Method for producing bimetallic catalyst ruthenium/tin, bi-metal catalyst obtained by this method and the method of producing aldehydes and their derivatives

 

(57) Abstract:

Describes how to obtain bimetallic catalyst ruthenium/tin containing a carrier and a metal phase comprising partially intermetallic compound at least partially in the form Ru3Sn7covering at least a portion of the specified media, including the application of a complex of ruthenium and tin, in which the ruthenium has a conductivity of 4, and a coordination number of 6, on a carrier, characterized in that use complex formulas (A)

[Ru (SnX3)6-nXn]4-(A)

where X is a halogen atom, preferably a chlorine atom or bromine, n is a number from O to 2, preferably 1, and the cation is N, and the complex is subjected to recovery. Describes the catalyst obtained by the above method, and a method of producing aldehydes and their derivatives. The technical result is a homogeneous catalyst, which can be manufactured on an industrial scale. 3 C. and 28 C.p. f-crystals.

The object of the present invention is a method for producing bimetallic catalyst ruthenium/tin.

In the patent EP-A-O 539 274 describes a method for aldehydes and their derivatives on the s acids, esters or anhydrides, in the presence of a bimetallic catalyst ruthenium/tin.

Although the catalysts of the type ruthenium/tin, including boron, suitable for implementing the described method, a particularly interesting catalysts are bimetallic catalysts comprising tin and ruthenium, not containing boron, which include ruthenium and tin in such quantities that the molar ratio of tin/ruthenium is at least 2, preferably from 2 to 10 inclusive, and more preferably from 2 to 6, inclusive.

You can use different types of catalysts that can be with the carrier or without the media.

Usually ruthenium is from 0.1 to 50 wt.% a catalyst.

In that case, when using a solid catalyst, the ruthenium is from 10 to 50 wt.% a catalyst.

In the preferred implementation method used, however, the catalyst carrier. For this purpose, the carrier may be selected, in particular, metal oxides, such as oxides of aluminium, silicon and/or zirconium, or among the coals, possibly activated by means of well-known treatment with nitric acid, acetylene soot or tar.

The disadvantage of this method is that it is not possible to obtain a completely homogeneous catalyst, which can be manufactured on an industrial scale. Indeed, chloride tin (II partially hydrolyses and precipitates on the surface of the carrier, whereas the chloride ruthenium (III penetrates into the pores of the carrier. It follows that the medium is non-uniformly impregnated precursors of the metals ruthenium and tin, and the catalyst is not homogeneous.

The purpose of the present invention consists in a method of producing a specified catalyst, which can eliminate the above disadvantages.

It was found, and this forms the subject of the present invention. Method for producing bimetallic catalyst ruthenium/tin is to implement the recovery of a complex of ruthenium with electrovalent-4 and a coordination number of 6, and coordination compounds are either a halogen atom or an anion of a halide of tin.

In the preferred implementation of the SPO is(SnX3)6-nXn]4-(A)

in this formula, X represents a halogen atom, and n is a number varying from 0 to 2 and preferably equal to 1.

In the method according to the invention use is preferably the following systems:

-[Ru(SnCl3)6]4-< / BR>
-[Ru(SnCl3)5Cl]4-< / BR>
-[Ru(SnCl3)4Cl2]4-< / BR>
It was noted that the obtained catalyst was high quality when it is received by the method of the invention, as specified.

Thus, in the method according to the invention using halide complex of ruthenium and tin, corresponding preferably to the formula (A).

The preferred method of carrying out the invention specified complex is produced by interaction of ruthenium halide and halide of tin in the presence of acid.

To this end take a ruthenium halide III, preferably the chloride, ruthenium (III. It is also possible to proceed from the salts of ruthenium IV, but the additional advantage that it is not, especially because it costs more.

Thus, it is preferable to apply the ruthenium halide III, which can be either in the form of an anhydride, or in hydrated form.

It is desirable that the specified connected to the fishing and having a chemical purity of the ruthenium 99% compared to other metals.

You can use the technical form of ruthenium chloride, RuCl3x H2O, containing about 42-43% wt. ruthenium.

As for the salts of tin, use a halide of tin, where tin is the degree of oxidation of the lower oxidation States of ruthenium. Use the tin halide II, preferably a chloride of tin II.

It is also possible to use salt in the form of an anhydride or in hydrated form. Preferably, also use technical salt tin of formula SnCl2H2O.

Most often, the halides of these metals are used in aqueous solution. The concentration of these solutions to obtain a homogeneous solution, able to impregnate the carrier.

As for the used amount of the halides of these metals, it is determined so that the ratio between the number of moles of ruthenium halide and the number of moles of the halide of tin was changed from 0.10 to 0.5 and preferably from 0.15 to 0.35. It should be noted that the lower limit is not critical character, because there are no problems with the use of excessive amounts of tin halide.

Obtaining complex through interaction of halides of ruthenium and tin is in pseudemoia complex.

You can use any strong acid, preferably inorganic, but prefer to use hydrogen acid halide which is the same as the halide used in the salts of ruthenium and tin.

So, generally, preference is given to hydrochloric acid.

The amount used of the acid is preferably at least 1 mol of acid per 1 mol of ruthenium halide and more preferably from 1 to 5 moles of acid per 1 mol of ruthenium halide. The upper limit is not critical and can easily be exceeded. The preferred amount of acid is within 3 moles of acid per mole of ruthenium halide.

From a practical point of view, obtaining the complex is carried out by mixing in any order of ruthenium halide (preferably chloride ruthenium (III), tin halide (preferably chloride tin (II) and strong acid (preferably hydrochloric acid).

The reaction mixture is heated to a temperature of from 20 to 100oC, preferably from 70 to 90oC.

The duration of this operation may vary within wide limits and for illustration clarifies that it is suitable duration from 1 up to and bring the temperature to the ambient temperature, i.e. to a temperature component most often from 15 to 25oC.

It is also possible to consider two variants of the method depending on whether I wanted to get a solid catalyst or carrier.

In the first case, carry out the hydrolysis of the resulting complex by adding water. The used amount of water is not critical: it is usually 1-100-fold by weight of the complex.

As a result of this hydrolysis, the complex precipitates.

It can be separated by conventional methods of solid/liquid separation, preferably filtration.

This separation is usually at ambient temperature.

The precipitate may be dried, then restored in the conditions defined below.

