Carbonylation method using catalysts with metal polydentate ligands

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

 

The present invention, in General, relates to a method of liquid-phase carbonylation of an alcohol and/or its reactive derivative. Thus, in particular, the present invention relates to the liquid-phase carbonyliron alcohol and/or its reactive derivative in the presence of hydrogen and a catalyst comprising rhodium or iridium, coordinated with polydentate ligand.

Obtaining carboxylic acids by means catalyzed by rhodium carbonylation known and described, for example, in EP-A-0632006 and US No. 4670570.

In EP-A-0632006 described by way of liquid-phase carbonylation of methanol or its reactive derivative, and this method comprises contacting carbon monoxide with a liquid reaction mixture containing methanol or its reactive derivative, halogen promoter and rhodium catalytic system containing a rhodium component and a bidentate phosphorus-sulphur ligand, and the ligand comprises phosphoric datiny center associated with sulfur datiny or anionic center essentially directionspanel structure of the main circuit containing two connecting carbon atom or the connecting carbon and connecting the phosphorus atoms.

Obtaining carboxylic acids by means catalyzed by iridium carbonylation known and described the, for example, in EP-A-0786447, EP-A and EP-A-0752406.

In EP A-0643034 describes a method for acetic acid carbonyliron methanol or its reactive derivative, including the introduction of methanol or its reactive derivative in contact with carbon monoxide in a liquid reaction mixture in the reactor for carbonylation, characterized in that the liquid mixture contains (a) acetic acid, (b) an iridium catalyst, (C) methyliodide, (d) water in at least a limited quantity, (e) acetate and (e) as a promoter, at least one of elements such as ruthenium and osmium.

Application chelat forming bidentate phosphorus or arsenic ligand in ways carbonylation is known, e.g. from GB 2336154, US 4102920 and US 4102921.

In GB 2336154 described by way of liquid-phase carbonylation of an alcohol and/or its reactive derivative with obtaining a carboxylic acid in the presence of a bidentate ligand of the formula R1R2X-Z-YR5R6in which X and Y independently represent N, P, As, Sb or Bi, Z represents a divalent connecting group.

In the US 4102920 describes how carbonylation of alcohols, esters, ethers and organohalogenated in the presence of rhodium complexes with polydentate phosphine or arsenic chelat forming ligand. In the US 4102921 described and the illogical way in the presence of iridium complexes with polydentate phosphine or arsenic chelat forming ligand.

It is known that the presence of hydrogen at carbonyliron methanol to obtain acetic acid leads to the formation of undesirable liquid by-products such as acetaldehyde, ethanol and propionic acid. To highlight obtained from acetic acid, propionic acid require expensive and energy-intensive distillation column. Moreover, acetaldehyde may be involved in participation in a number of reactions of condensation and other reactions with the formation ultimately higher organic iodide compounds. Some of these materials, particularly, for example, hexalite, it is difficult to remove by ordinary distillation, and for acetic acid of sufficient purity that requires additional processing stage. In the application EP-A-0849251, in which the described method catalyzed by iridium carbonylation of methanol to acetic acid, it is stated that the amount of hydrogen in the source of carbon monoxide in the preferred embodiment, is less than 1 mol.%, and the partial pressure of hydrogen in the reactor in the preferred embodiment, is less than 1 bar. Similarly, in application EP-A-0728727, in which the described method catalyzed by rhodium carbonylation of methanol to acetic acid, it is stated that the preferred partial pressure of hydrogen in the reactor is less than 2 bar.

what was also installed, when using some of rhodium catalysts for the carbonylation of methanol in the presence of hydrogen in the source of carbon monoxide leads to the formation of ethanol and acetaldehyde with only small amounts of produced acetic acid.

In the US 4727200, for example, describes the way in which homologation of alcohol by reaction with synthesis gas using registereda catalytic system. The main product obtained using the original synthesis gas, represents ethanol, and acetic acid is formed in relatively small quantities as a by-product.

Moloy and others (Organometallics, 1989, Vol.8, SS-2893) describe how catalyzed by rhodium reductive carbonylation of methanol using the synthesis gas in the presence of diposting ligand with obtaining large quantities of acetaldehyde. The addition of ruthenium to the catalyst promotes the hydrogenation of obtaining ethanol.

Thus, there remains a need to develop an improved method for obtaining carboxylic acids and/or esters of alcohols and carboxylic acids by the catalytic carbonyliron alcohol and/or its reactive derivative. Thus, in particular, there remains a need to develop ways carbonylation, which is tolerant to the presence of hydrogen in the sense of h is about liquid by-products of the hydrogenation are formed only in small amounts or not formed at all.

It was found that the improved method can be developed by use of a catalyst comprising rhodium or iridium, coordinated with polydentate ligand, where the said ligand has an angle of at least 145(or coordinated with metallic rhodium or iridium in the rigid structural conformation. In a suitable embodiment, the catalysts used in the method according to the present invention, have been found, increased compatibility with the hydrogen present in the carbonylation process, in the sense that in the process of formation of small amounts of liquid by-products or they are not formed at all. In addition, metallovedeniye ligand complexes in accordance with the present invention may have a higher stability in the carbonyl process than non-rigid metalloligands complexes or complexes containing ligands with an angle less than 145°. Moreover, the method according to the present invention can be implemented in the absence of the usual stabilizing catalyst compounds, such as lithium iodide.

Accordingly, an object of the present invention is a method of obtaining a carboxylic acid and/or a complex ester of the alcohol and carboxylic acid, and this method comprises the carbonylation of an alcohol and/or reactionsto the one derived carbon monoxide in a liquid reaction mixture in the reactor carbonyl and referred to the liquid reaction mixture contains the above-mentioned alcohol and/or its reactive derivative, the carbonylation catalyst, alkylhalogenide socialization and, optionally, water in limited concentrations, where the said catalyst includes at least one of rhodium and iridium, which is coordinated with polydentate ligand, where mentioned polydentate ligand has an angle of at least 145(or forms a stiff Rh or Ir metalloligands complex where mentioned polydentate ligand includes at least two steering groups independently contain R, N, As or Sb as a coordinating atom of at least two coordination groups, and where in the above-mentioned method maintain the concentration of hydrogen at a molar ratio of hydrogen:WITH at least 1:100 and/or carbon monoxide is directed to the carbonylation reactor contains at least 1 mol.% of hydrogen.

Polydentate ligand includes at least two steering groups as a coordinating atom (donor atom) in at least two coordinating groups independently contain R, N, As, or Sb. These two coordination groups can be identified, respectively, as L1 and L2.

When polydentate ligand forms a complex with rhodium or iridium metal is practical centre (atom), it usually forms a ring structure containing atoms of the metal coordinating atoms, R, N, As or Sb and the main chain of the ligand. The concept of "hard metalloligands complex"used in this description, means that the ring structure has a rigid conformation. The degree of hardness metalloligands complex can be defined by an expert in the field of technology, which is based on the structure of the ligand and the intended configuration of relations. Stiffness can be defined in General terms with regard to the structure of the resulting ligand complex of metal or, for a more precise definition can be established mathematically, for example, in terms of the range of flexibility of the ligand. The concept of "range of flexibility"used in this description, is defined as the range of angles allowed for angle L1-M-L2 (where the angle L1-M-L2 represents the angle formed by the two coordinating groups and the metal center M, where M denotes Rh or 1 g), for example, within the minimum energy of 3 kcal/mol. The angle and range of flexibility for bidentate ligand can be installed on the graph of potential energy, calculated in accordance with the method of Casey and others, published in the journal Israel Journal of Chemistry, t (1990), SS-304, the content of which is included in the present description as with Alki. In the preferred embodiment, for catalysts of the present invention, the range of flexibility is less than 40°, preferably less than 30°. Similar calculations can be used to determine the range of flexibility namedentity ligands.

