Method of producing acetic acid

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of preventing precipitation of a catalyst system when producing acetic acid via carbonylation of methanol and/or reactive derivative thereof with carbon monoxide in at least one carbonylation reaction zone, containing a liquid reaction composition containing an iridium carbonylation catalyst, a methyl iodide cocatalyst, water in an a limited concentration, acetic acid, methyl acetate and boron and gallium as promoters.

EFFECT: combination of boron and gallium as promoters enables to avoid problems with precipitation which are observed in ruthenium-promoted reactions, and the rate of reaction also remains the same compared with conventional ruthenium promoters.

15 cl, 2 tbl, 1 ex

 

The present invention relates to a method for producing acetic acid, in particular to a method for producing acetic acid by carbonyliron methanol and/or its reactive derivative in the presence of promoted iridium catalyst.

Obtaining acetic acid carbonyliron methanol in the presence of an iridium catalyst and promoter such as ruthenium, as described, for example, in EP-A-0752406, EP-A-0849248, EP-A-0849249 and EP-A-1002785.

In EP-A 0643034 describes how carbonylation of methanol and/or its reactive derivative in the presence of acetic acid, the iridium catalyst, under the conditions, the water in at least a limited concentration of acetate and promoter selected from ruthenium and osmium.

In EP-A 0749948 describes how carbonylation of aliphatic alcohol, such as methanol and/or its reactive derivative to obtain the corresponding carboxylic acid and/or a complex ester in the presence of iridium catalyst, alkylhalogenide, water and at least one promoter selected from cadmium, mercury, zinc, gallium, indium and tungsten, optional with copromotion selected from ruthenium, osmium and rhenium.

In the carbonylation process using the iridium catalyst promoted with ruthenium, it was found that the higher the concentration about otara, the higher the reaction rate. However, it was also found that in certain conditions can cause loss of catalytic systems in the sediment.

Thus, there remains a need to develop a method catalyzed by iridium-promoted carbonylation, in which the above disadvantages are reduced.

The implementation of the present invention enables to solve the above technical problem by applying not promoted by ruthenium-iridium catalyst system, which includes iridium, boron and gallium.

Accordingly, an object of the present invention is a method for acetic acid carbonyliron methanol and/or its reactive derivative with carbon monoxide in at least one reaction zone carbonyl containing a liquid reaction composition comprising iridium carbonylation catalyst, methyliodide socialization, water in limited concentrations, acetic acid, methyl acetate and as promoters of boron and gallium.

It was found that by applying promoted boron and gallium iridium catalytic system eliminates the need for the ruthenium promoter, while maintaining a satisfactory reaction rate of carbonylation. In addition, boron/gallium/iridium catalyst with the system, used in the proposed method, has a lower cost when compared with promoted ruthenium catalyst system.

In addition, there are environmental benefits associated with the proposed catalytic system because it has a lower toxicity compared to promoted with ruthenium iridium catalytic system.

In the method according to the present invention is acceptable reactive derivatives of methanol include methyl acetate, dimethyl ether and methyliodide. As reagents in the method according to the present invention can use a mixture of methanol and its reactive derivatives. As coreagent for ether or ester reagents required water. In the preferred embodiment, as reagents using methanol and/or methyl acetate.

Due to the reaction of the resulting carboxylic acid or solvent at least some amount of methanol and/or reactive derivative usually becomes and, hence, is contained in the liquid reaction compositions in the form of acetate. In a preferred embodiment, the concentration of methyl acetate in the liquid reaction composition is in the range from 1 to 70 wt.%, more preferably from 2 to 50 wt.%, most preferably from 3 to 35 wt.%.

In the liquid reaction compositions in situ may form water, for example due to the esterification reaction between methanol reagent and the resulting acetic acid. Water can enter into the reaction zone of a carbonylation together or separately from other components of the liquid reaction composition. Water can be separated from other components of the liquid reaction composition withdrawn from the reaction zone and can be returned to the process in regulated quantities to be maintained in the liquid reaction composition to the desired concentration with water. In a preferred embodiment, the water concentration in the liquid reaction composition is in the range from 0.1 to 20 wt.%, more preferably from 1 to 15 wt.% and yet even more preferably from 1 to 10 wt.%.

In a preferred embodiment, the concentration methyliodide of socializaton in the liquid reaction composition is in the range from 1 to 20 wt.%, preferably from 2 to 16 wt.%.

