The method of electrochemical preparation of the catalyst based on a transition metal and phosphine

 

(57) Abstract:

The present invention relates to a method of electrochemical produce compounds for use as catalysts. These compounds contain, in particular, at least one transition metal of the IV-VII subgroups and VIII group of the Periodic system with oxidation state 0 or 1 associated with at least one monodentate phosphine of the formula P(Ar1)and(AG)b(AG)c(D1)d(D2)e(D3)f(I) or bidentate water-soluble phosphine of the formula (Ar1)a(AG)b(D1)d(D2)eP-L-P (Ar1)g(Ar2)h(D1)i(D2)j(II). Method for electrochemical synthesis of catalysts is processed by electrolysis of an aqueous solution with a content of at least one of the compounds mentioned transition metal and one monodentate or bidentate water-soluble phosphine, located in the cathode compartment of an electrolytic cell of the electrolyzer. The method allows to obtain a catalyst that is able to regenerate. 21 C.p. f-crystals, 1 table.

The present invention relates to a method of electrochemical produce compounds which can be used as catalysts.

Such compounds can be used, for example, instead of the catalysts used in the reactions of hydrocyanide Ethylenediamine compounds described, for example, in French patent A-2338253. In this paper they will be referred to as catalysts, although they are not limited to their use.

Electrochemical synthesis of such catalysts is electrolytic treatment of an aqueous solution containing at least one compound of the transition metal and at least one monodentate or bidentate water-soluble phosphine, and is located in the cathode compartment of an electrolytic cell of the electrolyzer.

Water-soluble phosphine used in the method according to the invention, is a monodentate phosphine of General formula (I):

P(Ar1)a(Ar2)b(Ar3)c(D1)d(D2)e(D3)f< / BR>
where Ar1 and Ar2, identical or different, denote a group of the aryl or aryl containing one or more substituents, such as:

is an alkyl or CNS radical with 1-4 carbon atoms,

is a halogen atom,

- nitrile group,

the nitrogroup is ical cationic residue, choose from a proton, cations derived from alkali or alkaline earth metals, ammonium cations -- N(R)4the formula which the symbols R are identical or different, denote a hydrogen atom or an alkyl radical with 1-4 carbon atoms, other cations derived from metals, salts with arylcarbamoyl, arylsulfonate or arylphosphonate acids are water-soluble,

-N(R)3the formula which the symbols R are identical or different, denote a hydrogen atom or an alkyl radical with 1-4 carbon atoms,

- OH,

- Ar3 means aryl group with one or more substituents, such as:

is an alkyl or CNS radical with 1-4 carbon atoms,

is a halogen atom,

- nitrile group,

the nitrogroup,

- hydrophilic group, such as:

- COOM, -PO3M, where M means a mineral or organic cationic residue selected from a proton, cations derived from alkali or alkaline earth metals, ammonium cations -- N(R)4the formula which the symbols R are identical or different, denote a hydrogen atom or an alkyl radical with 1-4 carbon atoms, other cations derived from metals, salts with arylcarbamoyl or arylphosphonate to achut a hydrogen atom or an alkyl radical with 1-4 carbon atoms,

- OH,

at least one of these substituents Ar3 is a hydrophilic group, such as described above,

- a stands for 0 or 1,

- b means 0 or 1,

- c stands for 0 or 1,

- D1, D2, D3, identical or different, denote an alkyl group, cycloalkyl group or alkyl or cycloalkyl group with one or more substituents, such as:

- CNS radical with 1-4 carbon atoms,

is a halogen atom,

- nitrile group,

the nitrogroup,

- hydrophilic group, such as:

- COOM, -SO3M, -PO3M, where M means a mineral or organic cationic residue selected from a proton, cations derived from alkali or alkaline earth metals, cations - N(R)4ammonium in the formula which the symbols R are identical or different, denote a hydrogen atom or an alkyl radical with 1-4 carbon atoms, other cations derived from metals, salts with carboxylic, sulfonic or phosphonic acids are water-soluble,

-N(R)3, in the formula which the symbols R are identical or different, denote a hydrogen atom or an alkyl radical with 1-4 carbon atoms,

- OH,

- d, e, and f denote 0 or 1,

the sum (a+b+c+d+e+f) is equal to 3,
)h(D1)i(D2)j< / BR>
where Ar1, Ar2, D1 and D2 have the meanings indicated above for formula (I),

a, b, d, e, g, h, i and j denote each 0 or 1,

the sum (a+b+d+e) is equal to 2,

- sum (g+h+i+j) is equal to 2,

- L means a single valence bond or a bivalent hydrocarbon radical, such as alkalinity, cycloalkenyl, Allenby radical or a radical derived heterocycle containing one or two atoms of oxygen, nitrogen or sulfur in the cycle, the different cyclic radicals linked directly with one or two atoms of phosphorus or associated with one or with two phosphorus atoms via a linear or branched alkalinity radical with 1-4 carbon atoms, and the cycle or cycles that can be part of the divalent radical L can contain one or more substituents such as indicated for Ar1, Ar2, D1, D2.