In the preferred embodiment, each of the coordinating groups L1 and L2 as a coordinating atom contains phosphorus. Such phosphorus-containing group, denoted further as P1 and P2, in the preferred embodiment, have the General formula R1R2R and R3R4R, respectively, in which each of R1, R2, R3and R4independently selected from unsubstituted or substituted alkenyl groups, alkyl groups and aryl groups, mostly phenyl groups. In the preferred embodiment, each of R1, R2, R3and R4denotes phenyl group. One or more phenyl groups can be substituted or unsubstituted. For example, each of P1 and P2 may indicate diphenylphosphino group

(PPh2). Alternatively, one or more phenyl groups, R1, R2, R3and R4in groups P1 and P2 can be replaced. In a suitable embodiment, the phenyl group can be substituted in one or more of the ortho positions of at least one group selected from alkyl, and is safe and alkyloxy (OR). Especially preferred ortho substituents are Me, CF3, Et, ISO-Pr, OMe.

To increase the solubility of the polydentate ligand and, therefore, the catalyst in the liquid reaction mixture one or more groups R1, R2, R3and R4coordinating groups may be substituted one or more hydrophilic and/or polar groups. Examples of such groups include-CO2H, -CO2IU, -IT, -SO3H, -SO3Na, -NH2, -NH3+and-NR2H+.

Rigid conformation polydentate metalloligands complex is usually a direct consequence of the structure of the ligand. Thus, in particular, when the polydentate ligand is a bidentate ligand, the ligand must be difficult rotation along the main chain of the ligand. The main chain of the ligand, as indicated in the present description, is the part or parts of the ligand, which in metalloligands complex usually forms a ring structure containing a metal atom and coordination (donor) atoms). So, for example, the rigid conformation may be due to vinyl or aromatic main chain between the coordinating groups L1 and L2, which impedes or prevents the rotation of the main chain of the ligand. Alternatively or in addition ligand complex metal can be W is strict due to spatial effects, to prevent rotation of the main chain of the ligand.

Acceptable rigid bidentate postinterest ligands include ligands to the following General structural formulas 1 to 3, where P1 and P2 denote, respectively, R1R2P and R3R4P and R1-R4have the following values:

Each of the structures (1 through 3) usually forms metalbitrate ligand complexes with a rigid conformation. For example, the ligands of the General structure 1 generally form a five-membered ring with the metal centre, patterns which are hard due to the main chain of the vinyl. R5and R6in the structure 1 can be independently selected from H, alkyl and aryl. R5and R6can be associated with the formation of the aromatic ring, e.g. phenyl ring, as illustrated in the following structure 1A.

The ligands of the General structural formulas 2 and 3 usually form a rigid, respectively, six and semicolonies rings. Thus, in particular, believe that the rotation of the ligand structure 3 around a single bridge connection prevents spatial difficulty overlying hydrogen atoms in the structure.

In Celesio the different version of the above structure 1, 1a, 2 and 3 can be substituted by one or more substituents, such as one or more alkyl groups, including the substitution groups P1 and/or P2.

In particular, each of R1, R2, R3and R4groups P1 and P2 contained in the above structures 1, 1a, 2 and 3, in the preferred embodiment, is independently selected from phenyl groups and substituted phenyl groups. In a more preferred embodiment, one or more groups R1, R2, R3and R4substituted, preferably in one or more ortho-positions. Preferred ortho substituents include alkyl, aryl and alkyloxy (OR). Especially preferred ortho substituents represent Me, CF3, Et, ISO-Pr, OMe.

To increase the solubility of the bidentate ligands represented by the above structural formula 1, 1a, 2 and 3, and, thus, the catalyst in the liquid reaction mixture bidentate ligands can be substituted by one or more hydrophilic and/or polar groups. In a preferred embodiment, one or more phosphate groups bidentate ligand substituted. Examples of suitable substituents include-CO2H, -CO2IU, -IT, -SO3H, -SO3Na, -NH2, -NH3+and-NR2H+.

Preferred bidentate arsenovic and stilinovic whether the Andes can be represented by the above structural formula 1, 1a, 2 and 3 or their described variants, where the phosphorus atoms are replaced by atoms of arsenic or antimony. Preferred mixed bidentate ligands include the above structure 1, 1a, 2 and 3 or their described variants that include a combination of two groups selected from phosphorus-, arsenic - and surmuslerdi groups.

Preferred bidentate nitrogen ligands are aromatic ring systems, which as a donor atom containing a nitrogen atom. The aromatic ring may be either substituted or unsubstituted, and the ring system may also include other heteroatoms, such as oxygen atom. Examples of acceptable ring systems include substituted and unsubstituted bipyridine.

Polydentate ligand of the present invention can also be tridentate ligand.

Tridentate ligand has three steering group, through which the ligand forms a coordination bond with rhodium or iridium metal center. These three coordination groups can be designated as L1 and L2, which are presented above, and L3, the third coordination group, which in the preferred embodiment, contains P, As, Sb, O, N, S and Karben as donor (coordination) of the atom.

Preferred tridentate ligand represented by the formula L1(R7)L3(R8)L2, is which R 7and R8denotes a connecting group, which connect, respectively, L1 to L3 and L3 to L2. These connecting groups of R7and R8independently selected from aryl and alkenyl groups, preferably vinyl or phenyl groups. Themselves connecting group R7and R8can form at least one cyclic structure including L3, which may be expressed by following General formula

Preferred tridentate ligand is expressed by the formula L1(R7)L3(R8)L2, which is presented above, and forms a coordination bond with rhodium or iridium metal center of the catalyst in bridging conformation, resulting in L1 on L2 are in mutual transpareny relative to the metal center. Under the concept of "being in mutual TRANS-positions"used in the present description, assume that the angle formed by the two ligands and the metal center, for example, L1-M-L2, where M denotes Rh or Ir metal center, is at least 145°, preferably at least 150°. These angles can be determined using conventional methods, such as x-ray crystallography.

Preferred tridentate ligand is coordinated in such a way that the donor atoms in the groups L1, L2 is L3 are in the meridional (Mer-) coordination configuration relative to the metal center. In a more preferred embodiment, the tridentate ligand is coordinated in such a way that the donor atoms of the groups L1, L2 and L3 are essentially flat configuration relative to the metal center.