The iridium catalyst in the liquid reaction composition may include any iridectomies compound which is soluble in this liquid reaction composition. The iridium catalyst can be added to the liquid reaction composition in any acceptable form, in which it dissolves in the liquid reaction composition or is capable of becoming soluble in F. the RMU. In a preferred embodiment, iridium can be used as free from chloride compounds, such as acetates, which are soluble in one or more components of the liquid reaction composition, for example in water and/or acetic acid, and, thus, can be introduced into the reaction in the form of solutions in them. Examples of acceptable iridectomies compounds that can be added to the liquid reaction composition include IrCl3, IrI3, IrBr3, [Ir(CO)2I]2, [Ir(CO)2Cl]2, [Ir(CO)2Br]2, [Ir(CO)4I2]-H+, [Ir(CO)2Br2]-H+[Ir(CO)2I2]-H+, [Ir(CH3)I3(CO)2]-N+Ir4(CO)12, IrCl34H2O, IrBr34H2O Ir3(CO)12metal iridium, Ir2O3, IrO2Ir(ASAS)(CO)2Ir(ASAS)3acetate iridium [Ir3O(SLA)6(H2O)3][SLA] and hexachloroiridium acid, H2[IrCl6]preferably free from chloride complexes of iridium such as acetates, oxalates and acetoacetates.

The preferred concentration of the iridium catalyst in the liquid reaction composition is in the range from 100 to 6000 Mas. hours/million iridium.

The liquid reaction composition include Borovo and gallium promoters. Promoters monogamously in the liquid reaction composition for the carbonylation reaction in any acceptable form, in which it is dissolved in the liquid reaction composition or is able to turn into a soluble form.

Examples of acceptable geliysoderzhaschih compounds which can be used include gallium acetylacetonate, gallium acetate, GaCl3, Gabr data member3, GaI3, GaCl4and Ga(OH)3.

Examples of acceptable boron compounds which may be used include boric acid, BCl3and BI3.

In the preferred embodiment, each promoter is contained in an effective amount, up to the limit of its solubility in the liquid reaction composition and/or any liquid process streams returned from the stage of selection of acetic acid in the reactor for carbonylation. A suitable content of each promoter in the liquid reaction compositions is such that the molar ratio between the promoter and the iridium is [from greater than 0 to 15]:1, in particular in the range [1 to 10]:1. Acceptable concentration of each promoter in the liquid reaction composition is less than 8000 hours/million

In a suitable embodiment, the molar ratio of iridium/boron/gallium can be in interval 1:[from greater than 0 to 15]:[from greater than 0 to 15], in particular 1:[1 to 10]:[1 to 10].

In a preferred embodiment, iridium, boron and kalisoderjasimi connection free of impurities that create or about the will is formed in situ the ionic iodides, which are able to inhibit the reaction, for example, salts of alkaline or alkaline-earth metals, or other metals.

In the liquid reaction composition should maintain a minimum concentration of ionic impurities, such as, for example, (a) correlated metals, particularly Nickel, iron and chromium, and (b) phosphines, nitrogen-containing compounds or ligands which are capable of quaternization in situ, as they have, apparently, undesired influence on the course of the reaction due to the formation in the liquid reaction composition of ions of the I-that have a negative impact on reaction rate. Some correlated metallic impurities, such as molybdenum, are, as has been established, less sensitive to the selection of ions of the I-. The content of corroding metals, which have a negative effect on the rate of reaction can be reduced to a minimum by the use of acceptable corrosion resistant structural materials. Likewise, you should maintain a minimum concentration of such impurities as iodides of alkali metals, such as lithium iodide. The concentration of corroding metals and other ionic impurities can be reduced by applying a layer of ion-exchange resins suitable for processing of the reaction composition, the sludge is, preferably returned to the process stream with the catalyst. In a preferred embodiment, the content of ionic impurities is supported below the concentration at which they would have the ability to highlight in the liquid reaction composition 500 hours/million I-preferably less than 250 hours/million

Carbon monoxide as a reactant for carbonylation reactions may be substantially pure or may include inert impurities such as carbon dioxide, methane, nitrogen, noble gases, water and paraffin With1-C4the hydrocarbons. In a preferred embodiment, the concentration of hydrogen contained in the carbon monoxide formed in situ during the reaction the conversion of water gas, is maintained at a low level; for example, its partial pressure is less than 1 bar, as its presence can lead to the formation of hydrogenation products. Acceptable partial pressure of carbon monoxide is in the range from 1 to 70 bar, preferably from 1 to 35 bar, and more preferably from 1 to 15 bar.

