Method of preparing hydrocyanation catalyst with nickel/phosphorus-containing ligand

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to a method of preparing hydrocyanation catalyst, which is complex of nickel with bidentate phosphorus-containing compound. Method comprises interaction of at least one bidentate phosphorus-containing ligand, selected from group including bidentate phosphites, bidentate phosphinites, and bidentate phosphines, with nickel chloride in presence of nitrile solvent and reducing metal. The latter is more electropositive than nickel and can be selected form group consisting of Na, Li, K, Mg, Ca, Ba, Sr, Ti, V, Fe, Co, Cu, Zn, Cd, Al, Ga, In, and Sn. Nickel chloride is present in molar excess over reducing metal. Catalyst is prepared preferably at temperature between 30 and 100°C and pressure between 34 and 340 kPa.

EFFECT: lowered reaction temperature and reduced formation of by-products.

16 cl, 22 ex

 

This invention relates to a method for producing a catalyst hydrocyanide, which is a complex of Nickel with bidentate phosphorus-containing compound.

In the prior art it is well known that complexes of Nickel with phosphorus-containing ligands are useful as catalysts in the reactions of hydrocyanide. It is known that such complexes of Nickel using monodentate phosphites, catalyze hidrotsianova butadiene from a mixture of pentenenitrile. The catalysts are also useful in the subsequent hidrotsianova of pentenenitrile to get adiponitrile, an important intermediate compound in the production of nylon. In addition, it is known that to obtain catalysts based on Nickel for the implementation of such reactions hydrocyanide you can use bidentate vospitanie and phosphinite ligands.

U.S. patent 3903120 describes a method of obtaining complexes of Nickel zero valence as the reaction of elemental Nickel with monodentate phosphorus-containing ligand of the formula PZ3where Z is an alkyl or CNS group, preferably aryloxyalkyl group. In the method using fine elemental Nickel, and preferably conducted in the presence of a nitrile solvent. Describes what the reaction is, s is carried out in the presence of excess ligand.

U.S. patent 3846461 describes a method of obtaining complexes of Nickel zero valence with trehzameshchenny organic phosphites as the reaction of compounds trehzameshchenny organic phosphites with Nickel chloride in the presence of finely dispersed a reducing metal which is more electrophoretically than Nickel, and in the presence of an activator selected from the group consisting of NH3, NH4X, Zn(NH3)2X2and mixtures of NH4X and ZnX2where X represents a halogen. Reducing metals include Na, Li, Mg, Ca, Ba, Sr, Ti, V, Fe, Co, Cu, Zn, Cd, Al, Ga, In, Sn, Pb and Th, and Zn is preferred.

U.S. patent 5523453 describes a method of obtaining a Nickel catalysts hydrocyanide containing bidentate phosphorus-containing ligands. Compounds of Nickel zero valence containing ligands, which may be substituted bidentate phosphorus-containing ligands, are the preferred source of Nickel. Two such compounds are Ni(COD)2where COD is a 1, 5cyclooctadiene, and (oTTP)2Ni(C2H4), where oTTP is a P(O-ortho-C6H4CH3)3. Alternative to get a suitable source of Nickel, can be mixed compounds of divalent Nickel with reducing agents. In the latter method of obtaining katal is congestion with increasing temperature for preparation of the catalyst increases the rate of formation of the catalyst, but also increases the amount of decomposition products. Accordingly, there is a need in a way that gives a high response speed and a slight decomposition.

The present invention relates to a method for producing a catalyst hydrocyanide through the interaction of a bidentate phosphorus-containing ligand with Nickel chloride in the presence of a nitrile solvent and a reducing metal which is more electrophoretically than Nickel, and the Nickel chloride is present in a molar excess relative to the reducing metal.

The catalysts of the present invention can be prepared by the interaction of Nickel chloride with bidentate phosphorus-containing ligand in the presence of a reducing metal, and chloride Nickel is present in a molar excess relative to the reducing metal. Regenerating the metal may be any metal which is more electrophoretically than Nickel. Such metals include Na, Li, K, Mg, Ca, Ba, Sr, Ti, V, Fe, Co, Cu, Zn, Cd, Al, Ga, In, Sn, Pb and Th. Most preferred are Fe and Zn. Regenerating metal (hereinafter ″METH″), preferably, is fine. The expression ″fine″ means that the metal is in the form of particles with a size less than 20 mesh.

Suddenly it was obnarujeno, the reaction rate is essentially not dependent on the concentration of phosphorus-containing ligand or quantity of the reducing metal, but rather depends on the amount present NiCl2and the reaction temperature. Accordingly, the increase in the number of NiCl2increases the reaction rate. Since undesirable side reactions, especially decomposition, increases with temperature, the use of an excess of Nickel chloride to increase the rate of formation of the catalyst can reduce the reaction temperature, which will reduce unwanted side reactions. The reaction is usually carried out in such a way that regenerating the metal is the limiting reagent. In other words, the number of NiCl2, converterhome in the catalyst control number added to the reducing metal.