In a preferred embodiment, L1 and L2 denote the phosphorus-containing group, and L3 denotes an oxygen atom (O), resulting in the tridentate ligand has the formula P1-R7-O-R8-P2, where P1 and P2 denote postinterest group of the General formula R1R2P and R3R4P and in which each of R1, R2, R3and R4independently selected from unsubstituted or substituted alkenyl groups, alkyl groups, aryl groups, mostly phenyl groups. In the preferred embodiment, each of R1, R2, R3and R4in the tridentate ligand is phenyl group. Each of the phenyl groups may be substituted or unsubstituted. As P1 and P2 may indicate diphenylphosphino group (PPh2). Alternatively, one or more phenyl groups, R1, R2, R3and R4in groups P1 and P2 substituted. In a suitable embodiment, the phenyl group can be substituted in one or more of the ortho positions of at least one group selected from alkyl, aryl and alkyloxy (OR). Especially preferred ortho substituents are the two who are Me, CF3, Et, ISO-Pr, OMe.

To increase the solubility of the tridentate ligand and, therefore, the catalyst in the liquid reaction mixture one or more groups R1, R2, R3, R4, R7and R8the tridentate ligand can be substituted by one or more hydrophilic and/or polar groups. Examples of suitable substituents include-CO2H, -CO2Me, -IT, -SO3H, -SO3Na, -NH2, -NH3+and-NR2H+.

Rigid tridentate conformation metalloligands complex may be a direct consequence of the structure of the ligand, or may be a consequence of patterns metalloligands complex. So, for example, the rigid conformation may be due to the rigid structure of the entire ligand, such as Xanthos (below structure 4). Thus, tridentate canthony ligand, when it forms a complex with rhodium or iridium metal center (atom), forms a rigid ring structure containing an atom of the metal coordination atoms P, As or Sb and the main chain of the ligand (having as a third donor atom of oxygen).

Alternatively a rigid conformation may be a consequence of the fact that each of R7and R8independently is vinyl or aromatic main chain, which make it difficult or predotvrashchenie main chain of the ligand, accordingly, between L1 and L3 and between L3 and L2, but the ligand is rigid only when coordinated to the metal center. An example of such patterns is D, which is shown below as structure 5. In this example, the ligand when it is coordinated with rhodium or iridium metal center, forming a rigid ring structure containing two rigid five-membered rings, which give total hardness losangelesca complex. Alternatively or in addition losangelesalfresco complex can be hard due to the spatial effects that interfere with the rotation of the main chain of the ligand, as previously described for structure 3.

Specific examples of acceptable for use in performing the present invention tridentate fosforsoderzhashhikh ligands include Xanthos, Texinfo, sexinfo, holocanthus, fossetts, isopropanol, nikandros, benzoxanthenes, D, D and R-nikandros, structural formulas are 1 through 14 below. In a preferred embodiment, the group R to R-Nisantasi selected from alkyl and aryl groups, and in the preferred embodiment, is chosen from methyl, ethyl, propyl and benzyl.

In a suitable embodiment, the above structure with 4 to 14 can be substituted by one or more substituents, such as one or more alkyl groups. The structure of tert-VI-Xanthos below as structure 15.

The tridentate fosforsoderzhashhikh ligands represented by the above structural formulas from 4 to 15, diphenylphosphino group may be replaced by groups P1 and P2, which previously presented. Thus, particularly preferred groups P1 and P2 are the groups R1R2P and R3R4P, in which each of R1, R2, R3and R4independently selected from phenyl groups and substituted phenyl groups, and one or more groups R1, R2, R3and R4substituted, preferably in one or more ortho-positions, alkyl, aryl or alkyloxyaryl (OR). Especially preferred ortho substituents represent Me, CF3, Et, ISO-RG and OMe.

To increase the solubility of the tridentate ligand represented by structural formulas 4 through 15, and, in affect, is, catalyst in the liquid reaction mixture these tridentate ligands can be substituted by one or more hydrophilic and/or polar groups, mostly in one or more phosphine groups, the tridentate ligand. Examples of suitable substituents include-CO2H, -CO2IU, -IT, -SO3H, -SO3PA, -NH2, -NH3+and-NR2H+.

In a suitable embodiment, tridentate postinterest ligands any of the above structural formulas 4 through 15, or their substituted versions, as they are presented above, may have an oxygen atom in the component L3 is substituted by a sulfur atom or a nitrogen atom.

Preferred tridentate arsine - and steinstrasse ligands cover above patterns from 4 to 15 or described ways in which the phosphorus atoms are replaced by atoms of arsenic or antimony. Preferred mixed tridentate ligands cover above patterns from 4 to 15 or presented in this description of ways, including as L1 and L2, the combination of two groups selected from phosphorus-, arsenic - and surmuslerdi groups.

For example, patterns of As,As-tert-Bu-Xanthos and P,As-tert-VI-Xanthos below as structures, respectively, 16 and 17.

Preferably the e tridentate nitrogen ligands represent an aromatic ring system, which as donor atoms which contain a nitrogen atom. The aromatic ring may be either substituted or unsubstituted, and the ring system may also include other heteroatoms, such as oxygen atom. Examples of acceptable ring systems include substituted and unsubstituted terpyridine.

Bidentate and tridentate ligands or technically available or can be synthesized in accordance with methods known in the art. More specifically tridentate ligands represented by structural formulas 4 through 17, and described variants can be synthesized in accordance with methods that are described or similar to those outlined van der Veen and others in the work Chem.Commun., 2000, 333, the contents of which are incorporated into this description by reference.

The use of a catalyst which comprises rhodium or iridium, coordinated with polydentate ligand into a rigid structural conformation, or which has an angle of at least 145° in accordance with the present invention, in the presence of hydrogen provides, it has been found that increased selectivity for the resulting carboxylic acid and a lower selectivity for liquid by-products of hydrogenation, such as alcohols and aldehydes.

In a preferred embodiment, katal is the jam of the present invention includes rhodium. Proposed mechanisms catalyzed by rhodium carbonylation and reductive carbonylation can be detected, for example, in the work of Moloy and others in Organometallics, Vol.8, No. 12, 1989, the contents of which are incorporated into this description by reference. Not based on any theory, I believe that the rigid conformation metalloligands complexes in accordance with the present invention prevents or at least inhibits the ability metalloligands complex to change conformation, which, in turn, prevents or at least inhibits the adherence of hydrogen to metalloligands complex or prevents the elimination of the aldehyde (e.g. acetaldehyde) from metallically materials (for example, M-PINES3)formed during the carbonylation, in particular either the reaction of elimination, requiring occurrences of H2free CIS-portion relative to the acyl group or the reaction of reductive elimination between the metal hydride ligand (formed by joining N2and metallically ligand, which are in mutual CIS-positions. For example, in the case of the complex of the metal with the structure of a pyramid with a square cross-section, containing rigid bidentate ligand with apical acyl group (e.g., Soma) and two halide whether the Anda (for example, I)an open area is recorded in the TRANS-position relative to the acyl group, thus preventing its reaction with hydrogen with the formation of the aldehyde.

In addition, again not based on any theory, I also believe that through coordination with three donor tridentate ligands can exhibit more spatial locking action that prevents or inhibits the adherence of hydrogen to metalloligands complex.

