feed rate of the liquid in the case of methanol is in the range from 0.5 to 2.



 

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

35 cl, 5 ex, 3 tbl

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11 cl, 14 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for oxidation of (C2-C4)-alkane and preparing the corresponding alkene and carboxylic acid. Method involves addition of this alkane to contact with molecular oxygen-containing gas in oxidative reaction zone and optionally at least one corresponding alkene and water in the presence of at least two catalysts with different selectivity. Each catalyst is effective in oxidation of alkane to corresponding alkene and carboxylic acid resulting to formation of product comprising alkene, carboxylic acid and water wherein the molar ratio between alkene and carboxylic acid synthesized in the reaction zone is regulated or maintained at the required level by regulation the relative amounts of at least two catalyst in the oxidative reaction zone. Also, invention relates to the combined method for preparing alkyl carboxylate comprising abovementioned stage in preparing alkene and carboxylic acid in the first reaction zone. Then method involves the stage for addition of at least part of each alkene and carboxylic acid prepared in the first reaction zone to the inter-contacting in the second reaction zone the presence of at least one catalyst that is effective in preparing alkyl carboxylate to yield this alkyl carboxylate. Also, invention relates to a method for preparing alkenyl carboxylate comprising the abovementioned stage for preparing alkene and carboxylic acid in the first reaction zone and stage for inter-contacting in the second reaction zone of at least part of each alkene and carboxylic acid synthesized in the first reaction zone and molecular oxygen-containing gas in the presence of at least one catalyst that is effective in preparing alkenyl carboxylate and resulting to preparing this alkenyl carboxylate.

EFFECT: improved method for oxidation.

30 cl, 1 dwg, 5 tbl, 14 ex

FIELD: petrochemical processes.

SUBSTANCE: invention relates to improved C2-C4-alkane oxidation process to produce corresponding alkene and carboxylic acid, which process comprises bringing indicated alkane in oxidation reaction zone into contact with molecular oxygen-containing gas and corresponding alkene and optionally with water in presence of at least one catalyst efficient for oxidation of alkane into corresponding alkene and carboxylic acid. Resulting product contains alkene, carboxylic acid, and water, wherein alkene-to-carboxylic acid molar ratio in oxidation reaction zone is controlled or maintained at desired level by way of controlling alkene and optional water concentrations in oxidation reaction zone and also, optionally, controlling one or several from following parameters: pressure, temperature, and residence time in oxidation reaction zone. Invention also relates to integrated process of producing alkyl carboxylate including above-indicated stage of producing alkene and carboxylic acid in first reaction zone and stage of bringing, in second reaction zone, at least part of each of alkene and carboxylic acid obtained in first reaction zone in contact with each other in presence of at least one catalyst effective in production of alkyl carboxylate to produce the same. Invention further relates to production of alkenyl carboxylate including above-indicated stage of producing alkene and carboxylic acid in first reaction zone and stage of bringing, in second reaction zone, at least part of each of alkene and carboxylic acid obtained in first reaction zone plus molecular oxygen-containing gas into contact with each other in presence of at least one catalyst effective in production of alkenyl carboxylate to produce the same.

EFFECT: enhanced process efficiency.

55 cl, 1 dwg, 7 tbl, 22 ex

FIELD: chemical industry; production of synthesis gas, methanol and acetic acid on its base.

