The method of electrochemical preparation of catalysts

 

(57) Abstract:

The present invention relates to a process for the preparation of catalysts based on transition metal and phosphine, in particular, to obtain compounds comprising at least one transition metal with oxidation state 0 or 1 associated with at least one sulfonated phosphine. The method consists in the electrolysis of an aqueous solution containing at least one compound of a transition metal selected from Nickel, cobalt, iron, palladium, platinum, rhodium and iridium, and one sulfonated phosphine, placed in the cathode compartment of the cell of the electrolyzer. The compounds obtained can be used as a catalyst in the reaction of hydrocyanide Ethylenediamine compounds. 20 C.p. f-crystals, 5 PL.

The present invention relates to an electrochemical method of producing compounds which can be used as catalysts based on compounds comprising a transition metal and a phosphine.

Connections that are offered by the method according to the invention contain at least one transition metal with oxidation state 0 or 1 associated with at least aimer, as catalysts in the reaction of hydrocyanide ethyleneimine compounds, which are described in the patent FR-A-2338253. In this text they will be referred to as catalysts, but this does not limit the scope of their application.

Electrochemical method of producing catalysts containing at least one transition metal with oxidation state 0 or 1 associated with at least one sulfonated phosphine, is that treated by electrolysis of an aqueous solution containing at least one compound of a transition metal and one sulfonated phosphine and placed in the cathode compartment of an electrolytic cell of the electrolyzer.

Sulfonated phosphine used in the method according to the invention correspond to General formula (I):

< / BR>
in which

Ar1, Ar2and Ar3identical or different, represent aryl groups;

Y1, Y2and Y3identical or different, represent

alkyl radical having 1-4 carbon atoms,

CNS radical having 1-4 carbon atoms,

halogen atom,

the radical CN,

radical NO2,

the OH radical,

radical NR1R2in which Rcationic residue, mineral or organic, is selected so that the compound of formula (I) are soluble in water, which is:

H+,

cations derived alkaline or alkaline earth metal,

N(R3R4R5R6)+where R3, R4, R5and R6identical or different, represent an alkyl radical having 1-4 carbon atoms, or a hydrogen atom,

other cations derived from metals that form salts benzosulfimide, soluble in water,

m1, m2 and m3 are integers, the same or different, from 0 to 5;

n1, n2 and n3 are integers, the same or different, 0 to 3;

one of them is at least equal to or greater than 1.

As metals that form salts benzosulfimide, soluble in water include lead, zinc and tin.

Under the expression "water-soluble" is meant herein a compound that is soluble at least at a concentration of 0.01 g per liter of water.

Among phosphines of the formula (I) prefer such that:

- Ar1, Ar2and Ar3are phenyl groups;

- Y1, Y2and Y3performance is having 1-2 carbon atoms;

- M is a cation selected among the group including:

H+,

cations derived Na, K, Ca, Ba,

NH4+,

cation of Tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium;

- m1, m2 and m3 are integers from 0 to 3;

n1, n2 and n3 are integers from 0 to 3, with one of them at least more than 1.

Among phosphines are particularly preferred salts are sodium, potassium, calcium, barium, ammonium, Tetramethylammonium and tetraethylammonium mono(sulfophenyl)-diphenyl-phosphine, di(sulfophenyl)-phenyl-phosphine and three(sulfophenyl)-phosphine, in formulas which group SO3preferably located in the meta-position.

You can name other examples of the phosphines of formula (I), salts of alkaline and alkaline earth metals, salts of ammonia, salts of Quaternary ammonium, (3-sulfo-4-were)-di(4-were)-phosphine; (3 sulfo-4-methoxyphenyl)-di(4-methoxyphenyl)-phosphine; (3 sulfo-4-chlorophenyl)-di(4-chlorophenyl)-phosphine; di(3-sulfophenyl)-phenylphosphine; di(4-sulfophenyl)-phenylphosphine; di(3-sulfo-4-were) (4-were)phosphine; di(3-sulfo-4-methoxyphenyl) (4-methoxyphenyl)-phosphine; di-(3-sulfo-4-chlorophenyl) (4-chlorophenyl)phosphine; three(3 sulfophenyl)FOSFA the o-4-chlorophenyl)-phosphine; (2 sulfo-4-were) (3 sulfo-4-were) (3,5-disulfo-4-were)-phosphine; (3-sulfophenyl) (3 sulfo-4-chlorophenyl) (3,5-disulfo-4-chlorophenyl)-phosphine.

