Compound containing multimetal complex, metal complex and method of their production, method of producing catalyst for exgaust gas purification that uses said complexes

FIELD: process engineering.

SUBSTANCE: invention relates to compound that represents a multimetal complex comprising assemblage of metal complexes wherein ligand is coordinated by one metal atom or assemblage of atoms of one metal. Note here that assemblage of metal complexes are bound together by polydentant ligand which substitutes partially the ligands of metal complex assemblage and contains 2 to 1000 ligand atoms wherein each metal complex has carboxylic ligand and aforesaid polydentant ligand that represents dicarboxylic acid ligand, while metal is selected from the group consisting of Pt, Ni or Pd. Invention covers also the method of producing clusters of metal or metal oxide, the method of producing compound containing multimetal complex, and metal complex.

EFFECT: invention allows producing larger amount of controlled-size clusters.

25 cl, 3 ex, 8 dwg

 

The level of technology

The technical field to which the invention relates

The invention concerns compounds containing multimetallic complex, and complex metal and their method of manufacture, and method of manufacturing a catalyst for purification of exhaust gases with the use of these complexes. In particular, the invention concerns a method of manufacturing metal particles having a controlled size of the cluster by applying the compounds containing multimetallic complex, and complex metal.

Description of the prior art

Metal cluster with controlled size differs from an array of metal by chemical properties such as catalytic activity and the like, and such physical properties, such as magnetism and others.

In order to effectively apply specific properties of metal clusters, you need an easy way of producing large number of clusters with controlled size. A known method of manufacturing such clusters is a method in which (i) clusters of various sizes get, exposing the target metal evaporation in vacuum, and (ii) thus obtained clusters separated by size using the principle of a spectrum of masses. However, this method does not easily allow to obtain clusters in large to the icestar.

Specific properties of clusters are disclosed, for example, in “Adsorption and Reaction of Methanol Molecule on Nickel Cluster Ions, Nin+(n=3-11)”, M. Ichihashi, T. Hanmura, R.T. Yadav and T. Kondow, J. Phys. Chem. A, 104, 11885 (2000) (generic document). This document shows that the reactivity of molecules of methane and platinum catalyst in the gas phase is strongly influenced by the size of the cluster of platinum and shows that there is a specific cluster size of platinum, which is optimal for the reaction, as shown in figure 1.

Examples of the application of catalytic properties of noble metals include purification of exhaust gases emitted by internal combustion engine such as an automobile engine or the like. During the purification of exhaust gas components in exhaust gas, such as carbon monoxide (CO), hydrocarbons (HC), nitrogen oxides (NOXand so, convert to carbon dioxide, nitrogen and oxygen using a catalyst components, the main component of which is a noble metal, such as platinum (Pt), rhodium (Rh), palladium (Pd), iridium (Ir), etc. In General, a component of the catalyst is a noble metal, is applied on a substrate made of oxide such as aluminum oxide or similar, in order to increase the contact area of the exhaust gas and the catalyst component.

For the s to cause the noble metal oxide on the substrate, the oxide substrate is saturated with a salt solution of nitric acid and a noble metal or a complex of a noble metal, having one kind of atoms of the noble metal so that the compound of the noble metal is dispersed on the surface of the oxide substrate, and then impregnated with a solution of the substrate is dried and calcined. However, when applying this method, it is not easy to control the size and number of metal atoms in the cluster.

As for such catalysts for purification of exhaust gases, have also been proposed noble metals in the form of clusters to further improve the ability of the purification of exhaust gases. For example, Japanese patent application JP-A-11-285644 discloses a technology in which a catalytic metal is applied in the form of ultra fine particles directly on a substrate using cluster complex of the metal, which has a carbonyl group as a ligand.

In addition, Japanese patent application JP-A-2003-181288 discloses a technology in which a catalyst of a noble metal having a controlled cluster size produced by the introduction of the noble metal into the pores of the porous carbon material such as carbon nanotubes or the like, and fixing the carbon material with the included noble metal oxide on the substrate, and then p is avodat firing.

In addition, Japanese patent application JP-A-9-253490 discloses a technology in which a cluster of metal, made of an alloy of rhodium and platinum dissolved in the solid state, is obtained by adding a reducing agent to the solution containing ions of rhodium and platinum.

As for the complex of the metal, known for the production of polymer having a large number of metal atoms, when applying polydentate ligands. For example, Japanese patent application JP-A-2000-109485 discloses a technology for obtaining a polymer complex metal dicarboxylic acid, having a giant three-dimensional structure, with the use of dicarboxylic acid.

The invention

The invention provides a new compound containing multimetallic complex, which allows you to easily synthesize a large number of cluster controlled size, and complex metal, which can be used for the synthesis of this compound. The invention also provides methods of making compounds containing multimetallic complex, and the complex itself, and methods of using the compounds containing this complex, and very complex.

The first aspect of this invention concerns compounds containing multimetallic complex and composed of two or more metal complexes in each of which whether the Andes coordinate to one metal atom or set of atoms of metal of the same type, where two or more complexes of metal connected to each other through polydentate ligand, which is partially substituted by two or more ligands of the metal complexes and has from 2 to 1000 metal atoms.

In accordance with the above aspect, if the ligands are removed from compounds containing multimetallic complex, burning, or similar method, can be obtained cluster of metal or metal oxide having the same number of atoms of the metal, which is contained in the connection.

The second aspect of the present invention relates to a method of manufacturing clusters of metal or metal oxide, which have from 2 to 1000 metal atoms, which includes: (a) obtaining a solution containing a compound containing multimetallic complex according to the invention, and (b) drying and firing.

The third aspect of the invention relates to a method of making compounds containing multimetallic complex, which includes: obtaining complex metal; obtaining polydentate ligand or source polydentate ligand and the dissolution of a complex of metal and polydentate ligand or source polydentate ligand in the solvent.

In accordance with the foregoing aspect, the compound containing multimetallic complex and having a controlled number of metal atoms, can be obtained by m is Nisha least partial substitution of the ligands, coordinated in the metal complexes, polydentate ligand. It should be noted here that the term "source polydentate ligand or the source of ligand" in this description means polydentate ligand or compound (precursor), which gives the ligand, when dissolved in the solvent.

A fourth aspect of the invention concerns the complex of metal, in which the ligands coordinate to one metal atom or set of atoms of metal of the same type, and at least one ligand is coordinated functional group which is not coordinated to the metal atom and which is selected from the group consisting of-COOH, -COOR8, -CR8R9-OH, -NR8{C(=O)R9}, -NR8R9, -CR8=N-R9, -CO-R8, -PR8R9, -P(=O)R8R9, -P(OR8)(OR9), -S(=O)2R8-S+(-O-R8, -SR8, -CR8R9-SH, -CR8R9-SR10and-CR8=R9R10(each of R8-R10independently represents hydrogen or a monovalent organic group).

In accordance with the foregoing aspect of the properties of the functional group, which is not coordinated to the metal, can be used. More specifically, through the use of such functional groups it is possible to stably adsorb the complex metal substra is, to bind the metal complexes with each other, to associate a complex of a metal and another connection etc.

The fifth aspect of the invention relates to a method of manufacturing a catalyst for purification of exhaust gases, which includes: obtaining a solution containing a complex of the metal in accordance with the foregoing aspects; the saturation of the catalytic substrate solution, and drying and firing.

In accordance with this aspect of the complex metal adsorb on the catalytic substrate due to the affinity between the functional group is not coordinated to the metal atom, and a catalytic substrate in such a way that, when the complex metal annealed or carry out such methods, the metal contained in the complex metal may be deposited on the catalytic substrate with a high degree of dispersion.

The sixth aspect of the invention relates to a method of making compounds containing multimetallic complex, which includes: obtaining a complex of the metal, which is a ligand which has a coordinated carbon-carbon double bond, and the dissolution of a complex of the metal in the solvent, and the replacement alkylidene group coordinated carbon-carbon double bond through reaction cross-metathesis of carbon-carbon double bonds.

