Method of obtaining ethylenediammonium bis(1-hydroxyethane-1,1-diphosphonato(2-))cuprate(+2), zincate(+2) and nickelate(+2)

FIELD: chemistry.

SUBSTANCE: invention relates to obtaining etyheleneammonium bis(1-hydroxyethane-1,1-diphosphonato(2-))cuprate (+2), etyheleneammonium bis(1-hydroxyethane-1,1-diphosphonato(2-)) zincate(+2) and etyheleneammonium bis(1-hydroxyethane-1,1-diphosphonato(2-)) nickelate(+2) and can be used for processing toxic wastes of obtaining metal coatings - waste electrolytes of galvanic copper, zinc and nickel plating, waste solutions of chemical nickel plating and copper plating. Products, obtained by said method, can be used for preparation of electrolytes, metal corrosion inhibitors, for obtaining various copper, zinc and nickel compounds, including catalysts of organic and inorganic substance synthesis. Claimed method includes using liquid industrial wastes, containing metal(+2), ethyleneammonium and/or anion of 1-hydroxyethane-1,1-diphosphonic acid as reagents. Target products are obtained by crystallisation from reaction water solution with separation of sediment from solution, process is carried out at temperature from (-5) to 105°C and atmospheric pressure. Method allows to obtain pure crystalline products with yield up to 98%, to reduce expenditures on environment protection.

EFFECT: method simplification and increase of its manufacturability.

7 cl, 9 ex

 

The invention relates to chemical technology of organic compounds, in particular to a method for producing metal compounds(+2) with 1-hydroxyethane-1,1-diphosphonic acid composition of the N3NCH2CH2NH3M(CH3S(HE)(RHO3N)2)2·2H2O, where M stands for copper(+2), zinc(+2), Nickel(+2). The claimed method can be applied for processing of toxic waste for producing metallic coatings - waste electrolyte galvanic copper plating, galvanizing, Nickel plating, the spent chemical Nickel-plating solution, the spent solution chemical copper plating. The products obtained by this method can be used to prepare electrolyte galvanic copper plating, galvanizing, Nickel plating, for the production of corrosion inhibitors of metals to obtain various compounds of copper, zinc, Nickel, including catalysts for the synthesis of organic and inorganic substances.

To obtain high quality coatings with copper, zinc, Nickel apply complex electrolytes containing as the main components of metal(+2) and Ethylenediamine or anion 1-hydroxyethane-1,1-diphosphonic acid ligands that bind metal(+2) complex) (Haynes R.T., Irani R.R., Langguth R.P. US 3475293, publ. 1969. Kowalski X. US 3706634, publ. 1972. Nobel F.I., Yoen L.C. US 3833486, publ. 1974. G.O. Mallory, Johnson C.E. DE 2942792, publ. 198. Ratajewicz Z., Saneluta C. // Plating and Surface Finishing, 1999, v.86, no. 7, p.50. Electroplating. Handbook (edited by Genberg A.M., A.F. Ivanov, Kravchenko L.L.) - M.: metallurgy, 1987, s. Ivshin AV EN 2058436, publ. 1996). Very promising are complex electrolytes containing both of the ligand (Lviv V.M., Afonin Mrs x EN 2276205, publ. 2006). However, being bound in strong soluble complexes, copper(+2), zinc(+2), Nickel(+2) not deposited alkaline reagents in the processes of wastewater treatment, which creates a serious environmental problem in the use of such electrolytes. The claimed method allows us to extract from exhaust of electrolytes and solutions - waste receiving electrochemical and chemical coatings metals all three major components - metal(+2), Ethylenediamine and anion 1-hydroxyethane-1,1-diphosphonic acid in the form of easily recyclable compounds.

A method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(2-))zincate(+2) ethylendiamine composition (H3NCH2CH2NH3)Zn(CH3S(HE)(RHO3N)2)2·2H2O, comprising preparing a reaction of an aqueous solution containing zinc(+2), ethylendiamine and anion 1-hydroxyethane-1,1-diphosphonic acid, the crystallization of the desired product from the solution, separating the precipitate from the solution (Song N.-N., Zheng L.-M., Wang, Zh., Yan Ch.-H., Xin X.-Q. Zinc Diphosphonates Templated by Organic Amines: Sntheses and Characterization of [NH 3(CH2)2NH3]Zn(hedpH2)2·2H2O and [NH3(CH2)nNH3]Zn2(hedpH)2·2H2O (n=4,5,6) (hedp=1-Hydroxyethylidenediphosphonate) // Inorganic Chemistry, 2001, v.40, No. 19, p.5024-5029). The reaction aqueous solution is produced by interaction of sulfate or zinc chloride with 1-hydroxyethane-1,1-diphosphonic acid (the molar ratio of zinc(+2):1-hydroxyethane-1,1-diphosphonic acid is about 1:5) and Ethylenediamine at pH 3-4 and heated at 110°C under hydrothermal conditions (steel autoclave high pressure) for 3 days. The way the prototype is based on the following reaction:

ZnSO4+2CH3S(HE)(RHO3H2)2+2H2NCH2CH2NH2+2H2O→

H3NCH2CH2NH3Zn(CH3C(OH)(PO3H)2)2·2H2O+H3NCH2CH2NH3SO4.

The disadvantage of this method is its complexity, low technology, the need for additional costs for long-term maintenance of high constant temperature and additional cost of chemical reagents.