The catalyst according to the present invention can be prepared by creating coordination iridium - or registeruser connection with polydentate ligand. The catalyst may be prepared in situ in the liquid reaction mixture is separated by adding iridium - or registeruser connection and polydentate ligand in the liquid reaction mixture. Iridium - or registersee connection, you can add in any acceptable form, which dissolves in the liquid reaction mixture or can turn into a soluble form. However, in the preferred embodiment, the catalyst is added to the liquid reaction mixture in the form of pre-cooked metallogidridnogo ligand complex in which the polydentate ligand coordinated with iridium - or registertask connection. Before adding to the liquid reaction mixture p is AdwareDelete cooking metallogidridnogo ligand complex can be carried out, for example, a mixture of acceptable iridium - or registeruser compounds with can replace groups with polydentate ligand in an acceptable solvent, for example methanol.

Examples of pre-cooked hereditaments ligand complexes cover [{L1(R7)L3(R8)L2}Ir(COMe)I2], [{L1(R7)L3(R8)L2}Ir(CO)I], [{L1(R7)L3(R8)L2}Ir(CO)]+and [{L1(R7)L3(R8)L2}IrI(CO)Me]+in which L1(R7)L3(R8)L2 represents a tridentate ligand, which is described above.

Examples of pre-cooked redistributing ligand complexes cover [{L1(R7)L3(R8)L2}Rh(COMe)I2], [{L1(R7)L3(R8)L2}Rh(CO)I], [{L1(R7)L3(R8)L2}Rh(CO)]+and [{L1(R7)L3(R8)L2}RhI(CO)Me]+in which L1(R7)L3(R8)L2 represents a tridentate ligand, which is described above, in particular [{Xanthos}Rh(Soma)I2].

The preferred iridium - or registersee connection is a free from chloride compound, such as acetate, which is soluble in one or more components of the liquid reaction mixture, and, thus, may be introduced into the reaction mixture in the form of a solution in it.

Examples of acceptable iridectomies compounds include Irl3, IrI3, GVG3[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]-H+Ir4(CO)12, Irl3•4H2O, IrBr3•4H2O Ir3(CO)12metal iridium, Ir2O3, IrO2, Ir(acac)(CO)2Ir(ASAS)3acetate iridium [Ir3On(SLA)6(H2O)3][SLA] and hexachloroiridium acid, H2[Irl6]preferably free from chloride complexes of iridium such as acetates, oxalates and acetoacetates.

Examples of acceptable registergui compounds include [Rh(CO)2Cl]2, [Rh(CO)2I]2, [Rh(CO)2Cl]2, chloride, rhodium(III)chloride trihydrate rhodium(III)bromide, rhodium(III)iodide rhodium(III)acetate, rhodium(III), decarbonylation rhodium, RhCl(h3)3and Rhl(CO)(h3)2.

In a preferred embodiment, the concentration of iridium in the liquid reaction mixture is in the range from 100 to 6000 parts by weight per million, more preferably in the range of from 400 to 5000 hours/million, in particular in the range from 500 to 3000 parts by weight of/million

In a preferred embodiment, the concentration of rhodium in the liquid reaction mixture is in the range from 25 to 5000 parts by weight per million, more preferably in the range from 250 to 3500 hours/million

The optimal molar ratio m is a metallic rhodium or iridium to polydentate ligand in the reactor is approximately 1:1, mainly when using pre-cooked metalloligands complex. Another option in the liquid reaction mixture may contain an excess of ligand, mainly, for example, when metalloligands complex should be prepared in situ. Thus, the molar ratio of metallic rhodium or iridium to polydentate ligand may be less than 1:1, expediently in the range from 1:1 to 1:2.

The liquid reaction mixture may also include a promoter metal. Acceptable promoters selected from ruthenium, osmium, rhenium, cadmium, mercury, zinc, gallium, indium and tungsten. Preferred promoters are selected from ruthenium and osmium, the most preferred ruthenium. The promoter may include any acceptable promotor metallsoderjasimi compound which is soluble in the liquid reaction mixture. The promoter can be added to the liquid reaction mixture for the reaction of carbonyl in any acceptable form, which dissolves in the liquid reaction mixture or can turn into a soluble form.

Examples of acceptable ruteniysoderzhaschim compounds which can be used as sources of promoter include chloride, ruthenium(III)chloride trihydrate ruthenium(III)chloride, ruthenium(IV)bromide, ruthenium(III), metal ruthenium, oxides of ruthenium formate, ruthenium(III) [Ru(CO)3I 3]-H+, [Ru(CO)2I2]n, [Ru(CO)4I2], [Ru(CO)3I2]2, Tetra(Aceto)chloroethene(II, III)acetate, ruthenium(III)propionate, ruthenium(III)butyrate ruthenium(III), PENTACARBONYL ruthenium, tributenetherlands and mixed halocarbonyl ruthenium, such as dimer dichlorocarbanilide(II)dimer dibromodicyanobutane(II) and other romanialaisia complexes, such as tetrachlorobis-(4-Zimen)tirutani(II), tetrachlorobis-(benzene)tirutani(II), the polymer dichloro(cycloocta-1,5-diene)ruthenium(II) and Tris(acetylacetonate)ruthenium(III).

Examples of acceptable oslistarray compounds which can be used as sources of promoter include chloride hydrate and anhydrous chloride of osmium(III), the metal osmium, osmium tetroxide, trioctyldodecyl, [Os(CO)4I2], [Os(CO)3I2]2, [Os(CO)3I3]-H+, pentachlor-µ-microdisney and mixed halocarbonyl osmium, such as the dimer tricarbonylchromium(II) and other osteorganical complexes.

Examples of suitable registergui compounds which can be used as sources of promoter include Re2(CO)10, Re(CO)5Cl, Re(CO)5Br, Re(CO)5I, ReCl3•xH2O, [Re(CO)4I]2, [Re(CO)4I2]-H+and ReCl5•yH2O.

Examples of suitable cadmium-containing compounds which can be used, cover Cd(OAc)2, CdI2, CdBr2, CdCl2Cd(OH)2and cadmium acetylacetonate.

Examples of acceptable mercury-containing compounds which can be used to cover Hg(OAc)2, HgI2, HgBr2, HgCl2Hg2I2and Hg2Cl2.

Examples of suitable zinc-containing compounds which can be used, cover the Zn(OAc)2, Zn(OH)2, ZnI2, ZnBr2, ZnCl2and zinc acetylacetonate.

Examples of acceptable geliysoderzhaschih compounds which can be used include gallium acetylacetonate, gallium acetate, Gl3, Gr3, GaI3, Ga2Cl4and GA(OH)3.

Examples of acceptable indiadelhi compounds which can be used include acetylacetonate India, acetate India, Inl3, Pug3, InI3and In(OH)3.

Examples of suitable tungsten-containing compounds which can be used include W(OH)6, WCl4, WCl6, WBr5WI2C9H12W(CO)3and all wolfmangler-, -bromine - and-idornigie connection.