The source of Nickel for the present invention preferably is chloride Nickel (II), NiCl2. You can use hydrated or anhydrous form NiCl2. Anhydrous NiCl2it is preferable to minimize the hydrolytic decomposition of the ligand. The expression ″anhydrous″ means that the Nickel chloride contains less than 2% wt. water. Preferred is Nickel chloride containing 1% of water or less. Anhydrous Nickel chloride can be obtained by heating the hydrate is rowanne form NiCl 2to a temperature of from about 200°240°C. Heating NiCl2above about 240°gives NiCl2that is less reactive in the preparation of the catalyst and is not preferred. In addition, the heat NiCl2over an extended period of time will also result in a product with lower reactivity. Accordingly, NiCl2must not be heated above about 200°C for more than 12 hours.

The expression ″hydrated NiCl2″ means NiCl2containing 2% wt. water or more. Examples of hydrated NiCl2include dehydrate, and uranyl aqueous solutions NiCl2. The preferred sources of anhydrous NiCl2are hexahydrate product and an aqueous solution. NiCl2in aqueous solution is particularly preferred. An aqueous solution commercially available in the form of an aqueous solution of NiCl2with a concentration of about 29% wt. However, it is believed that the invention is not limited to these mass percent and will be included aqueous solutions with other mass percent NiCl2. In practice, the preferred aqueous solution contains from 20 to 31% by weight. NiCl2. The lower limit due to the cost effectiveness of degidrirovaniya dilute solution. The upper limit of the agreed solubility NiCl 2at room temperature, in particular, deposition of NiCl2(H2O)6.

The preferred method of drying a hydrated NiCl2consists of drying NiCl2first, spray drying or flash drying, and then further drying the resulting product by thermal drying. The specialist in this area known several types of spray or thermal drying. It is known that pneumatic belt dryers and flash dryers are interchangeable terminology in the field of drying. The choice of which type to use is not critical. Examples of spray dryers dryers are equipped with once-through flow, countercurrent flow and mixed flow. In this preferred method, the spray drying process must have an outlet temperature of 120 to 150°C, preferably from 130 to 135°C. the Average time of exposure to heat in the spray dryer should be from 1 to 75 seconds, preferably from 1 to 45 seconds. The resulting product typically is digitally product, which contains about 22% by weight. water.

After spray drying or flash-drying the product, preferably, optionally dried by thermal drying. Select the type of drying is not critical. Thermal drying can be a drying direct the sludge is indirect heating, where heat is mainly fail due to heat conduction or convection. Thermal drying can be performed under reduced pressure or in a stream of dry inert gas. For economic reasons a dry inert gas, preferably represents nitrogen. Thermal drying should be carried out at a temperature of from about 200 to 240°C. the drying Time should not exceed about 12 hours.

The receipt of the catalyst is carried out in the presence of a nitrile solvent, preferably 3-pentenenitrile or 2-methyl-butenonitrile. The concentration of the ligand can be in the range of from about 1% to 90% wt. In practice the preferred concentration range of the ligand is from 5% to 50%. The amount of the reducing metal (METH) is determined by the desired concentration of the Nickel catalytic product. The preferred amount of the reducing metal (METH) will typically be in the range from 0.1% to 5% of the reaction mass. The number of NiCl2will be in molar excess relative to the regenerating metal. The molar ratio of NiCl2to METAL is in the range from 1.1:1 to 100:1. The preferred ratio NiCl2to METAL is in the range from 2:1 to 50:1. The reaction temperature may be in the range of 0°to 120°C. the Preferred temperature range depends on the shape NiCl 2. Hydrated forms NiCl2quickly react at lower temperatures compared to anhydrous NiCl2. For NiCl2·2H2O the preferred temperature range is from 0°C to 60°and the most preferred range is from 25°C to 50°C. anhydrous NiCl2the preferred temperature range is from 30°to 100°and the most preferred range is from 50°to 90°C. the Reaction may proceed within a wide pressure range. In practice, the preferred pressure is in the range of from about 5 lb./square inch abs. up to 50 lb./square inch abs. (from 34 to 340 kPa). The reaction may proceed in batch or continuous mode.

Suitable ligands of the present invention are bidentate phosphorus-containing ligands selected from the group consisting of bidentate phosphites, bidentate phosphinites and bidentate phosphines. The most preferred ligands are bidentate fosfatnye ligands.

The preferred bidentate fosfatnye ligands have the following structural formulas:

(R1O)2P(OZO)P(OR1)2,

In these formulas, R1represents phenyl, unsubstituted or substituted by one or more 1-C12alkyl or C1-C12CNS groups; or naphthyl, unsubstituted or substituted by one or more1-C12alkyl or C1-C12CNS groups; and Z and Z1independently selected from the group consisting of compounds with the structural formula I, II, III and IV:

where:

R2and R9are the same and selected from H, C1-C12the alkyl and C1-C12alkoxy;

R3and R8are the same and selected from H, C1-C12the alkyl and C1-C12alkoxy;

R4and R7are the same and selected from H, C1-C12the alkyl and C1-C12alkoxy;

R5and R6are the same and selected from H, C1-C12the alkyl and C1-C12alkoxy;

where:

X represents O, S or CH(R18);

R10and R17are the same and selected from H, C1-C12the alkyl and C1-C12alkoxy;

R11and R16are the same and selected from H, C1-C12the alkyl and C1-C12alkoxy;

R12and R15are the same and selected from H, C1-C12the alkyl and C1-C12alkoxy;

R13and R14are the same and the gap from H, With1-C12the alkyl and C1-C12alkoxy and

R18represents H or C1-C12alkyl;

where:

R19and R20are the same and selected from H, C1-C12of alkyl, C1-C12alkoxy and CO2R21;

R21represents a C1-C12alkyl or C6-C10aryl, unsubstituted or substituted C1-C4alkyl groups. Aryl group, preferably represents phenyl or naphthyl.

where:

A represents O, S, CH(R24);

R22and R23are the same and selected from H and CO2R25;

R24represents H or C1-C12alkyl;

R25represents a C1-C12alkyl.