A method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(2-))nikeeta(+2) ethylendiamine composition

(H3NCH2CH2NH3)Ni(CH3S(HE)(RHO3N)2)2·2H2O, comprising preparing a reaction of an aqueous solution containing n is Kel(+2), ethylendiamine and anion 1-hydroxyethane-1,1-diphosphonic acid, the crystallization of the desired product from the solution, separating the precipitate from the solution (Song N.-N., Zheng L.-M., Lin Ch.-H., Wang S.-L., Xin X.-Q., Gao S. Effect of Organic Templates on Directing the Structures of Nickel(II)-l-Hydroxyethylidenediphosphonate Compounds: A Structural and Magnetic Study // Chemistry of Materials, 1999, v.11, No. 9, p.2382-2388). The reaction aqueous solution is produced by interaction of Nickel sulfate with 1-hydroxyethane-1,1-diphosphonic acid (the molar ratio of Nickel(+2):1-hydroxyethane-1,1-diphosphonic acid of 1.0: (0,33-2,8)) and Ethylenediamine at pH 3 and heated at 140°C under hydrothermal conditions (steel autoclave high pressure) for 2 days. The way the prototype is based on the following reaction:

With NISO4+2CH3S(HE)(RHO3H2)2+2H2NCH2CH2NH2+2H2O→

H3NCH2CH2NH3Ni(CH3S(HE)(RHO3N)2)2·2H2O+H3NCH2CH2NH3SO4.

The disadvantage of this method is its complexity, low technology, the need for additional costs for long-term maintenance of high constant temperature and additional cost of chemical reagents.

If a claimed invention was intended to simplify the method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(2-))cuprate(+2), zincate(+2) and nikeeta(+2) ethylendiamine, to improve the shape of its manufacturability, to reduce material costs to obtain the target product.

The problem is solved in that a method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(2-))cuprate(+2), zincate(+2), nikeeta(+2) ethylendiamine includes the preparation of the reaction of an aqueous solution containing metal(+2), selected from the group consisting of copper(+2), zinc(+2), Nickel(+2)and containing Ethylenediamine and anion 1-hydroxyethane-1,1-diphosphonic acid, the crystallization of the desired product from the solution, separating the precipitate from the solution. New in the claimed method is that for the preparation of the reaction of an aqueous solution as a source of metal(+2), ethylendiamine and/or anion 1-hydroxyethane-1,1-diphosphonic acid is used as a production waste metal coating selected from the group consisting of spent electrolyte galvanic copper plating, the spent electrolyte, galvanic, galvanizing, the spent electrolyte galvanic Nickel-plating, the spent chemical Nickel-plating solution, the spent solution chemical copper plating, and the process is carried out at a temperature of (-5) to 105°C and atmospheric pressure. It is desirable to use the spent electrolyte copper plating containing as main components copper(+2), Ethylenediamine, or the spent electrolyte copper plating containing to the operation of the main components copper(+2), anion 1-hydroxyethane-1,1-diphosphonic acid, or the spent electrolyte copper plating containing as main components copper(+2), Ethylenediamine, anion 1-hydroxyethane-1,1-diphosphonic acid, or the spent electrolyte galvanizing, containing as main components zinc(+2), Ethylenediamine and/or anion 1-hydroxyethane-1,1-diphosphonic acid, or the spent Nickel plating electrolyte containing as main components Nickel(+2), Ethylenediamine and/or anion 1-hydroxyethane-1,1-diphosphonic acid. In the reaction aqueous solution is desirable to establish a pH of from 0.5 to 8.5.

The method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(2-))cuprate(+2), zincate(+2) and nikeeta(+2) ethylendiamine is the preparation of an aqueous solution containing as the main components of metal(+2), ethylendiamine and anion 1-hydroxyethane-1,1-diphosphonic acid, the source of which is waste from the production of metallic coatings: waste electrolyte copper plating, galvanizing, Nickel plating, the spent chemical Nickel-plating solution, the spent solution chemical copper plating. In the reaction aqueous solution determine the optimal value of pH by mixing liquid waste each other in the calculated number and adding (if necessary) acid or base. Water rest the R leave for crystallization in the course of time, sufficient to achieve a high yield of the target product. The precipitate is separated from the solution one of the known ways, washed it (if necessary) water or an organic solvent and dried (if necessary) at room or elevated temperature.

The method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(2-))cuprate(+2), zincate(+2) and nikeeta(+2) ethylendiamine based on the following reactions.

K6[Cu(CH3S(HE)(RHO3)2)2]+H2NCH2CH2NH2+6HCl+2H2O→

H3NCH2CH2NH3Cu(CH3S(HE)(RHO3N)2)2·2H2O+6KCl.

K6[Cu(CH3S(HE)(RHO3)2)2]+2CH3S(HE)(RHO3K2)2+[Cu(H2NCH2CH2NH2)2]SO4+

6H2SO4+4H2O→2H3NCH2CH2NH3Cu(CH3S(HE)(RHO3N)2)2·2H2O+7K2SO4.

Na2[Ni(CH3C(OH)(PO3H)2)2]+[Ni(H2NCH2CH2NH2)3]Cl2+

2CH3S(HE)(RHO3HNa)2+6HCl+4H2O→

2H3NCH2CH2NH3Ni(CH3S(HE)(RHO3N)2)2·2H2O+H3NCH2CH2NH3Cl2+6NaCl.

K6[Zn(CH3S(HE)(RHO3)2)2]+H2NCH2CH2NH 2+6HNO3+2H2O→

H3NCH2CH2NH3Zn(CH3C(OH)(PO3H)2)2·2H2O+6KNO3.

K6[Zn(CH3S(HE)(RHO3)2)2]+2CH3S(HE)(RHO3K2)2+[Zn(H2NCH2CH2NH2)2]SO4+

6H2SO4+4H2O→2H3NCH2CH2NH3Zn(CH3C(OH)(PO3H)2)2·2H2O+7K2SO4.