The total gauge pressure of the carbonylation reaction in a suitable embodiment is in the range from 1.0 to 20.0 MPa (from 10 to 200 bar), preferably from 1.0 to 10.0 MPa (from 10 to 100 bar), more preferably from 1.5 to 5.0 MPa (15 to 50 bar). The preferred temperature reacts and carbonylation is in the range from 150 to 220C.

The method according to the present invention can be implemented in the form of periodic or continuous process, preferably as a continuous process.

The resulting carboxylic acid can be isolated from the reaction zone of a carbonylation drainage of the liquid reaction composition and separation of the resulting acetic acid by implementing one or more stages of a single equilibrium evaporation and/or fractional distillation from the other components of the liquid reaction composition, such as iridium catalyst, boron and gallium promoters, methyliodide, water and unused reagents that can be returned to the reaction zone of a carbonylation in order to maintain their concentration in the liquid reaction composition.

The method according to the present invention can be implemented in a single reaction zone or it can be implemented in two or more reaction zones. When using two or more reaction zones, the liquid reaction composition and the reaction conditions in the reaction zones may be the same or different.

The present invention is further illustrated only as an example with reference to the following examples.

General method for the reaction

All experiments were carried out in zirconium autoclave with a capacity of 300 cm3the equipment is consistent with a stirrer and a device for injection of fluid. The autoclave was tested with a gauge pressure of nitrogen of at least 30 bar, and then three times was purged with carbon monoxide under a gauge pressure up to 3 bar. In the autoclave was loaded source material, including the acetate, acetic acid, methyliodide, water and promoter, and in addition to the original material was injected a small amount of carbon monoxide. In the ballast tank was injected carbon monoxide under pressure.

The autoclave was heated with stirring (1500 rpm) up to 190C. the System for injection of the catalyst was filled with a solution of acetate of iridium (approx, 5 wt.% iridium, 26% water, 62.7% of acetic acid and acetic acid, and the contents were injectively under pressure of carbon monoxide with bringing gauge pressure in the autoclave up to 28 bar.

For the reaction rate was monitored via pressure drop of carbon monoxide supplied from the ballast vessel. During the whole reaction in the autoclave was maintained constant temperature of 190C and a gauge pressure of 28 bar. After cessation of absorption of carbon monoxide from the ballast vessel autoclave was separated from the product gas and cooled. After cooling, a sample was taken for gas analysis and the autoclave was ventolinbuy. The liquid components were extracted and analyzed for the liquid by-products on the known and proven methods of gas is howling chromatography. Detected components were quantified by integration of the peaks of these components relative to an external standard and expressed in mass parts per million (h/m). The main product obtained in each of the experiments with the carbonyl process was acetic acid.

The absorption rate of gas at some point in the course of the reaction was used to calculate the rate of carbonylation in the form of the number of moles of the spent reagent per liter of cold degassed composition in the reactor per hour (mol/l/h) at a particular composition in the reactor (the entire composition in the reactor in terms of the amount of cold degassed material).

The concentration of acetate in the course of the reaction was calculated by the original composition, assuming that for every mole of carbon monoxide, which was spent, spent one mol of acetate. No amendments to the organic components in the free space above the liquid in the autoclave did not. According to conventional methods of gas chromatography analyses of gaseous by-products of the cooled gas in the free space above the liquid and used the results calculated in the form of selectivity in % in terms of consumption of acetate to methane and consumption for CO2.

Examples

Experiment And

Babyexpert was performed using the autoclave, in the uploaded solution of iridium acetate and the acetate solution of ruthenium (5% ruthenium, 18% water and 72% acetic acid). The number of components loaded in the autoclave, is presented in the following table 1. The reaction rate for the calculation of the reaction composition, comprising 12% of methyl acetate, are presented in table 1.

Experiment B

The experiment was repeated except that the autoclave was loaded gallium iodide solution. The number loaded into the autoclave are shown in table 1, and the results of this experiment are shown in table 2.

Experiment

The experiment was repeated, except that instead of the ruthenium solution in the autoclave was loaded a solution of boric acid. The number loaded into the autoclave are shown in table 1, and the results of this experiment are shown in table 2.

Example 1

The experiment was repeated except that the autoclave was loaded a solution of boric acid and gallium iodide. The number loaded into the autoclave, are presented in table 1, and the results of this experiment are presented in table 2.