In the above structural formulas With1-C12alkyl and C1-C12CNS group can be linear or branched.

Examples of compounds dogsleding organic phosphites that can be obtained by the present method include compounds of formulas V-XXVI, which is shown below.

Suitable bidentate phosphites are described in U.S. patents 5512695, 5512696, 5663369 and 5723641, the description of which is included here as a reference. Suitable bidentate phosphinite described in U.S. patent 5523453 and 5693843, the description of which is included here as a reference.

The reaction can be performed so that the unreacted excess NiCl2can be separated from the reaction product by filtration or by centrifugation. Collected an excess of Nickel chloride and then can be reused in the reactor to obtain a catalyst.

EXAMPLES

The invention is illustrated in the following non-limiting examples. The following examples regenerating metal is the limiting reactant in each reaction, and therefore the degree of reaction (conversion) is expressed as the percent unreacted reducing metal. If not noted otherwise, the degree of reaction (conversion) is determined by analyzing the number of active Nickel obtained by the reaction of the synthesis catalyst. The analysis is performed, the processing does not contain solids Ali is the Voth reaction solution diethylazodicarboxylate (DMAD), which forms a stable complex with Nickel (ligand)Ni(DMID), and quantitatively analyzing the contents of this complex liquid chromatography high pressure (HPLC).

Examples 1-6 and 11-18 using anhydrous NiCl2obtained in example 20. Used in examples 7-10 NiCl2·2H2O obtained by heating uranyl chloride Nickel approximately 130°With under reduced pressure.

Examples 1-6 illustrate that the reaction rate of synthesis of the catalyst depends on the amount of anhydrous NiCl2loaded in the reaction vessel.

Example 1

In a 100 ml reaction vessel equipped with a mechanical stirrer, under nitrogen atmosphere download 3-pentenenitrile (80 ml, 830 mmol), ligand V (18 g, 19 mmol), NiCl2(3,22 g of 24.8 mmol) and powdered zinc (0,61 g, 9.3 mmol). The reaction mixture was stirred at 100°C for 3 hours, and samples are taken every 30 minutes for analysis. After 2 hours there is a 70% conversion (conversion) NiCl2in the catalyst, and after 3 hours is more than 95% conversion of NiCl2in the catalyst.

Example 2

The reaction is carried out as in example 1, except that the number of downloaded NiCl2(1,61 g, 12.4 mmol) half. After 2 hours there is almost 37% conversion NiCl2in the catalyst, and after 3 hours is about 60% to nverse NiCl 2in the catalyst.

The following examples 3-10 re-download the source of catalyst, which is exhausted by the active Nickel, called ″recycle catalyst″. In these cases, ″recycle catalyst″ contains 11 wt.%. ligand V 3-pentenenitrile.

Example 3

In a 100 ml reaction vessel equipped with a mechanical stirrer, under nitrogen atmosphere download recycle catalyst (100 g, containing 11 wt.%. ligand V), NiCl2(1,21 g, 9.3 mmol) and powdered zinc (0,61 g, 9.3 mmol). The reaction mixture was stirred at 80°C for 4 hours, and every 30 minutes take samples for analysis. After 4 hours there is conversion of NiCl2in the catalyst is less than approximately 2%.

Example 4

The reaction is carried out in the same manner as in example 3, except that the number of downloaded NiCl2(2,42 g of 18.6 mmol) in twice the amount used in example 3. After 4 hours there is a 35% conversion NiCl2in the catalyst.

Example 5

The reaction is carried out in the same manner as in example 3, except that the number of downloaded NiCl2(4,84 g that 37.2 mmol) in four times the amount used in example 3. After 4 hours there is a 75% conversion of NiCl2in the catalyst.

Example 6

The reaction is carried out in the same manner as in example 3, the and except the number of downloaded NiCl2(7,26 g, 56.0 mmol) in six times the amount used in example 3. After 2 hours there is a 77% conversion of NiCl2in the catalyst, and after 4 hours there is an 83% conversion of NiCl2in the catalyst.

The following examples 7-10 show that the use of hydrated NiCl2(NiCl2·2H2O) gives the same dependence of the rate on the concentration of Nickel chloride, as in the case of anhydrous NiCl2but at lower temperatures.

Example 7

In a 100 ml reaction vessel equipped with a mechanical stirrer, under nitrogen atmosphere download recycle catalyst (100 g, containing 11% of the mass. ligand V), NiCl2·2H2O (1,21 g, 7,3 mmol) and powdered zinc (0,61 g, 9.3 mmol). The reaction mixture was stirred at 25°C for 4 hours, and samples taken for analysis every 30 minutes. After 4 hours is about 13% conversion NiCl2in the catalyst.