In a preferred embodiment, the promoter is used in an effective amount, up to the limit of its solubility in the liquid reaction mixture and/or lubiniecki technological flows, returned from the stage of selection carboxylic acid in the reactor for carbonylation. Acceptable content promoter in the liquid reaction mixture is such that the molar ratio between the promoter and the rhodium or iridium is from 0.1:1 to 20:1, preferably from 0.5:1 to 10:1, more preferably from 2:1 to 10:1. Acceptable concentration of promoter is less than 8000 hours/million, in particular from 400 to 7000 hours/million

The liquid reaction mixture may also include an effective amount of stabilizer and/or promoter compounds selected from the iodides of alkali metals, alkaline earth metal iodides, metal complexes capable of generating I-, salts capable of generating I-, and mixtures of two or more of them. Examples of acceptable iodides of alkali metals include lithium iodide, sodium iodide and potassium iodide, the preferred lithium iodide. Acceptable iodides of alkaline earth metals include calcium iodide. Suitable metal complexes capable of generating I-include complexes of lanthanide metals, for example, samarium and gadolinium, cerium and other metals, such as molybdenum, Nickel, iron, aluminum and chromium. Salt capable of generating I-include, for example, acetates, which are able to transform in-situ I-usually LiOAc and organic salts, such as Quaternary ammoniated and phosphonite, is the quiet can be added as such.

A suitable amount of used connections is such that effectively increase the solubility of the catalytic system, and in the preferred embodiment does not cause a significant lowering of the reaction rate of carbonylation.

Concentration correlated metals such as chromium, iron and molybdenum, which may have a negative effect on the rate of reaction can be reduced to a minimum by the use of acceptable corrosion resistant structural materials. Concentration correlated metals and other impurities ions can be reduced by using a layer of ion-exchange resins suitable for processing liquid reaction mixture, or preferably returned to the process stream with the catalyst. This method is described in US 4007130.

Suitable alkylhalogenide acetalization may be lower alkylhalogenide, for example, with C1With4. In a preferred embodiment, alkylhalogenide is alkylated, such as methyliodide. Acceptable concentration alkylhalogenide of socializaton in the liquid reaction mixture is in the range from 1 to 30 wt.%, for example, 1 to 20 wt.%.

In the method according to the present invention the reagent is selected from alcohol and/or its reactive derivative, carbonylic carbon monoxide with the teachings of carboxylic acid and/or a complex ester of the alcohol and carboxylic acid.

Acceptable alcohol reagent is any alcohol comprising from 1 to 20 carbon atoms and at least one hydroxyl group. In a preferred embodiment, the alcohol is a monofunctional aliphatic alcohol, preferably containing from 1 to 8 carbon atoms. In the most preferred embodiment, the alcohol is a methanol, ethanol and/or propanol. You can use a mixture containing more than one alcohol. The product of the carbonylation of the alcohol is usually the carboxylic acid containing one carbon atom more than the alcohol, and/or ester of the alcohol and the resulting carboxylic acid. Particularly preferred alcohol is a methanol carbonylation product is acetic acid and/or methyl acetate.

Acceptable reactive derivative of the alcohol include esters, halides and ethers.

Suitable ester reactant is an ester of the alcohol and carboxylic acid. In a preferred embodiment, the ester reactant is an ester of carboxylic acid and alcohol, which contains from 1 to 20 carbon atoms. In a more preferred embodiment, the ester reactant is an ester of carboxylic acid and a monofunctional aliphatic alcohol, which which contains from 1 to 8 carbon atoms. In the most preferred embodiment, the ester reactant is an ester of carboxylic acid and methanol, ethanol or propanol. In a preferred embodiment, the ester reactant is an ester of the alcohol and the resulting carboxylic acid. In a preferred embodiment, the ester reagent contains up to 20 carbon atoms. You can use a mixture of ester reagents. Carboxylic acid as a product of ester carbonyl reagent is typically a carboxylic acid containing one carbon atom more than the alcohol component of the ester reagent. Especially preferred ester reagent is an acetate, a product of the carbonylation of which is an acetic acid.

Acceptable halide reagent is any Hydrocarbonated containing up to 20 carbon atoms. In a preferred embodiment, the halide reagent is an iodide or bromide. In a more preferred embodiment, halide component hydrocarboncontaining reagent represents the same halide as the halide alkylhalogenide of socializaton. In the most preferred embodiment, Hydrocarbonated is hydrocarbide, most preferably marked the bits ethyliodide or propyliodide. You can use a mixture of hydrocarboncontaining reagents. Carboxylic acid as the reaction product hydrocarboncontaining reagent is typically a carboxylic acid containing one carbon atom more than hydrocarboncontaining reagent. Ester product of the carbonylation of Hydrocarbonated is typically an ester of Hydrocarbonated and carboxylic acids containing one carbon atom more than Hydrocarbonated.

Acceptable simple essential reagent is any hydrocarbonyl ether containing up to 20 carbon atoms. In a preferred embodiment, a simple essential reagent is diakidoy ether, most preferably dimethyl ether, diethyl ether or DIPROPYLENE ether. You can use a mixture of simple esters. Products ether carbonylation reagent is usually a carboxylic acid containing one carbon atom more than each of hydrocarbonrich of groups, ether and/or ester derivatives. Especially preferred simple essential reagent is a dimethyl ether, carbonisation the reaction product of which is an acetic acid.

In the carbonylation process can use is with a mixture of alcohol, ester, halide and ether reagents. You can apply more than one alcohol, complex ether, halide and/or a simple ester. Particularly preferred reagent is a methanol and/or methyl acetate, carbonisation products carbonylation of which are acetic acid.

The liquid reaction mixture may be anhydrous, but in the preferred embodiment, contains a limited concentration of water. The term "anhydrous"as used in this description, assume that the liquid reaction mixture is essentially free of water, the resulting liquid reaction mixture contains less than 0.1 wt.% water. Under the concept of "limited water concentration used in the present description, referring to the fact that the liquid reaction mixture contains at least 0.1 wt.% water. In a preferred embodiment, water can be in a concentration in the range from 0.1 to 30%, for example from 1 to 15%, and more preferably from 1 to 10%, by weight, calculated on the total weight of the liquid reaction mixture.

Water can be added to the liquid reaction mixture as needed or it can be formed in situ in the carbonylation reaction. For example, when carbonyliron methanol, water may result from the esterification reaction between methanol reagent and obtained the acetic acid.

Water can be introduced into the carbonylation reactor independently or together with other reagents, such as esters, e.g. methyl acetate. Water can be isolated from the liquid reaction mixture withdrawn from the reactor, and return in regulated quantities to maintain the desired concentration in the liquid reaction mixture.

In the liquid reaction mixture of the present invention as a solvent may contain the resulting carboxylic acid, e.g. acetic acid.

Carbon monoxide for use in the implementation of the present invention (when it is served separately from the source of hydrogen) may be substantially pure or may include inert impurities such as carbon dioxide, methane, nitrogen, noble gases, water and paraffin hydrocarbons with C1With4.

Appropriate gauge the partial pressure of carbon monoxide in the reactor may be in the range from 1 to 70 bar.

Hydrogen can be directed into the reactor separately from the source of carbon monoxide, but in the preferred embodiment, it is sent to the reactor in the form of a mixture with carbon monoxide. In a preferred embodiment, the mixture of carbon monoxide and hydrogen obtained from a commercial source, in particular from the reforming of hydrocarbons. In industrial reforming of hydrocarbons receive cm is camping WITH, hydrogen and CO2and this mixture is usually referred to as synthesis gas. The synthesis gas typically contains hydrogen at a molar ratio of CO in the range from 1.5:1 to 5:1.