The results in table 2 show that a combination of boron and gallium promotiom catalyzed by iridium process for the carbonylation of methanol without any significant loss of speed carbonylation.

0,02
Table 1
The contents of the autoclave
ExperimentThe catalytic system (molar ratio)The acetate solution Ir (g)The acetate solution EN (g)Boric acid (g)The gallium iodide (g)The acetate (g)Water (g)Methyliodide (g)Acetic acid (g)
Experiment AndIr/Ru (1:2)6,66,870048,012,6413,3365,28
Experiment BIr/Ga (1:2)6,6001,5848,013,813,3366,7
ExperimentIr/B (1:2)6,60048,013,814,8066,7
Example 1Ir/B/Ga (1:1,3:1,3)9,900,22of 1.5748,013,1714,8064,65

Table 2
Data speed and side products
ExperimentThe speed with 12 wt.% Meoac, mol/l/hPropionic acid (h/m)The selectivity for methane, %The selectivity for CO2, %
Experiment And194001,51
Experiment B12,46501,01,4
The experimental is t 13,73800,61,0
Example 1176401,61,1

1. The way to prevent loss of the catalytic system in the sediment upon receipt of acetic acid carbonyliron methanol and/or its reactive derivative with carbon monoxide in at least one reaction zone carbonyl containing a liquid reaction composition comprising iridium carbonylation catalyst, methyliodide socialization, water in limited concentrations, acetic acid, methyl acetate and as promoters of boron and gallium.

2. The method according to claim 1, in which the boron promoter and gallium promoter each is contained in the liquid reaction composition at a molar ratio of promoter to iridium [from greater than 0 to 15]:1.

3. The method according to claim 1, in which the molar ratio of iridium:boron:gallium is in interval 1:[1 to 10]:[1 to 10].

4. The method according to one of claims 1 to 3, in which the concentration of each promoter in the liquid reaction composition is less than 8000 million-1.

5. The method according to claim 1, in which the concentration of iridium in the liquid reaction composition is in the range from 100 to 6000 m in the n -1.

6. The method according to claim 1, in which the water is contained in the liquid reaction composition at a concentration in the range of from 0.1 to 20 wt.%.

7. The method according to claim 6, in which the water concentration is in the range from 1 to 15 wt.%.

8. The method according to claim 7, in which the water concentration is in the range from 1 to 10 wt.%.

9. The method according to claim 1, wherein the acetate is contained in the liquid reaction composition at a concentration in the range from 1 to 70 wt.%.

10. The method according to claim 1, in which methyliodide contained in the liquid reaction composition at a concentration in the range from 1 to 20 wt.%.

11. The method according to claim 1, wherein the carbonylation reaction is performed under General gauge pressure in the range from 1 to 20 MPa.

12. The method according to claim 1, wherein the carbonylation reaction is carried out at a temperature in the range of from 150 to 220C.

13. The method according to claim 1, wherein the carbonylation reaction is carried out in a single reaction zone of a carbonylation.

14. The method according to claim 1, wherein the carbonylation reaction is carried out in at least two areas of the carbonylation reaction.

15. The method according to claim 1, which is carried out in a continuous process.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing acetic acid through carbonylation of methanol and/or reactive derivative selected from methyl acetate, methyl iodide, dimethyl ether and mixtures thereof, carbon monoxide in the presence of a catalyst in a liquid reaction mixture containing methyl iodide and water in concentration of 0.1-30 wt %, wherein the catalyst includes a complex of a metal with a chelate-like ligand of general formula (I), wherein Z represents carbon, each of L1 and L2 represents a coordination group containing a donor P atom or a donor N atom; each R3 is independently selected from hydrogen, or a C1-C6 alkyl group, and M is selected from Rh and Ir; or general formula (II), wherein Z represents carbon, each of L3 and L4 represents a coordination group containing a donor P atom or a donor N atom, and M is selected from Rh and Ir.

EFFECT: method provides high selectivity of formation of acetic acid.

14 cl, 2 tbl, 6 ex

FIELD: chemistry.

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

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

41 cl, 2 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing acetic acid via carbonylation of methanol and/or reactive derivative thereof with carbon monoxide in at least one carbonylation reaction zone, containing a liquid reaction composition containing a iridium carbonylation catalyst, a methyl iodide cocatalyst, water in an a limited concentration, acetic acid, methyl acetate and ruthenium and at least one of niobium salt or tantalum salt as promoters.

EFFECT: method enables to conduct carbonylation with considerably smaller amounts of by-products while simultaneously maintaining an acceptable rate of reaction.