To prepare the reaction of an aqueous solution containing metal(+2), ethylendiamine and anion 1-hydroxyethane-1,1-diphosphonic acid, you can use various liquid wastes of production of metallic coatings by electrochemical and chemical methods, in particular spent electrolytes ethylenediamino copper plating, which have the composition, for example:

Sulphate of copper(+2)60-80 g/l
The Ethylenediamine20-60 g/l
Ammonium sulfate45-60 g/l
The sodium sulfate20-65 g/l

or

Sulphate of copper(+2)60-70 g/l
trendily 110-130 g/l
Sulphate of ethylendiamine70-90 g/l

spent electrolytes ethylenediamino galvanizing, which have the composition, for example:

Sulphate of zinc(+2)20-25 g/l
The Ethylenediamine30-40 g/l
Ammonium chloride20-50 g/l

spent electrolytes ethylenediamino Nickel plating, which have the composition, for example:

Chloride Nickel(+2)10-20 g/l
The Ethylenediamine25-35 g/l
Ammonium chloride20-50 g/l

spent copper plating electrolytes based on 1-hydroxyethane-1,1-diphosphonic acid, which have a composition, for example:

Sulphate of copper(+2)15-150 g/l
1-Hydroxyethane-1,1-diphosphonate(4-)potassium35-700 g/l

spent electrolytes galvanizing on the basis of the 1-hydroxyethane-1,1-diphosphonic acid, which have the composition, for example:

Sulphate of zinc(+2)16-160 g/l
1-Hydroxyethane-1,1-diphosphonate(4-)potassium35-700 g/l

spent electrolytes Nickel-based 1-hydroxyethane-1,1-diphosphonic acid, which have a composition, for example:

Sulfate Nickel(+2)15-150 g/l
1-Hydroxyethane-1,1-diphosphonate(4-)potassium35-700 g/l

spent electrolytes containing as ligands for the binding of metal cations(+2) complexes at the same time as Ethylenediamine, and the anion of 1-hydroxyethane-1,1-diphosphonic acid, which have a composition, for example:

Sulphate of copper(+2)15-150 g/l
1-Hydroxyethane-1,1-diphosphonate(4-)potassium70-500 g/l
The Ethylenediamine6-60 g/l

or

Sulphate of zinc(+2)16-80 g/l
1-Hydroxyethane-1,1-diphosphonate(4-)potassium40-500 g/l
The Ethylenediamine10-50 g/l

or

Chloride Nickel(+2)35-110 g/l
1-Hydroxyethane-1,1-diphosphonate(4-)potassium150-350 g/l
The Ethylenediamine20-200 g/l

the spent chemical Nickel-plating solution, based on Ethylenediamine, in particular the spent solution coating alloy Nickel-boron, which has a composition, for example:

Chloride Nickel(+2)2-20 g/l
The Ethylenediamine20-70 g/l
Borohydride sodium0.1 to 1.5 g/l
The sodium borate30-150 g/l
Hydroxide and sodium carbonate30-80 g/l

or spent solution coating alloy Nickel-phosphorus-based 1-hydroxyethane-1,1-diphosphonic acid, which has a composition, for example:

Sulfate Nickel(+2)6-15 g/l
1-Hydroxyethane-1,1-diphosphonate(2-)sodium15-55 g/l
Hypophosphite sodium5-20 g/l
Postit sodium20-100 g/l
Sodium acetate10-15 g/l

waste solutions of the chemical copper plating, which have the composition, for example:

Sulphate of copper(+2)1-8 g/l
1-Hydroxyethane-1,1-diphosphonate(4-)potassium20-40 g/l
Formaldehyde0.5 to 2 g/l
Formate sodium20-50 g/l

(Haynes R.T., Irani R.R., Langguth R.P. US 3475293, publ. 1969. Kowalski X. US 3706635, publ. 1972. G.O. Mallory, Johnson C.E. DE 2942792, publ. 1980. Sudakov GA electroplating. - M.: Mechanical Engineering. 1987. Electroplating. Handbook (edited by Genberg A.M., A.F. Ivanov, Kravchenko L.L.) - M.: metallurgy, 1987. Berezin, S., Sageev P.M., Amirov RR // Protection of metals, 1987, volume 23, No. 6, s. Lviv V.M., Afonin Mrs x EN 2293144, publ. 2007).

To obtain pure desired products with wysockiego in the reaction aqueous solution, it is desirable to maintain an optimal pH value. This is because in a very acidic solubility of target products increases, and their output is reduced in the reaction:

H3NCH2CH2NH3M(CH3S(HE)(RHO3N)2)2·2H2O+4H+↔H3NCH2CH2NH32++M2+

+2CH3S(HE)(RHO3H2)2+2H2O.

In alkaline solubility of target products also increases, and their output is reduced in the reaction:

H3NCH2CH2NH3M(CH3S(HE)(RHO3N)2)2·2H2O+ON-

[M(H2NCH2CH2NH2)(CH3S(HE)(RHO3)2)2]6-+8H2O.

Therefore, high yield and high purity of the target product can be ensured if the crystallization is from the reaction of an aqueous solution with a pH from 0.5 to 8.5.

Target products crystallize from the reaction of aqueous solutions under normal atmospheric pressure and a temperature of (-5) to 105°C, so there is no need for maintaining strict synthesis conditions (hydrothermal conditions), as in the method according to the prototype (the temperature of 110-140°C., the pressure is higher than 100 ATM).

Example 1.

Mix 100 ml of spent electrolyte galvanic copper plating with the concentration of sulphate of copper(+2) to 0.40 mol/l Ethylenediamine 0.80 mol/l, sulfate is the atrium of 0.15 mol/l, ammonium sulphate 0.34 mol/l and a solution of 14.0 g of dihydrate 1-hydroxyethane-1,1-diphosphonate(1 -), potassium 200 ml of water. To the obtained solution under stirring was added concentrated sulfuric acid to achieve a pH of 2.3. The solution is allowed to stand for crystallization for 30 hours at room temperature. The precipitate is filtered off under reduced pressure on a glass filter, washed with water and dried in air at room temperature to constant weight. Output 95,0%.