You can, of course, to use a mixture of these phosphines. In particular, you can apply a mixture of mono-, di - and tri-methanesulfonic phosphines.

Preferably, in compounds of transition metals are used compounds of Nickel, cobalt, iron, palladium, platinum, rhodium and iridium. Apply compounds soluble in water or capable of go in solution under the reaction conditions. In this case, the balance connected with metal, not significant.

Among these compounds the most preferred are compounds of Nickel. Can be called as non-limiting examples of such compounds as Nickel salt of carboxylic acid (in particular, acetate, formate, citrate, carbonate, Nickel bicarbonate of Nickel, Nickel borate, Nickel bromide, Nickel chloride, Nickel iodide, Nickel thiocyanate, cyanide, Nickel, Nickel hydroxide, Nickel phosphate, postit Nickel, phosphate, Nickel and their derivatives, Nickel nitrate, Nickel sulfate, Nickel sulfite, aryl - and alkyl-sulfonates Nickel.

There is no need to self connection is carried out in an aqueous solution of sulfonated phosphine.

Electrolytic cell electrolytic cell used in the present method, includes a cathode compartment and an anode compartment separated by a separator.

The cathode of the electrolysis cell may be of a material such as platinum, gold, iridium, ruthenium, palladium, Nickel, graphite, stilografica, iron, stainless steel, special steel, lead, mercury, amalgam. It may also be composed of titanium, tantalum, Nickel, stainless steel, covered with a layer of platinum, gold, iridium, ruthenium, a mix of several of these metals, oxides of platinum, palladium, iridium, rhodium, ruthenium, osmium, tantalum, or a mixture of several of these oxides.

The cathode may have a flat structure, such as a plate, grid, or three-dimensional structure; it may, in particular, to be perforated, or expanded. As an example, the volumetric structure, you can use granulated packaging of the above material, felt or sponge forms of these materials.

The anode may be of a material such as platinum, gold, iridium, ruthenium, palladium, Nickel, graphite, stilografica, stainless steel, special steel, lead. It may also consist of titanium or tantalum coated with a layer of pay is or mixtures of these oxides.

The design of the anode may be of different types, such as has not been specified for the cathode.

The separator cell for electrolysis consists of a membrane of an ion exchanger or a porous diaphragm.

And outreach to consumers can be cationic type, in particular made from cation exchange resins having acidic groups such as sulfonic or carboxyl group. It is preferable to use a membrane prepared from sulfonol. As the membranes of this type can be called, for example, membranes, which are sold under the trademarks Nafion(perfluorinated sulfonic membrane) or Selemion.

These membranes can also be anionic type, but generally, the preferred cationic membrane, i.e., they have a number of advantages. In particular, they are more sturdy than the anionic membrane, and allow you to work with higher amperage.

Porous diaphragm can be, in particular, porous ceramic diaphragms, diaphragms made of woven synthetic fibers or non-woven synthetic fibers, applied diaphragms based on asbestos fibers or synthetic fibers.

The separator can be located on the anode or the cathode.

inania transition metal. The initial concentration of sulfonated phosphine is usually between 10-3mol/l and 1 mol/liter. The initial concentration of the transition metal compounds, in particular compounds of Nickel is usually between 10-5mol/l and 1 mol/liter.

In the cathode compartment can add other compounds that help increase the conductivity of the electrolyte, such as soluble salts.