Example 8

The reaction is carried out in the same manner as in example 7, except that the number of downloaded NiCl2·2H2O (2,42 g, 14.6 mmol) in twice the amount used in example 7. After 4 hours there is a 27% conversion NiCl2in the catalyst.

Example 9

The reaction is carried out in the same manner as in example 7, except that the quantity is loaded STV NiCl 2·2H2O (4,84 g, 29.2 mmol) in four times the amount used in example 7. After 4 hours there is a 93% conversion of NiCl2in the catalyst.

Example 10

The reaction is carried out in the same manner as in example 7, except that the number of downloaded NiCl2·2H2O (7,26 g that 43.8 mmol) in six times the amount used in example 7. After 30 minutes the conversion NiCl2in the catalyst is greater than 95%.

Example comparison 1 illustrates that increasing the molar ratio of the reducing metal to NiCl2does not increase the reaction rate. In this example, NiCl2is the limiting reagent, and the degree of reaction is reported in the form of conversion NiCl2. NiCl2is the same as obtained in example 20.

Example comparison 1

Solution ″recycle catalyst″ (9 g 30% of the mass. ligand V) process NiCl2(0.11 g) and zinc (0.10 g). The mixture is intensively stirred and heated at a temperature of about 100°C. Analysis of transparent liquid sample after 2 hours shows 54% conversion NiCl2. The reaction is carried out in the same manner except that the loaded amount of zinc is 0.20 g and 0.40 g, leading to a conversion of 54% and 50%, respectively.

The following examples 11-17 show that the method according to the present image the structure is applicable for additional phosphorus-containing ligands, and that similar effects are observed, when in use as a reducing agent in iron. In these examples, the degree of reaction is determined by measuring the content of Nickel in the solution spectrometry with inductively coupled plasma (ICP).

Example 11

Prepare a solution of ligand XXIV, dissolving 2,497 g ligand XXIV in 24,008 g of dry 3-pentenenitrile. An aliquot of this solution (13,0 g) is mixed with anhydrous NiCl2(1.22 g) and zinc (is 0.102 g). The mixture is intensively stirred and heated at a temperature of about 80°C. Analysis of transparent liquid sample taken after 2 hours, shows 56% conversion. In a similar reaction, except that the mixture downloads only 0.20 g NiCl2after 2 hours find a conversion component only 10%.

Example 12

Prepare a solution of ligand XXI, dissolving 3.03 g of the ligand XXI in 24,16 g of dry 3-pentenenitrile. An aliquot of this solution (13,38 g) is mixed with 1.20 g of anhydrous NiCl2and 0.10 g of zinc. The mixture is intensively stirred and heated at a temperature of about 81°C. Analysis of transparent liquid sample taken after 2 hours, shows 41% conversion. In a similar reaction, except that the mixture downloads only 0.20 g NiCl2after 2 hours find a conversion component only 10%.

Example 13

Prepare a solution of ligand XVIII, dissolving 2,59 g ligand XVIII 24,0 g dry what about the 3-pentenenitrile. An aliquot of this solution (13,38 g) is mixed with 1.20 g of anhydrous NiCl2and 0.10 g of zinc. The mixture is intensively stirred and heated at a temperature of about 80°C. Analysis of transparent liquid sample taken after 2 hours, shows 73% conversion. In a similar reaction, except that the mixture downloads only 0.20 g NiCl2after 2 hours find a conversion component only 14%.

Example 14

Prepare a solution of ligand XIX, dissolving 2.85 g of the ligand in the nineteenth 24,0 g of dry 3-pentenenitrile. An aliquot of this solution (13,4 g) is mixed with 1.20 g of anhydrous NiCl2and 0.10 g of zinc. The mixture is intensively stirred and heated at a temperature of about 78°C. Analysis of transparent liquid sample taken after 2 hours, shows 38% conversion. In a similar reaction, except that the mixture downloads only 0.20 g NiCl2after 2 hours find a conversion component only 10%.

Example 15

Prepare a solution of ligand XX, dissolving 2.67 g of the ligand XX 24,0 g of dry 3-pentenenitrile. An aliquot of this solution (13,0 g) is mixed with 1.23 g of anhydrous NiCl2and 0.10 g of zinc. The mixture is intensively stirred and heated at a temperature of about 81°C. Analysis of transparent liquid sample taken after 2 hours, shows 59% conversion. In a similar reaction, except that the MCA is ü load only 0.20 g NiCl 2after 2 hours find a conversion component only 10%.

Example 16

Prepare a solution of ligand XXV, dissolving of 2.68 g of the ligand XXV in 24,0 g of dry 3-pentenenitrile. An aliquot of this solution (13,1 g) is mixed with 1.20 g of anhydrous NiCl2and 0.10 g of zinc. The mixture is intensively stirred and heated at a temperature of about 81°C. Analysis of transparent liquid sample taken after 2 hours, shows 45% conversion. In a similar reaction, except that the mixture instead of the zinc load iron powder (0,43 g), after 2 hours to find a conversion component 34%.