SUBSTANCE: the invention is dealt with the methods of production of synthesis gas, production of methanol and acetic acid on its base. The method of upgrading of the existing installation for production of methanol or methanol/ ammonia provides for simultaneous use of the installation also for production of acetic acid or its derivatives. The existing installation contains a reformer, to which a natural gas or other hydrocarbon and a steam (water), from which a synthesis gas is formed. All the volume of the synthesis gas or its part is processed for separation of carbon dioxide, carbon monoxide and hydrogen. The separated carbon dioxide is fed into an existing circuit of synthesis of methanol for production of methanol or is returned to the inlet of the reformer to increase the share of carbon monoxide in the synthesis gas. The whole volume of the remained synthesis gas and carbon, which has not been fed into the separator of dioxide, may be transformed into methanol in the existing circuit of a synthesis of methanol together with carbon dioxide from the separator and-or carbon dioxide delivered from an external source, and hydrogen from the separator. Then the separated carbon monoxide is subjected to reactions with methanol for production of acetic acid or an intermediate compound of acetic acid according to the routine technology. A part of the acetic acid comes into reaction with oxygen and ethylene with formation of monomer of vinyl acetate. With the help of the new installation for air separation nitrogen is produced for production of additional amount of ammonia by the upgraded initial installation for production of ammonia, where the separated hydrogen interacts with nitrogen with the help of the routine technology. As the finished product contains acetic acid then they in addition install the device for production of a monomer of vinyl acetate using reaction of a part of the acetic acid with ethylene and oxygen. With the purpose of production of the oxygen necessary for production of a monomer of vinyl acetate they additionally install a device for separation of air. At that the amount of nitrogen produced by the device of separation of air corresponds to nitrogen demand for production of additional amount of ammonia. The upgraded installation ensures increased production of additional amount of ammonia as compared with the initial installation for production of methanol. The invention also provides for a method of production of hydrogen and a product chosen from a group consisting of acetic acid, acetic anhydride, methyl formate, methyl acetate and their combinations, from hydrocarbon through methanol and carbon monoxide. For this purpose execute catalytic reforming of hydrocarbon with steam in presence of a relatively small amount of carbon dioxide with formation of the synthesis gas containing hydrogen, carbon monoxide and carbon dioxide, in which synthesis gas is characterized by magnitude of the molar ratio R = ((H2-CO2)/(CO+CO2)) from 2.0 up to 2.9. The reaction mixture contains carbon monoxide, water -up to 20 mass %, a dissolvent and a catalytic system containing at least one halogenated promoter and at least one rhodium compound, iridium compound or their combination. The technical result provides, that reconstruction of operating installations increases their productivity and expands assortment of produced industrial products.

EFFECT: the invention ensures, that reconstruction of operating installations increases their productivity and expands assortment of produced industrial products.

44 cl, 3 ex, 6 dwg

Cleaning method // 2237652
The invention relates to an improved method of purification of the reaction products of the process of direct connection, comprising the reaction of ethylene with acetic acid in the presence of an acid catalyst to obtain ethyl acetate, and cleaning products, recycling, and this cleaning method includes the following stages: (I) feeding the reaction product in column (A) to remove the acid from the base which divert acetic acid, and with its top pick at least a fraction comprising boiling components containing, inter alia, hydrocarbons, ethyl acetate, ethanol, diethyl ether and water, and is directed to the apparatus (A1) for decanting in order to share these top shoulder straps on the phase rich in ethyl acetate, and water (rich in water) phase, (II) a separate return at least part of the rich ethyl acetate phase and almost all of the aqueous phase from the apparatus (A1) for decanting as phlegmy in the upper part of the column (A) or near its top, (III) the filing of the rest of the rich ethyl acetate phase from the apparatus (A1) for decanting in the upper part of the Westfalia refinery unit column (s) or near its top, (IV) the removal from the column (C): and nedogona, including significantly refined ethyl acetate, which is directed to the treatment of the colon is his, acetaldehyde and diethyl ether, which is sent to the column to remove aldehyde, and (C) lateral fraction comprising mainly ethyl acetate, ethanol and some water, which is directed to a point below the point of entry is rich in ethyl acetate phase is removed from the column (A), (V) challenging reset, including acetaldehyde, from the top or near the top of the column for removal of aldehyde and return diethyl ether, isolated from the base of the column to remove aldehyde, etherification reactor and (VI) purification of refined ethyl acetate in column (E)

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: 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: method includes carbonylation of the alcohol and/or of its reactive derivative with carbon monooxide in liquid reaction mixture carried out in carbonylation reactor. The said liquid reaction mixture contains the said alcohol and/or its reactive derivative, carbonylation catalyst, alkyl halide cocatalyst whereat the said catalyst includes at least one metal selected from rhodium or iridium coordinated with polydentate ligand whereat the said polydentate ligand has the bite angle at least 145 or forms the "hard" Rh or Ir metal-ligand complex; the said polydentate ligand includes at least two coordination groups; at least two of them independently contain P, N, As or Sb as coordination atoms. The hydrogen/carbon monooxide mole ratio is supported in the range at least 1:100 and/or carbon monooxide directed to carbonylation reactor contains at least 1 mole % of hydrogen; catalyst flexibility range is less 40. The method is tolerable to hydrogen presence i.e. liquid side-products are formed in small amounts or are not formed at all.