You can also add complexing agents capable of changing the capacity in which you are restoring the transition metal. As examples of such agents can be called cyanide.

In addition, the solution in the cathode compartment may contain links whose role is to complement the catalyst prepared by the method of the invention. These compounds are, in particular Lewis acids.

Under Lewis acid refers in the present invention compounds - acceptors electronic doublets.

It is possible, in particular, to apply such a Lewis acid listed in the work of G. A. OLAH "Friedel-Crafts and related Reactions", vol. 1, pp. 181-197 (1963).

A Lewis acid introduced into the cathode compartment, vybirayutsya, so these compounds were at least partially soluble and stable in water or in a more General form, in aqueous solution, intended to be processed by electrolysis. These compounds are the most commonly salts, in particular halides, preferably chlorides and bromides, sulfates, nitrates, sulfonates, in particular, triftoratsetata, carboxylates, acetylacetonates, tetrafluoroborate and phosphates.

As non-limiting examples of Lewis acids can be called zinc chloride, zinc bromide, zinc iodide, triftorbyenzola zinc, zinc acetate, zinc nitrate, tetrafluoroborate zinc, manganese chloride, manganese bromide, magnesium chloride, Nickel chloride, Nickel bromide, cyanide, Nickel, Nickel acetylacetonate, cadmium chloride, bromide, cadmium, tin bromide, tin chloride, tin sulfate, tin tartrate, chlorides, bromides, sulfates, nitrates, carboxylates or triptorelin-sulfonates of rare earth elements such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, the terbium, dysprosium, Helmi, erbium, thulium, ytterbium and lutetium, cobalt chloride, iron chloride, yttrium chloride.

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

Among the Lewis acid is a, the tin bromide, a mixture of chloride of zinc/tin dichloride, Nickel chloride, Nickel bromide, Nickel acetylacetonate.

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

The anode compartment contains an aqueous solution of the analyte, which may, in particular, to consist of such acids as sulfuric acid, nitric acid, water-soluble carboxylic acids such as acetic acid, their salts, in particular salts of sodium, potassium, ammonium or Quaternary ammonium, or such reasons as, in particular, potassium hydroxide or sodium. Preferably, the anolyte choose sulfuric acid and its salts, in particular, ducally sulfate, acid sulfate, potassium, danariely sulfate, acidic sodium sulphate.

The anolyte may also consist of one or more sulfonic phosphines defined above.

The initial concentration of analyte in the solution of the anode compartment, as a rule, 10-2mol/l to 3 mol/liter.

Electric current according to the invention is determined by its intensity and potential on the cathode. The potential can be maintained p is tensively current (inconsistency). In continuous operation, these two options are equivalent.

If you are at a constant potential, its value is easily determined by the expert by tracing the curves of intensity/potential.

The current density can reach 30 A/DM2. It is regulated depending on the amount of recoverable transition metal.

The temperature at which work is usually between 0oC 95oC.

An interesting variant of the method of the invention is to regenerate the used catalyst, i.e. the catalyst, being in work and become at least partially deactivated. Thus, the catalyst based on sulfonated 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, gradually deactivated, in particular by oxidation of the transition metal. The transition metal, in particular Nickel, becomes at least partially in the cyanide. At the end of the reaction hydrocyanide aqueous phase containing, in particular, sulfonated phosphine, and the compound of the transition metal is tion of the parent compounds, such as butadiene and/or pentenenitrile or compounds formed during the reaction, such as adiponitrile, methyl-glutaronitrile, ethylsuccinate, penten-NITRILES, methylbutan-NITRILES. Then the aqueous phase is treated by electrochemical, as described above, and obtain a regenerated catalyst.

The following examples illustrate the invention.

Examples

Used equipment

The electrolysis cell consists of a cylindrical glass vessel having a useful volume of about 100 ml, which is the cathode in the form of a platinum mesh anode cylindrical compartment placed inside the cathode grid and having at the base membrane of the resin type Nafion 417and immersed anode in the form of a platinum plate.