Examples of metals whose salts with carboxylic, sulfonic or phosphonic acids are soluble in water, can serve as lead, zinc and tin.

Under the expression "water-soluble" herein means a compound which is soluble in the amount of at least 0.01 g per liter of water.

Preferred water-soluble phosphinyl more substituents, like stated above, Ar3 is a phenyl group with one or two substituents, such as described above, D1, D2 and D3, identical or different, denote an alkyl group with 1-6 carbon atoms, cycloalkyl group with 5-8 carbon atoms, or alkyl group with 1-6 carbon atoms or cycloalkyl group with 5-8 carbon atoms, containing one or more substituents, such as above, L is a single valence bond, alkalinity radical with 1-6 carbon atoms, monocyclic or bicyclic cycloalkenyl radical with 4 to 12 carbon atoms, phenylenebis radical, definitely radical, Neftyanoy radical, dinately radical, the radical derived heterocycle containing one or two atoms of oxygen, nitrogen or sulfur cycle, with different cyclic radicals linked directly with one or two atoms of phosphorus or associated with one or with two phosphorus atoms via a linear or branched alkalinity radical with 1-4 carbon atoms, and the cycle or cycles that can be part of the divalent radical L can contain one or more substituents such as an alkyl group with 1-4 carbon atoms.

Preferred water-soluble phosphines allessie, mean group, such as:

is an alkyl or CNS radical with 1 to 2 carbon atoms,

a chlorine atom,

- hydrophilic group, such as:

- COOM, -SO3M, -PO3M, where M means a mineral or organic cationic residue selected from a proton, cations derived sodium, potassium, calcium or barium, ammonium cations, Tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, cations derived zinc, lead or tin,

- N(R)3the formula which the symbols R are identical or different, denote a hydrogen atom or an alkyl radical with 1-4 carbon atoms,

- OH,

Deputy or Deputy Ar3, identical or different, denote a group, such as:

is an alkyl or CNS radical with 1 to 2 carbon atoms,

a chlorine atom,

- hydrophilic group, such as:

- COOM, -PO3M, where M means a mineral or organic cationic residue selected from a proton, a cation derived from sodium, potassium, calcium or barium, ammonium cations, Tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, cation - derived zinc, lead or tin,

- N(R)3the formula which the symbols R are identical or different the VA of these substituents Ar1, Ar2, Ar3, D1, D2 and D3 in the phosphines of formula (I), and Ar1, Ar2, D1 and D2 in the phosphines of formula (II) are hydrophilic group described above.

As non-limiting examples of the phosphines of General formula (I) can, in particular, to lead Tris(hydroxymethyl)phosphine, Tris(2-hydroxyethyl)phosphine, Tris(3-hydroxypropyl)phosphine, Tris(2-carboxymethyl)phosphine, sodium salt of Tris(3-carboxyphenyl)phosphine, Tris(3-carboxyethyl)phosphine, iodide Tris(4-trimethylammoniumphenyl)phosphine, sodium salt of Tris(2-fostaty)phosphine, bis(2-carboxyethyl)phenylphosphine, peroxyketal-bis(2-hydroxyethyl)phosphine, sodium salt of Tris(para-postfinal)phosphine, sodium salt of bis(metasulfite)-percarboxylic-phosphine, sodium salt of bis(metasulfite)-2-sulfotyrosine.

As non-limiting examples of the phosphines of General formula (II) may, in particular, to indicate the sodium salt of 2,2'-bis[di(sulfonatophenyl)phosphino] -1,1'-binaphthyl, sodium salt of 1,2-bis[di(sulfonatophenyl)phosphonomethyl] CYCLOBUTANE (CBDTS), 1,2-bis(dihydroxymethyl-phosphino)ethane, 1,3-bis(dihydroxyethylene)propane sodium salt of 2,2'-bis[di(sulfonatophenyl)phosphonomethyl]-1,1'-dinaphthyl.