Example 17

Prepare a solution of ligand XXVI, dissolving 2,77 g ligand XXVI in 24,0 g of dry 3-pentenenitrile. An aliquot of this solution (12,6 g) is mixed with 1.20 g of anhydrous NiCl2and 0.10 g of zinc. The mixture is intensively stirred and heated at a temperature of about 80°C. Analysis of transparent liquid sample taken after 2 hours, shows 37% conversion. In a similar reaction, except that the mixture instead of the zinc load iron powder (0,42 g), after 2 hours to find a conversion component 38%.

Example 18

Prepare a solution of the ligand V, dissolving 3.03 g of the ligand V 24,0 g of dry 3-pentenenitrile. An aliquot of this solution (13.3 g) is mixed with 1.20 g of anhydrous NiCl2and 0.44 g of iron. The mixture is intensively peremeshivayte heated at a temperature of about 81° C. Analysis of transparent liquid sample taken after 2 hours, shows a 16% conversion. In a similar reaction, except that the mixture downloads only 0.2 g NiCl2after 2 hours find a conversion component only 7%.

Examples 19-24 illustrate preferred methods of drying NiCl2. Examples of comparisons 2-3 presents for comparison with the present invention and show that overheating during drying will result in a less reactive material. Analysis ″surface area by BET″ refers to an analytical method to measure the surface area of a solid substance, well known to the person skilled in the art. Letters ″BET″ refer to Brunauer, Emmett, Teller, who developed theory of multilayer adsorption/absorption of gas on solid surfaces. For example, using nitrogen gas at 77 K, we can estimate the surface area of solids by measuring the number of moles of adsorbed nitrogen as a function of partial pressure of gas for a given sample solids. Using theory of sorption BET for the resulting adsorption isotherm curve, it is easy to determine the effective surface area of solids.

Example 19

10 g of uranyl chloride Nickel finely distributed in pure quartz boat in lined with the second quartz tube furnace, equipped with a feeder stream of dry nitrogen at a rate of 100 ml/min. output stream of nitrogen is passed through the bubbler with mineral oil and is produced in a fume cupboard. The sample was then heated to 240°C for 15 minutes and incubated for a full 60 minutes. The sample was then cooled, sealed and placed in a nitrogen purged protective camera with gloves for collection and storage prior experiments on the preparation of the catalyst. A small part of the substance analyzed for water content by thermogravimetric analysis (TGA), heating to 400°With a speed of 10°C/min, the mass Loss at about 200°gives a measure of water in the sample.

This sample contains 0.3 wt.%. water has a surface area according to BET 35 m2/g and the estimated crystallite size of 9 nm. When used for the preparation of the catalyst is similar to the procedure of example 1, this material gives 76% conversion.

Example 2 comparison

Repeat the procedure of example 19 except that the Nickel chloride is additionally heated to 350°C for 30 minutes in nitrogen atmosphere. The sample obtained is less than 0.05% wt. water surface area by BET 13 m2/g and the estimated crystallite size of 22 nm. When used for the preparation of the catalyst is similar to the procedure of example 1, this material gives a conversion of 36%.

Por the measures comparison 3

Repeat the procedure of example 19 except that the Nickel chloride advanced heat up to 500°C for 30 minutes in nitrogen atmosphere. The sample obtained is less than 0.05% wt. water surface area by BET 2 m2/g and the estimated crystallite size of 44 nm. When used for the preparation of the catalyst is similar to the procedure of example 1, this material gives a conversion rate of 1%.

Example 20

9.1 kg of hydrate NiCl2containing 10.9% of wt. H2O, are loaded into a vacuum drum drier. In the dryer, add 20 kg of uranyl NiCl2, leading to the equivalent load NiCl2containing 34.7% of wt. H2O. the Pressure in the dryer is reduced to 100 Torr (690 kPa)and the temperature in the dryer is gradually increased up to 100°during the 5-hour period. The expression ″temperature in the dryer″ refers to the temperature of the contents of the volume. The vacuum dryer is indirectly heated by the supply of hot oil with a temperature greater than the measured temperature of a volume of not more than 20°C. the TGA Tests confirm that the contents of the dryer dehydration to a residual moisture content of 21.5 wt.%. H2O equivalent digitalnow state. Then the temperature in the dryer is increased to 200°C for 4 hours and then raised to 240°during the 2-hour period. The TGA tests show that stationality reduced to less than 0.1% wt. H2O. the surface Area by BET is 24 m2/g, and the estimated crystallite size is 17 nm. Get about 17 kg of anhydrous NiCl2product. When used for the preparation of the catalyst is similar to the procedure of example 1, this material gives a conversion of 79%.

Example 21

An aqueous solution containing about 29% wt. NiCl2, pump the spray dryer at an average speed of 33.5 kg/hour. Passed through the filter atmospheric air is indirectly heated to 400°and Inuktitut parallel with an average speed of 327 kg/hour. Under these conditions the average temperature at the outlet of the spray dryer is 135°C. for 4-hour tests will receive a 50 kg dihydrate NiCl2containing about 22% by weight. H2O.