In accordance with the foregoing aspect of the m connection containing multimetallic complex, can be made of complex metal, which has coordinated the carbon-carbon double bond, with the reaction cross-metathesis of carbon-carbon double bond (olefin).

Brief description of drawings

The foregoing and/or further aspects, the specific features and advantages of the invention will be more apparent from the following description of preferred embodiments with reference to the accompanying drawings, in which identical numerals are used to denote identical elements and where:

Figure 1 is a diagram illustrating the relationship between the Pt cluster size and reactivity obtained from the above generic document;

Figure 2 shows a TEM photograph showing the appearance of Pt on MgO obtained by the method described in the comparative example;

Figure 3 shows a scheme of the synthesis of the compounds according to example 1;

Figure 4 shows a TEM photograph showing the appearance of Pt on MgO obtained by the method described in example 1;

Figure 5 shows a scheme of the synthesis of the compounds according to example 2;

6 shows a scheme of the synthesis of the compounds according to example 2;

Fig.7 shows a TEM photograph showing the appearance of Pt on MgO obtained by the method described in example 2;

Fig shows schemes for the synthesis of compounds according to example 3.

A detailed description of the preferred variants of the invention

In the following description of the present invention will be described in more detail by the example of the preferred variants of the invention.

(Compound containing multimetallic complex)

The compound containing multimetallic complex, in accordance with one embodiment of the invention has many metal complexes, in which each ligand is coordinated to one metal atom or set of atoms of metal of the same species. In this connection many of the metal complexes are connected to each other through polydentate ligand, which partially replaces the ligands and has from 2 to 1000 metal atoms. The number of metal atoms can be from 2 to 100, for example from 2 to 50, or from 2 to 20, or from 2 to 10.

(Ligand complex metal)

The ligands of the metal complexes or compounds containing multimetallic complex, in accordance with a particular embodiment can be freely chosen, taking into account the properties of the obtained compounds containing multimetallic complex steric difficulty between metal complexes that need to communicate, etc. Ligand can be either monodentate or polydentate, such as chelating ligand.

This ligand may be a group containing hydrogen, is knitted with one functional group, selected from the group of functional groups listed below, or an organic group that is associated with one or more functional groups mentioned below, in particular organic group that is associated with one or more functional groups of the same type selected from the group consisting of: -COO-(carboxyl group), -CR1R2-O-(CNS group), -NR1-(amide group), -NR1R2(the amino group), -CR1=N-R2(aminogroup), -CO-R1(carbonyl group), PR1R2(phosphine group), -P(=O)R1R2(phosphinoxide group), -P(OR1)(OR2) (Fofana group), -S(=O)2R1(sulfonic group), -S+(-O-R1(sulfoxide group), -SR1(sulfide group) and CR1R2-S-(tialata group); and, in particular: -COO-(carboxyl group), -CR1R2-O-(CNS group), -NR1-(amide group),- NR1R2(the amino group) (each of R1and R2independently represent hydrogen or a monovalent organic group).

Organic group that is associated with the functional group may be a substituted or unsubstituted hydrocarbon group, particularly a substituted or unsubstituted hydrocarbon group, a C1-C30(that is, where h is the layer of carbon atoms is from 1 to 30; this (short) will be applied also in the following descriptions), which may have a heteroatom, ether bond or ester bond. In particular, this organic group may be an alkyl group, alkenylphenol group, alkenylphenol group, aryl group, aranceles group or a monovalent alicyclic group C1-C30in particular, C1-C10. More specifically, this organic group may be an alkyl group, alkenylphenol group, alkylamino group C1-C5in particular, C1-C3.

Each of R1and R2can independently represent hydrogen or substituted or unsubstituted hydrocarbon group, particularly a substituted or unsubstituted hydrocarbon group, a C1-C30, which may have a heteroatom, ether bond or ester bond. In particular, R1and R2can be a hydrogen or alkyl group, alkenylphenol group, alkylamino group, aryl group, aracelio group or a monovalent alicyclic group C1-C30in particular, C1-C10. More specifically, R1and R2can be a hydrogen or alkyl group, alkenylphenol group or alkylamino group C1-C5in particular, C1-C3.

Examples if the Anda complex metal include: carboxyl ligand (R-COO -), CNS ligand (R-CR1R2-O-), amide ligand (R-NR1-), amine ligand (R-NR1R2), kinowy ligand (R-CR1=N-R2), a carbonyl ligand (R-CO-R1), phosphine ligand (R-PR1R2), phosphinoxide ligand (R-P(=O)R1R2), fosfatnyi ligand (R-P(OR1)(OR2)), sulfonovy ligand (R-S(=O)2R1), sulfoxide ligand (R-S+(-O-R1), sulfide ligand (R-SR1and tiality ligand (R-CR1R2-S-) (R represents hydrogen or an organic group, and R1and R2described above).

Specific examples of carboxyl ligands include ligands of formic acid (formity), the ligand of acetic acid (acetate), ligand propionic acid (propionate) and ethylenediaminetetraacetate ligand.

Specific examples of CNS ligands include ligands methanol (metaxylene), the ligand of ethanol (ethoxyline), ligand propanol (propoxyphenyl), ligand butanol (butoxyphenyl), the ligand of pentanol (pentoxil), ligand dodecanol (dodecyloxyphenyl) and ligand phenol (phenoxyl).

Specific examples of amide ligands include dimethylamine ligand, diethylamine ligand, di-n-Propylamine ligand, Diisopropylamine ligand, di-n-butylamine ligand, di-tert-butylamine ligand and nicotinamide ligand.

Specific examples of amine ligands include methylamine, ethylamine, methylethylamine, trimethylamine, triethylamine, Ethylenediamine, tributylamine, hexamethylenediamine were, aniline, Ethylenediamine, Propylenediamine, trimethylenediamine, Diethylenetriamine, Triethylenetetramine, Tris-(2-amino-ethyl)amine, ethanolamine, triethanolamine, ethanolamine, triethanolamine, diethanolamine, trimethylenediamine, piperidine, Triethylenetetramine, triethylenediamine.

Specific examples eminovic ligands include Diemen, ethylenimine, propylenimine, hexamethylenimine, benzophenones, methylethylketone, pyridine, pyrazole, imidazole and benzimidazole.

Specific examples of the carbonyl ligand include carbon monoxide, acetone, benzophenone, acetylacetone, acenaphthene, hexafluoroacetylacetone, benzoylacetone, triflluoroacetylacetone and dibenzoylmethane.

Specific examples of the phosphine ligand include a hydride of phosphorus, methylphosphine, dimethylphosphine, trimethylphosphine and diphosphine.

Specific examples phosphinoxide ligand include tributylphosphine oxide, triphenylphosphine oxide and tri-n-octylphosphine oxide.

Specific examples Fofanova ligand include triphenylphosphite, titleleft, tributylphosphite and triethylphosphite.

Specific examples of sulfonic ligand include hydrogen sulfide, dimethyl sulfone and debutylation.

Specific examples sulfoxide ligand include dimethylsulfoxide Li gang and dibutylsebacate ligand.

Specific examples of the sulfide ligand include ethylsulfate, butylsulfide etc.

Specific examples timetogo ligand include Retentivity ligand and sensativity ligand.

(Polydentate ligand)

As polydentate ligand, which partially replaces the numerous ligands of metal complexes and which connects the metal complexes with each other, can be applied to arbitrary polydentate ligand that can perform the above-mentioned role. It is considered preferable when polydentate ligand has a specific length in order to avoid destabilizing compounds containing multimetallic complex due to steric difficulties arising between metal complexes. In particular, when the compound containing multimetallic complex, in accordance with a specific embodiment of the invention is subject to annealing or similar destruction, in order to obtain the cluster that has the same number of atoms of metals, which was held in this connection, an excessively large length polydentate ligand may make it difficult obtaining a single view of the clusters of this connection.