Found, %: Cu - 10,9; - 12,5; N - 4,3; N - 4,5; P - 21,5.

Calculated for C6H22N2P4O14Cu·2H2O, %: Cu - Of 11.15; - 12,65; N - 4,60; N To 4.92; P - A 21.75.

Example 2.

To 100 ml of spent electrolyte galvanic copper plating with the concentration of sulphate of copper(+2) 0.35 mol/l, 1-hydroxyethane-1,1-diphosphonate(4-) potassium of 1.03 mol/l with stirring add first 19,0 ml of an aqueous solution of Ethylenediamine concentration 3,70 mol/l, then the solution of sulfuric acid with a concentration of 1.0 mol/l to achieve a pH of 3.2. The solution is allowed to stand for crystallization to 5 days at a temperature of 26-28°C. the Precipitate is filtered off under reduced pressure on a glass filter, washed first with water, then with ethanol and dried in air at room temperature to constant weight. The yield of 97.4%.

Found, %: Cu - 10,9; - 12,2; N - 4,4; N - 4,6; P - 21,4.

Calculated for C6H22N2P 4O14Cu·2H2O, %: Cu - Of 11.15; - 12,65; N - 4,60; N To 4.92; P - A 21.75.

Example 3.

Mix 50 ml of the spent electrolyte galvanic copper plating with the concentration of sulphate of copper(+2) 0.35 mol/l, 1-hydroxyethane-1,1-diphosphonate(4-) potassium of 1.03 mol/l, 50 ml of water and 15 ml of spent electrolyte galvanic copper plating with the concentration of sulphate of copper(+2) to 0.40 mol/l Ethylenediamine 2.0 mol/l, sulphate of ethylendiamine 0.50 mol/liter To the obtained solution under stirring was added a 50%solution of sulfuric acid to achieve a pH of 1.9. Contribute to the solution of the crystal seed dihydrate bis(1-hydroxyethane-1,1-diphosphonate(2-))cuprate(+2) ethylendiamine and leave the solution to stand for crystallization for 4 days at room temperature. The precipitate is filtered off under reduced pressure on a glass filter, washed first with water, then with ethanol and dried in air at room temperature to constant weight. Output 86,0%.

Found, %: Cu - 11,2; - 12,3; 4,1; N - 4,4; P - 21,5.

Calculated for C6H22N2P4O14Cu·2H2O, %: Cu - Of 11.15; - 12,65; N - 4,60; N To 4.92; P - A 21.75.

Example 4.

To 100 ml of the spent solution from the chemical copper plating hole PCB concentration of sulphate of copper(+2) 0,0080 mol/l, 1-hydroxyethane-1,1-diphosphonate(4-) potassium 0.10 mol/l, formaldehyde 0.10 mol/l of sodium formiate 0.67 mol/l of sodium sulfate and 0.25 Mall under stirring was added concentrated sulfuric acid to achieve a pH of 1.6. To 8.0 ml of spent electrolyte galvanic copper plating with the concentration of sulphate of copper(+2) to 0.40 mol/l Ethylenediamine 2.0 mol/l, sulphate of ethylendiamine 0.50 mol/l with stirring was added concentrated sulfuric acid to achieve a pH of 2.0. Mix the two specified solution, making the solution so obtained crystalline seed dihydrate bis(1-hydroxyethane-1,1-diphosphonate(2-))cuprate(+2) ethylendiamine and leave the solution to stand for crystallization for 30 days at a temperature of 20-25°C. the Precipitate is filtered off under reduced pressure on a glass filter, washed with water and dried in air at room temperature to constant weight. The output of 31.4%.

Found, %: Cu - 11,2; C - 12, 0mm; N - 4,6, N - 4,6; P - 21,4.

Calculated for C6H22N2P4O14Cu·2H2O, %: Cu - Of 11.15; - 12,65; N - 4,60; N To 4.92; P - A 21.75.

Example 5.

Mix 100 ml of spent electrolyte galvanic zinc concentration of zinc sulfate 0.22 mol/l, 1-hydroxyethane-1,1-diphosphonate(4-)potassium 0.80 mol/l and 70 ml of spent electrolyte galvanic zinc concentration of zinc sulfate of 0.14 mol/l Ethylenediamine 0.59 mol/l To the obtained solution under stirring was added concentrated sulfuric acid to achieve a pH of 3.3. In the solution contribute crystalline seed dihydrate bis(1-hydroxyethane-1,1-diphosphonate(2-))CIN the ATA(+2) ethylendiamine and leave the solution to stand for crystallization for 20 hours at room temperature. The precipitate is filtered off under reduced pressure on a glass filter, washed with water and dried in air at room temperature to constant weight. Output 95,1%.

Found, %: Zn - 11,2; - 12,2; N - 4,5; N - 4,3; P - 21,2.

Calculated for C6H22N2P4O14Zn·2H2O, %: Zn - 11,44; - 12,61; N - 4,59; N - 4,90; P - 21,68.

Example 6.

To 100 ml of spent electrolyte galvanic zinc concentration of zinc sulfate(+2) 0.20 mol/l, 1-hydroxyethane-1,1-diphosphonate(4-)potassium 0.71 mol/l Ethylenediamine 0.41 mol/l with stirring, add concentrated nitric acid to achieve a pH of 3.4. In the resulting solution make crystal seed dihydrate bis(1-hydroxyethane-1,1-diphosphonate(2-))zincate(+2) ethylendiamine and leave the solution to stand for crystallization at 60 hours at room temperature. The precipitate is filtered off under reduced pressure on a glass filter, washed with water and dried in air at room temperature to constant weight. Output 89,0%.