16 cl, 2 tbl, 2 ex

FIELD: chemistry.

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

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

23 cl, 1 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a 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 600C. 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

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 purifying acetic acid, which can be used in microelectronics, liquid chromatography, in chemical, food and medical industry. The purification method involves treating the initial acetic acid with a chemical reagent, rectification purification of the pre-treated acetic acid, where the chemical reagent used at the pre-treatment step is hydrogen peroxide with volume ratio of acetic acid to hydrogen peroxide equal to 180-220:1, where treatment is carried out while stirring at a rate of 40-80 rpm at temperature 0-20C, and the periodic rectification step is carried out in a column filled with filtered inert gas, with reflux ratio of 20-10 with collection of the solvent stripper and 8-5 with collection of the product, at pressure 200-700 mmHg, and temperature at the bottom of the column equal to 90-120C and 80-118C at the head of the column.

EFFECT: obtaining a product containing 99,96-99,99 wt % basic substance and suspended particles on the level of 80-200 per cm3.

5 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of increasing utilisation factor of silver during adsorption and removal of decyl iodide from acetic acid which contains decyl iodide as an impurity, by passing acetic acid through a packed layer of a cation-exchange resin at temperature 50C or lower, where the cation-exchange resin is a macroporous-type polystyrene resin with average particle size ranging from 0.3 to 0.6 mm and average pore size from 15 to 28 nm, and where the resin has sulpho groups, and silver occupies 40-60% of the active sites of sulpho groups.

EFFECT: high utilisation factor of silver during adsorption and removal of decyl iodide from acetic acid.

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 an improved method of producing acetic acid through carbonylation of methanol and/or reactive derivative selected from methyl acetate, methyl iodide, dimethyl ether and mixtures thereof, carbon monoxide in the presence of a catalyst in a liquid reaction mixture containing methyl iodide and water in concentration of 0.1-30 wt %, wherein the catalyst includes a complex of a metal with a chelate-like ligand of general formula (I), wherein Z represents carbon, each of L1 and L2 represents a coordination group containing a donor P atom or a donor N atom; each R3 is independently selected from hydrogen, or a C1-C6 alkyl group, and M is selected from Rh and Ir; or general formula (II), wherein Z represents carbon, each of L3 and L4 represents a coordination group containing a donor P atom or a donor N atom, and M is selected from Rh and Ir.

EFFECT: method provides high selectivity of formation of acetic acid.

14 cl, 2 tbl, 6 ex

FIELD: chemistry.

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

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

41 cl, 2 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing acetic acid via carbonylation of methanol and/or reactive derivative thereof with carbon monoxide in at least one carbonylation reaction zone, containing a liquid reaction composition containing a iridium carbonylation catalyst, a methyl iodide cocatalyst, water in an a limited concentration, acetic acid, methyl acetate and ruthenium and at least one of niobium salt or tantalum salt as promoters.

EFFECT: method enables to conduct carbonylation with considerably smaller amounts of by-products while simultaneously maintaining an acceptable rate of reaction.

16 cl, 2 tbl, 2 ex

FIELD: chemistry.

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

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

23 cl, 1 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a 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 600C. 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

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: oil and gas industry.

SUBSTANCE: invention refers to the formed catalyst with specified high density and with specified low ratio of platinum group component to stannum, and deals with application method of catalyst for conversion of hydrocarbons. There described is conversion catalyst of hydrocarbons, which includes platinum group metal, stannum and substrate, and has average bulk density which is more than 0.6 g/cm3, and preferably more than 0.65 g/cm3, in which mass ratio of platinum group metal to stannum is less than 0.9, and preferably less than 0.85, where platinum is platinum group metal in amount of 0.01 to 2.0 wt %, on a per element basis, and where the above catalyst includes associated stannum in specific clusters from stannum and metals of platinum group in quantity of at least 33 wt %, and effective molar ratio of associated stannum to platinum in the above clusters is at least 0.65 as per Moessbauer spectroscopy analysis. There also described is conversion method of hydrocarbons, which involves contact of hydrocarbon material with the above catalyst at conversion conditions of hydrocarbons, converted hydrocarbon, where catalyst includes metal of platinum group, stannum and substrate, has average bulk density which is more 0.6 g/cm3, where mass ratio of metal of platinum group to stannum is less than 0.9.

EFFECT: technological advantages of conversion of hydrocarbon material.

10 cl, 3 ex, 6 tbl

Up!