The electrolyzer is connected to the voltage regulator, which allows you to maintain the cathode potential at the level of 1.2 V relative to the reference electrode Ag/AgCl.

Abbreviations

TFTS - sodium salt risulteranno triphenylphosphine

PN = 3-pentenenitrile

ADN = adiponitrile

2 M3 = 2-methyl-3-butenonitrile

BD = butadiene

TT - degree of conversion

RT - selectivity for poloczek NITRILES or dinitriles in mmol introduced Ni(O)

DPC = cyclo-octadiene

Examples 1-5

The synthesis of the catalyst Ni(0)TFTS by electrochemical reduction of Ni(CN)2in aqueous solution TFTS

In the cathode compartment is filled with 50 ml of an aqueous solution of cyanide of Nickel [Ni(CN)2: 10.6 g/kg] and TFTS (300 g/kg of water).

In the anode compartment injected 20 ml of anolyte (its composition is specified in the following table.1). The electrolysis is carried out at 25oC at a controlled potential of 1,2 Century Regular sampling, in order to make a quantitative analysis of the remaining Ni(II) by polarographic.

Experiments (a, b, c and d) hidrotsianova 3-penten-nitrile in the catalytic solutions 1, 2, 4, and 5, obtained by electrochemical (see tab. 2).

Working conditions hydrocyanide:

PN: 320 mmol; ZnCl2: 20 mmol; 65oC; 3 hours

CE1*= comparative experience with a catalyst prepared by ligand exchange data center in Ni(DPC)2on TFTS;

CE2**= comparative experience with a solution of Ni(CN)2(TFTS)2not handled by the electroreduction.

Experience (e) hidrotsianova butadiene in the catalytic solution 1 obtained by electrochemical (see tab. 3).

Working conditions hydrazinophenyl by ligand exchange data center in Ni(DPC)2on TFTS.

CE4**= comparative tests with a solution of Ni(CN)2- (TFTS)2not processed by the electroreduction.

Example 6

The synthesis of the catalyst Ni(0) TFTS by restoring NiCl2in aqueous solution TFTS

In the cathode compartment is injected 50 ml of an aqueous solution of Nickel chloride (NiCl2: to 17.4 g/kg), TPPTS (300 g/kg of water) and sodium cyanide (NaCN: 6.6 g/kg).

In the anode compartment injected 20 ml of aqueous saturated solution of K2SO4. The electrolysis is carried out at 25oC with controlled potential 1,2 Century, the sampling is carried out regularly for the quantitative analysis of residual Ni(II) by polarographic (see tab. 4).

Experience (f) hydrocyanide PN solution 6 catalyst, regenerated electrochemically (see tab. 5).

Example 7

Regenerative aqueous solution of Ni/TFTS coming after hydrocyanide 3-pentenenitrile

a) In a glass reactor with a volume of 150 ml, stir turbine, enter:

- 38 ml of an aqueous solution containing 5 mmol of Nickel (0), 20 mmol TFTS and 20 mmol of zinc chloride.

- 32,4 ml PN (320 mmol).

The contents are heated at 65oC and injected pure hydrocyanic kicanaria both the phases are separated. The organic phase is analyzed quantitatively by chromatography in gas phase (HGF):

3-Pentenenitrile - 177 mmol

Ethylsuccinate - 13 mmol

Methylglutaronitrile - 35 mmol

Adiponitrile - 92 mmol

i.e., 28 mmol - educated dinitriles in mmol of Nickel.

b) the Aqueous phase is completely inactive, electrolityc at a potential of 1.2 V relative to the reference electrode Ag/Ag/Cl within 3 hours

C) In the reactor is placed again:

- 29 ml aqueous solution thus regenerated catalyst

- 10 mmol ZnCl2,

- 32,4 ml PN (320 mmol).