Polydentate ligand, which partially replaces the ligands of the metal complexes can be represented by the following the formula:

(L1)-R3-(L2)

(where R3represents a bond or a bivalent organic group, and L1and L2are either the same or different functional groups selected from the group consisting of-COO-(carboxyl group), -CR4R5-O-(CNS group), -NR4-(amide group), -NR4R5(the amino group), -CR4=N-R5(aminogroup), -CO-R4(carbonyl group), PR4R5(phosphine group), -P(=O)R4R5(phosphinoxide group), -P(OR4)(OR5) (Fofana group), -S(=O)2R4(sulfonic group), -S+(-O-R4(sulfoxide group), -SR4(sulfide group) and CR1R4-S-(tialata group) (each R4and R5independently represents hydrogen or a monovalent organic group)).

In particular, L1and L2can represent the same functional group selected from the group consisting of-COO-(carboxyl group), -CR4R5-O-(CNS group), -NR4-(amide group),- NR4R5(the amino group) (each R4and R5independently represents hydrogen or a monovalent organic group).

R3can be a link or a substituted or unsubstituted bivalent hydrocarbon group, in particular substituted or unsubstituted bivalent hydrocarbon group, C1-C30, which may have a heteroatom, ether bond or ester bond. In particular, R3can be alkylenes group, alkynylamino group, alkynylamino group, Allenova group, Aracinovo group or a bivalent alicyclic group C1-C30and, in particular, C1-C10.

R4and R5can represent organic groups mentioned in connection with R1and R2.

(Combination polydentate ligand and ligand complex metal)

The ligands of the metal complexes and polydentate ligand, partially replacing the ligands of the metal complexes, can have the same functional group. For example, each of the ligands of the metal complexes and polydentate ligands may have a carboxyl group, CNS group, amide group or amino group.

(Metal, which becomes the core of the complex metal)

The metal, which becomes the core of the complex metal may be any metal of main group or transition metal. In particular, the metal may be a transition metal, and more specifically may be a transition metal of the fourth through the seventh group, for example a metal selected from the group consisting of titanium, vanadium, chromium,manganese, iron, cobalt, Nickel, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold.

In addition, when the catalyst was prepared using compounds containing multimetallic complex in accordance with this embodiment, the applied metal can be a metal, is advantageous from the point of view of application of the catalyst, for example element of the iron group (iron, cobalt, Nickel, copper, platinum group element (ruthenium, rhodium, palladium, osmium, iridium and platinum), gold or silver.

(Complex metal)

For compounds containing multimetallic complex, in accordance with this embodiment, each set of metal can be arbitrary complex metal, in which the ligand coordinate to one metal atom or set of atoms of metal of the same type. That is, the complex metal can be a polynuclear complex, for example the complex, which has from 2 to 10 atoms of metal, in particular from 2 to 5 atoms of metal.

This set of metal can be arbitrary complex metal. Specific examples of the metal complexes include [Pt4(CH3COO)8], [Pt(acac)2] (“acac” represents acetylacetonate ligand), [Pt(CH3CH2NH2)4]Cl2, [Rh2(C6 H5COO)4], [Rh2(CH3COO)4], [Rh2(OOCC6H4COO)2], [Pd(acac)2], [Ni(acac)2], [Cu(C11H23COO)2]2, [Cu2(OOCC6H4COO)2], [Cu2(OOCC6H4CH3)4], [Mo2(OOCC6H4COO)2], [Mo2(CH3COO)4] and [N(n-C4H9)4][FeIIFeIII(ox)3] (“ox” is an oxalate ligand).

(The form in which the compound containing multimetallic complex has a carboxyl ligands)

The compound containing multimetallic complex, in accordance with this embodiment may be in the form in which the metal complexes are complexes of metals which have a carboxyl ligands, in particular the acetate ligands, for example octachlorostyrene ([Pt(µ-CH3COO)8]), and in which polydentate ligand, partially replacing the ligands of the metal complexes, is a ligand dicarboxylic acid.

Ligand dicarboxylic acids may be represented by the following formula:

-OOC-R6-COO-

(R6represents alkylenes group, alkynylamino group, alkynylamino group, Allenova group, Aracinovo group or a bivalent alicyclic group C1-C30and, in particular, C1-C0 ).

R6can be selected from the group consisting of p-phenylenebis group and alkenylamine groups represented by the following formula:

-(CH2)nC=C(CH2)n-

(n is an integer from 1 to 5).

(The form in which the metal complexes are octachlorostyrene)

The compound containing multimetallic complex, in accordance with this embodiment can be represented by the following formula:

R7represents alkylenes group, alkynylamino group, alkynylamino group, Allenova group, Aracinovo group or a bivalent alicyclic group C1-C30in particular, C1-C10.

R7can be selected from the group consisting of p-phenylenebis group and alkenylamine groups represented by the following formula:

-(CH2)nC=C(CH2)n-

(n is an integer from 1 to 5).

(Method of manufacturing clusters of metal or metal oxide)

In accordance with the method of manufacturing a cluster of metal or metal oxide having from 2 to 1000 metal atoms, in the present invention: (a) obtain a solution containing a compound containing, in turn, multimetallic complex according to the invention, and (b) saturated solution of the m substrate is dried and fired.

Drying and firing the substrate containing compound containing, in turn, multimetallic complex, can be produced at such temperature and time conditions that are suitable for obtaining clusters of metals or metal oxides. For example, the drying may be performed at a temperature of from 120 to 250°C for 1-2 hours, and then can be fired at a temperature from 400 to 600°C. for 1-3 hours. The solvent used for the solution may be any solvent which is capable of stably maintaining a connection containing multimetallic complex according to the invention, for example an aqueous solvent or an organic solvent, such as dichloromethane or the like.

This method may also include saturation of the porous substrate with a solution before drying and firing stages (b).

When the catalyst, particularly a catalyst for purification of exhaust gases shall be manufactured with the use of this method used the porous substrate can be a porous substrate of a metal oxide, for example a porous substrate of a metal oxide selected from the group consisting of oxides of aluminum, cerium, zirconium, silicon, titanium, and combinations thereof.

(Method of manufacturing the compounds according to the invention, containing multimetal the economic complex)

A method of making compounds according to the invention, containing multimetallic complex, includes: (a) obtaining a complex of metal and (b) obtaining polydentate ligand or source polydentate ligand, and (c) mixing in a solvent of the complex metal and polydentate ligand or source polydentate ligand.

Polydentate ligand used in this method, is chosen so that the selected polydentate ligand may be substituted ligands coordinated in the complex of the metal, which is used as the starting material. Therefore, in General, you can use polydentate ligand, which has a stronger coordination ability than the ligands coordinated in the complex of the metal, which is used as a starting material, in particular polydentate ligand, which has a more tightly coordinated communication than the ligands coordinated in the complex metal for use as initial substances, and which has the same number of functional groups, and (as mentioned) ligands.

Polydentate ligand can be used in relatively large quantities in order to accelerate the substitution of the ligands of the complex metal polydentate ligand. However, the number polydentate ligand used in this way, can be the ü less than the amount want to full substitution of the ligands coordinated in the complex of the metal. The number polydentate ligand used in this method may be 1/2 or less, or 1/4 or less, or 1/8 or less of the quantity required for complete replacement of the ligands coordinated in the complex of the metal, from the viewpoint numbers of the controlled binding of metal complexes with respect to each other.

The solvent used in this method may be any solvent capable of stably maintaining a connection according to the invention, containing multimetallic complex, for example aqueous solvent or an organic solvent, such as dichloromethane or the like.

