Method of producing carbonylation products

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

 

The present invention in General relates to the production of product by carbonylation carbonylation of alcohol and/or its reactive derivative, in particular the production of product a vapor-phase carbonylation carbonyliron alcohol and/or its reactive derivative in the presence of water and heterogeneous carbonylation catalyst.

Catalyzed by rhodium iodide promoted by carbonyliron methanol in a homogeneous liquid phase reaction medium, in particular, as described, for example, in US 3769329, can be obtained from acetic acid. Catalyzed by rhodium iodide promoted by liquid-phase carbonylation of methanol is a well known process which is carried out in an industrial scale. There is a need in the application of heterogeneous catalysts for carbonylation to facilitate separation of the product from the catalyst. Heterogeneous carbonylation catalysts and their use are described in several patent publications, including, for example, WO 98/57918, EP 0885870 A1 and EP 0353722 A2.

In WO 98/57918 described a method of obtaining a carboxylic acid carbonyliron alcohol and/or its reactive derivative in the liquid phase over heterogeneous carbonylation catalyst comprising noble metals of group VIII of the polymeric resin, having fun is implementing groups, selected from nitrogen-containing heterocycles. To reduce the leaching of the active catalytic material from the material of the carrier during the carbonylation process for the carbonylation add hydrogen.

In EP 0885870 A1 describes a method for carboxylic acids and/or anhydrides of carboxylic acids, which comprises contacting the alcohol and/or ether carboxylic acids, optionally water, the first Hydrocarbonated and/or hydrocellulose essential reagent and the second hydrocarboncontaining promoter with carbon monoxide in the presence of a catalyst comprising an insoluble imidazolidones resin as a carrier metal of group VIII. This method can be carried out in the liquid or vapor phase.

In EP 0353722 A2 describes a method of vapor-phase carbonylation of one or more alcohols, ethers or partial esters of polyhydric alcohols to esters and optional to carboxylic acids over a solid catalyst comprising polyoxometallate anion, the metal of which are taken from groups V and VI of the Periodic table of elements, such as Mo, W, V, Nb, CR and TA, forming a complex with at least one cation of group VIIIA, such as Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt.

In the US 6127432 describes how to transform the source material that includes carbon monoxide and hydrogen in stream p is the FL, including at least one of ester, acid, acid anhydride and mixtures thereof. In the US 6127432 also described a way of turning alcohol, simple ester and/or a partial ester of a polyhydric alcohol in the oxidized products, such as esters, acids, acid anhydrides and their mixtures, which can be carried out in the vapor phase over a heterogeneous catalyst for the carbonylation of alcohols selected from solid superacids, clay, zeolite or molecular sieve. The catalysts for the carbonylation of alcohols include heteroalicyclic, including polyoxometallate anion, the metal or mixture of metals which are selected from metals of groups 4, 5, 6 and 7, form a complex with the cation of the representatives of the metals of groups 7, 8, 9, 10 and/or 11, such as Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt. Preferred heteroalicyclic includes MW12PO40where M denotes Ir, Ru, Rh, Pd and combinations thereof. In the US 6127432 argues that the stability of heterogeneous catalyst for the carbonylation of alcohols improve the application process for the carbonylation of hydrogen or a source material containing hydrogen.

When creating the present invention, it was found that the addition of water in the source material in the vapor phase in heterogeneous carbonylation process in which use heterophilically catalyst comprising one or several who are metal cations, achieve high catalyst activity.

Accordingly, an object of the present invention is a method for carbonylation to obtain a product of the carbonylation introduction of carbon monoxide into contact with the source material, including alcohol and/or its reactive derivative, in the vapor phase using a heterogeneous heteropolyanions catalyst comprising one or more metal cations selected from cu, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt, characterized in that the source material contains at least 0.5 wt.% water.

The present invention also proposes the use of the original material submitted to the carbonyl process water at a concentration of at least 0.5 wt.% to improve the activity of heterogeneous heteropolyanions catalyst comprising one or more metal cations selected from cu, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt, upon receipt of the product carbonylation introduction of carbon monoxide into contact with alcohol and/or its reactive derivative in the vapor phase above mentioned catalyst.

Water can serve as fresh water and/or recycle water.

In a preferred embodiment, water (fresh and/or recycle) in the original material submitted to the carbonyl process is contained in concentric and at least 1 wt.%, in particular at least 2 wt.%.

In a more preferred embodiment, the water in the original material submitted to the carbonyl process is contained in a concentration of at least 5 wt.%.