Obviously, you can apply a mixture of several of these pogotowie other phosphines can be specified on a shared or private methods of synthesis of phosphines, described in General works, such as Houben-Weyl, Method der organischen Chemie, organische Phosphor-Acidic (Method of organic chemistry, organic phosphorus compounds), including 1, 1963

Finally to obtain undescribed water-soluble derivatives simply enter one or more of these hydrophilic substituents in the phosphines, which does not contain the above water-soluble substituents. For example, sulphonate groups may be introduced by the reaction of SO3of sulfuric acid. Group, carboxylate and phosphonate and the Quaternary ammonium group can be introduced using chemical methods known for this type of synthesis.

Preferably, as the transition metal compounds used compounds of Nickel, cobalt, iron, palladium, platinum, rhodium and iridium. Use of compounds soluble in water or capable of passing into solution under the reaction conditions. The remainder associated with metal is not of critical importance, unless he satisfies the given conditions.

Of these compounds the most preferred are compounds of Nickel. You can specify as a non-limiting example, such compounds as Nickel is I, the Nickel bromide, Nickel chloride, Nickel iodide, Nickel thiocyanate, cyanide Nickel hydroxide Nickel, hydrophosphite Nickel, postit Nickel, Nickel phosphate and its derivatives, Nickel nitrate, Nickel sulfate, Nickel sulfite, aryl - and alkyl sulphonates Nickel.

It is not necessary that the connection of Nickel was also soluble in water. For example, cyanide Nickel, little soluble in water, soluble in an aqueous solution of water-soluble phosphine.

Electrolytic cell electrolytic cell used in this method consists of a cathode and anode compartments separated by a dividing element.

The cathode of the electrolytic cell can be made of a material such as platinum, gold, iridium, ruthenium, palladium, Nickel, graphite, stilografica, iron, stainless steel, special steel, lead, zinc, cadmium, mercury, amalgam. It can also be made of titanium, tantalum, Nickel and stainless steel with a coating of platinum, gold, iridium, ruthenium, and mixtures of several of these metals, oxides of platinum, palladium, iridium, rhodium, ruthenium, osmium, tantalum, or of a mixture of several oxides.

The cathode may have a flat structure, such as plate, mnoi patterns can be called granules of the above materials, felt, or these materials are porous structure.

The anode may be made of such material as platinum, gold, iridium, ruthenium, palladium, Nickel, graphite, stilografica, stainless steel, special steel, lead. It can also be made of titanium or tantalum coated with platinum, gold, iridium, ruthenium, of a mixture of several of these metals, oxides of platinum, palladium, iridium, rhodium, ruthenium, osmium, tantalum and mixtures of several of these oxides.

The structure of the anode may be of different type, as described for the cathode.

Dividing element electrolytic cell formed by the ion-exchange membrane or a porous diaphragm.

The membrane can be of the cationic type, in particular made of a cation exchange resin having acidic groups such as sulfonic or carboxylic groups. It is preferable to use membranes made of sulfonic resin. Of membranes of this type can be specified, for example, on membrane commercially available under the trademarks Nafion(perforated sulfonic membrane) and Selemion.

In addition, the membrane can be of the anionic type, however, as a rule, predpochtitelney membranes and allow you to work with higher amperage.

Porous diaphragms can be, in particular, a membrane of a porous ceramic diaphragm of woven or non-woven fabrics of synthetic fibers, caused the diaphragm on the basis of asbestos or synthetic fibers.

The separation element can be supported on the anode or the cathode.

As described above, in the cathode compartment is an aqueous solution containing monodentate or bidentate water-soluble phosphine and the compound of the transition metal. Initial concentration monodentate or bidentate water-soluble phosphine is generally from 10-3mol/l to 1 mol/l Initial concentration of transition metal compounds, in particular compounds of Nickel, is usually from 10-5mol/l to 1 mol/L.

In the cathode compartment can be entered and other compounds that improve the conductivity of the electrolyte, such as, for example, soluble salts.

You can also enter complexing agents that cause the change of potential at which the recovery of the transition metal. As examples of such complexo-forming agents can be specified on the cyanide and chloride.

The solution in the cathode procedure according to the invention. Such compounds are, in particular, the Lewis acid.

Under Lewis acid in this text are understood according to the generally accepted definition of the compounds, which are acceptors of electron pairs.