Found, %: Zn - 11,5; - 12,3; N - 4,2; N - 4,1; P - 21,0.

Calculated for C6H22N2P4O14Zn·2H2O, %: Zn - 11,44; - 12,61; N - 4,59; N - 4,90; P - 21,68.

Example 7.

Mix 150 ml of the spent chemical Nickel-plating solution with a chloride concentration of Nickel(+2) 0,058 mol/l Ethylenediamine 0.40 mol/l, sodium borohydride 0,005 mol/who, borate sodium 0.55 mol/l hydroxide and sodium carbonate in 1.5 mol/l and 250 ml of the spent chemical Nickel-plating solution with the concentration of Nickel sulfate(+2) to 0.060 mol/l, 1-hydroxyethane-1,1-diphosphonate(2-)potassium 0.20 mol/l, hypophosphite sodium 0.05 mol/l, phosphite sodium 0.20 mol/l sodium acetate and 0.15 mol/liter To the obtained solution under stirring was added concentrated sulfuric acid to achieve a pH of 2.9. In the solution contribute crystalline seed dihydrate bis(1-hydroxyethane-1,1-diphosphonate(2-))nikeeta(+2) ethylendiamine and leave the solution to stand for crystallization for 25 days at room temperature. The precipitate is filtered off under reduced pressure on a glass filter, washed with water and dried in air at room temperature to constant weight. The output is 60.1%.

Found, %: Ni - 10,2; - 12,2; N - 4,3; N - 4,5; P - 21,6.

Calculated for C6H22N2P4O14Ni·2H2O In %: Ni - Accounted For 10.39; - 12,76; N With 4.64; N - 4,96; P - 21,93.

Example 8.

Mix 200 ml of the spent chemical Nickel-plating solution with the concentration of Nickel sulfate(+2) to 0.060 mol/l, hypophosphite sodium 0,048 mol/l, phosphite sodium 0.23 mol/l, 1-hydroxyethane-1,1-diphosphonate(2-)potassium 0.22 mol/l sodium acetate 0.14 mol/l and 50 ml of spent electrolyte galvanic Nickel-plating with a chloride concentration of Nickel(+2) 0.10 mol/l Ethylenediamine 0.52 mol/L. the resulting solution under stirring was added concentrated sulfuric acid to achieve a pH of 3.3. In the solution contribute crystalline seed dihydrate bis(1-hydroxyethane-1,1-diphosphonate(2-))nikeeta(+2) ethylendiamine and leave the solution to stand for crystallization of 28 days at a temperature of 17-20°C. the Precipitate is filtered off under reduced pressure on a glass filter, washed with water and dried in air at room temperature to constant weight. The yield of 68.2%.

Found, %: Ni - 10,4; - 12,5; N - 4,2; N - 4,4; P - 21,8.

Calculated for C6H22N2P4O14Ni·2H2O In %: Ni - Accounted For 10.39; - 12,76; N With 4.64; N - 4,96; P - 21,93.

Example 9.

100 ml of the spent chemical Nickel-plating solution with a chloride concentration of Nickel(+2) 0,058 mol/l Ethylenediamine 0.40 mol/l, sodium borohydride 0,005 mol/l sodium borate 0.55 mol/l hydroxide and sodium carbonate in 1.5 mol/l with stirring dissolve 4.1 g of dihydrate 1-hydroxyethane-1,1-diphosphonate(1 -), potassium. To the obtained solution under stirring was added concentrated sulfuric acid to achieve a pH of 2.9. In the solution contribute crystalline seed dihydrate bis(1-hydroxyethane-1,1-diphosphonate(2-))nikeeta(+2) ethylendiamine and leave the solution to stand for crystallization to 20 days at room temperature. The precipitate is filtered off under reduced pressure on a glass filter, washed with water and dried in air at room temperature to constant weight. The output of 7.5%.

Found, %: Ni - 10,1; C - 12, 0mm; N - 4,5; N - 4,5; P - 21,4.

Calculated for C6H22N2P4O14Ni·2H2O In %: Ni - Accounted For 10.39; - 12,76; N With 4.64; N - 4,96; P - 21,93.

The resulting dihydrate bis(1-hydroxyethane-1,1-diphosphonate(2-))cuprate(+2)ethylendiamine, dehydrate bis(1-hydroxyethane-1,1-diphosphonate(2-))zincate(+2) ethylendiamine, dehydrate bis(1-hydroxyethane-1,1-diphosphonate(2-))nikeeta(+2) ethylendiamine are crystalline substances in blue, white, green yellow, respectively. The substance is moderately soluble in water, soluble in 10%solutions of ammonia, sodium hydroxide, sulfuric acid, slightly soluble in ethanol, acetone, acetic acid.

As seen from the above examples, the claimed method allows to obtain the target products in high yield, using as sources of metal(+2), ethylendiamine and anion 1-hydroxyethane-1,1-diphosphonic acid waste solutions production of copper, zinc and Nickel coatings of different composition, which reduces material costs to obtain the desired products. Simplification of the method and increase its maintainability is achieved by implementation of the process of obtaining the desired products in more mild conditions than in the method according to the prototype: a normal (moderately high or low) temperature and under normal (atmospheric) pressure.

1. The method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(2-))cuprate(+2), zincate(+2), nikeeta(+2) ethylendiamine comprising preparing a reaction of an aqueous solution containing metal(+2), selected from the group consisting of copper(+2), zinc(+2), Nickel(+2)and containing Ethylenediamine and anion 1-hydroxyethane-1,1-diphosphonic acid, the crystallization of the desired product from the solution, separating the precipitate from the solution, characterized in that for the preparation of the reaction of an aqueous solution as a source of metal(+2), ethylendiamine and/or anion 1 - hydroxyethane-1,1-diphosphonic acid is used as a production waste metal coating selected from the group consisting of spent electrolyte galvanic copper plating, the spent electrolyte, galvanic, galvanizing, the spent electrolyte galvanic Nickel-plating, the spent chemical Nickel-plating solution, the spent solution chemical copper plating, and the process is carried out at a temperature of (-5) to 105°C and atmospheric pressure.