Another option is that when the carrier is a powder, such as, for example, aluminum oxide or silicon oxide, is added to a solution of the obtained complex, then spend the hydrolysis, as previously described, separating the resulting solid phase, preferably by filtration, and mix and ekstragiruyut it. Thus is retenu solution previously obtained complex is used for impregnation of the carrier.

The carrier may be in any form, for example, in the form of powder, beads, pellets, extruded form.

As for the media type, the following are examples of media, such as metal oxides, oxides of aluminum, silicon and/or zirconium, or among activated carbon or resins.

In the case of the catalyst carrier of the content of ruthenium is regulated by a specialist, depending on media type, specific surface area).

Usually the content of ruthenium in the catalyst mainly selected from 0.1 to 20.0 wt.% and even more preferably from 0.5 to 3.0 wt.%.

From a practical point of view, the metals are precipitated on the carrier, impregnating the specified carrier with a solution of the complex obtained by the above method.

An aqueous solution impregnation includes a complex of ruthenium and tin in an amount of from 1 to 20 wt.% ruthenium.

From a practical point of view it is possible to carry out the impregnation, spraying on the media driven, for example by rotation of the drum, a solution containing a complex of ruthenium and tin.

It is also possible to use a medium obtained by agglomeration of particles by well-known methods, for example, by extrusion or cabletenna variant of the invention, the impregnation is carried out "dry", i.e. the total volume of solution used complex is approximately equal to the volume of pores on the media. To determine the amount of time it is possible to use any known method, in particular, the method with mercury Porosimeter (norm ASTM D 4284-83) or to measure the sample absorbed amount of water.

At the next stage, the impregnated carrier or dedicated precipitate obtained in the first embodiment, is subjected to recovery.

A preferred variant of the invention consists in carrying out in the early stages of drying.

Drying is carried out most often in air at a temperature that can vary from ambient temperature, for example, 20oC to 100oC.

Drying continues until a constant weight.

Typically, the duration ranges from 1 to 24 hours, depending on the temperature selected.

The next step is carried out restoration of the complex, giving the catalyst in solid form or in the medium in contact with the reducing agent.

Possible use of chemical reductant, but it does not give any special benefits. So, the reduction is carried out preferably with hydrogen.

DIMMs from 1 to 2 bar.

Hydrogen can also be diluted with an inert gas such as nitrogen or helium.

Mainly, the reduction is carried out at a temperature of at least 350oC, preferably from 350 to 600oC and even more preferably from 400 to 500oC.

Naturally, recovery may also be carried out using a catalyst, suggesting it is used in the reduction reaction of the substrate in the presence of hydrogen.

Thus, in the method of producing aldehydes and their derivatives, described in EP-A-O 539 274, the method consisting in the implementation of the recovery in the vapor phase in the presence of hydrogen, carboxylic acids, esters or anhydrides, in the presence of a bimetallic catalyst ruthenium/tin, this catalyst can be obtained at the beginning of the reaction, the recovery of a complex of ruthenium and tin as defined in the invention.

Thus obtained catalyst on the carrier type ruthenium-tin especially homogeneous and can be easily obtained on an industrial scale.

It includes a metallic phase, covering at least partially the specified carrier comprising at least partially Internet is SS="ptx2">

Mainly phase containing the ruthenium and tin has an atomic ratio Sn/Ru, at least equal to 2/3, mainly 3/2, preferably 7/3.

At the same time,it is preferable that the atomic ratio Sn/Ru would be no higher than 3, preferably 5/2.

In the preferred catalysts of this phase, covering at least partially the specified media contains at least 50%, mainly 80%, preferably at least 90% of the said intermetallic phase.

Finally, it is desirable that at least 90%, mostly at least 95%, preferably 98% ruthenium present on the media, it would be in the form specified phase, covering the specified device.

It is advisable to use the catalyst obtained according to the invention, in the method of producing aldehydes and derivatives, described in EP-A-O 539 274, which is included by reference in this application.

Indeed, it may be useful for the implementation of reduction with hydrogen carboxylic acids, esters or anhydrides in the vapor phase.

In particular, the catalyst suitable for producing aldehydes of General formula:

< / BR>
in which R is one is which can be saturated or unsaturated, linear or branched acyclic aliphatic radical series; carbocyclic or heterocyclic saturated, unsaturated or aromatic, monocyclic or polycyclic radical, by reduction of esters, anhydrides or acids of the formula:

< / BR>
where:

- R has the meaning defined above,

- R' is:

group R such as defined above,

group

in which R" has the meaning given R

- both groups R and R ' can be linked to the formation of saturated or unsaturated cycle having 5 to 7 atoms and including anhydrite group

- both groups R and R by means of two vicinal atoms may together form a bridge of the bicyclic artecontemporanea system.

In accordance with the method according to the invention it is possible to use any carboxylic acid can be in the gaseous state under the conditions of the invention.

The method according to the invention applies to any carboxylic acid mono - or polycarboxylic, such as saturated or unsaturated aliphatic acid; carbocyclic or heterocyclic, saturated, unsaturated or aromatic, monocyclic as carbocyclic or heterocyclic, saturated, unsaturated or aromatic cycle, acid.

It could therefore be used as a starting material carboxylic acid of formula (II) where the remainder R is a substituted or unsubstituted hydrocarbon radical, which may be linear or branched, saturated or unsaturated acyclic aliphatic radical; a monocyclic or polycyclic, saturated, unsaturated or aromatic, carbocyclic or heterocyclic radical.

Preferred carboxylic acids correspond to the formula (II) in which R is a hydrocarbon radical, possibly substituted, containing from 1 to 20 carbon atoms.

Particularly suitable for implementing the method according to the invention the carboxylic acid of General formula (II) in which R means an aromatic hydrocarbon monocyclic or polycyclic possibly substituted residue.

Any Deputy may be present in the cycle, but he would not prevented the reduction reaction of carboxyl functions.