Can be used, in particular, a Lewis acid is given in a book published by G. A. OIah "Friedel-Crafts and related Reactions", I. 1, pp. 191-197, 1963

A Lewis acid which can be used in the cathode compartment is selected from compounds of elements of groups Ib, IIb, IIIa, IIIb, IVa, IVb, Va, Vb, VIb, VIIb and VIII of the Periodic system of elements, which is published in the Handbook of chemistry and physics, 51st Edition (1970-1971) of Chemical Rubber Co. provided that these compounds are at least partially soluble and stable in water or in aqueous solution, processed by electrolysis. Such compounds are often, but not in a restrictive sense salts, in particular halides, preferably chlorides and bromides, sulfates, nitrates, sulfonates, in particular triftoratsetata, carboxylates, acetylacetonates, tetrafluoroborate and phosphates.

As non-limiting examples of such Lewis acids can be specified on zinc chloride, zinc bromide, zinc iodide, triftorbyenzola zinc, zinc acetate, zinc nitrate, tenet Nickel, the cadmium chloride, bromide, cadmium, chloride, divalent tin bromide divalent tin, ferrous sulfate tin tartrate divalent tin, chlorides, bromides, sulfates, nitrates, carboxylates or triftoratsetata rare earth elements such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, cobalt chloride, iron chloride, yttrium chloride.

Of course, you can apply a mixture of several Lewis acids.

Suitable Lewis acids include, in particular, zinc chloride, zinc bromide, zinc sulfate, tetrafluoroborate zinc chloride divalent tin bromide divalent tin, a mixture of zinc chloride and ferrous chloride tin, Nickel chloride, Nickel bromide, Nickel acetylacetonate.

Used the Lewis acid is usually 0-50 moles per mole of transition metal compounds, in particular compounds of Nickel, preferably 0-10 moles per mole.

In the anode compartment is an aqueous solution of the analyte, which may consist of acid, such as sulfuric acid, nitric acid, water-soluble carboxylic acids, such as acetic acid, and the surrounding area, sodium hydroxide or potassium hydroxide. Preferably, the anolyte was chosen from sulfuric acid and its salts, in particular Dunaliella sulfate, potassium hydrosulfate, disodium sulfate, sodium hydrosulphate.

The anolyte may also consist of one or more of the above-described water-soluble phosphines.

The initial concentration of analyte in the solution used in the anodic compartment is from 10-3mol/l to 3 mol/L.

Prislonyaetsya in the method according to the invention the electric current is determined by the strength of the current and the potential at the cathode. The potential can be maintained constant during the electrolysis process (potentiostatic). Another possibility is to maintain a constant current (static current). In the continuous method, the method according to the invention both of these options are equivalent.

When working with a constant potential and its value can easily be determined by the average specialist nature of the curves "current/potential".

The current density can reach 30 A/DM2. It set taking into account the amount subject to recovery of the transition metal.

Operating temperature with the Xia regeneration of used catalyst, i.e., the catalyst used and become at least partially deactivated. Thus, the catalyst based on monodentate or bidentate water-soluble phosphine and a transition metal with oxidation state 0 or 1, optionally containing one or more Lewis acids used in the reaction of hydrocyanide butadiene and/or penten-NITRILES, rapidly loses its activity, in particular due to the oxidation of the transition metal. The latter, in particular Nickel, at least partially converted into cyanide. At the end of the reaction hydrocyanide aqueous phase containing, in particular, monodentate or bidentate water-soluble phosphine and the compound of the transition metal at least partial oxidation number greater than 0, can be easily separated from the organic phase. This aqueous phase may contain different amounts of initially introduced compounds, such as butadiene and/or penten-NITRILES, or formed during the reaction, such as adiponitrile, methylglutaronitrile, ethyl succinonitrile, penten-NITRILES, methylbutyronitrile. Treatment of the aqueous phase is carried out electrochemically, as described above, for the regeneration of the catalyst.
The electrolytic cell consists of a glass vessel of cylindrical shape with a useful volume of about 100 ml, within which is located the cathode in the form of platinum mesh, cylindrical anode cavities, located inside the cathode grid and having in its base membrane of the resin type Nafion 417and in which the immersed anode in the form of a platinum plate.

The electrolyzer is connected to the potentiostat, which helps to maintain the potential at the cathode is equal to 1.2 In relation to a reference electrode Ag/AgCl.