In a preferred embodiment, water (fresh and/or recycle) in the original material submitted to the carbonyl process is contained in a concentration up to 20 wt.%, in particular up to 15 wt.%. In the most preferred embodiment, the water in the original material submitted to the carbonyl process is contained in a concentration of from 5 to 15 wt.%.

The concept of "heterophilically catalyst comprising one or more metal cations selected from cu, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt"used in this description refer to heteroalicyclic, in which one or more hydrogen ions free heteroalicyclic substituted by at least one of the cations (later replaced by heteroalicyclic). In addition to one or more metal cations selected from cu, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt, heteroalicyclic may include additional cations, such as residual hydrogen ions and/or cations of alkali metals selected from Li, Na, Rb and Cs.

Typically, the anion heteroalicyclic includes from 2 to 18 are linked by oxygen atoms of atoms of polyvalent metals, which in this area is ehniki known as peripheral atoms. These peripheral atoms symmetrically surround the one or more Central atoms. Peripheral atoms are usually one or more atoms of molybdenum, tungsten, vanadium, niobium and tantalum, but they can serve or they can include other metals. The Central atoms are usually atoms of silicon or phosphorus, but they may include any one of a wide variety of atoms of groups I through VIII of the Periodic table of elements. These include, for example, ions of divalent copper, divalent ions of beryllium, zinc, cobalt and Nickel; trivalent ions of boron, aluminum, gallium, iron, cerium, arsenic, antimony, phosphorus, bismuth, chromium and rhodium; ions of tetravalent silicon, germanium, tin, titanium, zirconium, vanadium, sulfur, tellurium, manganese, Nickel, platinum, thorium, hafnium, cerium and other rare earth ions, elements, ions, pentavalent phosphorus, arsenic, vanadium, antimony; ions, hexavalent tellurium ions and heptavalent iodine. Such heteroalicyclic also known as "polyoxoanion", "polyoxometalate or metal oxide clusters. Structures of some well-known anions received the name in honor of the first researchers in this field of technology, for example, the data structures are known as patterns of Keggin (Keggin, wells-Dawson (Wells-Dawson) and Anderson-Evans-Perlova (Anderson-Evans-Perloff).

p> Preferred for use in the method in accordance with the present invention heteroalicyclic include one or more of molybdenum, tungsten, vanadium, niobium, chromium and tantalum as peripheral atoms and silicon or phosphorus as the Central atoms.

Typically, substituted heteroalicyclic contains from 1 to 6 wt.% substituting metal cation, preferably from 3 to 5 wt.%. Substituted heteroalicyclic usually characterized by a high molecular weight, for example in the range from 2000 to 8000, preferably in the range from 2000 to 4000, and may include dimeric complexes.

In a preferred embodiment, substituted heteroalicyclic selected from substituted kremnipolymer acids, criminalizing acids, phosphorus-tungsten acid, phosphomolybdenum acids, such as substituted heteroalicyclic the following free acids:

12-molybdenum-silicon acid -
12-wolframalpha acid -H3[PW12O40]xH2O
12-molybdophosphoric acid -H3[RMO12O40]xH2O
12-valtravaglia acid -H4[SiW12O40]xH2O
H4[SiMo12O40]xH2O

In a preferred embodiment, a metal cation selected from one or more of the atoms of rhodium, iridium and copper, it represents, in particular, rhodium or iridium cation. Rhodium is the most preferred metal cation.

Substituted heteroalicyclic in the preferred embodiment, supported on a carrier. In a suitable embodiment, the carrier may be selected from oxide carriers such as silica, silica/alumina, zeolites, clays, diatomaceous earth, titanium dioxide and aluminum oxide. Other, non-oxide carriers that can be used include silicon carbide, organic polymers, such as cross-linked polystyrene, and coals. Media, such as silicon-containing media, in a suitable embodiment is in the form of granules, beads, balls, extrudates or tablets.

When substituted heteroalicyclic applied to the media, this replaced heteroalicyclic usually contained in an amount of from 20 to 70 wt.% from the total mass supported on a carrier substituted heteroalicyclic, i.e. substituted heteroalicyclic is from 20 to 70 wt.% from the total mass of substituted heteroalicyclic and media. When in the preferred embodiment, samisen the th heteroalicyclic applied to the carrier, this replaced heteroalicyclic is contained in an amount of from 30 to 65 wt.% from the total mass supported on a carrier substituted heteroalicyclic.

In a preferred embodiment, the alcohol is an aliphatic alcohol containing from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, including methanol, ethanol, propanol, isopropanol, butanol, pentanol and hexanol. The preferred alcohol is methanol.

The reactive derivative of the alcohol, which can be used as an alternative or in addition to alcohol, include one or more simple dialkylamino esters, esters of alcohol and alkylhalogenide. Acceptable reactive derivatives of methanol include, for example, 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.