Approximately 30 kg of dried spray dried product is loaded into the same vacuum drum dryer as in example 20. The pressure in the drum dryer is reduced to 50 Torr (345 kPa)and the temperature in the dryer is increased to 220°during the 2-hour period and maintained for an additional 3 hours. The TGA tests show that the residual moisture is reduced to less than 0.1% wt. H2O, and the estimated crystallite size equal to 18 nm. When used for the preparation of the catalyst is similar to the procedure of example 1, this material gives the env is this 82%. Using similar procedure for preparation of the catalyst, except that the reaction temperature is about 80°C, the conversion was 64% after 2 hours.

Example 22

This example 22 shows that the product of the spray drying can be continuously delivered to the plant for treatment, and that to obtain satisfactory results low pressure in the plant for the heat treatment is not required.

Repeat the procedure of example 21 except that the dihydrate NiCl2from spray dryers are then continuously fed to the plant for heat treatment, which is indirectly heated by hot oil with a temperature of 244°C, causing the temperature of the volume of about 10°below. The pressure in the plant for the heat treatment of the support is slightly below atmospheric. Unloaded from the installation for the heat treatment of the anhydrous product contains residual moisture less than 1% wt. H2O. When used for preparation of the catalyst is similar to the procedure of example 1, except that the reaction temperature is about 80°With, this material gives a conversion of 62%.

1. The method of producing catalyst hydrocyanide, including the interaction of at least one bidentate phosphorus-containing ligand selected from the group, ostoja of bidentate phosphites, bidentate phosphinites and bidentate phosphines with Nickel chloride in the presence of a nitrile solvent and a reducing metal which is more electrophoretically than Nickel, and the Nickel chloride is present in a molar excess relative to the reducing metal.

2. The method according to claim 1, characterized in that the regenerating metal selected from the group consisting of Na, Li, K, Mg, Ca, Ba, Sr, Ti, V, Fe, Co, Cu, Zn, Cd, Al, Ga, In and Sn.

3. The method according to claim 2, characterized in that it further includes separating unreacted chloride Nickel catalyst hydrocyanide.

4. The method according to claim 2, characterized in that the regenerating metal is Zn or Fe.

5. The method according to claim 4, characterized in that the catalyst was prepared at a temperature of from 30 to 100°and a pressure of from 5 to 50 lb./square inch abs.(from 34 to 340 kPa).

6. The method according to claim 5, characterized in that the catalyst was prepared at a temperature of from 50 to 90°C.

7. The method according to claim 6, characterized in that the molar ratio of Nickel chloride to the regenerating metal is from 1.1:1 to 50:1.

8. The method according to claim 7, characterized in that the molar ratio of Nickel chloride to the regenerating metal is from 2:1 to 25:1.

9. The method of claim 8, wherein the bidentate phosphorus-containing ligand is a compound of the formula

(R1O)2P(OZ)P(OR 1)2,

and

where R1represents phenyl, unsubstituted or substituted by one or more C1-C12alkyl or C1-C12CNS groups; naphthyl, unsubstituted or substituted by one or more C1-C12alkyl or C1-C12CNS groups;

Z and Z1independently selected from the group consisting of radicals having the formulas I, II, III and IV

where R2and R9are the same and selected from H, C1-C12the alkyl and C1-C12alkoxy;

R3and R8are the same and selected from H, C1-C12the alkyl and C1-C12alkoxy;

R4and R7are the same and selected from H, C1-C12the alkyl and C1-C12alkoxy;

R5and R6are the same and selected from H, C1-C12the alkyl and C1-C12alkoxy;

where X represents O, S or CH(R18);

R10and R17are the same and selected from H, C1-C12the alkyl and C1-C12alkoxy;

R11and R16are the same and selected from H, C1-C12Alki the a and C 1-C12alkoxy;

R12and R15are the same and selected from H, C1-C12the alkyl and C1-C12alkoxy;

R13and R14are the same and selected from H, C1-C12the alkyl and C1-C12alkoxy and

R18represents N or C1-C12alkyl;

where R19and R20are the same and selected from H and CO2R21;

R21represents a C1-C12alkyl or C6-C10aryl, unsubstituted or substituted C1-C4alkyl groups;

where a represents O, S, CH(R24);

R22and R23are the same and selected from H and CO2R25;

R24represents N or C1-C12alkyl;

R25represents a C1-C12alkyl.

10. The method according to claim 9, characterized in that the Nickel chloride is an unreacted Nickel chloride, which is separated from the catalyst hydrocyanide obtained according to the item 3.

11. The method according to claim 9, characterized in that the Nickel chloride is anhydrous.

12. The method according to claim 11, characterized in that the anhydrous Nickel chloride is produced by the method comprising processing hydration the frame of Nickel chloride at a temperature of from about 200 to 240° With over a period of time less than 12 hours

13. The method according to item 12, characterized in that the hydrated Nickel chloride is a NiCl2·6H2O or NiCl2·2H2O.

14. The method according to claim 11, characterized in that the anhydrous Nickel chloride receive method, including:

(a) spray drying an aqueous solution of Nickel chloride in the exit temperature from about 120 to 150°and

(b) thermal drying of the product from stage (a) at a temperature of from about 200 to 240°C for a period of time less than 12 hours

15. The method according to 14, characterized in that the outlet temperature of the spray drying is from about 130 to 135°s, and the total time of heat exposure is from 1 to 45 C.