Abbreviations used:

3PN = 3-penten-nitrile,

ADN = adiponitrile,

RT = the selectivity obtained connection in relation to the original converted connection,

t. o. = turn-over = the number of mmol of the resulting dinitrile in mmol used Ni(O),

COD = cyclooctadiene.

In the cathode compartment of the electrolytic cell load 50 ml of an aqueous solution containing 7.5 mmole cyanide Nickel Ni(CN)215 thoughts sodium salt of 1,2-bis[di(sulfonatophenyl)phosphonomethyl]CYCLOBUTANE (CBDTS).

In the anode compartment is filled with 50 ml of an aqueous solution of sulfuric acid (0,02 N).

The electrolysis is carried out at 25oC in controlled p is Ecodom polarographic.

After 15 hours of electrolysis 80% Ni (II) has turned into a Ni(O).

1. The method of electrochemical preparation of the catalyst containing at least one transition metal of the IV - VII subgroups and VIII group of the Periodic system with oxidation state 0 or 1 associated with at least one water-soluble phosphine, by electrolysis in the cathode compartment of an electrolytic cell, electrolysis of an aqueous solution containing at least one connection of the specified transition metal and at least one phosphine, characterized in that the phosphine used monodentate phosphine of General formula I

P(Ar1)a(Ar2)b(Ar3)c(D1)d(D2)e(D3)f,

where Ar1 and Ar2, identical or different, denote aryl groups or aryl groups containing one or more substituents, such as alkyl or CNS radical with 1 to 4 carbon atoms, halogen atom, nitrile group, a nitro-group, a hydrophilic group, such as COOM, -SO3M, -PO3M, where M means a mineral or organic cationic residue selected from a proton, cations derived from alkali or alkaline earth metals, cations-N(R)4ammonium in the formula which char is a new - derivatives of metals, salts with arylcarbamoyl, arylsulfonate or arylphosphonate acids are water-soluble, N(R)3the formula which the symbols R are identical or different, denote a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms, OH;

Ar3 means aryl group with one or more substituents, such as alkyl or CNS radical with 1 to 4 carbon atoms, halogen atom, nitrile group, a nitro-group, a hydrophilic group, such as COOM, -PO3M, where M means a mineral or organic cationic residue selected from a proton, cations derived from alkali or alkaline earth metals, cations-N(R)4ammonium in the formula which the symbols R are identical or different, denote a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms, other cations derived from metals, salts with arylcarbamoyl or arylphosphonate acids are water-soluble, N(R)3the formula which the symbols R are identical or different, denote a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms, OH, at least one of these substituents Ar3 is a hydrophilic group, such as described above;

a denotes 0 or 1,cycloalkyl group or alkyl or cycloalkyl group, containing one or more substituents, such as CNS radical with 1 to 4 carbon atoms, halogen atom, nitrile group, a nitro-group, a hydrophilic group, such as COOM, -SO3M, -PO3M, where M means a mineral or organic cationic residue selected from a proton, cations derived from alkali or alkaline earth metals, cations-N(R)4ammonium in the formula which the symbols R are identical or different, denote a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms, other cations derived from metals, salts with carboxylic, sulfonic or phosphonic acids are water-soluble, -N(R)3the formula which the symbols R are identical or different, denote a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms, OH,

d, e and f denote 0 or 1,

the sum (a + b + C + d + e + f) is equal to 3,

or bidentate phosphine of General formula II

(Ar1)a(Ar2)b(D1)d(D2)eP-L-P(Ar1)g(Ar2)h(D1)i(D2)j,

where Ar1, Ar2, D1 and D2 have the meanings indicated above for formula I;

a, b, d, e, g, h, i and j denote each 0 or 1,

the sum (a + b + d + e) is equal to 2;

the sum (g + h + i + j) is equal to 2;

L is a single valence bond or a divalent pleurosigma, containing one or two atoms of oxygen, nitrogen or sulfur in the cycle, the different cyclic radicals linked directly with one or two phosphorus atoms or associated with one or two phosphorus atoms via a linear or branched alkalinity radical with 1 to 4 carbon atoms, and the cycle or cycles that can be part of the divalent radical L can contain one or more substituents, such as indicated for Ar1, Ar2, D1, D2.

2. The method according to p. 1, characterized in that the electrolytic cell electrolytic cell consists of a cathode and anode compartments separated by a dividing element, formed by the ion-exchange membrane or a porous diaphragm.