When in conjunction with alcohol use reactive derivative, such as a simple ether and ester alcohol, this simple ether and/or ester is contained in an amount up to equimolar relative to the amount of water in the source material.

Reactive derivative, such as a simple ether and ester alcohol, can be used in the form of fresh source material or obtained from the recycle stream.

The carbonylation product is a carboxylic acid and/or the corresponding ester of carboxylic acid. Thus, when the spirit of the source material using methanol carbonylation product comprises acetic acid and/or methyl acetate.

During the carbonylation process as a by-product of the esterification can be obtained from water. This water may be returned to the reactor. In order to maintain the target water concentration in the source material is directed into the reactor, in addition to all the water that can be returned to the process, it may be necessary to add in the source material for the carbonylation reaction of "fresh" water.

Carbon monoxide as a reactant may be essentially pure or may include impurities such as carbon dioxide, methane, nitrogen, inert gases and paraffin hydrocarbons with C1With4.

Carbon monoxide (CO) can be contained in the reaction medium under any acceptable partial pressure, such as partial pressure of at least 0.1 bar. More specifically, it is possible to send to the reactor at an acceptable molar ratio to the spirit of the source material (and/or a reactive derivative), preferably with a molar ratio WITH the alcohol of at least 1:1, in particular at m is re 5:1, and/or up to 20:1, most preferably in the range from 5:1 to 15:1.

In a preferred embodiment of the present invention, the carbonylation reaction can be carried out in the presence of hydrogen. Hydrogen reagent can be directed into the reactor in the form of essentially pure hydrogen source material, or the flow of the hydrogen source material may include impurities, such as oxides of carbon and nitrogen. When the method according to the present invention using hydrogen as a source of both hydrogen and carbon monoxide is particularly expedient synthesis gas.

Hydrogen, when used, can be contained in the reaction medium in any acceptable concentrations, in particular under a partial pressure of at least 0.1 bar, and it serves mainly either alone or in combination with carbon monoxide, resulting in a molar ratio of hydrogen to carbon monoxide in the reactor is at least 1:20, in particular from 1:20 to 20:1, most preferably in the range from 1:10 to 10:1.

The method according to the invention can be carried out under a pressure below atmospheric, but in the preferred embodiment, performed under General gauge pressure in the range from 1 to 100 bar, preferably from 1 to 20 bar.

In a useful embodiment, this method is carried out at a temperature in the range from 100 d is 300C, moreover, the practical upper operating temperature depends on thermal stability of the catalyst. In a preferred embodiment, the temperature is in the range from 150 to 250C., most preferably in the range from 200 to 250C.

In an expedient embodiment, the method is carried out by introduction of reagents into contact with the catalyst at an average hourly rate of gas supply (SPG) in the range from 100 to 10000 h-1preferred is SPG is in the range from 500 to 5000 h-1.

The method can be carried out by periodic or continuous process, preferably as a continuous process.

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

Examples

The preparation of the catalyst And

Substituted rhodium heterophilically catalyst was prepared as follows. RhCl3H2O (company Aldrich, FW: 209,26, 0,774 g) was dissolved in methanol (about 200 ml) with stirring for 30 minutes, stirring Once rhodium mixture with stirring for 1 h was added 12-wolframite acid (H3[W12About40]xH2About the firm Aldrich, FW: 2280 g/mol, 10,657 g). Then added 6,416 g of silicon dioxide (company Grace, grade G57, FW: 60 g/mol, with a particle size of from 1 to 2 mm). Then, the solution was stirred for 4 h after 4 h, the flask was transferred into a rotary evaporate the and under reduced pressure 337 mbar for 1 h, methanol was removed by obtaining a red-orange solid. This solid material was crushed using mortar and pestle and then sieved to obtain catalyst with a particle size of from 0.5 to 1.0 mm

Test method for catalyst

Conducted a series of experiments with varying concentrations of water in the source material, and two different hourly average flow rates of gas (SPG).