2. The method according to claim 1, characterized in that use the spent electrolyte copper plating containing as main components copper(+2), Ethylenediamine.

3. The method according to claim 1, characterized in that use the spent electrolyte copper plating containing as main components copper(+2), anion hydroxyethane-1,1-diphosphonic acid.

4. The method according to claim 1, characterized in that use the spent electrolyte copper plating containing as main components copper(+2), Ethylenediamine, anion 1-hydroxyethane-1,1-diphosphonic acid.

5. The method according to claim 1, characterized in that use the spent electrolyte galvanizing, containing as main components zinc(+2), Ethylenediamine and/or anion 1-hydroxyethane-1,1-diphosphonic acid.

6. The method according to claim 1, characterized in that use exhaust Nickel plating electrolyte containing as main components Nickel(+2), Ethylenediamine and/or anion 1-hydroxyethane-1,1-diphosphonic acid.

7. The method according to claim 1, characterized in that the reaction aqueous solution establish a pH of from 0.5 to 8.5.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to novel compounds of formula (I), including its pharmaceutically acceptable salts, solvates, ethers and amides, possessing ability to bind ERα- and ERβ-estrogen receptors, to pharmaceutical composition based on them, to versions of applying claimed compounds in medication preparation and to method of binding ERα- and ERβ-estrogen receptors. (I), where R1 represents H, OH or C1-12alkoxy, or halogen; R2 represents H, OH or halogen; R3 represents C1-12alkyl, halogeno-C1-12alkyl, C3-10cycloalkyl, C1-12alkoxy or C1-12alkoxyC1-12alkyl; R4 represents H or C1-12alkoxy; R5 represents H, halogen or halogeno-C1-12alkyl; R6 represents -(Y)z-R7; R8 represents phenyl or 5- or 6-member heteroaryl, containing N, O or S as heteroatom, where said phenyl and heteroaryl are possibly substituted with OH, halogeno, halogenoC1-12alkyl or C1-12alkoxy. Values R7, Y and z are presented in invention formula.

EFFECT: novel compounds possess useful biological properties.

19 cl, 7 dwg, 1 tbl, 70 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel chemical compounds as salt-deposition inhibitors and can be used in oil industry in oil extraction, in particular in system of sewage water utilising, as well as in systems of circulating water supply of industrial enterprises. Suggested is complexonate of nitrylotri(methylenephosphonato)-2-phenyl-3-ethyl-8-oxychinolin sodium salt of formula as salt-deposition inhibitor.

EFFECT: obtaining salt-deposition inhibitor characterised by high efficiency with low consumption rate under conditions of intensive degasing.

1 cl, 1 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to phosphoroorganic chemistry, namely, to method of obtaining long-chain alkylphosphonic acids, possessing anticorrosion activity, based on α-olefins of industrial fraction C16-C18 and C20-C26. Invention can be applied for protection of pipelines, reservoirs, construction metallic structures, equipment for extraction, transportation and processing oil and gas, in metal processing. Long-chain alkylphosphonic acids are obtained by interaction of α-olefins of industrial fraction C16-C18 and C20-C26 with O,O-dimethylphosphorous acid in molar ratio 1:(1.0-2.0) in presence of benzoyl peroxide in amount of 1.0-5.0% of weight of dimethylphosphorous acid at 110-150°C during 10-12 hours in absence of solvent with further hydrolysis of intermediate higher O,O-dimethyl(alkyl) phosphonates with hydrochloric acid with heating, obtaining target product which represents mixture of long-chain alkylphosphonic acids.

EFFECT: elaboration of novel method of obtaining mixture of alkylphosphonic acids and soft steel corrosion inhibitor.

2 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention refers to method of production of amorphous alendronate monosodium and to solid pharmaceutical composition having property to invoke bone bulk expansion and containing therapeutically effective amount of amorphous alendronate monosodium, produced by stated method. Method of production of amorphous alendronate monosodium includes solvent removal from alendronate monosodium solution using spray drying.

EFFECT: development of production method of amorphous alendronate monosodium.

4 cl, 1 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: the invention pertains to an acidic phosphorous containing reagent, is used in the oil industry, heat energy, textile industry, production of mineral fertilizers and household chemistry, and to methods of obtaining the reagent. The reagent (conventional name "АФК-1") contains the following in given mass %: acetoxyethylidenediphosphonic acid 50.0-95.0 mass %, acetic acid - 29.5-0.5 mass %, the rest is acetic anhydride to 100. The quantitative composition of the indicated reagent is determined by the method of obtaining it and the ratios of the initial reagents. The method of obtaining the reagent involves adding acetic anhydride to a suspension of acetic and phosphorous acid at temperature of 60-90°C for a period of 1.5 hours. The reaction mixture is kept at 100-110°C for 1 hour and acidic impurities are distilled off to a controlled volume of distillate. Similar methods are developed based on phosphorous containing wastes from production of acid chlorides of higher fatty acids. The wastes are treated with water or a water solution of acetic acid with subsequent separation of the organic layer of fatty acids, after which the residue, containing phosphorous acid, is treated with phosphorous tri-chloride and acetic anhydride at 115-130°C, and acidic impurities are distilled off to the controlled distillate volume.

EFFECT: simplification of the process of obtaining acidic phosphorous containing reagent and increase in its ecological safety with reduction of the quantity of wastes.