R is preferably an aromatic hydrocarbon and, in particular, benzene residue of General formula (III):

< / BR>
in the specified thefunctional groups or radicals:

linear or branched alkyl having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl,

linear or branched alkenyl having from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, such as vinyl, allyl,

linear or branched alkoxy radical having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy radical,

acyl having from 2 to 6 carbon atoms,

the radical of the formula:

-R2-OH

-R2-COOR5< / BR>
-R2-CHO

-R2-NO2< / BR>
-R2CN

-R2-N(R5)2< / BR>
-R2-CO-N(R5)2< / BR>
-R2-SH

-R2-X

-R2-CF3< / BR>
moreover, in the above formulas, R2mean valence bond or a divalent hydrocarbon of linear or branched saturated or unsaturated radical having from 1 to 6 carbon atoms, such as, for example, methylene, ethylene, propylene, isopropylene, isopropylidene; the radicals R5identical or different, denote a hydrogen atom or a linear or branched what the Torah.

- Q implies R3one of the following more complex radicals:

radical

< / BR>
in which R1and R2have the above value, and m is an integer from 0 to 5, preferably from 0 to 3,

the radical R2-A-R4in which R2has the above meaning, R4means a linear or branched alkyl having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, or a radical of the formula

< / BR>
and A denotes one of the following groups:

< / BR>
in these formulas, R6means a hydrogen atom or a linear or branched alkyl having from 1 to 4 carbon atoms, preferably methyl or ethyl. When n is greater than 1, the radicals Q can be the same or different; and 2 consecutive carbon atoms of the benzene ring may be linked katelnym bridge; such as external methylendioxy or Ethylenedioxy-underlyme links.

Preferably, n is 0, 1, 2, or 3.

Among these residues, R is particularly preferably used in the method according to the invention, a carboxylic acid or derivative of General formula (III); in which R means an aromatic residue of General formula (III) in which:

n is 0, 1, 2 or 3;


linear or branched alkoxy radical having from 1 to 4 carbon atoms;

methylene or Ethylenedioxy,

the group-HE;.

the group-CHO;

the group NH2;

phenyl;

halogen atom;

group CF3.

Even more preferably choose the compounds of formula (II) in which the radicals Q, same or different, are a hydrogen atom, a hydroxyl group, stands, methoxy, group-CHO.

As radicals R of the formula (III) may be mentioned more particularly phenyl, tolyl or xylyl radicals and biphenyl methylene-1,1'-biphenyl isopropylidene-1,1'-biphenyl hydroxy-1, 1'-biphenyl, imino-1,1'-biphenyl radicals: these radicals can be substituted by one or more radicals Q, such as those mentioned above, preferably a hydroxyl group or a halogen atom.

R may also mean polycyclic aromatic hydrocarbon residue; however, loops can form between artecontemporanea, ortho - and pericontusional system. In particular, it is possible to lead naphthalene residue; these cycles can be substituted by 1-4 radicals R1, preferably 1-3, and R1has anormale (II) carboxylic acids R can also mean carbocyclic residue, saturated or containing 1 or 2 unsaturated communication cycle having usually from 3 to 7 carbon atoms, preferably 6 carbon atoms in the cycle; this cycle may be substituted by 1-5 radicals R1, preferably 1-3, and R1has the above values for the substituents of the aromatic hydrocarbon residue of General formula (III).

As preferred examples of radicals R1you can lead cyclohexyl and cyclohexen, possibly substituted linear or branched alkyl radicals having from 1 to 4 carbon atoms.

As indicated above, R may denote a saturated or unsaturated, linear or branched acyclic aliphatic residue.

More precisely, R is a linear or branched acyclic aliphatic residue, preferably having from 1 to 12 carbon atoms, saturated or containing one or more unsaturated bonds in the chain; usually 1-3 unsaturated bonds, which may be simple or double conjugated bonds or triple bonds.

The hydrocarbon chain may be:

- interrupted one of the following groups:

< / BR>
in these formulas, R6means hydrogen is th or ethyl radical,

and/or carry one of the following substituents:

-OH, -COOR5, -CHO, -NO2, -CN, -NH2, -SH, -X, -CF3,

in these formulas, R5has the above value.

In a preferred method of carrying out the invention R has the following formula:

< / BR>
in which R7, R8and R9identical or different, are chosen from among hydrogen atom, a linear or branched alkyl radical containing from 1 to 10 carbon atoms, linear or branched alkylene containing from 1 to 10 carbon atoms, linear or branched alkoxy radical containing from 1 to 10 carbon atoms, hydroxyl group, amino group or halogen atom or the group-CF3.

Preferably R7and R8and/or R9mean unsaturated group.

More preferably in formula (IV) one of the 3 groups of R7, R8and R9has a conjugated double bond with the carbonyl group of the carboxylic acid of ester or anhydride.

It is also possible to use carboxylic acid or derivative of the formula (II) in which R denotes a linear or branched, saturated or unsaturated aliphatic acyclic carbocycles or heterocyclic saturated, unsaturated or aromatic cycle.

Acyclic aliphatic residue may be associated with the cycle of the valence bond or one of the following groups:

< / BR>
In these formulas, R6has the above value.

As examples of cyclic substituents can include cycloaliphatic, aromatic or heterocyclic substituents, in particular cycloaliphatic containing 6 carbon atoms in the cycle, or benzene substituents, and these cyclic substituents themselves may optionally include 1, 2, 3, 4 or 5 identical or different radicals R1and R1has the above values for the substituents of the aromatic hydrocarbon residue of General formula (III).

As examples of such radicals may be mentioned, among others, benzene.

In the General formula (II) carboxylic acids R can also mean a saturated or unsaturated heterocyclic residue, including, in particular, 5 or 6 atoms in the cycle, of which 1 or 2 heteroatoms, such as nitrogen atoms, sulfur and oxygen, with the carbon atoms of the heterocycle can optionally be substituted completely or some of them only the radicals R1and R is s (III).

R can also mean polycyclic heterocyclic residue which is either the radical formed at least 2 aromatic heterocycles or not containing at least one heteroatom in each cycle and forming between them ortho - or ortho - and pericontusional system, or a radical formed by at least one aromatic or no hydrocarbon cycle and at least one aromatic or not heterocycle or not forming between them ortho - or ortho - and pericontusional system, and the carbon atoms of these cycles may optionally be substituted wholly or in part only by the radicals R1and R1have some higher values for the substituents of the aromatic hydrocarbon residue of General formula (III).

As examples of groups R heterocyclic type can lead, among others, furyl radicals, pyrrolyl, thienyl, isoxazolyl, furutani, isothiazolin, imidazolyl, pyrazolyl, pyridyl, pyridazinyl, pyrimidinyl and radicals chenail, naphthyridine, benzofuranyl, indolyl.