EFFECT: improvement of the method of carboxylic acid and its ester obtaining.

49 cl, 3 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention concerns improved method of obtaining carboxylic acid and/or complex alcohol ether and carboxylic acid, involving carbonylation of C1-C8 aliphatic alcohol and/or its reactive derivative by carbon monoxide in liquid reaction mix in carbonylation reactor. Liquid reaction mix includes indicated alcohol and/or its reactive derivative, carbonylation catalyst, alkylhalide co-catalyst and optionally water in limited concentration, the catalyst including cobalt, rhodium or iridium coordinated with tridentate ligand, or their mix. Also invention concerns application of carbolylation catalyst including cobalt, rhodium or iridium coordinated with tridentate ligand, or their mix, in carbonylation method of obtaining carboxylic acid and/or complex alcohol ether and carboxylic acid.

EFFECT: enhanced carbonylation speed and selectivity.

36 cl, 6 tbl, 3 ex

FIELD: chemical industry; production of synthesis gas, methanol and acetic acid on its base.

SUBSTANCE: the invention is dealt with the methods of production of synthesis gas, production of methanol and acetic acid on its base. The method of upgrading of the existing installation for production of methanol or methanol/ ammonia provides for simultaneous use of the installation also for production of acetic acid or its derivatives. The existing installation contains a reformer, to which a natural gas or other hydrocarbon and a steam (water), from which a synthesis gas is formed. All the volume of the synthesis gas or its part is processed for separation of carbon dioxide, carbon monoxide and hydrogen. The separated carbon dioxide is fed into an existing circuit of synthesis of methanol for production of methanol or is returned to the inlet of the reformer to increase the share of carbon monoxide in the synthesis gas. The whole volume of the remained synthesis gas and carbon, which has not been fed into the separator of dioxide, may be transformed into methanol in the existing circuit of a synthesis of methanol together with carbon dioxide from the separator and-or carbon dioxide delivered from an external source, and hydrogen from the separator. Then the separated carbon monoxide is subjected to reactions with methanol for production of acetic acid or an intermediate compound of acetic acid according to the routine technology. A part of the acetic acid comes into reaction with oxygen and ethylene with formation of monomer of vinyl acetate. With the help of the new installation for air separation nitrogen is produced for production of additional amount of ammonia by the upgraded initial installation for production of ammonia, where the separated hydrogen interacts with nitrogen with the help of the routine technology. As the finished product contains acetic acid then they in addition install the device for production of a monomer of vinyl acetate using reaction of a part of the acetic acid with ethylene and oxygen. With the purpose of production of the oxygen necessary for production of a monomer of vinyl acetate they additionally install a device for separation of air. At that the amount of nitrogen produced by the device of separation of air corresponds to nitrogen demand for production of additional amount of ammonia. The upgraded installation ensures increased production of additional amount of ammonia as compared with the initial installation for production of methanol. The invention also provides for a method of production of hydrogen and a product chosen from a group consisting of acetic acid, acetic anhydride, methyl formate, methyl acetate and their combinations, from hydrocarbon through methanol and carbon monoxide. For this purpose execute catalytic reforming of hydrocarbon with steam in presence of a relatively small amount of carbon dioxide with formation of the synthesis gas containing hydrogen, carbon monoxide and carbon dioxide, in which synthesis gas is characterized by magnitude of the molar ratio R = ((H2-CO2)/(CO+CO2)) from 2.0 up to 2.9. The reaction mixture contains carbon monoxide, water -up to 20 mass %, a dissolvent and a catalytic system containing at least one halogenated promoter and at least one rhodium compound, iridium compound or their combination. The technical result provides, that reconstruction of operating installations increases their productivity and expands assortment of produced industrial products.

EFFECT: the invention ensures, that reconstruction of operating installations increases their productivity and expands assortment of produced industrial products.

44 cl, 3 ex, 6 dwg

The invention relates to a method for producing ester of formic acid or methanol and the catalyst of this method

The invention relates to the production of acetic acid and/or methyl acetate

The invention relates to the production of acetic acid

The invention relates to the production of acetic acid

The invention relates to a method for producing methyl acetate

The invention relates to a process for the carbonylation alkylaromatics alcohols, in particular methanol, or ethers of alcohols in the liquid phase with the use of carbon monoxide with its partial pressure to 7 kg/cm2
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