4 cl, 17 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention pertains to the chemistry of phosphorous organic compounds, and specifically to an acidic phosphorous containing complex-forming reagent, which can be used in the oil industry, heat energy, textile industry, production of mineral fertilizers and household chemistry, and to the method of obtaining it. The acidic phosphorous containing complex-forming reagent (conventional name "АФК-2") contains the following in mass %: acetoxyethylidenediphosphonic acid - 50-95 mass %, acetic acid - 50-5 mass %. The method of obtaining the composition involves adding phosphorous tri-chloride, acetic acid and water simultaneously to glacial acetic acid in molar ratios equal to 1:(4.5-5.5):(1.93-1.95), at temperature of 35-45°C with subsequent keeping of the reaction mixture at 110-120°C for a period of 2 hours and controlled distillation of acidic impurities to the required distillate volume.

EFFECT: simplification of the process of obtaining phosphorous containing complex-forming reagent and increasing its ecological safety with reduction on the quantity of wastes.

2 cl, 15 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention pertains to the method of obtaining an inhibitor of precipitation of mineral salts, The inhibitor is obtained by reaction of hexamethylenediamine and ammonium chloride with formaldehyde and phosphorous acid in a medium of diluted hydrochloric acid at high temperature with subsequent neutralisation of the obtained solution using sodium hydroxide to pH of 6.5±1.0. The process is carried out with molar ratio of hexamethylenediamine to ammonium chloride of 1:3-6.

EFFECT: high inhibition effect with stabilised treatment of water.

1 cl, 1 tbl, 6 ex

FIELD: organic chemistry, medicine, biochemistry.

SUBSTANCE: invention describes compound of the formula (I): wherein R1 means hydrogen atom (H); R2 means -SH, -S-C(O)-R8, -P(O)(OR5)2, -P(O)(OR5)R6, -P(O)(OR5)-R7-C(O)-R8, -P(O)(OR5)-R7-N(R5)-S(O)2-R9 or -P(O)(OR5)-R7-N(R5)-C(S)-N(R6)2; R3 means tetrazole, -C(O)OR6, -C(O)O-R7-OC(O)R5; R4 means optionally substituted aryl, or R4 means N-heterocyclyl. Also, invention describes compounds of the formula (II): and (III): wherein X means -CH2- or -O-, and pharmaceutical compositions comprising indicated compounds. Proposed compounds possess inhibitory effect on activity of plasma carboxypeptidase B and used as anti-thrombosis agents.

EFFECT: valuable medicinal and biochemical properties of compounds.

34 cl, 19 ex

FIELD: chemistry of organophosphorus compounds, chemical technology.

SUBSTANCE: invention describes a method for synthesis of monohydroperfluoroalkanes, bis-(perfluoroalkyl)phosphinates and perfluoroalkylphosphonates. Method involves treatment of at least one perfluoroalkylphosphorane with at least one base wherein base(s) are chosen from group consisting of alkali-earth metal hydroxides, metalloorganic compound in useful solvent or at least one organic base and an acid in useful reaction medium. Also, invention describes novel perfluoroalkylphosphonates and bis-(perfluoroalkyl)phosphinates, using novel perfluoroalkylphosphonates and bis-(perfluoroalyl)phosphinates as ionic liquids, catalysts of phase transfer or surfactants.

EFFECT: improved method of synthesis.

18 cl, 19 ex

FIELD: chemistry of metalloorganic compounds, chemical technology.

SUBSTANCE: invention relates to a method for preparing copper (II), zinc (II), nickel (II) and cobalt (II) nitrilotri-(methylenephosphonates)(2-) that involves crystallization from aqueous solutions prepared by interaction of metal (II) compound with nitrilotri-(methylenephosphonic) acid or its salt with sodium potassium or ammonium in aqueous medium at temperature from -5°C to 105°C under atmosphere pressure. As a reactive of the metal (II) compound source the waste from manufacturing printing plates and galvanic covers can be used. The end products can be used in preparing the complex electrolytes and solutions for applying metallic covers by electrochemical and chemical methods in aims for inhibition against the equipment corrosion, and for preparing other compounds of metals with nitrilotri-(methylenephosphonic) acid.

EFFECT: improved method of synthesis.

16 cl, 1 tbl, 19 ex

FIELD: chemistry.

SUBSTANCE: as photosensibilizers emulsions of alkylthiosubstituted phalocyanides of general formula , where R1=R4=Cl, R2=R3=n-C10H21S, M=Zn or R1=t-C4H9S, R2=R3=R4=H, M=HH or R1=t-C4H9S, R2=R4=H, R3=t-C4H9, M=HH or R1=R3=t-C4H9S, R2=R4=H, M=HH or R1=R2=R3=R4=t-C4H9S, M=HH or R1=R4=Cl, R2=R3=t-C4H9S, M=Zn, in water solution of Proxanol 268 are suggested.

EFFECT: elaboration of highly selective and efficient photosensibilizers for application in photodynamic therapy of tumours.

3 cl, 18 ex, 4 tbl, 9 dwg

FIELD: chemistry.

SUBSTANCE: invention concerns a new compound, zinc meso-trans-dihexadecyltetrabenzoporphyrinate .

EFFECT: compound can be applied as a fat-soluble green colorant for solution dyeing of paraffin and polyethylene.

1 cl, 2 ex, 2 dwg

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention proposes an improved method for synthesis of bis-(1-vinylimidazole)-zinc diacetate representing a complex compound of zinc diacetate with 1-vinylimidazole and known as medicinal preparation acizol. Acizol is an effective antidote and antihypoxic agent of the broad spectrum of effect. Method for synthesis of 1-vinylimidazole metal with zinc diacetate of the composition 2:1 involves carrying reaction in the absence of solvent and using available commercial zinc diacetate of the formula Zn(OCOCH3)2 x 2 H2O in the stoichiometric mole ratio 1-vinylimidazole : salt in the range from 2.9:1 to 2:1, and synthesized pure product is isolated by water distilling off or its azeotropic mixture with 1-vinylimidazole. Method provides excluding the dehydration step of parent zinc salt from technological process and to decrease consumption of used reagent 1-vinylimidazole significantly, Invention provides significant reducing energetic and industrial consumptions, simplifying and decreasing cost of process and retaining the quantitative yield of highly pure pharmacopoeia acizol preparation.