As examples of carboxylic acids containing at least one carboxyl group, the General formula (II), can be used on the s, such as formic, acetic, propionic, butane, isobutane, Valerian, isovalerianic, pihlava, lauric, medicinova, palmitic, stearic acid,

saturated aliphatic dicarboxylic acids such as oxalic, malonic, succinic, glutaric, adipic, Emelyanova, cork, azelaic, sebacina acid,

unsaturated aliphatic monocarboxylic or dicarboxylic acids, such as acrylic, pravilova, methacrylic, crotonic, Sekretareva, senecioneae, Tihonova, oleic acid, maleic, fumaric, Tarakanova, musicanova acid,

saturated or unsaturated carbocyclic carboxylic acids, such as camphoric acid, Hrizantema acid,

- heterocyclic carboxylic acids, such as furancarbinol, thiencarbazone, terracarbon, pyrazinecarboxamide acid, nicotinic, isonicotinoyl acid, picolina acid,

- aromatic carbocyclic carboxylic acids such as benzoic, benzylcarbamoyl, isophthalic, terephthalic acid, naphthaleneboronic acid, Truelove acid,

- saturated arylaliphatic carboxylic acids, such as, in particular, allpr the traveler acid, 2-(6-methoxy-2-naphthyl)propionic acid or unsaturated acid, such as 2-phenylpropionate acid, cinnamic acid,

- halogenated aliphatic or aromatic carboxylic acids, such as monohloruksusnoj, diflorasone, monochloracetic, dichloracetic, trichloroacetic, monochloropropane, bromopropionate, -bromotova, triperoxonane acid, monitor-o-benzoic acid, monitor-m-benzoic acid, monitor-p-benzoic acid, 2,3-differentia acid, 2,4-differentia acid, 2,5-differentia acid, 3,4-differentia acid, 2,3,6-triptoreline acid, 2,4,5-triptoreline acid, 2,3,4,5-tetrafluorobenzoic acid, pentafluorobenzoic acid, --- Cryptor-o-tolarova acid, --- Cryptor-m-tolarova acid, --- Cryptor-p-tolarova acid, monochloro-o-benzoic acid, monochloro-m-benzoic acid, monochloro-p-benzoic acid, 2,3-dichlorobenzene acid, 2,4-dichlorobenzene acid, 2,5-dichlorobenzene acid, 2,6-dichlorobenzene acid, 3,4-dichlorobenzene acid, 3,5 - dichlorobenzene acid, 2,3,5-trichlorobenzoic acid, 2,3, 6-trichlorobenzoic acid, 2-chloro-4,5-differentia acid, 3-chloro-2,4,5-triptoreline acid, monobromo-limfaticheskie, arylaliphatic hydroxy acid such as glycolic acid, lactic acid, glyceric acid, 2-oxobutanoate acid, 3-oxobutanoate acid, 2-methylmalonate acid, 2-hydroxy-4-methylthiourea acid, castronova acid, malic acid, tartaric acid, 1-oxacyclopropane acid, 2-oxyphenylbutazone acid, 2-oksikorichnye acid, 3-oksikorichnye, 4-oksikorichnye acid,

- the following oxybenzone acid: 2-oxybenzone acid (salicylic acid), 3-oxybenzone acid, 4-oxybenzone acid, 3-methylsalicylic acid, 4-methylsalicylic acid, 5-methylsalicylic acid, 3-hydroxy-4-methylbenzoic acid, 3-methoxystilbene acid, 4-methoxystilbene acid, 5-methoxystilbene acid, 3-hydroxy-4-methoxybenzoic acid (isovanillin acid), 4-hydroxy-3-methoxybenzoic acid (vanillic acid), 3-hydroxy-4,5-dimethoxybenzoic acid, 4-hydroxy-3,5-dimethoxybenzoic acid (ciriminna acid), 5-oxidizability acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 3-hydroxy-2-amino-benzoic acid, 3-nitrosalicylic acid, 3-hydroxy-4-nitrobenzoic acid, 4-hydroxy-3-nitrobenzoic acid, 3-hydroxy-4-methyl-2-H2,5-deoxybenzoin acid, 2,6-deoxybenzoin acid, 3,4-deoxybenzoin acid (protocatechuic acid), 3,5-deoxybenzoin acid, 3,5-dioxy-4-methylbenzoic acid, 2,3,4-trioxypurine acid, 2,4,6-trioxypurine acid, 3,4,5-trioxypurine acid,

- alkoxy and fiexibility, such as metacercaria, venexiana, 2,4-dichlorophenoxyacetate, phenoxypropionate, 2,4-dichlorophenoxyacetate, p-oxygenotherapy, m-chlorphenoxamine acid, 4-phenoxybenzoic acid, (4-carboxy-4-phenoxy)benzoic acid, piperova acid,

- oxyacids, such as 2-acetylbenzoic acid, 4 - acetylbenzoic acid, 2-benzoylbenzene acid, 4 - benzoylbenzene acid,

- alloccolor, such as 3-benzyloxypropionic acid, 2-acetoxybenzoic acid, 4-acetoxybenzoic acid,

- amicability, such as 2-acetamidoacrylic acid, 2-acetamidobenzoic acid, 3-acetamidobenzoic acid, 4-acetamidobenzoic acid,

- amino acids, possibly N-substituted by a protective group, such as, for example, the following acyl group (acetyl, benzoyl), SIDE (butyloxycarbonyl), CBZ (carbobenzoxy), FMOC (feranil-9 - methoxycarbonyl), ISIC (methanesulfonyl-2-etoxycarbonyl).


- gidroksilirovanii amino acids: serine, threonine,

- sulfur-containing amino acids: cysteine, methionine,

- dicarboxylic amino acids and their amides: aspartic acid, asparagine, glutamic acid, glutamine,

amino acids with two main groups: lysine, arginine, histidine,

aromatic amino acids: phenylalanine, tyrosine, tryptophan,

aminokisloty: Proline, hydroxyproline.