3. The method according to p. 1 or 2, characterized in that the cathode of the electrolytic cell is made of a material such as platinum, gold, iridium, ruthenium, palladium, Nickel, graphite, stilografica, iron, stainless steel, special steel, lead, zinc, cadmium, mercury, amalgam, or may be made of titanium, tantalum, Nickel and stainless steel with a coating of platinum, gold, iridium, ruthenium, and mixtures of several of these metals, oxides of platinum, palladium, iridium, rhodium, ruthenium, osmium, t is troficheskoi cells have a flat structure, such as plate, mesh, or three-dimensional structure, and that they made perforated or solid.

5. The method according to PP.1 to 4, characterized in that the cathode or the anode are three-dimensional structure, which can be made from granules of the material forming the anode or the cathode, or felt, or from the specified material of the porous structure.

6. The method according to PP.1 to 5, characterized in that the anode is made of a material such as platinum, gold, iridium, ruthenium, palladium, Nickel, graphite, stilografica, stainless steel, special steel, lead, or made of titanium or tantalum coated with platinum, gold, iridium, ruthenium, and mixtures of several of these metals, oxides of platinum, palladium, iridium, rhodium, ruthenium, osmium, tantalum or mixtures of several of these oxides.

7. The method according to PP.1 - 6, characterized in that the separating element selected from membranes of cationic type, made of cation-exchange resins containing acid groups such as sulfonic or carboxylic groups, preferably of membranes made of sulfonic resin.

8. The method according to PP.1 - 6, characterized in that the separating element is selected from a diaphragm of porous ceramics, diaphragms made of woven or natcan the CLASS="ptx2">

9. The method according to PP.1 to 8, characterized in that the preferred water-soluble phosphines are phosphines of the formula I or formula II, in which Ar1 and Ar2 is a phenyl group or a phenyl group containing one or more substituents, such as indicated in paragraph 1 of the claims, Ar3 is a phenyl group containing one or two substituent, such as indicated in paragraph 1 of the claims, D1, D2 and D3, identical or different, denote an alkyl group with 1 to 6 carbon atoms, cycloalkyl group with 5 to 8 carbon atoms, alkyl group with 1 to 6 carbon atoms or cycloalkyl group with 5 to 8 carbon atoms, containing one or more substituents such as are indicated above in paragraph 1 of the formula of the invention, L is a single valence bond, alkalinity radical with 1 to 6 carbon atoms, monocyclic or bicyclic cycloalkenyl radical with 4 to 12 carbon atoms, phenylenebis radical, definitely radical, Neftyanoy radical, dinately radical, the radical derived heterocycle containing one or two atoms of oxygen, nitrogen or sulfur cycle, in addition, these different cyclic radicals linked directly with one or two atoms of phosphorus or associated with one or two phosphorus atoms of hell to be part of the divalent radical L, can contain one or more substituents such as an alkyl group with 1 to 4 carbon atoms.

10. The method according to PP.1 to 9, characterized in that the preferred water-soluble phosphines are phosphines of the formula I or formula II, in which the Deputy or deputies Ar1 and Ar2, identical or different, denote a group, such as alkyl or CNS radical with 1 to 2 carbon atoms, a chlorine atom, a hydrophilic group, such as COOM, -SO3M, -PO3M, where M means a mineral or organic cationic residue selected from a proton, a cation derived from sodium, potassium, calcium or barium, ammonium cations, Tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, cations derived from zinc, lead or tin, -N(R)3where R are identical or different, denote a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms, OH, Deputy or deputies Ar3, identical or different, denote a group, such as alkyl or CNS radical with 1 to 2 carbon atoms, a chlorine atom, a hydrophilic group, such as COOM, -PO3M, where M means a mineral or organic cationic residue selected from a proton, a cation derived from sodium, potassium, calcium or barium, ossadnik zinc, lead or tin, -N(R)3where R are identical or different, denote a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms, OH, in General, at least two of these substituents Ar1, Ar2, Ar3, D1, D2 and D3 for the phosphines of formula I and Ar1, Ar2, D1 and D2 for the phosphines of the formula II are hydrophilic group described above.