(Complex metal)

Complex metal according to the invention is a complex of metal, in which the ligands are coordinated by one atom of metal or multiple metal atoms of the same species, and at least one ligand is coordinated functional group which is not coordinated to the metal atom and which is selected from the group consisting of: -COOH (carboxyl group), -COOR8(ester group), -CR8R9-OH (alcohol group), -NR8{C(=O)R9} (amide group), -NR8R9(the amino group), -CR8=N-R9(aminogroup),-CO-R 8(carbonyl group), PR8R9(phosphine group), -P(=O)R8R9(phosphinoxide group), -P(OR8)(OR9) (Fofana group), -S(=O)2R8(sulfonic group), -S+(-O-R8(sulfoxide group), -SR8(sulfide group), -CR8R9-SH (Tolna group), -CR8R9-SR10(thioester group),- CR8=R9R10(ethylene group) (each of R8and R10independently represents hydrogen or a monovalent organic group).

Each of R8-R10independently represents an organic group mentioned above in connection with R1and R2that can be considered as examples.

The ligand of the complex metal according to the invention may be a hydrogen-containing group associated with the functional group of the following functional groups, which are coordinated to the metal atom, or an organic group associated with one or more of the following functional groups are coordinated to the metal atom: -COO-, -CR11R12-O-, -NR11-, -NR11R12, -CR11=N-R12, -CO-R11, -PR11R12, -P(=O)R11R12, -P(OR11)(OR12), -S(=O)2R11-S+(-O-R11, -SR11and-CR11R12-S-(each of R11The R 12independently represents hydrogen or a monovalent organic group).

Examples of the ligand of the complex metal according to the invention include ligands mentioned above in connection with the metal complexes of the compounds according to the invention, containing multimetallic complex. Therefore, each of R11and R22independently represents an organic group mentioned above in connection with R1and R2that can be considered as examples.

It is possible that each ligand complex metal according to the invention has only one functional group, coordinated with the metal atom.

(The form in which the complex of the metal in accordance with this embodiment has a carboxyl group as uncoordinated functional group)

In the case when the complex metal in accordance with this embodiment has a carboxyl group as uncoordinated functional group ligand complex metal may have a carboxyl group, which is coordinated to the metal atom. For example, complex metal may be in the form in which the ligand with uncoordinated functional group is a ligand dicarboxylic acid, and the ligand, not having uncoordinated functional group is a ligand of acetic acid.

SL is therefore complex metal may be octachlorostyrene ([Pt(CH3COO)8]), in which at least one ligand of acetic acid (acetate ligand) substituted ligand dicarboxylic acid.

Ligand dicarboxylic acids may be represented by the following formula:

-OOC-R13-COOH

(R13represents alkylenes group, alkynylamino group, alkynylamino group, Allenova group, Aracinovo group or a bivalent alicyclic group C1-C30in particular, C1-C10).

(The form in which the complex of the metal in accordance with this embodiment represents a substituted dicarboxylic acid octachlorostyrene)

Complex metal can be represented by the following formula:

(R14represents alkylenes group, alkynylamino group, alkynylamino group, Allenova group, Aracinovo group or a bivalent alicyclic group C1-C30in particular, C1-C10).

R14can represent, for example, p-fenelonov group.

(The form in which the complex of the metal in accordance with this embodiment has a carbon-carbon double bond as uncoordinated functional group)

In the case when the complex metal according to this embodiment has a carbon-carbon double bond as uncoordinated functional group, the ligand of the complex metal may have a carboxyl group, which is coordinated to the metal atom. For example, complex metal may be in the form in which the ligand with uncoordinated functional group is a carboxylic acid ligand, which has a carbon-carbon double bond, namely unsaturated carboxylic acid, and in which the ligand without uncoordinated functional group is a ligand of acetic acid.

Therefore, the complex metal can be octachlorostyrene ([Pt(CH3COO)8]), in which at least one ligand acetic acid, substituted carboxylic acid ligand, which has a carbon-carbon double bond.

Ligand carboxylic acids having carbon-carbon double bond, can be represented by the following formula:

-OOC-R15

(R15represents alkenylphenol group C1-C30in particular, C1-C10).

(The form in which the complex of the metal in accordance with this embodiment, is octachlorostyrene, substituted carboxylic acid which has a carbon-carbon double bond)

Complex metal according to the invention can be represented by the following formula:

(R16PR is dstanley a linear or branched alkenylphenol group C 1-C30in particular, C1-C10).

(Method of manufacturing a catalyst for purification of exhaust gases with the use of complex metal in accordance with this embodiment)

In the method of manufacturing a catalyst for purification of exhaust gases in accordance with this embodiment: (a) obtain a solution containing a complex metal according to the invention, in particular the complex of metal having as the core of the atom of the metal, which is preferred for use as catalyst (b) saturate the catalytic substrate (data) solution, and (C) is impregnated with a solution of the substrate is dried and fired.

Catalytic substrate may be a substrate made of a metal oxide, for example a substrate made of a porous metal oxide selected from the group consisting of oxides of aluminum, cerium, zirconium, silicon, titanium, and combinations thereof.

Drying and firing poloski containing compound containing multimetallic complex, can be produced at such temperature and time conditions that are suitable for obtaining clusters of metals or metal oxides. For example, the drying may be performed at a temperature of from 120 to 250°C for 1-2 hours and then may be annealed at a temperature of from 400 to 600°C. for 1-3 hours. The solvent used for this process is and, can be any solvent that is capable of stably maintaining a connection containing multimetallic complex according to the invention; for example, an aqueous solvent or an organic solvent, such as dichloromethane or the like.

(Method of producing compounds containing multimetallic complex, with complex metal in accordance with this embodiment, which has a carboxylic acid ligand, which has a carbon-carbon double bond)

In the method of manufacturing compounds containing multimetallic complex with the use of complex metal in accordance with this embodiment: (a) receive a set of metal having a ligand carboxylic acids having carbon-carbon double bond, and (b) dissolved complex metal in the solvent, and alkylidene group coordinated carbon-carbon link replaced with the reaction cross-metathesis of carbon-carbon double bonds.

The reaction cross-metathesis of carbon-carbon double bond (olefin) is the following reaction:

RaRbC=CRcRd+ ReRfC=CRgRh

→ RaRbC=CRgRh+ ReRfC=CRcRd

(each of Ra-Rhindependently represents such organizations the practical group, as alkyl or the like).

The reaction cross-metathesis and the catalyst used for this reaction are disclosed in, for example, Japanese patent application JP-A-2004-123925, Japanese patent application JP-A-2004-043396 and published the translation of Japanese patent application PCT JP-T-2004-510699. The catalyst for the reaction cross-metathesis can be a catalyst for the verification of the fourth generation. Therefore, the reaction may proceed under mild conditions.

Comparative example

(Getting [Pt4(CH3COO)8])

The connection is carried out using the method described in “Jikken Depending Kouza (Experimental Chemistry Course)”, 4th edition, volume 17, str, Maruzen, 1991. That is getting carried out as follows: 5 g of K2PtCl4dissolved in 20 ml of warm water and to the solution was added 150 ml of glacial acetic acid. At this time begins to fall precipitate K2PtCl4. Not taking into account precipitation, add 8 g of silver acetate. The resulting material in suspension is boiled for 3 to 4 hours while stirring. The material is then cooled and the black precipitate is filtered off. Using a rotary evaporator to remove acetic acid and concentrated brown precipitate as possible. This concentrate is combined with 50 ml of acetonitrile and the mixture was kept insisting. Drop down sieges which it is filtered and the filtrate is again concentrated. In General, this concentration procedure was performed three times. The final concentrate is combined with 20 ml dichloromethane and adsorb on a column of silica gel. The elution is conducted with a mixture of dichloromethane-acetonitrile (5:1); red extract are combined and concentrated to obtain a crystal.

(Applying to the substrate).