Preferred acids are especially carboxylic acids such as benzoic acid, 3,4-diferencia acid, 4-chlorbenzene acid, 4-triftorperasin acid, salicylic acid, 3-oxybenzone acid, 4-oxybenzone acid, vanillic acid, 3,4-dimethoxybenzoic acid, 4-methoxybenzoic acid, 3,4-dioxymethylene acid, cinnamic acid, 6-methoxy-2-natalymartynova acid, 6-hydroxy-2-natalymartynova acid, acetic acid, triperoxonane acid, 2-methylbutanoate acid, saturated or unsaturated aliphatic fatty acids, having from 6 to 20 carbon atoms, preferably heptane acid, novanova acid, undecisive acid, oleic acid, heptacellular acid, stearic sour the slot, senecioneae acid, cyclohexane acid.

In accordance with the present invention it is possible to use the carboxylic acid in the form of its anhydride.

As examples of carboxylic anhydrides may be mentioned especially the anhydrides of the abovementioned carboxylic acids and cyclic anhydrides.

Indeed, when the anhydride corresponds to the formula (II) in which R' is a group

< / BR>
both groups R and R ' can be linked to the formation of saturated or unsaturated cycle having 5-7 atoms, including anhydrite group. They form a preferably linear or branched alkylene having from 2 to 6 carbon atoms, or more preferably the radical - (CH2)twith t equal to from 2 to 4.

As examples of cyclic anhydrides can lead succinic anhydride or maleic anhydride.

When the anhydride has the formula (II) in which R' is a group of the two groups R and R" can form two vicinal atoms to form together a bridge artecontemporanea bicyclic system.

The preferred compounds are bicyclic and educated benzene ring and a heterocycle, as in the examples of such cyclic anhydrides of polycarboxylic acids can be mentioned phthalic anhydride.

The method according to the invention is carried out in the gas phase.

Mostly the reaction is carried out at a temperature in the range from 100 to 500oC and even more preferably from 200 to 400oC. Naturally, the temperature is regulated by a specialist, depending on the source of the acid and the desired reaction rate.

At the same time can be especially helpful to pre-activation of the catalyst by strong heating. In particular, the catalyst can be pre-heated to the temperature close to a temperature of approximately 500oC, and preferably 450oC. Activation is carried out mainly in the stream of hydrogen.

A practical way of carrying out the invention consists in applying to the reactor required amount of catalyst, if necessary, between 2 layers of quartz to enhance contact of the reagents. The temperature of the reactor was then reduced in a stream of hydrogen to a certain value, allowing you to activate the catalyst, and then brought to the reaction temperature. Then add the acid with the desired flow rate and remove the formed aldehyde.

Preferably, the acid is supplied in gaseous form after vypai. In particular, it is possible to bring an inert aliphatic solvents (e.g. hexane), alicyclic (e.g., cyclohexane), aromatic (e.g., toluene) hydrocarbons or ethers (for example, dimethoxyethane).

Under high temperature consequently, the acid is evaporated on the level of the first quartz layer. Hydrogen can be introduced at atmospheric pressure or at low pressure, compatible with vapor phase (several bar, for example, 0.5-10 bar). Hydrogen can also be diluted in an inert gas, such as nitrogen or helium.

Mainly in 1 ml of catalyst, the hydrogen is fed at a rate of 0.1-10 l/h, and acid with a flow rate not exceeding 10 ml/h, and preferably from 0.5 to 5 ml/h

At the end of the reaction remove the aldehyde using any suitable means, such as distillation or crystallization. In some cases, in particular, in the case of triftoruranmetilidina, the aldehyde can be obtained in hydrated form.

The catalyst obtained according to the method according to the invention can be used in the method of obtaining many of aldehydes, which are used as intermediate of pharmaceutical and agrochemical products, microwave aldehyde, which can be used, along with the other for receiving coumarin: it is obtained the well-known and widely described in the literature cyclization (KIRK-OTHMER - Encyclopedia of Chemical Technology 7, p. 198, 3rd edition).

Obtained according to the invention the catalyst is also suitable for other aromatic aldehydes such as 3-oxybenzaldehyde, 4-oxybenzaldehyde, vanilla, veratraldehyde; p-anisaldehyde, piperonal, cinnamic aldehyde.

The present invention can also be used for the synthesis of various aldehydes. It can be used to obtain saturated aldehydes, such as cryptanalytically or acetaldehyde. It is particularly suitable for the synthesis of unsaturated aldehydes, in particular, in the chemistry of terpenes (prenal; citral... ), intermediate for the synthesis of vitamins and or E.

Without leaving the scope of the present invention is made according to the method according to the invention, the aldehydes in the form of their derivatives such as acetals or hemiacetals, the interaction of the aldehyde and alcohol, which is served either with acid or at the end of the reaction. As examples of traditionally used alcohols can lead to methanol or ethanol.

Below are examples of OS is LASS="ptx2">

Example 1

Getting soaked dry catalyst

In a three-neck flask 1.92 g RuCl3x H2Oh, containing 42 wt.% ruthenium, and 10.7 g of SnCl2, 2H2O and 13 ml of aqueous 3N hydrochloric acid solution.

Heated with stirring to 90oC.

Incubated for 1 hour at this temperature.

Then this solution is cooled.

Impregnated with 40 g of balls-aluminum oxide (specific surface area = 5-10 m2/g and pore volume = 44-54 cm3per 100 g) sold by Rhone Poulenc under the name of Starlit 512 having a ball diameter of 2-4 mm

Then dry impregnated beads in a ventilated drying Cabinet to obtain a constant weight.

The catalyst is then treated at 450oC in a stream of hydrogen for 4 hours.

Example 2

Obtaining catalyst powder media

In a three-neck flask 1.92 g RuCl3x H2O, containing 42 wt.% ruthenium and 10.7 g of SnCl2, 2H2O and 13 ml of aqueous 3N hydrochloric acid solution.

Heated with stirring to 90oC for 1 hour.

Then cool the solution to 20oC.

Then add 80 g of dvuoksid silicon Degussa OX is filtered, washed with water.

The cake is then mixed and extruded.

Extruded material is then dried in air to obtain a constant weight.

The catalyst is then treated with hydrogen at 450oC for 4 hours.

Example 3

Hydrogenation triperoxonane acid

In tubular Nickel reactor with a diameter of 2.54 cm serves 60 g of the catalyst prepared according to example 1.

Process it in a stream of hydrogen in the amount of 11 l/h, heating to 450oC.

Maintain these conditions for 15 hours.

Bring the temperature up to 320oC and enter triperoxonane acid in an amount of 20 g/L.

The factor of conversion of 80%, and the yield of hydrated triptoreline - 70%.