11. The method according to PP.1 to 10, characterized in that the water-soluble monodentate phosphine of General formula I are selected from Tris(hydroxymethyl)phosphine, Tris(2-hydroxyethyl)phosphine, Tris(3-hydroxypropyl)phosphine, Tris(2-carboxymethyl)phosphine, sodium salt of Tris(3-carboxyphenyl)phosphine, Tris(3-carboxyethyl)phosphine, iodide, Tris(4-trimethylammoniumphenyl)phosphine, sodium salt of Tris(2-fostaty)phosphine, bis(2-carboxyethyl)phenylphosphine, hydroxymethylene(2-hydroxyethyl)phosphine, sodium salt of Tris(prepostional)phosphine, sodium salt of bis(metasulfite)procarboxypeptidase, sodium salt of bis(metasulfite)-2-sulfotyrosine and bidentate phosphine of General formula II are selected from sodium salt of 2,2'-bis[di(sulfonatophenyl)phosphino]-1,1'-binaphthyl, sodium salt of 1,2-bis[di(sulfonatophenyl)phosphonomethyl]CYCLOBUTANE (CBDTS), 1,2-bis(dihydroxymethyl-phosphino)-ethane, 1,3-bis(dihydroxyethylene)prochowice fact, the transition metal compound selected from compounds of Nickel, cobalt, iron, palladium, platinum, rhodium and iridium, which are soluble in water or capable of passing into solution under the reaction conditions.

13. The method according to PP.1 - 12, characterized in that the compound of the transition metal is chosen from compounds of Nickel, such as carboxylates, in particular the acetate, formate, citrate, Nickel, Nickel carbonate, bicarbonate Nickel, Nickel borate, Nickel bromide, Nickel chloride, Nickel iodide, Nickel thiocyanate, cyanide Nickel hydroxide Nickel, hydrophosphite Nickel, postit Nickel, Nickel phosphate and its derivatives, Nickel nitrate, Nickel sulfate, Nickel sulfite, aryl - and alkyl sulphonates Nickel.

14. The method according to PP.1 - 13, characterized in that the initial concentration of phosphine sulfonic cathode compartment is 10-3- 1 mol/l, and the initial concentration of the transition metal compounds, in particular compounds of Nickel, 10-5- 1 mol/L.

15. The method according to PP.1 to 14, characterized in that the cathode compartment are other compounds that enhance the conductivity of the electrolyte, such as soluble salts, complexing agents capable of changing a potential at which p. 15, characterized in that the Lewis acid is selected from zinc chloride, zinc bromide, zinc iodide, triftoratsetata zinc, zinc acetate, zinc nitrate, tetrafluoroborate zinc, manganese chloride, manganese bromide, Nickel chloride, Nickel bromide, cyanide, Nickel, Nickel acetylacetonate, cadmium chloride, bromide, cadmium, chloride, divalent tin bromide divalent tin, ferrous sulfate tin tartrate divalent tin, chlorides, bromides, sulfates, nitrates, carboxylates or triftormetilfullerenov rare earth elements such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, cobalt chloride, iron chloride, yttrium chloride.

17. The method according to PP.15 - 16, characterized in that the Lewis acid is selected from zinc chloride, zinc bromide, zinc sulfate, tetrafluoroborate zinc chloride divalent tin bromide divalent tin, mixtures of zinc chloride and ferrous chloride tin, Nickel chloride, Nickel bromide, Nickel acetylacetonate.

18. The method according to one of paragraphs.1 to 17, characterized in that the Lewis acid is contained in an amount of 0 to 50 moles per mole of the compound transition is C PP.1 - 18, characterized in that the anode compartment is filled with a water solution of anolyte consisting of acids, such as, in particular, sulfuric acid, nitric acid, water-soluble carboxylic acids, such as acetic acid, from their respective salts, such as salts of sodium, potassium, ammonium or Quaternary ammonium, or bases such as sodium hydroxide or potassium hydroxide, preferably sulfuric acid and its salts.

20. The method according to one of paragraphs.1 to 18, characterized in that the anode compartment is filled with a water solution of anolyte consisting of one or more monodentate or bidentate water-soluble phosphine.

21. The method according to PP.1 to 20, characterized in that the initial concentration of the anolyte solution in the anode compartment is 10-3- 3 mol/L.

22. The method according to PP.1 to 21, characterized in that in the cathode compartment is filled with an aqueous solution of the used catalyst based on monodentate or bidentate water-soluble phosphine and a transition metal, in particular Nickel, transformed at least partially into the cyanide, and this used catalyst optionally contains one or more Lewis acids, and the specified rest or adiponitrile, methylglutaronitrile, ethylsuccinate, methylbutyronitrile.