16. The method according to item 15, wherein regenerating the metal has a particle size of 20 mesh or less.



 

Same patents:

FIELD: chemical industry, in particular two-component heterogeneous immobilized catalyst for ethylene polymerization.

SUBSTANCE: claimed catalyst includes alumina, mixture of transition metal complexes with nitrogen skeleton ligands (e.g., iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex). According the first embodiment catalyst is prepared by application of homogeneous mixture of transition metal complexes onto substrate. iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex (or vise versa) are alternately applied onto substrate. According the third embodiment catalyst is obtained by mixing of complexes individually applied onto substrate. Method for polyethylene producing by using catalyst of present invention also is disclosed.

EFFECT: catalyst for producing polyethylene with various molecular weights, including short chain branches, from single ethylene as starting material.

7 cl, 5 tbl, 27 ex

The invention relates to new derivatives of metalloporphyrins that can primeneniia as pigments, catalysts, materials sensitive elements gases

The invention relates to electrochemical obtain Ni(O) fofanah and diphosphite complexes in the cell with the use of DC and AC

The invention relates to ORGANOMETALLIC compounds, to compositions containing them and their use

The invention relates to petrochemistry, specifically to the production dialkyldithiocarbamate accelerators of vulcanization of rubbers

The invention relates to a new method of obtaining metallizovannyh derived bacteriochlorophyll for use in the methods of photodynamic therapy (PDT) and in vivo diagnostics and photodynamic destruction of viruses and microorganisms in vitro, as well as some new metallosalen derived bacteriochlorophyll

,,,-tetramethylcyclotetrasiloxane and methods for their production" target="_blank">

The invention relates to chemistry and chemical technology, and more specifically to the synthesis of a new breed of macroheterocyclic compounds, tetrasauropus chlorine, namely,,,-tetramethylcyclotetrasiloxane

The invention relates to a method for Organoelement compounds, which can be used as additives to lubricating oils

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for the hydrocyaniding reaction of unsaturated compounds. Method involves at least one step of the hydrocyaniding reaction in the presence of catalytic system comprising metalloorganic complex. Complex comprises one or some organophosphorus ligands of monodentate organophosphite type, one or some bidentate organophosphorus ligands, and, optionally, a promoter of Lewis acid type. Also, method involves the separating step by distillation of reagent used in the method, or compound synthesized during the hydrocyaniding reaction from medium containing the above indicated catalytic system. Medium subjected for the separating step by distillation shows the ratio of mole of organophosphorus ligands expressed as number of phosphorus atoms to number of metal atoms less or equal 15, and/or the mass ratio of the metal content forming the metalloorganic complex less or equal 1.3%. The vat temperature in the distillation step is lower or equal 180°C. Method provides separating and extracting catalyst and final substances with minimal loss of compounds forming the catalytic system.

EFFECT: improved hydrocyaniding method.

15 cl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of dinitrile compounds. Method involves the hydrocyaniding reaction of mononitrile compounds comprising unsaturated double bond with hydrogen cyanide in the presence of catalytic system comprising a metalloorganic chelate compound and co-catalyst. Method involves the following successive steps: (1) treatment of reaction medium E1 prepared after hydrocyaniding of unsaturated nitrile compounds in order to separate organometallic chelate compound of the catalytic system by liquid-phase extraction and to obtain the second medium E; (2) treatment of abovementioned second medium E2 with ion-exchange resin in order to extract at least metal ions arising from co-catalyst and to obtain the third medium E3; (3) isolating formed dinitriles from the third medium E3 wherein organometallic chelate compound is prepared from nickel compounds and organophosphorus ligand and co-catalyst represents Lewis acid. Method provides isolation and regeneration of Lewis acid from the reaction medium followed by possibility for its repeated using at the hydrocyaniding step.

EFFECT: improved method of synthesis.

12 cl, 2 tbl, 4 ex

FIELD: organic chemistry.

SUBSTANCE: claimed method includes reaction of diolefinic compounds or compounds containing at least one ethylenic bond and cyano group with hydrocyanic acid in presence of catalytic system containing nickel compound, bound with organophosphorus ligands selected from group including organophosphonites, organophosphinites, organophosphites, organophosphines, and organophosphoramidites, wherein said ligands represent mixture containing at least first ligand, selected from group of monodentate organophosphites of general formula I (wherein R1, R2, R3 are independently linear or branched C1-C12-alkyl optionally containing heteroatom, optionally substituted aromatic or cycloaliphatic radical, optionally containing heteroatoms, optionally substituted aromatic or cycloaliphatic radical, optionally containing heteroatoms and one ore more optionally condensed rings; or R1, R2, R3, may be bound to by to), and at least second ligand selected from group containing bidentate organophosphorus ligans of general formula II (wherein R1, R2, R3, R4 are independently linear or branched C1-C12-alkyl optionally containing heteroatom, optionally substituted aromatic or cycloaliphatic radical, optionally containing heteroatoms and one ore more optionally condensed rings; or R1 and R2 and/or R3 and R4 may be bond together; X1, X2, X3, X4, X5, X6 are independently covalent bond, oxygen atom or divalent radical -NR5-, wherein R5 represents hydrogen atom or alkyl, aryl, sulfonyl, cycloalkyl or carmonyl radical; L is covalent bond or divalent linear C1-C12-alkyl optionally containing heteroatoms, divalent optionally substituted aromatic or cycloaliphatic radical, optionally containing heteroatoms and one ore more optionally condensed rings, divalent alkylaryl or arylalkyl radical). Also disclosed is method for hydrocyanating of nitryle ethylenically unsaturated compounds under abovementiones conditions including addition cocatalyst in catalytic system. Said cocatalyst contains at least one Lewis acid.