After 300 hours parameters of the catalyst are the same.

1. Method for producing bimetallic catalyst ruthenium/tin containing a carrier and a metal phase comprising partially intermetallic compound at least partially in the form Ru3Sn7covering at least a portion of the specified media, including the application of a complex of ruthenium and tin, in which the ruthenium is elektroprovod the)6-nXn]4-(A)

where X is a halogen atom, preferably a chlorine atom or bromine;

n is a number from 0 to 2, preferably 1,

and the cation is N,

and this complex is subjected to recovery.

2. The method according to p. 1, wherein the complex has the following formula (A):

[Ru(Snl3)6]-4< / BR>
[Ru(Snl3)5Cl]-4< / BR>
[Ru(SnCl3)4Cl2]-4< / BR>
3. The method according to PP.1 and 2, characterized in that use complex obtained by reacting the ruthenium halide and halide of tin in the presence of acid.

4. The method according to p. 3, characterized in that the ruthenium halide is a halide of ruthenium III in anhydrous or hydrated form, preferably chloride ruthenium III, and the tin halide is a halide of tin II in anhydrous or hydrated form, preferably the chloride of tin II.

5. The method according to any of paragraphs.3 and 4, characterized in that the ratio between the number of moles of ruthenium halide and the number of moles of tin halide varies between 0.10 and 0.5 and preferably between about 0.15 and 0.35.

6. The method according to any of paragraphs.3 to 5, characterized in that the acid is a strong inorganic acid, and tin.

7. The method according to any of paragraphs.3 to 6, characterized in that the acid is used in amounts of preferably at least 1 mol of acid per mole of ruthenium halide, preferably 1 to 5 moles of acid per mole of ruthenium halide and more preferably about 3 moles of acid per mole of ruthenium halide.

8. The method according to any of paragraphs. 1 to 7, characterized in that use complex obtained by mixing, in any order of ruthenium halide, preferably chloride ruthenium III, tin halide, preferably chloride tin II, and a strong acid, preferably hydrochloric acid.

9. The method according to p. 8, characterized in that the reaction mixture is heated to 20 to 100°C., preferably 70 to 90°C.

10. The method according to any of paragraphs.1 to 9, characterized in that the carrier is added in powder form in a solution of the obtained complex, hydrolyzing complex by adding water and separating the resulting solid phase, which is stirred and ekstragiruyut obtaining a molded catalyst.

11. The method according to p. 10, characterized in that the amount of water used is 1 to 100 times by weight of the complex.

12. The method according to p. 1, characterized in that the deposition of metals on the carrier implement .

13. The method according to p. 12, characterized in that the use of media in the form of powder, beads, pellets, extrusions and other things.

14. The method according to p. 12 or 13, characterized in that the medium is selected from a metal oxide, preferably alumina, silica and/or Zirconia, activated carbon and resins.

15. The method according to any of paragraphs.12 to 14, characterized in that the content of ruthenium in the catalyst on the carrier chosen from 0.1 to 20.0 wt.%, preferably from 0.5 to 3.0 wt.%.

16. The method according to any of paragraphs.1 - 13, characterized in that for impregnation using an aqueous solution of a complex of ruthenium and tin content of 1-20 weight. % ruthenium.

17. The method according to any of paragraphs.1 to 16, characterized in that the implement carrier impregnated driven, for example by rotation of the drum, by spraying an aqueous solution containing a complex of ruthenium and tin.

18. The method according to any of paragraphs.1 to 17, characterized in that the impregnated molded carrier carried by immersion in an aqueous solution of the specified property.

19. The method according to any of paragraphs.1 to 17, characterized in that the impregnation of the carrier have a "dry" using an aqueous solution containing a complex of ruthenium and tin.

21. The method according to any of paragraphs.1 to 21, characterized in that the recovery of the specified complex carried by contact with hydrogen.

22. The method according to p. 21, characterized in that the hydrogen is served at atmospheric pressure or at low pressure, for example, 1-2 bar, or diluted with an inert gas such as nitrogen or helium.

23. The method according to p. 21 or 22, characterized in that the recovery is carried out at a temperature of at least 350°C., preferably from 350 to 600°C., more preferably from 400 to 500°C.

24. The method according to any of paragraphs.23 to 25, characterized in that the recovery is carried out using a catalyst.

25. The method according to any of paragraphs.1 to 24, characterized in that the catalyst containing the intermetallic compound ruthenium/tin in an atomic ratio of tin: ruthenium is at least equal to 2:3, preferably 3:2, preferably 7:3.

26. The method according to p. 25, characterized in that the atomic ratio of tin:ruthenium is not more than 3, preferably 5:2.

27. The method according to any of paragraphs.1 to 26, characterized in that the catalyst containing at least 50%, mainly 80%, prepona specified device.

28. The method according to any of paragraphs.1 to 27, characterized in that the catalyst containing ruthenium, and at least 90% of which, mainly at least 95%, preferably 98%, is present on the carrier in the form specified intermetallic compounds, covering the specified device.

29. A method of producing aldehydes of General formula I

< / BR>
where R means a hydrogen atom or a hydrocarbon radical, possibly substituted, containing from 1 to 40 carbon atoms which may be linear or branched, saturated or unsaturated, acyclic aliphatic radical, a carbocyclic or heterocyclic saturated, unsaturated or aromatic, monocyclic or polycyclic radical, or their derivatives by recovery in the vapor phase with hydrogen carboxylic acids, esters or anhydrides of carboxylic acids of the formula II

< / BR>
where R has the above meanings;

R1means a group R as defined above, a group in which RIIhas the meaning given for R;

moreover, both groups R and RIIcan be linked for the formation of a saturated or unsaturated cycle having 5 to 7 atoms and including anhydrous gr is IR bicyclic artecontemporanea system, in the presence of a catalyst obtained by the method according to any of paragraphs.1 - 28.

30. The method according to p. 29, characterized in that the carboxylic acid or derivative of General formula (II) is chosen from: saturated aliphatic monocarboxylic acids, saturated aliphatic dicarboxylic acids, unsaturated aliphatic monocarboxylic or dicarboxylic acids, saturated or unsaturated carbocyclic carboxylic acids, heterocyclic carboxylic acids, aromatic carbocyclic carboxylic acids, saturated or unsaturated arylaliphatic carboxylic acids, halogenated aliphatic or aromatic carboxylic acids, aliphatic, cycloaliphatic, arylaliphatic hydroxy acids, oxybenzoic acid, alkoxy - and tenoxtitlan, oxacyclic, alloccolor, amino acids, possibly N-substituted.