Mixed original hydrogen/carbon monoxide can include at least 1 mol.% hydrogen, in particular at least 2 mol.% hydrogen, and more preferably at least 5 mol.% of hydrogen. The most preferred molar ratio of hydrogen to CO in the source material is in the range from 1:100 to 10:1, in particular from 1:20 to 5:1.

When hydrogen is sent to the reactor WITH the consumption of CO in the reactor leads to the fact that the molar ratio of hydrogen to CO in the reactor is usually higher than the molar ratio of hydrogen to CO in the source material fed to the reactor. In addition to the hydrogen flowing into the reaction, the hydrogen can also be obtained in situ by the reaction of the conversion of water gas. Thus, when hydrogen is contained in this directed into the reactor source material, in particular for the carbonyl process conducted at high CO conversion, such as a periodic process, the concentration of CO in the reactor may become very low and the molar ratio of hydrogen to CO in the reactor may be correspondingly high, such as 100:1 or higher. However, in the preferred embodiment, the molar ratio of bodoro is and to CO in the reactor is maintained at a level below 100:1. In a preferred embodiment, the carbonylation reactor maintain the concentration of hydrogen at a molar ratio of hydrogen:WITH at least 1:100. In a more preferred embodiment, the carbonylation reactor maintain the concentration of hydrogen at a molar ratio of hydrogen:WITH at least 1:10, most preferably at least 1:1. The preferred partial pressure of hydrogen in the reactor is above 1 bar, most preferably above 2 bar.

The carbonylation reaction can be performed under General gauge pressure in the range from 10 to 100 bar. Suitable temperatures can be in the range from 50 to 250°C., typically from 120 to 200°C.

The proposed method can be implemented in the form of periodic or continuous process, preferably as a continuous process.

The resulting carboxylic acid from the liquid reaction mixture can be distinguished removal from the carbonylation reactor for vapor and/or liquid and remove it from the exhaust material carbolic acid. In a preferred embodiment, the carboxylic acid is recovered from the liquid reaction mixture by continuous removal of this liquid reaction mixture from the reactor for carbonylation and removing the carboxylic acid of the withdrawn liquid reaction mixture through the implementation of one or more stages of od is Kratovo equilibrium evaporation and/or fractional distillation, on which this acid is separated from other components of the liquid reaction mixture, such as rhodium or iridium catalyst, alkylhalogenide socialization, an optional promoter, ether carboxylic acids, unreacted alcohol, optional water and carboxylic acid as the solvent that can be returned to the reactor.

In the usual process of obtaining a carboxylic acid to maintain in the reactor low partial pressure of hydrogen (hydrogen is accumulated due to the presence of impurities in the feed of carbon monoxide and formation of in situ hydrogen), normally carried out by purging. Because hydrogen can be valid only at low concentrations, blowing a stream often contains hydrogen at low concentrations and significant quantities of carbon monoxide, which are removed. Since it was found that the method according to the present invention can be performed at higher concentrations of hydrogen in the reactor, blowing a stream typically contains hydrogen at higher concentrations and, thus, for its removal from the reactor by purging should be significantly less carbon monoxide, thereby improving the overall yield.

An additional advantage of the method according to the present invention is that a high selectivity in relation to the integral is o liquid products can be achieved in the presence of hydrogen, allowing the use of the carbonyl process contains carbon monoxide flows of raw materials with higher hydrogen concentrations. This provides a significant cost savings. Thus, in particular, contains a carbon monoxide source material with the concentration of N2above 1 mol.% allows the use of less expensive, non-cryogenic separation methods of synthesis gas, such as membrane separation methods.

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

Examples

General method for the reaction

Methanol, methyliodide, Rul3•hydrate and DFFP (DFFP denotes bis-1,3-diphenylphosphinoethyl) was obtained from Aldrich company. (acac)Rh(CO)2Xanthos and DINAH received from the company Strem Chemicals. RuI3received from the company Johnson Matthey.

Experiments were performed using 300 ml of zirconium autoclave equipped with a magnetic agitator and system getdisplaymode blades, a device for injection of liquid catalyst and cooling coils. The gas in the autoclave was provided by the ballast tank, and gas during the reaction was applied to maintain the autoclave constant pressure.

Comparative example a

This experiment demonstrates the reaction of the methanol, the carbon monoxide in the presence of hydrogen, rhodium catalyst, DFFP and ruthenium promoter during the 2-hour period. DFFP is a bidentate phosphine ligand. Used hydrogen and carbon monoxide at a molar ratio of N2:2:1 (CO2in the synthesis gas is not contained). In parts of the loaded methanol suspended 2,031 g (DFFP)Rh(Soma)I2and 2,115 g Rul3and was introduced into the autoclave. Next, the reactor felt the pressure of nitrogen, the contents were discharged into the atmosphere through the gas-sampling and three times blew the synthesis gas. Through the hole for adding fluids in the autoclave was administered to the remaining liquid components of the reaction mixture (the remaining methanol and methyliodide). Then the pressure in the autoclave was increased synthesis gas under a gauge pressure of 5 bar and slowly dumped the contents into the atmosphere. After that, the pressure in the autoclave was increased synthesis gas (gauge pressure of approximately 20 bar) and the contents were heated with stirring (1220 rpm) until the reaction temperature of 140°C. After reaching a stable temperature (approximately 15 min) feed synthesis gas from the ballast tanks, the total pressure was increased to the target operating pressure. Gauge pressure in the reactor during the experiment was maintained at a constant level (±0.5 bar) gas from the ballast tanks. Gas absorption from BA who regional capacity during the whole experiment was determined using the devices for recording and outputting of data. Using a heating jacket connected to a regulating system Eurotherm (trademark), the reaction temperature was maintained with an accuracy of ±1°C relative to the target reaction temperature. After a reasonable amount of time T (see table 1B) ballast tank insulated and with cooling coils in the reactor was rapidly cooled.

Data on the distribution of products are shown in table 2, and data selectivity with respect to the products listed in table 3. The prevailing liquid products were ethanol and its derivatives (EtOMe and Et2O) plus his predecessor acetaldehyde. Acetic acid and its derivative, Meoac formed in relatively small amounts.

Comparative example B

This experiment demonstrates the reaction of methanol with carbon monoxide in the presence of hydrogen, rhodium catalyst, DFFP and ruthenium promoter during the 30-minute period. Used a synthesis gas including hydrogen and carbon monoxide at a molar ratio of H2:co of 2:1 (CO2in the synthesis gas is not contained).

In this experiment, the phosphine-rhodium complex was obtained in situ. In the portion of the loaded methanol (approximately 60 g) were placed 1,114 g DFFP with 0,658 g (acac)Rh(CO)2obtaining a slurry of the catalyst precursor. In the autoclave was loaded 2,590 g RuCl3•3H2About together with p is blithedale 5 g of methanol, and the autoclave was experiencing pressure. To the autoclave was added Me acetalization, after which the slurry of the catalyst precursor. Added the remaining methanol and synthesis gas (gauge pressure of approximately 20 bar) was created in an autoclave under high pressure. Further, this experiment was performed as in the case of comparative example A. the Reaction conditions shown in table 1B. Data on the distribution of products are shown in table 2, the selectivity with respect to the products listed in table 3. The prevailing liquid products were ethanol plus its predecessor acetaldehyde. Acetic acid and its derivative, Meoac formed in relatively small amounts.