 

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The invention relates to a method of preparing phosphoroclastic catalysts for processes of oligomerization of low molecular weight olefins and alkylation of benzene by propylene and can be used in refining and petrochemical industries

The invention relates to chemistry, in particular to a method for photochemical catalyst and its use for hydrogen in the course of photochemical reactions

The invention relates to catalytic chemistry, namely a process for the production of catalytically active layers, and receive carriers of catalysts that can be used for deep oxidation of organic compounds and carbon monoxide in the exhaust gas chemistry, petrochemistry and internal combustion engines

The invention relates to methods of activation unprocessed catalysts used in the synthesis of intermediates of medicines and vitamins
The invention relates to the field of catalytic chemistry, and in particular to methods of manufacturing catalytic converters to neutralize the harmful gas emissions and industrial exhaust gases when the engine is

The invention relates to the production of graphite materials in the process of decomposition of methane and intended primarily for the preparation of ferromagnetic ink, graphite pigments to copy, synthetic carbon rubber and plastics
The invention relates to a catalytic composition comprising at least one compound of Nickel in the form of a mixture or in the form of a complex with at least one tertiary phosphine dissolved at least partially in non-aqueous ionic nature, resulting from the contacting of at least one aluminum halide (C) at least one Quaternary ammonium (A) at least one hydrocarbon (S) and with organic derivative of aluminum (D), characterized in that the hydrocarbon (C) is an aromatic hydrocarbon, and as an organic derivative of aluminum (D) use of the compound of General formula AlRxX3-xwhere R denotes a linear or branched alkyl radical with 2-8 carbon atoms; X denotes chlorine or bromine; x = 1,2 or 3

The invention relates to catalysts on the substrate, deposited on inorganic carriers, the following formula (I) ethylene, which is used in the basic reactions, including polymerization, copolymerization and polycondensation in the petrochemical industry and in fine organic synthesis, and their preparation

MA Pc/S

In addition, the invention relates to a new method of producing ethylene by means of direct conversion of methane or purified natural gas in the presence of the above catalyst and nitrogen at a temperature of from about 670 to 810oC, preferably in the range from 710 to 810oC, which is significantly below the reaction temperature normal synthesis of hydrocarbon(s) by dehydrogenation

The invention relates to additive catalysts hydrogenation, specifically to the additive catalysts hydrogenation of chloroethanol General formula

R CH=CRR"

where

R is H or Cl;

R' - CH3or CH2Cl;

R" is H, Cl, CH3or CH2Cl

The invention relates to a new catalyst for the conversion of methane to ethylene, its preparation and method of producing ethylene using said catalyst

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides a method for preparing improved oxirane hydroformylation catalyst, improved oxirane hydroformylation catalyst, and single-stage process for production of 1,3-diol in presence of such catalyst. Preparation of catalyst comprises preparing complex A by contacting ruthenium(0) compound with di-tertiary phosphine ligand and preparing complex B via redox reaction of complex A with cobalt(0) carbonyl compound. Single-stage 1,3-diol production process involves reaction of oxirane with synthesis gas under hydroformylation conditions in inert solvent in presence of aforesaid catalyst, where recovery of product is preferably accomplished through separation of product-rich phase.

EFFECT: reduced number of stages to a single one or increased yield of 1,3-diol without by-products and preserved catalytic activity after catalyst regeneration operation.

10 cl, 3 dwg, 6 tbl, 21 ex

FIELD: processes catalyzed by metal-phosphoro-organic ligand complexes when target product may be selectively extracted and separated from liquid product.

SUBSTANCE: Specification gives description of methods of separation of one or several products of decomposition of phosphoro-organic ligand, one or several reaction byproducts and one or several products from liquid reaction product synthesized continuously and containing one or several non-consumed reagents, catalyst in form of complex of metal-phosphoro-organic ligands, not obligatory free phosphoro-organic ligand, one or several said decomposition products of phosphoro-organic ligand, one or several said reaction byproducts, one or several said products, one or several non-polar solvents and one or several polar solvents by separation of phases where (i) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several products expressed by ratio of distribution coefficient Ef1 whose magnitudes exceeds about 2.5; (ii)is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several decomposition products expressed by ratio of distribution coefficients Ef2 whose magnitude exceeds proximately 2.5; and (iii) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several reaction byproducts expressed by ratio of distribution coefficients Ef3 whose magnitude exceeds approximately 2.5 (versions). Description is also given of continuous methods of obtaining one or several products (versions) and reaction mixture containing one or several aldehyde products.

EFFECT: increased conversion of initial materials and selectivity by product; avoidance or exclusion of deactivation of catalyst.

20 cl, 2 tbl

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