31. The method according to PP.29 and 30, characterized in that the carboxylic acid or a derivative thereof selected from: benzoic acid, 3, 4-diferential acid, 4-chlorbenzoyl acid, 4-triftorperasin acid, salicylic acid, 3-oksibenzoynoy acid, 4-oksibenzoynoy acid, vanillic acid, 3,4-dimethoxybenzoic acid, 4-methoxybenzoic acid, 3,4-dioxy-metilen is s, acetic acid, triperoxonane acid, 2-methylbutanoic acid, saturated or unsaturated aliphatic fatty acids having from 6 to 20 carbon atoms, preferably heptane acid, nonnovel acid, undecanoic acid, oleic acid, stearic acid, lauric acid, undecanoic acid, 2-methylnonanoic acid, 3,7-dimethyl-2,6-octadecenoic acid, senecioneae acid, a cyclohexane acid.

 

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FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides isodewaxing catalyst for petroleum fractions containing supported platinum and modifiers wherein supporting carrier is fine powdered high-purity alumina mixed with zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40 at following proportions of components, wt %: platinum 0.15-0.60, alumina 58.61-89.43, zeolite 5-40, tungsten oxide (modifier) 1-4, and indium oxide (modifier) 0.24-0.97. Preparation of catalyst comprises preparing carrier using method of competitive impregnation from common solution of platinum-hydrochloric, acetic, and hydrochloric acids followed by drying and calcinations, wherein carrier is prepared by gelation of fine powdered high-purity alumina with the aid of 3-15% nitric acid solution followed by consecutive addition of silicotungstenic acid solution and indium chloride solution, and then zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40.

EFFECT: increased yield of isoparaffin hydrocarbons.

7 cl, 2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: description is given of a method of obtaining olefins. The method involves passing a mixture of a hydrocarbon and oxygen containing gas through a catalyst zone, which is capable of maintaining burning over the upper limit the inflammability of the fuel, with obtaining of the above mentioned olefin. The catalyst zone consists of at least, a first layer of catalyst and a second layer of catalyst, where the second catalyst layer is put in the process line after the first catalyst layer, has different content from the first layer and has general formula: M1aM2bM3cOz, where M1 is chosen from IIA, IIB, IIIB, IVB, VB, VIB, VIIB groups of lanthanides and actinoides, M2 is chosen from IIA, IB, IIB, IIIB, IVB, VB, VIB groups, and M3 is chosen from IIA, IB, IIB, IIIB, IVB, VB, VIB and VIIIB groups, a, b, c and z represent atomic ratios of the M1, M2, M3 and O components respectively. The value of a lies in the interval from 0.1 to 1.0, the value of b lies in the interval from 0.1 to 2.0, the value of c lies in the interval from 0.1 to 3.0, and the value of z lies in the interval from 0.1 to 9.0. The catalyst zone has a perovskite type structure.

EFFECT: perfection of the method of obtaining olefins.

9 cl, 4 tbl, 1 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: present invention refers to catalytic system and to the method of reduction of nitrogen oxides emissions using the said system. The described catalytic system for NOx reduction contains: the catalyst containing the metal oxide substrate, catalytic metal oxide which is gallium oxide or silver oxide or both of them and initiating metal chosen from the group consisting of silver, cobalt, molybdenum, wolfram, indium, bismuth and their mixtures, gas flow containing the organic reducing agent and sulfur-containing substance. The described catalytic system for NOx reduction contains: the catalyst consisting of (i) the metal oxide substrate, containing aluminium oxide, (ii) catalytic metal oxide which is gallium oxide or silver oxide or both of them in quantity 1-31 mole %; and (iii) initiating metal or their combination selected from the group consisting of silver, cobalt, molybdenum, wolfram, indium, bismuth, indium and wolfram, silver and cobalt, indium and molybdenum, indium and silver, bismuth and silver, bismuth and indium and molybdenum and indium in quantity 1-31 mole %, gas flow containing (A) water in quantity 1-15 mole %; (B) gaseous oxygen in quantity 1-15 mole %; and (C) organic reducing agent selected from the group consisting of alcanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates and their combinations; and sulfur oxide; where at the specified organic reducing agent and NOx are present in approximate molar ratio carbon to NOx from 0.5:1 to 24:1. The described method of NOx reducing includes the stages of gaseous mixture containing NOx, organic reducing agent and sulfur-containing substance inflow and of said gaseous mixture contact with specified catalyst. The described method of NOx reduction includes: inflow of gaseous mixture containing (A) NOx, (B) water in quantity 1-15 mole %; (C) oxygen in approximate quantity 1-15 mole %; (D) organic reducing agent selected from the group consisting of alcanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates and their combinations and (E) sulfur oxide; and contact of said gaseous mixture with catalyst described above and containing the specified components in the defined molar ratio.

EFFECT: improved action of the catalyst.

35 cl, 10 tbl, 84 ex

FIELD: chemistry.

SUBSTANCE: present invention refers to naphtha reforming catalyst. There is disclosed a catalyst effective in naphtha reforming involving particles of heat-resistant inorganic oxide carrier containing dispersed bivalent tin, platinum group metal and rhenium and optionally halogen, characterised that tin uniformly coats the catalyst, and platinum group metal uniformly coats the catalyst; tin is impregnated into the carrier with using tin chelate resulted from reaction of chelating agent representing amino acid and bivalent tin salts. There is also disclosed catalytic reforming of naphtha as feed stock, wherein feed stock contacts with said catalyst in reforming environment involving temperature 315°C-600°C, pressure 100 KPa - 7 MPa (abs.), liquid hourly space velocity 0.1-20 h-1, and molar ratio of hydrogen to naphtha feed stock 1-20.

EFFECT: new naphtha reforming catalyst and new catalytic reforming of naphtha.