Magnesium oxide 10 g (MgO) was dispersed in 200 g of acetone. With stirring to this dispergirovannom solution of MgO added to the solution obtained, in turn, dissolution 16,1 mg [Pt4(CH3COO)8] in 100 g of acetone. The mixture is stirred for 10 minutes. When the stirring stops, precipitation of MgO and get pale red supernatant (i.e. [Pt4(CH3COO)8] not adsorbed on MgO). This mixed solution was concentrated and dried using a rotary evaporator. The dried powder is calcined at 400°C in air for 1.5 hours. The concentration of Pt on the substrate is 0.1 wt.%.

(TEM - observation cluster)

The appearance of Pt on MgO prepared with the above method, was observed using TEM. When using an electron microscope of the type HD-2000 Hitachi watched STEM image at an accelerating voltage of 200 kV. STEM image of comparative example 1 is shown in figure 2. This image shows the Pt particles having a pore diameter of 0.6 nm, which is calculated from the article is ucture 4-atom clusters of platinum, demonstrating that using the above method 4-nuclear platinum clusters can be deposited on an oxide substrate.

Example 1

(Getting [Pt4(CH3COO)4{o-C6H4(COO)(COOH)}4])

Getting this connection is shown in the diagram in figure 3.

More specifically, this compound is synthesized as follows. [Pt4(CH3COO)8] (460 mg, 369 mmol)synthesized in comparative example, and o-C6H4(CO2H)2(1.50 g, 9,00 mmol) was placed in 50 ml Slink filled with argon; properly add 10 ml of CH2Cl2and 10 ml of MeOH. The solution immediately becomes orange-red color. Then the solution was stirred at room temperature for 2 hours, the solvent is removed by evaporation under reduced pressure to obtain a solid residue. This residue was dissolved in CH2Cl2and filtered. The filtrate is dried under reduced pressure and get solid yellow substance.

Spectral data and elemental analysis results of the substance is shown below.

1H NMR (300 MHz, CDCl3, 308K) δ: a 1.96 (s, 12H, CH3), 7,55-to 7.67 (m, 12H, aromatic H), 8,40-8,43 (m, 4H, aromatic H), 12,3 (USS, w1/2=32,4 Hz, 4H, -CO2H).

13C{1H} NMR (75 MHz, CDCl3, 308K) δ: 21,3 (O2 3), 126,3, 129,1, 129,8, 131,1, 132,1, 135,8 (aromatic C), 176,9 (CO2H), 180,1 (O2CCH3).

IR (KBr disk, ν/cm-1): 1715 (C=O), 1557, 1386 (CO2-). Analysis calculated for C40H32O24Pt4: C, 28,65; H, 1,92. Found: C, 28,63; H, 2,15.

(Confirmation link structure)

The structure was determined by x-ray diffraction analysis of a single crystal of the compound obtained in the solution of CH2Cl2.

(Substrate).

MgO (10 g) was dispersed in 200 g of acetone. With stirring to this dispergirovannom solution of MgO added to the solution obtained, in turn, by the dissolution of 21.5 mg [Pt4(CH3COO)4{o-C6H4(COO)(COOH)}4] in 100 g of acetone. The mixture is stirred for 10 minutes. Then stop stirring, precipitation of MgO, and the supernatant becomes transparent (i.e. [Pt4(CH3COO)4{o-C6H4(COO)(COOH)}4] adsorbed on MgO). This mixed solution was concentrated and dried using a rotary evaporator. The dried powder is calcined at 400°C in air for 1.5 hours. The concentration of deposited Pt is 0.1 wt.%.

(TEM - observation cluster)

The appearance of Pt on MgO prepared with the above method, was observed using TEM. When using an electron microscope of the type HD-2000 Hitachi watched STEM images at accelerating the em voltage of 200 kV. STEM image of sample 1 is shown in figure 4. This image shows the Pt particles having a pore diameter of 0.6 nm, which is calculated from the structure of the 4-atom of platinum clusters, demonstrating that using the above method 4-nuclear platinum clusters can be deposited on an oxide substrate.

Example 2

(Getting [Pt4(CH3COO)7{O2C(CH2)3CH=CH(CH2)3CO2}(CH3COO)7Pt4])

Getting this connection is shown in the diagram in figure 5 and 6.

More specifically, this compound is obtained as follows. CH2=CH(CH2)3CO2H (to 19.4 μl, 18.6 mg) was added to the CH2Cl2to a solution (10 ml) octachlorostyrene [Pt4(CH3COO)8] (0,204 g, 0,163 mmol)obtained by the method described above in comparative example 1. After adding the color of the solution changed from orange to red-orange. After stirring at room temperature for 2 hours the solvent is removed by evaporation under reduced pressure; the residue is washed twice with diethyl ether (8 ml). The result is a solid orange color [Pt4(CH3COO)7{O2C(CH2)3CH=CH2}].

[Pt4(CH3COO)7{O2C(CH2 )3CH=CH2}] (362 mg, 0,277 mmol), synthesized as described above, and the catalyst for the verification of the first generation (of 6.7 mg, 8.1 μmol, of 2.9 mol.%) placed in filled with argon, Slink and dissolved in CH2Cl2(30 ml). Device Slanka provide reflux condenser and heated in an oil bath. After boiling for 60 hours the solvent is removed by evaporation under reduced pressure and the residue dissolved in CH2Cl2, then filtered through a glass filter. The filtrate is concentrated under reduced pressure and get solid. The solid is washed with diethyl ether (10 ml) three times and get a solid orange color [Pt4(CH3COO)7{O2C(CH2)3CH=CH(CH2)3CO2}(CH3COO)7Pt4] a mixture of E/Z isomers.

(Spectral data)

[Pt4(CH3COO)7{O2C(CH2)3CH=CH2}]

1H NMR (300 MHz, CDCl3, 308K) δ: 1,89 (TT,3JHH=to 7.5, 7.5 Hz, 2H, O2CCH2CH2-), of 1.99 (s, 3H,axO2CCH3), from 2.00 (s, 3H,axO2CCH3), a 2.01 (s, 6H,axO2CCH3), 2,10 (typ. kV, 2H, -CH2CH=CH2), is 2.44 (s, 6H,eqO2CCH3), a 2.45 (s, 3H,eqO2CCH3), 2,70 (t,3JHH=7.5 Hz, 2H, O2CCH2CH2-), 4,96 (DDT,3JHH=10.4 Hz,2JHH=1,8 Hz4 HH=? Hz, 1H, -CH=C (H)CISH), 5,01 (DDT,3JHH=17.3 Hz,2JHH=1,8 Hz4JHH=? Hz, 1H, -CH=C (H)TRANSH)of 5.81 (DDT,3JHH=17,3, 10,4, and 6.6 Hz, 1H, -CH=CH2).

13C{1H} NMR (75 MHz, CDCl3, 308K) δ: 21,2, 21,2 (axO2CCH3), 22,0, 22,0 (eqO2CCH3), 25,8 (O2CCH2CH2-), 33,3 (-CH2CH=CH2), 35,5 (O2CCH2CH2-), 115,0 (-CH=CH2), 137,9 (-CH=CH2), 187,5, 193,0, 193,1 (O2CCH3), 189,9 (O2CCH2CH2-).

MS (ESI+, the solution of CH3CN) m/z: 1347 ([M+Rast.]+).

IR (KBr disk, ν/cm-1): 2931, 2855 (νC-H), 1562, 1411 (νCOO-), 1039, 917 (ν-C=C-).

(Spectral data)

[Pt4(CH3COO)7{O2C(CH2)3CH=CH(CH2)3CO2}(CH3COO)7Pt4]

Major (E-isomer):

1H NMR (300 MHz, CDCl3, 308K) δ: 1,83 (J=7.7 Hz, 4H, O2CCH2CH2-), from 2.00 (s, 6H,axO2CCH3), a 2.01 (s, 18H,axO2CCH3), 2,02 is 2.10 (m, 4H, -CH2CH=CH-), 2,44 (s, 18H,eqO2CCH3), to 2.67 (t,3JH-H=7.2 Hz, 4H, O2CCH2CH2-), lower than the 5.37-of 5.45 (m, 2H, -CH=).