The contents are heated at 65oC and enter hydrocyanic acid with a flow rate of 34 mmol/h for 6 h After cooling and degassing do quantitative analysis by HGF various NITRILES:

3-Pentenenitrile - 183 mmol

Ethylsuccinate - 14 mmol

Methylglutaronitrile - 39 mmol

Adiponitrile - 78 mmol

i.e., 32 mmol educated dinitriles in mmol of Nickel.

These results show that the catalyst is fully regenerated.

1. The method of electrochemical preparation of catalysts containing at least one transition metal with oxidation state 0 and roles aqueous solution, containing at least one transition metal compound selected from compounds of Nickel, cobalt, iron, palladium, platinum, rhodium and iridium, soluble in water or capable of passing into solution under the reaction conditions, and sulfonated phosphine, placed in the cathode compartment of the electrolysis cell of the electrolyzer, and sulfonated phosphine satisfies the General formula I

< / BR>
where Ar1, Ar2and Ar3identical or different, denote aryl group;

Y1, Y2and Y3identical or different, mean: an alkyl radical containing 1-4 carbon atoms, alkoxyalkyl containing 1-4 carbon atoms, a halogen atom, a CN radical, the radical NO2, radical, radical NR1R2and R1, R2identical or different, denote an alkyl radical containing 1-4 carbon atoms;

M - means a mineral or organic cationic residue, with which the compound of the formula I are soluble in water, selected from the group comprising H+the cations derived alkaline or alkaline-earth metals, N(R3R4R5R6)+where R3, R4, R5and R6identical or different, denote an alkyl radical containing 1-4 at which the water-soluble;

m1, m2and m3mean integers, the same or different, from 0 to 5;

n1n2and n3mean integers, the same or different, 0 to 3, with one of them at least equal to or greater than 1.

2. The method according to p. 1, characterized in that the electrolytic cell electrolytic cell includes a cathode compartment and an anode compartment separated by a separator, representing an ion-exchange membrane or a porous diaphragm.

3. The method according to one of the p. 1 or 2, characterized in that the cathode of the electrolysis cell is made of such material as platinum, gold, iridium, ruthenium, palladium, Nickel, graphite, stilografica, iron, stainless steel, special steel, lead, mercury, amalgam, or may consist of titanium, tantalum, Nickel or stainless steel coated with a layer of 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.

4. The method according to one of paragraphs.1 to 3, characterized in that the cathode and anode of the electrolysis cell has a flat structure, such as a plate, grid, or three-dimensional structure and can be perforated or expanded.

6. The method according to one of paragraphs.1 to 5, characterized in that the anode is such materials as platinum, gold, iridium, ruthenium, palladium, Nickel, graphite, stilografica, stainless steel, special steel, lead, or may consist of titanium or tantalum coated with a layer of 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 one of paragraphs.1 - 6, characterized in that the separator is selected from a cationic membranes of the type prepared from cation exchange resins having an acid group such as sulfonic group or carboxyl group and preferably from membranes derived from sulfonic resins.

8. The method according to one of paragraphs.1 - 6, characterized in that the separator is selected from a diaphragm made of porous ceramics, diaphragms made of woven or non-woven synthetic fibers, deposited diaphragms based on asbestos fibers or synthetic fibers.

9. The method according to one of paragraphs.1 to 8, characterized in that the use of sulfonated phosphine of General formula I, in which Arthe C alkyl radicals, having 1-2 carbon atoms, CNS radical having 1-2 carbon atoms, M represents a cation selected from the group comprising H+the cations derived Na, K, Ca, Ba, NH4+the cations of Tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, m1, m2and m3are integers from 0 to 3, n1n2and n3are integers from 0 to 3, with at least one more 1.

10. The method according to one of paragraphs.1 to 9, characterized in that the sulfonated phosphine selected from salts of sodium, potassium, calcium, barium, ammonium, Tetramethylammonium, tetraethylammonium, mono (sulfenyl)-diphenylphosphine, di(sulfophenyl)phenyl-phosphine and three(sulfophenyl)-phosphine in the formula which group SO3are preferably in meta-position.