EFFECT: improved method of synthesis.

4 ex

FIELD: luminescent substances, organic chemistry.

SUBSTANCE: invention relates to electroluminescent materials containing organic luminescent substance. Invention describes novel electroluminescent material consisting of injection layer, active luminescent layer based on chelate metal complex, hole-transporting layer and hole-injecting layer. Material comprises metal complexes based on sulfanyl derivatives of 8-aminoquinoline as a luminescent substance, in particular, zinc complexes of 8-(methylsulfanylamino)-quinoline and 8-(3,5-difluorophenylsulfanylamino)-quinoline. Material comprises a mixture of triphenylamine oligomers as a hole-transporting layer. Invention provides creature of electroluminescent material showing the enhanced moisture resistance, enhanced resistance to crystallization and enhanced thermal stability.

EFFECT: improved and valuable properties of material.

4 cl, 5 ex

FIELD: organic chemistry.

SUBSTANCE: invention relates to novel compounds, namely zinc bis-[2-(tosylamino)benzylidene-N-alkyl(aryl, hetaryl)aminates] of the general formula (I): wherein Ts means tosyl; R means (C1-C6)-alkyl with exception isopropyl, (C1-C6)-alkyl-substituted phenyl, (C1-C6)-alkoxy-substituted phenyl with exception para- and ortho-methoxyphenyl, pyridyl, (C1-C6)-alkylpyridyl, or R + R form in common disulfidodialkyl group -(CH2)n-S-S-(CH2)n- wherein n = 1-3, but preferably to zinc bis-[2-(tosylamino)benzylidene-N-alkylidenemercaptoaminates] of the general formula (Ia): Compounds can be used for synthesis of light-radiating organic diode of white and visible light. Fluorescence can be observed in blue region of spectrum with fluorescence bands maximum at 428-496 nm. Quantum yields are 0.2-0.25.

EFFECT: valuable physical properties of compounds.

5 cl, 8 ex

FIELD: medicine, in particular photosensitizing agents for antimicrobial photodynamic therapy.

SUBSTANCE: invention relates to new photosensitizing agents for antimicrobial photodynamic therapy namely cationic phthalocyanines of general formula MPc(CH2X)nCln, wherein Pc is phthalocyanine rest C32H16N8; M is Zn, AlY; n = 6-8; X is Y is Cl, OH, OSO3H. Claimed agents is characterized by wide range of antimicrobial activity. Single complex action of nontoxic in darkness micromolar (up to 2.0 muM) concentration thereof and low dose of red irradiation make it possible to produce high inactivation levels (up to 97-99 %) both gram-negative bacteria and yeast fungi of genus Candida.

EFFECT: improved agents for treatment of various severe complications of inflammation diseases.

3 dwg, 13 ex, 2 tbl

FIELD: medicine, in particular photosensitizing agents for photodynamic therapy.

SUBSTANCE: invention relates to quaternary phthalocyanines of general formula MPc(CH2X)nCln, wherein Pc is phthalocyanine rest C32H16N8; M is Zn, AlY; n = 6-8; X is Y is Cl, OH, OSO3H, useful as photosensitizing agents in photodynamic therapy having high photoinduced activity in vivo and in vitro.

EFFECT: new class of effective photosensitizing agents useful in treatment of various tumors by photodynamic therapy.

1 dwg, 8 ex

FIELD: chemistry, chemical technology.

SUBSTANCE: invention relates to quaternized phthalocyanines and their using for treatment of water against bacterial pollution. Invention describes novel quaternized phthalocyanines representing poly-(trialkylammoniomethyl)-substituted zinc and aluminum phthalocyanines that are sensitizing agents in formation of singlet oxygen by effect of visible light. Also, invention relates to a method for photodisinfection of water by using these quaternized phthalocyanines or their mixtures with dyes of acridine, rhodamine or phenothiazine series and radiation in visible range in the presence of oxygen that provides the effective treatment of water against bacterial pollution.

EFFECT: valuable properties of compounds, improved method of water treatment.

3 cl, 5 tbl, 16 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for synthesis of zinc phthalocyanine of high purity degree that can be used as a photosensitizing agent for photodynamic therapy. Method is carried out by interaction of phthalonitrile with zinc salt at heating in the presence of a tertiary amine - N,N-dialkylaniline, N,N-dialkylethanolamine or trialkylamine in an aprotonic dipolar solvent medium, for example, dimethylformamide. Method provides preparing the end product with 97-99% content of the basic substance. Method shows the technological effectiveness as it suggests using inexpensive reagents, small amount of solvent and it doesn't require the complex purifying procedures.

EFFECT: improved method of synthesis.

2 cl, 4 ex

FIELD: production of high temperature superconductors.

SUBSTANCE: invention relates to electrochemical synthesis of metal β-diketonates, in particular acetylacetonates. Synthesis of Cu(II) and Zn(II) acetylacetonates in carried out by electrolysis of acetylacetone solution and base electrolyte in acetonitryl in ratio of (1:10):0.5:100, with electrodes made of metal presenting in produced acetylacetonate, at current density not more mA/cm2 by using pulse current. Pulse time is controlled by pulse forming unit connected in parallel to elecrtolyzer. As base electrolyte preferably lithium perchlorate or lithium chloride is used.

EFFECT: controlled process for production of metal acetylacetonates.

5 cl, 2 ex, 1 dwg

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

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