Examples 1 to 3

5 ml (approx. 5 g) of catalyst was loaded in a quartz tubular reactor with a support Frit located in the middle of the tube. Next, the reactor above the catalyst additionally filled borosilicate glass beads. The reactor was placed in the middle of the vertical furnace with an insulating sheath at the top and the bottom of the furnace. In a quartz reactor was applied monoxide and methanol in a molar ratio of FROM:Meon 9:1. In the upper part of the reactor through a flow meter was sent monoxide in gas flow rate of 150 ml/min. After I made steady stream, after 2 to 3 min, the furnace is gradually heated (5C/min) to 100C. Oven kept at 100C for 20 min to remove from the catalyst main parts of water, and after this time the furnace was slowly heated (5C/min) to 230C. the System was left at a high temperature for 15 min for complete equilibration, and then at the top part of the reactor through a syringe is th pump filed liquid methanol and water (when used) (the parameters of the flow of the liquid source material, see below in table 1). Liquid and gaseous reagents passed down the reactor in the liquid trap. Liquid trap consisted of a coil condenser immersed in an ice bath, where he identified the liquid products. Gaseous products were discharged into the atmosphere through the T-shaped element including a membrane for gas-sampling using a gas syringe. Liquid trap, usually replaced every hour and in the middle of each time interval, a sample was taken for gas. Liquid samples were analyzed in a gas chromatograph equipped with a column of boiling point and TKD detector. Samples of gas were analyzed chetyrehkolenny a gas chromatograph. After the reaction before removing the reactor from the installation of the system was fully purged with nitrogen. SSPG was 1800/h the reaction Products were acetic acid and methyl acetate.

The results of examples 1 to 3 are presented below in table 2.

Experiment And

Test method of the catalyst was carried out as in examples 1 to 3, except that the source material for the carbonylation reaction of water was added. The results of the experiment And are presented below in table 2.

Examples 4 and 5

Test method of the catalyst was carried out as in examples 1 to 3, except that SPG 900/h, and used 10 ml of catalyst A. financial p the tats experiments 4 through 6 are presented below in table 3.

Experiment B

Test method of the catalyst was carried out as in examples 4 and 5, except that the source material for the carbonylation reaction of water was added. The results of experiment B are presented below in table 3.

Table 1
The parameters of the liquid source material
The water in the source material (wt.%)The feed rate of methanol (ml/h)The feed rate of H2O (ml/h)
01,600,00
51,520,08
10the 1.440,16
151,360,24

Table 2
The results for examples 1 to 3 and experiment And
conditions: 230C., a gauge pressure: 1 bar, reaction time: 3 h
Example/Experiment The water content (wt.%)Pribram. Meon (%)The selectivity in respect of the product (%)
And017,894,0
1522,795,8
21032,895,9
31529,395,5

Table 3
The results for examples 4 and 5 and experiment B
conditions: 230C., a gauge pressure: 1 bar, reaction time: 3 h
Example/ExperimentThe water content (wt.%)Pribram. Meon (%)The selectivity in respect of the product (%)
B022,098,1
4523,0 the 98.9
51023,8the 98.9

The results presented in tables 2 and 3 show that increasing the amount of water in the source material, which is directed to the carbonylation reaction can be achieved by improved conversion of methanol. In the presence together feedwater note also the increase of selectivity with respect to the product in comparison with what happens in its absence. In experiments at higher space velocities in the reactor also become more noticeable increase in activity and selectivity. Thus, in particular, in example 2 it is shown that the conversion of methanol increases from 17.8 wt.% in the absence of a joint water supply to 32.8 wt.% in a joint submission 10 wt.% water, whereas the selectivity for the relevant product increases with 94,0 to 95.9 per cent.

1. The way carbonylation to obtain a product of the carbonylation by contacting the carbon monoxide with the source material, including alcohol and/or its reactive derivative, in the vapor phase using a heterogeneous heteropolyanions catalyst comprising one or more metal cations selected from Cu, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt, characterized in that the source materialsmaterials from 0.5 to 20 wt.% water and the water in the source material is fresh and/or recycle water.

2. The method according to claim 1, wherein the source material comprises at least 1 wt.% water.

3. The method according to claim 1, wherein the source material comprises at least 2 wt.% water.

4. The method according to claim 1, wherein the source material comprises at least 5 wt.% water.

5. The method according to claim 1, wherein the source material comprises up to 15 wt.% water.

6. The method according to claim 1, wherein the source material comprises from 5 to 15 wt.% water.

7. The method according to claim 1, in which heteroalicyclic contains from 1 to 6 wt.% metal cations (cations).

8. The method according to claim 1, in which heterophilically the catalyst comprises a metal cation selected from rhodium, iridium and copper.

9. The method according to claim 8, in which the metal cation is rhodium.

10. The method according to claim 1, in which heteroalicyclic includes peripheral atom selected from the group comprising molybdenum, tungsten, vanadium, niobium, chromium and tantalum, and the Central atom selected from silicon and phosphorus.

11. The method according to claim 1, in which heteroalicyclic chosen from the group comprising substituted crenneville acid, criminalidade acid, phosphorus-tungsten acid and phosphomolybdenum acid.