11. The method according to one of paragraphs.1 to 10, characterized in that the compound of the transition metal is selected from such compounds Nickel 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, phosphite Nickel, Nickel phosphate and its derivatives, n is from PP.1 - 11, wherein the cathode compartment of the initial concentration of sulfonated phosphine is between 10-3mol/l and 1 mol/liter, and the initial concentration of the transition metal compounds, in particular compounds of Nickel is between 10-5mol/l and 1 mol/liter.

13. The method according to one of paragraphs.1 - 12, characterized in that the cathode compartment contains other compounds that help increase the conductivity of the electrolyte, such as soluble salts, complexing agents capable of changing the capacity in which you are restoring the transition metal, such as cyanide and acid Lewis.

14. The method according to p. 15, characterized in that the Lewis acid is chosen from compounds of elements of groups Ib, IIb, IIIa, IIIb, IVa, IVb, Va, Vb, VIb, VIIb and VIII of the Periodic system so that the above-mentioned compounds at least partially soluble and stable in water or aqueous solution, processed by electrolysis, preferably, of the salts, in particular halides, preferably chlorides and bromides, sulfates, nitrates, sulfonates, in particular triftormetilfullerenov, carboxylates, acetylacetonates, tetrafluoroborates and phosphates.

16. The method according to one of paragraphs.13 to 15, characterized in that the Lewis acid is selected from zinc chloride, zinc bromide, zinc sulfate, tetrafluoroborate zinc, tin chloride, tin bromide, mixtures of zinc chloride/tin dichloride, Nickel chloride, Nickel bromide, Nickel acetylacetonate.

17. The method according to one of paragraphs.13 to 16, characterized in that the Lewis acid is used in amounts of 0 to 50 mol per mole of transition metal compounds, in particular compounds of Nickel, preferably 0 to 10 mol per mole.

18. The method according to one of paragraphs.1 to 17, characterized in that the anode compartment contains an aqueous solution is from, such as acetic acid, the corresponding salts, such as sodium, potassium, ammonium, Quaternary ammonium, or bases, such as sodium hydroxide, potassium hydroxide, preferably, the anolyte selected from sulfuric acid and its salts.

19. The method according to one of paragraphs.1 to 17, characterized in that the anode compartment contains an aqueous solution of anolyte representing one or more sulfonated phosphines.

20. The method according to one of paragraphs.1 to 19, characterized in that the initial concentration of analyte in the solution of the anode compartment is equal to 10-2mol/l to 3 mol/liter.

21. The method according to one of paragraphs.1 to 20, characterized in that the cathodic branch of the injected aqueous solution used catalyst based on sulfonated phosphine and a transition metal, in particular Nickel, transformed at least partially into the cyanide, and the used catalyst contains, if necessary, one or more Lewis acids, and this solution may contain a relatively small number of compounds such as butadiene and/or penten-NITRILES, or as adiponitrile, methyl-glutaronitrile, ethylsuccinate, methylbutan-NITRILES.

 

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36 cl, 25 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to synthesis of aliphatic 1,3-diol, especially 1,3-propanediol from ethylene oxide and syngas in one step. More specifically, invention relates to catalytic composition, which ensures good yield under mild conditions in single-step 1,3-propanediol synthesis process and manifests advantages regarding expenses and efficiency. Catalytic composition comprises cobalt component including one or more non-alloyed cobalt compounds and ruthenium component including mainly ruthenium carbonyl compound alloyed with phospholanoalkane ligand. Single-step 1,3-propanediol synthesis process is carried out in presence of catalytic composition at 30 to 150°C and pressure at least 690 kPa over a period of time long enough to obtain two-phase reaction product mixture including upper phase containing major part of solvent, at least 50% of catalytic composition and unconverted ethylene oxide and lower phase containing major part of 1,3-propanediol.

EFFECT: enhanced process efficiency and reduced expenses.

10 cl, 4 tbl, 17 ex

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