13C NMR (75 MHz, CDCl3, 308K) δ: 21,17(kV,1JC-H=130,9 HzaxO2CCH3), 21,22(kV,1JC-H=RB 131.1 HzaxO2CCH3), 21,9 (kV,1JC-H=129,4 HzeqO2CCH3), 22,0 (kV,1JC-H=129,4 Hz eqO2CCH3)of 26.4 (t,1JC-H=RUB 127.3 Hz, O2CCH2CH2-), 32,0 (t,1JC-H=RUB 127.3 Hz, -CH2CH=CH-), 35,5 (t,1JC-H=130,2 Hz, O2CCH2CH2-), to 130.1 (d,1JC-H=of 148.6 Hz, -CH=), 187,3, 187,4, 193,0 (O2CCH3), 189,9 (O2CCH2CH2-).

Minor (Z-isomer):

1H NMR (300 MHz, CDCl3, 308K) δ: 1,83 (J=7.7 Hz, 4H, O2CCH2CH2-), from 2.00 (s, 6H,axO2CCH3), a 2.01 (s, 18H,axO2CCH3), 2,02 is 2.10 (m, 4H, -CH2CH=CH-), 2,44 (s, 18H,eqO2CCH3), 2,69 (t,3JH-H=7.2 Hz, 4H, O2CCH2CH2-), lower than the 5.37-of 5.45 (m, 2H, -CH=).

13C NMR (75 MHz, CDCl3, 308K) δ: 21,17(kV,1JC-H=130,9 HzaxO2CCH3), 21,22(kV,1JC-H=RB 131.1 HzaxO2CCH3), 21,9 (kV,1JC-H=129,4 HzeqO2CCH3), 22,0 (kV,1JC-H=129,4 HzeqO2CCH3), 26,5 (t,1JC-H=RUB 127.3 Hz, O2CCH2CH2-), 26,7 (t,1JC-H=RUB 127.3 Hz, -CH2CH=CH-), 35,5 (t,1JC-H=130,2 Hz, O2CCH2CH2-), 129,5 (d1JC-H=154,3 Hz, -CH=), 187,3, 187,4, 193,0 (O2CCH3), 189,9 (O2CCH2CH2-).

MS (ESI+, the solution of CH3CN) m/z: 2584 ([M]+).

(Substrate).

MgO 10 g was dispersed in 200 g of acetone. Under stirring to dispergirovannom solution of MgO added to the solution obtained, its about ered, the dissolution of 16.6 mg [Pt4(CH3COO)7{O2C(CH2)3CH=CH(CH2)3CO2}(CH3COO)7Pt4] in 100 g of acetone. The mixture is stirred for 10 minutes. This mixed solution was concentrated and dried using a rotary evaporator. The dried powder is calcined at 400°C in air for 1.5 hours. The concentration of deposited Pt is 0.1 wt.%.

(TEM - observation cluster)

The appearance of Pt on MgO prepared with the above method, was observed using TEM. When using an electron microscope of the type HD-2000 Hitachi watched STEM image at an accelerating voltage of 200 kV. STEM image of sample 2 is shown in Fig.7. This image shows the Pt particles having pores with a diameter of 0.9 nm, which is calculated from the structure of the 8-atom of platinum clusters, demonstrating that using the above method 8-nuclear platinum clusters can be deposited on an oxide substrate.

Example 3

(Getting [Pt4(CH3COO)7{O2C-(p-C6H4)-CO2}(CH3COO)7Pt4])

Getting this connection is shown in the diagram in Fig.

More specifically, this compound is obtained as follows. CH2Cl2(10 ml) solution of [Pt4(CH3COO)8] (0,204 g, 0,163 mmol who), obtained, in General, similar to the method in the comparative example, mixed with terephthalic acid (HO2C-(p-C6H4)-CO2H) (0,0135 g, 0,0815 mmol) in an amount equal to half the number of [Pt4(CH3COO)8]. In the fall a black precipitate. The residue is washed twice CH2Cl2(10 ml) and receive crystals of [Pt4(CH3COO)7{O2C-(p-C6H4)-CO2}(CH3COO)7Pt4].

(Identity)

The connection is identified using elemental analysis, because the crystals of this compound does not dissolve in solvents. The results are shown below. Analysis calculated for C36H46O32Pt8: C 16,95; H, 1,82. Found: C, 20,10; H, 1,78.

Although the invention has been described with reference to its specific embodiments, it should be clear that the invention is not limited to typical embodiments or devices. On the contrary, it is understood that the invention includes various modifications and equivalent devices. Additionally, although various elements of embodiments are shown in various combinations and configurations, which are private, other combinations and configurations, including more, less or only a single element, are also included in the nature and scope of the claims of this invention.

1. Connected to the e, representing multimetallic complex, containing many metal complexes, in which each ligand coordinated one metal atom or set of atoms of metal of the same species, which is characterized by the fact that many metal complexes are connected to each other by means of a polydentate ligand, which partially replaces the many ligands of metal complexes and has from 2 to 1000 metal atoms, where each of the metal complexes has a carboxyl ligand and polydentate ligand, which partially replaces the ligands of the metal complexes, is a ligand dicarboxylic acid and a metal selected from the group consisting of Pt, Ni or Pd.

2. The Union, representing multimetallic complex according to claim 1, having from 2 to 100 atoms of metal.

3. The Union, representing multimetallic complex according to claim 1 or 2, where the ligand of the metal complexes represents a hydrogen containing group associated with one functional group mentioned below, or an organic group associated with the one or more functional groups mentioned below: -soo-.

4. The Union, representing multimetallic complex according to claim 3, where the organic group that is associated with the functional group is a heteroatom, ether bond or slozhnoefirnoi.

5. The Union, representing multimetallic complex according to claims 1 or 2, where polydentate ligand, which partially replaces the ligands of the metal complexes may be represented by the following formula:
(L1)-R3-(L2),
where R3represents a bond or a bivalent organic group, and L1and L2represent functional groups mentioned below: -soo-.

6. The Union, representing multimetallic complex according to claim 1 or 2, where R3represents a bond or a substituted or unsubstituted hydrocarbon group, which is a heteroatom, ether bond or ester bond.

7. The Union, representing multimetallic complex according to claim 1, where each of the metal complexes is octachlorostyrene.

8. The compound containing multimetallic complex according to claim 1, which is represented by the following formula:
[Pt4](CH3COO)7{O2C-R7-CO2}(CH3COO)7Pt4]

where R7represents alkylenes group, alkynylamino group, alkynylamino group, Allenova group, Aracinovo group or a bivalent alicyclic group C1-C30.

9. A method of manufacturing clusters of metal or metal oxide is, which is characterized by the fact that includes obtaining a solution containing a compound containing multimetallic complex according to any one of claims 1, 2 or 8; adding the resulting solution to a solution of a metal oxide, and drying and firing.

10. The method according to claim 9, characterized in that it also includes the saturation of the porous substrate with a solution before drying and firing.

11. The method according to claim 10, where the porous substrate is a catalytic substrate of the oxide of the metal.

12. A method of making compounds containing multimetallic complex, characterized in that it includes obtaining complex metal according to any one of claims 1, 2 or 8; obtaining polydentate ligand according to any one of claims 1, 2, 7 or 8 or source polydentate ligand to obtain polydentate ligand (predecessor polydentate ligand); and the mixing of complex metal and polydentate ligand or source polydentate ligand (predecessor) in a solvent.

13. The method according to item 12, where polydentate ligand or source polydentate ligand receive fewer than that required for full replacement of the ligands of the metal complexes.