EFFECT: bidentate compounds with improved stability in reaction medium without losses of catalytic properties such as selectivity.

17 cl, 1 tbl, 13 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing organic compounds comprising at least one nitrile group. Method involves interaction of hydrogen cyanide and organic compound with at least one ethylene-unsaturated bond in the presence of catalyst comprising element taken among the group including nickel, platinum, palladium and an organophosphorus ligand. Reaction is carried out in the presence of ionogenic liquid comprising at least one cation that is taken among the group including cation of tetraalkyl ammonium, N-alkyl imidazolium, N-alkyl pyridinium, N-alkyl picolinium, N-alkyl triazolium, N-alkyl fluoropyrazolium, N-pyrrolidinium, alkylsulfonium, tetraalkylphosphonium, alkyloxonium and at least one anion that is taken among the group including anion of halogen, nitrate, phosphate, hydrosulfate, perfluoroalkyl sulfonate, bis-(perfluoroalkylsulfonyl)amides, bis-(fluorosulfonyl)amide, bis-(fluorophosphoryl)amide, tris-(perfluoroalkylsulfonyl)methylates, boron, aluminum, gallium and iron tetrahalides, phosphorus, arsenic and antimony hexahalides, zinc and tin trihalides, copper dihalides and wherein this liquid is in the liquid state at least at temperature for the reaction carrying out. Method allows increasing yield and selectivity of nitriles and to provide higher stability of catalytic system.

EFFECT: improved preparing method.

23 cl, 5 tbl, 5 ex

FIELD: organic chemistry, catalysts.

SUBSTANCE: invention relates to method for hydrocyanation of olefins containing at least one ethylenically unsaturated bond by reaction thereof with hydrogen cyanide in presence of catalytic system comprising transition metal and organophosphorous ligand of formula I , followed by isomerization of formed nitrile compound. In formula: R1 and R2 are hydrogen atom; R4, R5 and R6 are independently aliphatic, unsaturated C1-C40-hydrocarbon radical, or carbocyclic aromatic hydrocarbon radical; R3 is X radical, wherein X is selected from carbocyclic aromatic monocyclic radical; R7 is aromatic hydrocarbon radical or hydrocarbon radical containing aldehyde group.

EFFECT: catalytic system of improved catalytic activity and stability.

20 cl, 3 tbl, 6 ex

The invention relates to a method for producing mixtures monoolefinic of mononitriles 5 carbon atoms, including non-conjugate double carbon-carbon triple carbon-nitrogen relationships, by catalytic hydrocyanide 1,3-butadiene or containing 1,3-butadiene mixture of hydrocarbons at elevated temperature and pressure, the process is carried out in the presence of a catalyst containing a metallocene complex with trivalent phosphorus and Nickel zero valency, including monodentate or bidentate metallocene ligand with trivalent phosphorus of the General formula (I), where R1means the rest of the formula PL2and the remains of L may be the same or different and denote alkyl, cycloalkyl or aryl; R1means a hydrogen atom, alkyl or the residue of formula PL2and the remains of L have the abovementioned meaning; R2, R2’, R3, R3’, R4, R4’, R5, R5’independently from each other, are selected from the group consisting of a hydrogen atom, cycloalkyl, aryl or alkyl which may be interrupted by oxygen atom or may be substituted by a residue of the formula NE1E2and E1and E2may be the same or different and mean the3’, R4’, R5’in adjacent positions together with the connecting part cyclopentadienyls ring may form an aromatic or non-aromatic five - to semichasnoho carbocycle or heterocycle, which can contain one, two or three heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur; M denotes an atom of iron, cobalt, Nickel, ruthenium, osmium, rhodium, manganese, chromium or vanadium; or their salts and mixtures

The invention relates to the production of catalysts for the synthesis of adiponitrile

The invention relates to a method for producing mixtures monoolefinic5-mononitriles with niaprazine bonds C= C and C= N and production method of adipodinitrile based on them

The invention relates to an improved method of hydrocyanide aliphatic organic compounds with unsaturated ethylene communication, in particular aliphatic compounds containing one double ethylene bond, interaction with hydrogen cyanide in the presence of an aqueous solution of a catalyst containing a compound of transition metal, such as Nickel, and a water-soluble phosphine of General formula I or General formula II, where d is an integer from 1 to 2; D is alkyl or cycloalkyl, possibly containing one or more substituents; Ar1, AG2, AG3identical or different arily containing one or more substituents; a, b, e, f each denotes 0 or 1; C is an integer from 0 to 3; g is an integer from 1 to 2

The invention relates to an improved method of producing dinitriles

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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