10 cl, 2 dwg, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry and petrochemistry, particularly to designing and using catalysts. Described is a catalyst for dehydrogenation of isopentane and isopentane-isoamylene fractions based on platinum and tin, deposited on a carrier - zincalume spinel. The catalyst is distinguished by that, the carrier is in form of nanocrystalline particles with average crystal size of 22-35 nm with components in the following ratio, wt %: platinum - 0.05-2.0, tin - 0.1-6.0, zincalume spinel - the rest. Also described is a method of preparing said catalyst, involving grinding and mixing oxygen-containing zinc and aluminium compounds, gradual addition of water until obtaining a homogeneous pasty mass, stirring and moulding, drying the granules at room temperature and calcination, subsequent saturation of the formed carrier with an aqueous solution of platinum and tin compounds, final drying of the catalyst mass in air; the method is distinguished by that, the carrier is calcined while gradually raising temperature to 800-900°C at a rate of 10-200°C/hour, and then for 5-40 hours at 850-1000°C, while constantly controlling size of the formed crystals until formation of nanocrystalline particles with average crystal size of 22-35 nm.

EFFECT: increased efficiency of dehydrogenation process due to increased output of isoprene, with high selectivity on dehydrogenation products, as well as due to longer inter-regeneration period of the catalyst.

3 cl, 1 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst system and a method of reducing nitrogen oxide emissions. The described catalyst system for reducing NOx contains: a catalyst having a support which contains at least one compound selected from a group consisting of aluminium oxide, titanium dioxide, zirconium dioxide, cerium oxide, silicon carbide and mixtures thereof, a catalytic metal oxide containing at least one of gallium oxide or silver oxide and at least one activating metal selected from a group consisting of silver, cobalt, molybdenum, tungsten, indium or mixtures thereof; and a gas stream containing oxygen ranging from approximately 1 mol % to approximately 12 mol % and an organic reducing agent selected from a group consisting of alcohol, carbonate or combinations thereof, where the said organic reducing agent and the said NOx are present in molar ratio carbon: NOx ranging from approximately 0.5:1 to approximately 24:1. A catalyst system for reducing NOx which contains the following is described: a catalyst consisting of (i) metal oxide support which contains aluminium oxide, (ii) at least one of the following oxides: gallium oxide or silver oxide, present in amount ranging from approximately 5 mol % to approximately 31 mol %; and (iii) an activating metal or a combination of activating metals, present in amount ranging from approximately 1 mol % to approximately 22 mol % and selected from a group consisting of silver, cobalt, molybdenum, tungsten, indium and molybdenum, indium and cobalt, and indium and tungsten; and a gas stream containing (A) water in range from approximately 1 mol % to approximately 12 mol %; (B) oxygen in the range from approximately 1 mol % to approximately 15 mol %; and (C) an organic reducing agent containing oxygen and selected from a group consisting of methanol, ethanol, butyl alcohol, propyl alcohol, dimethyl carbonate or combinations thereof; where the said organic reducing agent and NOx are present in molar ratio carbon: NOx ranging from approximately 0.5:1 to 24:1. Also described are methods of reducing NOx which involve the following steps: providing a gas mixture and bringing the said gas mixture into contact with above described catalysts for reducing NOx (versions).

EFFECT: reduced ill effects of air contamination caused by by-products of incomplete high-temperature combustion of organic substances.

21 cl, 34 ex, 4 tbl

FIELD: oil and gas industry.

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

EFFECT: technological advantages of conversion of hydrocarbon material.

10 cl, 3 ex, 6 tbl

FIELD: chemistry.

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

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

15 cl, 2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to catalysts from metals of platinum group on oxide carrier, intended for removal of harmful components, in particular of gaseous carbon monoxide in engine exhaust fumes of automobile engines or for application in electrodes of gas-sensitive sensors, in fuel elements, which work on synthesis-gas, and in other electrochemical devices. Described is nano-structured catalyst for after-burning of carbon monoxide, which as carrier contains tin dioxide, alloyed with antimony oxide with ratio of antimony to tin being 2 mol % and particles of nano-crystalline platinum, content of which in catalyst constitutes 2 wt %, with oxide carrier having one-phase composition, and particles of nano-crystalline platinum, precipitated on oxide carrier, have size 3-5 nm.

EFFECT: obtaining highly active catalyst for carbon monoxide oxidation.

2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the field of hydrocarbon conversion. Claimed is a catalyst for catalytic reforming of a hydrocarbon raw material, which contains at least one metal M of a group of platinum, tin, a phosphorus promoter, a halogen-containing compound, a porous substrate and at least one promoter X1, selected from the group, consisting of gallium and indium. The said catalyst in a reduced form demonstrates, in accordance with Mossbauer spectroscopy 119Sn, a signal, which has a value of quadrupole splitting from 0 to 0.45 mm/s and a chemical shift IS from 1.5 to 2.4 mm/s relative to CaSnO3, with an area of the said signal constituting from 1 to 30% of the total surface of signals. The catalyst is obtained by a method, including the introduction of the said promoter X1 and phosphorus at the stage of the substrate preparation.

EFFECT: increase of selectivity with respect to C5+ compounds and reduction of coke formation.

10 cl, 2 tbl, 11 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides reforming catalyst containing Pt and Re on oxide carrier, in particular Al2O3, wherein content of Na, Fe, and Ti oxides are limited to 5 (Na2O), 20 (Fe2O3), and 2000 ppm (TiO2) and Pt is present in catalyst in reduced metallic state and in the form of platinum chloride at Pt/PtCl2 molar ratio between 9:1 and 1:1. Contents of components, wt %: Pt 0.13-0.29, PtCl2 0.18-0.04, Re 0.26-0.56, and Al2O3 99.43-99.11. Preparation of catalyst comprises impregnation of alumina with common solution containing H2PtCl6, NH4ReO4, AcOH, and HCl followed by drying and calcination involving simultaneous reduction of 50-90% platinum within the temperature range 150-550оС, while temperature was raised from 160 to 280оС during 30-60 min, these calcination conditions resulting in creation of reductive atmosphere owing to fast decomposition of ammonium acetate formed during preparation of indicated common solution.

EFFECT: increased catalytic activity.

2 cl, 1 tbl, 3 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: cobalt-based catalyst precursor is prepared by impregnation of porous catalyst carrier particles with cobalt salt followed by partial drying and subsequent calcination of impregnated carrier, after which calcined product is partially reduced, impregnated with cobalt salt, partially dried and finally calcined. Preparation of Fischer-Tropsch catalyst comprises similar preparation of precursor thereof and reduction of the latter.

EFFECT: increased catalytic activity.

12 cl, 3 dwg, 1 tbl, 2 ex

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