Comparative example

This experiment demonstrates the reaction of methanol with carbon monoxide in the presence of hydrogen, rhodium catalyst, DFFP, but in the absence of ruthenium promoter, within a 2-hour period. Used a synthesis gas including hydrogen and carbon monoxide at a molar ratio of N2:2:1 (CO2in the synthesis gas is not contained).

The reaction was carried out in accordance with the method of comparative example B using downloadable composition and reaction conditions, which are presented in the following tables 1A and 1B. Data on the distribution of products are shown in table 2. Data selectivity in which the compared products are shown in table 3. In the absence of ruthenium main liquid product was acetaldehyde. Was also formed acetic acid and its derivative, Meoac.

Example 1

This example demonstrates the reaction of methanol with carbon monoxide in the presence of hydrogen, a catalyst based on rhodium-Xanthos and ruthenium promoter. Used a synthesis gas including hydrogen and carbon monoxide at a molar ratio of N2:2:1 (CO2in the synthesis gas is not contained).

In this experiment, the phosphine-rhodium complex was obtained in situ. In the portion of the loaded methanol (approximately 60 g) were placed 1,571 g Xanthos with 0,646 g (acac)Rh(CO)2and 2,084 g RuCl3obtaining a slurry of the catalyst precursor. The system of injection of the catalyst together with a small amount (5 g) of methanol were placed Me socializaton. In the autoclave was loaded suspension catalyst precursor, after which the remaining methanol and synthesis gas (gauge pressure of approximately 20 bar) was created in an autoclave under high pressure. Further, this experiment was performed as in comparative example A, using the loaded composition and reaction conditions, which are presented in tables 1A and 1B. The obtained distribution data products are shown in table 2. Data selectivity with respect to the products listed in table 3.

Example 2

This is what the example demonstrates the reaction of methanol with carbon monoxide in the presence of hydrogen and of a catalyst based on rhodium-Xanthos in the absence of ruthenium promoter. Used a synthesis gas including hydrogen and carbon monoxide at a molar ratio of N2:2:1 (CO2in the synthesis gas is not contained).

The reaction was carried out in accordance with the method of the comparative example using downloadable composition and reaction conditions, which are presented in tables 1A and 1B. Distribution data products are shown in table 2. Data selectivity with respect to the products listed in table 3.

Examples 3 through 13

The experiments of examples 3 through 11 were carried out in accordance with the method of comparative example B using downloadable compositions and reaction conditions, which are presented in detail in tables 1A and 1B. Distribution data products are shown in table 2. Data selectivity with respect to the products listed in table 3.

The ligands of examples 3, 4 and 6 through 13 have the following structure:

0,1 0,1
Table 2
Distribution products
ExampleMeonAsónMeOAcEtOHEt2OEtOMeIU2AboutAcH
And28,61,14,514,20,43,58,20,9
B54,00,33,75,30,1BUT7,71,9
In35,10,42,80,050,1<0,0510,83,1
151,70,914,150,10,00,82,9
250,81,015,40,00,00,04,10,1
360,20,14,30,10,10,77,40,1
440,70,89,01,10,1BUTthe 9.70,4
548,51,113,11,30,1BUT7,70,3
641,71,7the 13.42,50,2BUT8,4
734,42,011,22,10,1BUT10,00,7
835,91,610,61,90,3BUT8,91,0
941,60,87,26,00,2BUT9,40,4
1044,70,55,93,20,1BUT12,40,2
1132,91,69,33,20,1BUT10,8 0,7
1240,02,113,60,30,1BUT7,40,3
1339,81,311,90,60,1BUT7,20,7
BUT means were not defined

Table 3
The selectivity for products
ExampleThe transformation of the Meon, %(a)Select. in respect of EtOH and derivatives, %(b)Select. in respect of the Asón and derivatives, %(C)Sat. in respect. AcH %(g)Sat. in respect. CH4%(d)
And40,566,415,73,4 14.4V
B16,842,720,015,3of 21.9
In38,81,228,142,926,9
131,12,635,70,560,7
229,20to 38.30,360,9
328,717,471,31,49,0
42910,654,73,730,7
5256,538,81,452,7
6 3410,936,60,452,0

By examining the data of tables 2 and 3 can clearly see that in the experiments of examples 1 to 11 using hard metalloligands catalysts and in the experiments of examples 12 and 13 using catalysts possessing an opening angle of at least 145°, has been a significant decrease in the yield of ethanol and ethanol derivatives in comparison with the results obtained in comparative examples a and B. moreover, the main liquid carbonylation product was a mixture of acetic acid and methyl acetate.

You can also clearly see that in comparison with catalysts based Xanthos examples 1 and 2, in the experiments of examples 3 and 4 was significant decrease in the number of generated methane in the case of catalysts containing DINAH and on-talks.info.

1. A method of obtaining a carboxylic acid and/or a complex ester of the alcohol and carboxylic acid, comprising carbonylation of alcohol and/or its reactive derivative with carbon monoxide in a liquid reaction mixture in the reactor carbonylation, and referred to the liquid reaction mixture contains the above-mentioned alcohol and/or reactive deposition is Noah, the carbonylation catalyst, alkylhalogenide socialization where the above-mentioned catalyst includes at least one of rhodium or iridium, which is coordinated with polydentate ligand, where mentioned polydentate ligand has an angle of at least 145°, or forms a stiff Rh or Ir metalloligands complex, and the above-mentioned polydentate ligand includes at least two steering groups as a coordinating atom of at least two coordinating groups independently contain P, N, As, or Sb, and in this way maintain the concentration of hydrogen at a molar ratio of hydrogen:WITH at least 1:100 and/or carbon monoxide, is directed to the carbonylation reactor contains at least 1 mol.% hydrogen, and in which the range of flexibility of the catalyst is less than 40°.

2. The method according to claim 1, in which the liquid reaction mixture additionally contains water in a concentration of from 0.1 to 30% based on the total weight of the reaction mixture.

3. The method according to claim 1 or 2, wherein the polydentate ligand is a bidentate ligand or a tridentate ligand.

4. The method according to claim 3, in which the polydentate ligand is a bidentate ligand, each of two coordinating groups which contains phosphorus as a coordinating atom.

5. The method according to claim 4 in which the two coordinating groups have the formula R 1R2P and R3R4P, where each of R1, R2, R3and R4independently selected from unsubstituted or substituted alkenyl groups, alkyl groups and aryl groups.

6. The method according to claim 5, in which one or more aryl groups are substituted or unsubstituted phenyl group.

7. The method according to claim 5 or 6, in which each of R1-R4denotes a substituted or unsubstituted phenyl group.

8. The method according to claim 1 or 2, wherein the polydentate ligand is selected from structures of the formulae 1 to 3 and 1A




where P1and R2denote, respectively, R1R2P and R3R4P, where each of R1, R2, R3and R4independently selected from unsubstituted or substituted alkenyl groups, alkyl groups and aryl groups; each of R5and R6independently selected from hydrogen, alkyl groups, aryl groups, or they may be connected so that the result is an aromatic ring.