14. Complex metal, in which the ligands are coordinated by a single metal atom or set of atoms of metal of the same species, characterized by the fact that
for men is our least one of the ligands is coordinated functional group, which necoordinirovannami on the metal atom and that represents-COOH, and each of the metal complexes has a carboxyl ligand and polydentate ligand, which partially replaces the ligands of the metal complexes, is a ligand dicarboxylic acid and a metal selected from the group consisting of Pt, Ni or Pd.

15. Complex metal 14, where each of the ligands is a hydrogen group, which is associated with a functional group selected from the groups listed below, which is coordinated to the metal atom, or an organic group, which is associated with one or more functional groups selected from the groups listed below, which is coordinated to the metal atom: -soo-.

16. Complex metal indicated in paragraph 15, where the organic group is associated with one or more functional groups, which are coordinated to the metal atom, and represents a hydrocarbon group that has a heteroatom, ether bond or ester bond.

17. Complex metal 14, where uncoordinated functional group is a carboxyl group.

18. Complex metal 17, where the ligand has a carboxyl group, which is coordinated to the metal atom.

19. Complex metal p, which is octachlorostyrene, in which man is our least one ligand acetic acid substituted ligand dicarboxylic acid.

20. Complex metal 14, which is represented by the following formula:
[Pt4](CH3COO)7{O2CR14(COOH)}]

where R14represents alkylenes group, alkynylamino group, alkynylamino group, Allenova group, Aracinovo group or a bivalent alicyclic group C1-C30.

21. Complex metal 14, where uncoordinated functional group is a carbon-carbon double bond.

22. Complex metal item 21, where the ligands have a carboxyl group, which is coordinated to the metal atom.

23. Complex metal indicated in paragraph 15, which is octachlorostyrene, in which at least one ligand of acetic acid substituted ligand carboxyl group, which has a carbon-carbon double bond.

24. Complex metal 14, which is represented by the following formula:
[Pt4(CH3COO)7{O2CR16)]

where R16represents a linear or branched alkenylamine group1-C30.

25. The method of obtaining compounds representing multimetallic complex represented by the following formula:
[Pt4](CH3COO)7{O2C-R7-CO2}(CH3COO)7Pt4]

where R7represents (CH2)3CH=CH(CH2)3, including the production of complex metal following formula:
[Pt4(CH3COO)7{O2CR16)]

where R16represents (CH2)3CH=CH2and
dissolving the above-mentioned complex of the metal in the solvent and substitution alkylidene group coordinated carbon-carbon double bond through reaction cross-metathesis of carbon-carbon double bond.



 

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SUBSTANCE: invention relates to a catalyst for combustion of carbon-bearing material contained in exhaust gas of an internal combustion engine, to a method of preparing said catalyst, as well as a support for said catalyst and method of preparing said support. The invention describes a method of preparing a carbon-bearing material combustion catalyst which is attached to a ceramic substrate, involving mixing aluminium silicate having atomic equivalent ratio Si/Al≥1 and an alkali and/or alkali-earth metal source in a polar solvent such as water or another, drying the liquid mixture to obtain a solid substance and burning it at temperature of 600°C or higher. The aluminium silicate is sodalite. Alternatively, the carbon-bearing material combustion catalyst is prepared through a sequence of steps for mixing, drying and burning, whereby the method involves burning sodalite at temperature of 600°C or higher. A catalyst prepared using the method given above is described. Described also is a method of preparing a catalyst support involving a step for attaching the combustion catalyst to a ceramic substrate, and a catalyst support made using said method.

EFFECT: stable combustion and removal of carbon-bearing material at low temperature for a long period of time.

26 cl, 3 ex, 1 av ex, 27 dwg

FIELD: process engineering.

SUBSTANCE: proposed invention relates to catalyst composition and can be used for treatment of, for example ICE exhaust gases. Composition based on zirconium oxide with concentration equal at least 25% comprises, in % by wt: 15 to 60 of cerium oxide, 10 to 25 yttrium oxide, 2 to 10 of lanthanum oxide and 2 to 15 of oxide of the other rare-earth metal Besides said composition, after incineration for 10 h at 1150°C, features specific surface equal to at least 15 m2/g, and crystalline phase with cubic lattice. Composition results from formation of the mix containing compounds of zirconium, cerium, yttrium, lanthanum and additional rare-earth element, extraction of sediment from said mix with the help of base, heating said sediment in water, adding surfactant to sediment and its incineration. This composition can be used as a catalyst.

EFFECT: high reducing capacity and stable specific surface.

23 cl, 5 tbl, 3 dwg, 13 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to catalysts supports which are used as supports for metal and metal oxide components of catalysts used in different chemical reactions. The invention describes a catalyst support precursor which contains a mixture of alpha aluminium oxide and/or transition aluminium oxide; binder; and a solid sponging agent which expands or releases gas when sufficient heat is supplied. A method of making a catalyst support is described, which involves preparation of the catalyst support precursor described above and water, moulding the obtained precursor into a structure, heating the said structure for a sufficient time and at temperature sufficient for formation of a porous structure as a result of the effect of the sponging agent, and then heating the porous structure for a sufficient time and at temperature sufficient for melting of the porous structure, thereby forming a porous catalyst support. A catalyst preparation method is described, which involves the above described steps for making a porous catalyst support and depositing a catalytically effective amount of silver onto the surface of the support. Described also is a catalyst made using the method described above and a method for oxidising ethylene in the presence of the said catalyst. Described also are catalyst support precursors which contain alpha aluminium oxide and/or transition aluminium oxide, binder, a sponging agent and/or talc or a water-soluble titanium compound, and methods of making the said precursors.

EFFECT: increased bearing strength of the carrier, optimum surface area and porosity, which eliminates diffusion resistance for reagents and gaseous products under reaction conditions.

33 cl, 1 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to removal of sulphur from hydrocarbon streams, to a composition which is suitable for use in desulphuration of streams of cracked petrol and diesel fuel, and a method of preparing the said composition. A method of preparing a composition for removing sulphur from hydrocarbon streams involving the following is described: (a) mixing: 1) a liquid, 2) first metal formate, 3) material containing silicon dioxide, 4) aluminium oxide and 5) second metal formate, to form a mixture of the said components; (b) drying the said mixture to form a dried mixture; (c) calcination of the dried mixture; and (d) reduction of the calcined mixture with a reducing agent under reduction conditions to form a composition which contains a low valency activator, (e) separation of the obtained composition, where the said calcined reduced mixture facilitates removal of sulphur from a stream of hydrocarbons under desulphuration conditions, and where the said liquid is ammonia, and the composition obtained using the method described above. A method of removing sulphur from a stream of hydrocarbons involving the following is described: (a) bringing the stream of hydrocarbons into contact with the composition obtained using the method described above in a desulphuration zone under conditions which facilitate formation of a desulphurated stream of hydrocarbons from the said sulphonated composition and formation of a separate desulphurated stream of hydrocarbons and a separate sulphonated composition; (c) regeneration of at least a portion of the said separate sulphonated composition in the regeneration zone to remove at least a portion of sulphur contained in it and/or on it and formation of a regenerated composition as a result, (d) reduction of the said regenerated composition in an activation zone to form a composition containing a low valency activator which facilitates removal of sulphur from the stream of hydrocarbons when it touches such a composition, and e) subsequent return of at least a portion of the said reduced composition to the said desulphuration zone. Cracked petrol and diesel fuel obtained using the method described above are described.

EFFECT: more stable removal of sulphur from streams of hydrocarbons during desulphuration.