12. The method according to claim 1, in which heteroalicyclic includes one or more cations selected and the residual hydrogen ions and cations of alkali metals.

13. The method according to claim 1, in which heterophilically the catalyst is applied to the media.

14. The method according to item 13, in which the carrier is selected from an oxide carrier and non-oxide media.

15. The method according to 14, in which the oxide carrier selected from the group comprising silicon dioxide, aluminium oxide, silica/alumina, zeolites, clays, diatomaceous earth and titanium dioxide.

16. The method according to item 15, in which the non-oxide carrier selected from the group including silicon carbide, coal, and organic polymers.

17. The method according to item 13, in which heteroalicyclic is from 20 to 70 wt.% in terms of the total weight of heteroalicyclic and media.

18. The method according to claim 1, wherein the alcohol is an aliphatic alcohol with C1C12.

19. The method according to p, in which the alcohol is selected from methanol, ethanol, propanol, isopropanol, butanol, pentanol and hexanol.

20. The method according to claim 1, in which a reactive derivative of an alcohol selected from at least one of dialkylamide ester, complex ester of the alcohol and alkylhalogenide.

21. The method according to claim 20, in which a reactive derivative selected from at least one of methyl acetate, dimethyl ether and under the conditions.

22. The method according to claim 1, wherein the source material includes alcohol and its reactive derivative.

23. The method according to item 22, in the cat the rum reactive derivative is a simple ether or ester of the alcohol.

24. The method according to item 23, in which a simple ether and/or ester is contained in an amount up to equimolar relative to the amount of water in the source material.

25. The method according to claim 1, wherein the carbonylation product selected from at least one carboxylic acid and ether carboxylic acid.

26. The method according A.25, in which the carbonylation product selected from at least one of acetic acid and methyl acetate.

27. The method according to claim 1, in which the molar ratio of carbon monoxide to alcohol is in the range from 5:1 to 15:1.

28. The method according to claim 1, wherein the source material includes hydrogen.

29. The method according to p, in which the molar ratio of hydrogen to carbon monoxide is in the range from 1:20 to 20:1.

30. The method according to claim 1, in which carbon monoxide is used in the form of synthesis gas.

31. The method according to claim 1, in which the process is carried out at a temperature in the range from 100 to 300C.

32. The method according to claim 1, in which the process is performed under a gauge pressure in the range from 1 to 100 bar.

33. The method according to claim 1, in which the hourly average gas flow rate is in the range from 100 to 10000 h-1.

34. The method according to claim 1, wherein the process is conducted as a continuous process.

35. The way carbonylation to obtain a product of the carbonylation by contacting the carbon monoxide with the source material, on the expectation methanol, in the vapor phase using a heterogeneous heteropolyanions catalyst comprising one or more metal cations selected from rhodium, iridium and copper, characterized in that the source material contains from 5 to 15 wt.% water, and the water in the source material is fresh and/or recycle water.



 

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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.

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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)

The invention relates to a method for producing acetic acid and/or methyl acetate in the liquid phase, in the presence of carbon monoxide and the catalytic system, and to a method of increasing the stability and lifetime of the catalyst utilized

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

The invention relates to the production of carboxylic acids (C2- C11or the corresponding esters by the interaction of carbon monoxide with at least one reagent selected among alcohols, alkylhalogenide, simple or complex esters, in the presence of a catalytic system comprising at least one rhodium compound and at least one iridium compound or at least one compound containing both metal and at least one halogenated promoter

FIELD: explosives.

SUBSTANCE: method is described for reducing amount and/or removing permanganate-reducing compounds for methanol carbonylation process to produce acetic acid, where the method involves a stage for separating the said carbonylation product, resulting in a volatile fraction containing acetic acid, organic iodide, water and at least one permanganate-reducing compound, and a less volatile fraction; distillation of the said volatile fraction, resulting in a purified acetic acid product and a first overhead fraction containing organic iodide, water, acetic acid and at least one permanganate-reducing compound; distillation of at least part of the first overhead fraction in a first distillation apparatus to form a second overhead fraction rich in permanganate-reducing compound; addition of dimethyl ether to the second overhead fraction, extraction of the second overhead fraction with water to form a second overhead extraction stream and a water stream containing at least one permanganate-reducing compound and separation from the water stream, containing at least one permanganate-reducing compound; and returning at least the first part of the extracted second overhead fraction to the said distillation apparatus, method of producing acetic acid and method of separating a mixture obtained during carbonylation of methanol.

EFFECT: more efficient removal of permanganate-reducing compound from a system by returning part of the stream of purified product, reduced loss during waste removal.

34 cl, 2 dwg

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