9. The method according to claim 8, in which at least one of R1-R4denotes a substituted or unsubstituted phenyl group.

10. The method according to claim 1 or 2, wherein the polydentate ligand is a tridentate League is D.

11. The method according to claim 10, in which the coordination atoms of the coordinating groups are in the meridional coordination configuration relative to the rhodium or iridium metal center.

12. The method according to claim 10, in which the coordination atoms of the coordinating groups are essentially in a flat configuration relative to the rhodium or iridium metal center.

13. The method according to claim 10, in which a third coordination group has a coordinating atom selected from atoms of P, As, Sb, oxygen, nitrogen, sulfur and vinylcarbene.

14. The method according to item 13, in which two of the coordinating groups defined in any of PP-8.

15. The method according to claim 10, in which the tridentate ligand has the formula L1(R7)L3(R3)L2, where each of L1-L3 denotes a steering group, each of L1 and L2 as a coordinating atom contains P, N, As or Sb; R7and R8independently selected from aryl or alkenylphenol group, or jointly form a cyclic structure.

16. The method according to item 15, in which R7and R8independently chosen from vinyl and phenyl groups.

17. The method according to item 15, in which the tridentate ligand forms a coordination bond with rhodium or iridium metal center bridging conformation so that L1 and L2 relative to the metal center are in mutual transposagen the s.

18. The method according to item 15, in which each of L1 and L2 as a coordinating atom contains phosphorus, a L3 has a coordinating atom selected from atoms of oxygen, nitrogen and sulphur.

19. The method according to p, which has a coordination atom at L3 is an oxygen atom.

20. The method according to p or 19, in which L1 and L2 is represented by the formula R1R2P and R3R4P, respectively, in which each of R1, R2, R3and R4independently selected from unsubstituted or substituted alkenyl groups, alkyl groups and aryl groups.

21. The method according to claim 20, in which each of R1-R4denotes a substituted or unsubstituted phenyl group.

22. The method according to item 21, in which each R1for R4denotes unsubstituted phenyl group.

23. The method according to item 15, in which each of L1, L2, and L3 denotes a nitrogen atom.

24. The method according to claim 10, in which the tridentate ligand selected from the group including Xanthos, Texinfo, sexinfo, holocanthus, fossetts, isopropanol, nikandros, benzoxanthenes, DPE, DBP and their alkyl and aryl derivatives.

25. The method according to paragraph 24, in which the oxygen atom of the tridentate ligands substituted by a nitrogen atom, or sulfur.

26. The method according A.25, in which at least one of phosphoric coordinating atoms replaced by an atom of arsenic or antimony.

27. The method according to item 23, to the m tridentate ligand is a substituted or unsubstituted terpyridine.

28. The method according to claim 1 or 2, in which the catalyst comprises rhodium.

29. The method according to claim 1 or 2, in which the catalyst is added to the liquid reaction mixture in the form of pre-cooked metallogidridnogo ligand complex or receive in-situ in the liquid reaction mixture.

30. The method according to claim 1 or 2, in which the molar ratio of the metal of iridium or rhodium to the polydentate ligand is in the range from 1:1 to 1:2.

31. The method according to claim 1 or 2, in which the liquid reaction mixture further comprises a promoter and a catalyst.

32. The method according to p in which the promoter is chosen from the group comprising ruthenium, osmium, rhenium, cadmium, mercury, zinc, gallium, indium and tungsten.

33. The method according to claim 1 or 2, in which the liquid reaction mixture also contains an effective amount of a compound selected from the group including iodides of alkali metals, alkaline earth metal iodides, metal complexes capable of generating I-, salts capable of generating I-, and mixtures thereof.

34. The method according to claim 1 or 2, in which alkylhalogenide acetalization is alkylhalogenide with C1With4.

35. The method according to claim 1 or 2, wherein the alcohol is an aliphatic alcohol with C1C8.

36. The method according to p, in which the alcohol is selected from methanol, ethanol, propanolol and mixtures thereof.

37. The method according to claim 1 or 2, Kotor is m reactive derivative of the alcohol is chosen from esters, halides, ethers and mixtures thereof.

38. The method according to claim 2, in which the water concentration is in the range of 1-10 wt.%.

39. The method according to claim 1 or 2, in which carbon monoxide and hydrogen is fed into the reactor separately or as a mixture.

40. The method according to § 39, in which carbon monoxide and hydrogen is fed into the reactor in the form of a mixture.

41. The method according to p, in which a mixture of hydrogen and carbon monoxide obtained from the reforming process of hydrocarbons.

42. The method according to paragraph 41, in which the ratio of hydrogen to carbon monoxide is in the range from 1.5:1 to 5:1.

43. The method according to p or 41, in which the mixture contains at least 2 mol.% of hydrogen.

44. The method according to p, in which the molar ratio of hydrogen to carbon monoxide is in the range from 1:100 to 10:1.

45. The method according to item 44, which in the process maintain the concentration of hydrogen at a molar ratio of hydrogen to carbon monoxide of at least 1:10.

46. The method according to item 45, in which the molar ratio of hydrogen:carbon monoxide is at least 1:1.

47. The method according to claim 1 or 2, in which the partial pressure of hydrogen exceeds 1 bar.

48. The method according to claim 1, wherein the angle is at least 150°.

49. The method according to claim 1 or 2, in which the product of the carbonylation process is chosen from acetic acid, methyl acetate and mixtures thereof.



 

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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)

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

Synthesis of esters // 2227138
The invention relates to an improved method for producing a lower aliphatic esters, including the interaction of lower olefin with a saturated lower aliphatic monocarboxylic acid, preferably in the presence of water in the vapor phase in the presence of heteropolyanions catalyst, characterized in that the reaction is carried out sequentially placed in several reactors or in one long reactor with several successive layers heteropolyanions catalyst and b) initial reagents practically cleared of metallic impurities or compounds of metals so that before coming in contact with heteropolyanions catalyst metals and/or metal compounds is not more than 0.1 ppm

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

The invention relates to the field of technologies for industrial organic synthesis, in particular, to methods for producing methylformate

FIELD: chemistry.

SUBSTANCE: proposed method involves the following stages: (a) reaction of carbon monoxide with at least one reagent chosen from a group, consisting of methanol, methyl acetate, methyl formate and dimethyl ether and their mixture in a reaction medium, containing water, methyl iodide and catalyst for obtaining the reaction product, containing acetic acid; (b) gas-liquid separation of the said reaction product to obtain a volatile phase, containing acetic acid, water and methyl iodide and a less volatile phase, containing the said catalyst; (c) distillation of the above mentioned volatile phase to obtain a purified product of acetic acid and a first overhead fraction, containing water, methylacetate and methyl iodide; (d) phase separation of the above mentioned first overhead fraction to obtain the first liquid phase, containing water, and second liquid phase, containing methyl iodide and methyl acetate; and (e) feeding dimethyl ether directly or indirectly into a decantation tank of light fractions for phase separation of the said first overhead fraction in a quantity, sufficient for increasing separation of the first overhead fraction to form the first and second liquid phases.

EFFECT: improvement of the method of producing acetic acid.

8 cl, 1 dwg

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