26 cl, 8 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a crust catalyst specifically designed for oxidising methanol to formaldehyde, a method of preparing the said catalyst and use of a catalyst for oxidising methanol to formaldehyde. A catalyst is described, which contains at least one coating layer on an inert, preferably essentially non-porous carrier, where the said coating layer, before removal of organic components b) and c), contains (a) oxides or precursor molybdenum and iron compounds transformed to corresponding oxides, where molar ratio Mo:Fe ranges from 1:1 to 5:1, and, if necessary, other metal or metal oxide compounds or precursor compounds transformed to corresponding oxides, (b) at least one organic binder material, preferably an aqueous dispersion of copolymers selected from vinylacetate/vinylaurate, vinylacetate/ethylene, vinylacetate/acrylate, vinylacetate/maleate, styrene/acrylate or mixtures thereof, and (c) at least one other component selected from a group consisting of SiO2 sol or its precursor, Al2O3 sol or its precursor, ZrO2 sol or its precursor, TiO2 sol or its precursor, liquid glass, MgO, cement, monomers, oligomers or polymers of silanes, alkoxysilanes, aryloxysilanes, acryloxysilanes, aminosilanes, siloxanes or silanols. Described also is a method of preparing the catalyst and its preferred use in the method with a fixed bed catalyst.

EFFECT: obtaining an active, selective and wear-resistant catalyst.

35 cl, 4 ex,1 dwg

FIELD: mechanics.

SUBSTANCE: present invention relates to method for manufacturing of catalyst on metal substrate. Method includes the following actions: binding compound that contains coordinated functional group with catalyst substrate; impregnation of catalyst substrate, with which compound is connected, by solution, which contains polynuclear metal complex, where ligand is coordinated by one atom of catalyst metal or multiple atoms of catalyst metal of the same type, and substitution, at least partially, of ligand coordinated by polynuclear metal complex, with coordinated functional group of compound; and drying and annealing of catalyst substrate impregnated with solution. At the same time metal complex is multinuclear complex. Coordinated functional group of compound and functional group of ligand, which is coordinated by metal of catalyst, are each independently selected from the group, that consists of the following: -COO-, -CR1R2O-, -NR1-, -NR-1R2, -CR1=N-R2, -CO-R1, -PR1R2, -P(=O)R1R2, -P(OR1)(OR2), -S(=O)2R1, -S+(-O-)R1, -SR1 and -CR1R2-S-, where R1 and R2 each independently is hydrogen or univalent organic group.

EFFECT: invention makes it possible to produce catalyst on substrate, in which metal of catalyst is applied on substrate with high extent of dispersity.

3 cl, 4 ex, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to the process of obtaining olefin or diolefin hydrocarbons C3-C4 through catalytic dehydrogenation of corresponding paraffin hydrocarbons, and specifically to preparation of a dehydrogenation catalyst, and can be used in chemical and petrochemical industry. The method of preparing a catalyst for dehydrogenating paraffin hydrocarbons C3-C4 by impregnating the γ-Al2O3 catalyst support with a solution of Cr and K salts with subsequent drying and tempering at high temperature is distinguished by that, before impregnation with salt solutions, the γ-Al2O3 catalyst support undergoes high temperature treatment with hydrogen at 300-500°C and impregnation of the support with the metal salts is carried out in 24-65 hours.

EFFECT: obtained catalyst surpasses known catalysts on activity and selectivity.

9 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to dehydrogenation catalysts, their preparation and use. Described is a dehydrogenation catalyst composition based on iron oxide which includes an iron oxide component with low concentration of titanium, where the said iron oxide component is obtained through thermal treatment of a residue of yellow iron oxide prepared via precipitation from a solution of an iron salt, and where the said dehydrogenation catalyst composition based on iron oxide has first titanium concentration which is less than approximately 300 parts per million. Also described is a method of preparing a dehydrogenation catalyst based on iron oxide, with a first titanium oxide concentration less than approximately 300 parts per million, with the said method involving: obtaining a component in form of red iron oxide with low content of titanium, through thermal treatment of a residue of yellow iron oxide prepared by via precipitation of from a solution of an iron salt, where the said yellow iron oxide has a second titanium concentration; mixing the said component in form of red iron oxide with an additional component of the dehydrogenation catalyst and water with formation of a mixture; moulding particles from said mixture; and thermal treatment of said particles thereby obtaining said dehydrogenation catalyst based on iron oxide. Also described is a dehydrogenation method involving: bringing a hydrocarbon which can be dehydrogenated, under hydrogenation reaction conditions, into contact with a dehydrogenation catalyst composition based on iron oxide, which contains an iron oxide component with low content of titanium, where the said iron oxide component is obtained through thermal treatment of a residue of yellow iron oxide prepared via precipitation from a solution of an iron salt, and an additional component of the dehydrogenation catalyst, where the said dehydrogenation catalyst composition based on iron oxide has a first titanium concentration which is less than approximately 300 parts per million; and separation of the dehydrogenation product. Also described is a method of improving operation of a dehydrogenation reactor installation which includes a dehydrogenation reactor containing a first dehydrogenation catalyst volume which can reduce titanium concentration, with the said method involving: removal of the dehydrogenation catalyst from the said dehydrogenation reactor and its replacement with a dehydrogenation catalyst composition based on iron oxide containing an iron oxide component with low content of titanium, where the said iron oxide component is obtained through thermal treatment of a residue of yellow iron oxide prepared via precipitation from a solution of an iron salt, and an additional component of dehydrogenation catalyst, where the said dehydrogenation catalyst composition based on iron oxide has a first titanium concentration which is less than approximately 300 parts per million, and thereby obtaining a second dehydrogenation reactor installation; and carrying out processes in the said second dehydrogenation reactor installation in dehydrogenation reaction conditions.

EFFECT: more efficient method of preparing dehydrogenation catalyst.

19 cl, 1 tbl, 1 dwg, 2 ex

FIELD: oil-and-gas production.

SUBSTANCE: invention related to oil-and-gas production, particularly to crude oil refinery with low temperature initiated cracking, and can be use for distilled motor fuel production increase. The method includes of oil residue processing into distillate fraction by adding catalyst followed by thermal-cracking, as a catalyst use ashes micro sphere magnetic fractions d from heat and power plants in a quantity 2.0-20.0% wt, containing 40.0-95.0% wt, iron oxide (III), with micro sphere diametres 0.01-0.60 mm, tempered at 600-800°C, process itself to be executed at temperature 400-500°C.

EFFECT: increase in distilled fractions total outcome up to 58,0% wt with the temperature up to 350°C, outcome of gasoline fractions up to 18,0% wt (with the temperature up to 200°C).

1 cl, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts for preparing petroleum fractions with low content of sulphur and nitrogen, methods of preparing such catalysts and processes for hydrofining hydrocarbon material. The invention describes a catalyst for hydrofining hydrocarbon material, having pore volume of 0.3-0.7 ml/g, specific surface area of 200-350 m2/g and average pore diametre of 9-13 nm, and containing a boron compound and a bimetallic complex compound [M(H2O)x(L)y]2[Mo4O11(C6H5O7)2], where: M=Co2+ and/or Ni2+; L is a partially deprotonated form of citric acid C6H8O7; x=0 or 2; y=0 or 1; - 30-45 wt %, a boron compound in amount of 1.06-3.95 wt %, Al2O3 -51.05-68.94 wt %, which corresponds to the following content in a catalyst annealed at 550°C, wt %: MoO3 - 14.0-23.0; CoO and/or NiO - 3.6-6.0; B2O3 -0.6-2.6 Al2O3 - the rest. The catalyst is prepared through saturation of aluminium oxide with a pre-synthesised solution of a bimetallic complex compound [M(H2O)x(L)y]2[Mo4O11(C6H5O7)2] and a boron compound, wherein concentration of the bimetallic compound in the solution provides 40-45 wt % bimetallic complex compound in the ready catalyst. The process of hydrofining hydrocarbon material is carried out at temperature 320-400°C, pressure 0.5-10 MPa, weight flow rate of material of 0.5-5 h-1, volume ratio hydrogen/material equal to 100-1000 m3/m3 in the presence of the catalyst described above.

EFFECT: maximum catalyst activity in target reactions taking place when hydrofining hydrocarbon material, which ensures obtaining petroleum products with low residual content of sulphur.

8 cl, 8 ex, 2 tbl

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