RU2280647C2 - Method for preparing copper (ii) bis-(1-hydroxyethane-1,1-diphosphonate (1-)) from production waste - Google Patents

Abstract

FIELD: organophosphorus compounds, chemical technology.

SUBSTANCE: invention relates to technology of organic substances, in particular, to the improved method for preparing copper (II) bis-(1-hydroxyethane-1,1-diphosphonate (1-)). The final copper (II) bis-(1-hydroxyethane-1,1-diphosphonate (1-)) is prepared by crystallization from aqueous solution with concentrations of copper salt (II) from 0.5 to 2.0 mole/l and 1-hydroxyethane-1,1-diphosphonic acid with concentration from 2.0 to 6.0 mole/l prepared by using copper-containing waste in galvanic and electronic engineering manufacture, or by using a semi-finished product from production of 1-hydroxyethane-1,1-diphosphonic acid. Invention provides reducing cost in production of copper (I) bis-(1-hydroxyethane-1,1-diphosphonate (1-)) in combination with retaining purity, expanded raw base for preparing the end product and utilization of manufacture waste.

EFFECT: improved preparing method.

9 cl, 1 tbl, 8 ex

Description

The invention relates to the chemical technology of organic compounds, in particular to a method for producing bis (1-hydroxyethane-1,1-di-phosphonate (1-)) copper (II). The product obtained by this method can be used to prepare complex electrolytes of galvanic and chemical copper plating, to inhibit corrosion of equipment in the oil and oil refining industries, as a bactericidal preparation, as a fungicide and copper micronutrient fertilizer in agriculture, as a microelement additive to multivitamin preparations and animal feed, as a medicine in veterinary medicine, to obtain other complex compounds of copper.

Copper (II) bis (1-hydroxyethane-1,1-diphosphonate (1-)) is a complex compound (chelate) of copper (II) with 1-hydroxyethane-1,1-diphosphonic acid CH ₃ C (OH) (PO) ₃ H ₂ ) ₂ [C ₂ H ₈ O ₇ P ₂ ] composition Cu (C ₂ H ₇ O ₇ P ₂ ) ₂ · 4H ₂ O.

A known method of producing bis (1-hydroxyethane-1,1-diphosphonate (1-)) copper (II), comprising preparing an aqueous solution containing copper (II) chloride and 1-hydroxyethane-1,1-diphosphonic acid in a molar ratio of 1 , 0: 3.0, addition of acetic acid, crystallization of the target product, separation of crystals from solution and their drying (Afonin E.G., Aleksandrov G.G., Sergienko V.S. // Coordination chemistry, 1997, V.23 No. 11, p. 846). The disadvantage of this method is the additional material costs for the reagent is copper (II) chloride and the solvent is acetic acid.

Closest to the claimed method is a method for producing bis (1-hydroxyethane-1,1-diphosphonate (1-)) copper (II), comprising preparing an aqueous solution with a concentration of copper (II) salt from 0.5 to 2.0 mol / l and a concentration of 1-hydroxyethane-1,1-diphosphonic acid from 2.0 to 6.0 mol / l, crystallization of the target product, separation of crystals from solution and their drying (Afonin E.G., Lvovsky V.M., Barinov A.V. RF Patent No. 2224763 C2, Cl. 7 C 07 F 9/38, publ. 02.27.2004). As the salt of copper (II) in the prototype, sulfamate, sulfate, chloride, perchlorate, nitrate, tetrafluoroborate, hexafluorosilicate and other copper (II) salts are used. The prototype method allows to obtain single-phase bis (1-hydroxyethane-1,1-diphosphonate (1-)) copper (II) in high yield. The disadvantage of this method is the need for additional costs for the reagent is a salt of copper (II).

When creating the invention, the task was to reduce material costs for obtaining bis (1-hydroxyethane-1,1-diphosphonate (1-)) copper (II), expand the range of materials used to obtain the target product, and utilize toxic production waste.

The problem is solved in that the method for producing bis (1-hydroxyethane-1,1-diphosphonate (1-)) copper (II) involves the preparation of an aqueous solution with a concentration of copper (II) salt from 0.5 to 2.0 mol / l and a concentration of 1-hydroxyethane-1,1-diphosphonic acid from 2.0 to 6.0 mol / l, crystallization of the target product, separation of crystals from solution and their drying. New in the claimed method is that as a source of a salt of copper (II) use liquid copper-containing waste products and / or as a source of 1-hydroxyethane-1,1-diphosphonic acid use an intermediate product of the production of 1-hydroxyethane-1,1-diphosphonic acid . As a liquid copper-containing production waste, it is desirable to use a spent electrolyte of galvanic copper plating or a spent solution of etching printed circuit boards or an eluate of ion-exchange wastewater treatment from copper (II) ions. If necessary, the liquid copper-containing waste product is pre-concentrated or diluted with water, or copper (II) oxide, hydroxide, and hydroxocarbonate are pre-added to it. As a source of 1-hydroxy-ethane-1,1-diphosphonic acid, it is desirable to use technical 1-hydroxyethane-1,1-diphosphonic acid with a basic substance content higher than 85% or an intermediate of the production of 1-hydroxyethane-1,1-diphosphonic acid containing as the main components of 1-hydroxyethane-1,1-diphosphonic acid, water, acetic acid. It is desirable to prepare an aqueous solution containing a salt of copper (II) and 1-hydroxyethane-1,1-diphosphonic acid in a molar ratio of 1.0: (1.8-4.0).

A method for producing bis (1-hydroxyethane-1,1-diphosphonate (1-)) copper (II) from production waste consists in mixing liquid copper-containing production waste and crystalline 1-hydroxyethane-1,1-diphosphonic acid (its aqueous solution) or in mixing a salt of copper (II) (its aqueous solution) and a semi-product of the production of 1-hydroxyethane-1,1-diphosphonic acid, crystallization of the target product when the solution is standing for a certain time, separating the crystals from the solution using one of the known methods, washing (if necessary ) sediment on Filtering the solvent, drying the crystal in air.

Bis (1-hydroxyethane-1,1-diphosphonate (1-)) of copper (II) is readily soluble in water. Therefore, to obtain it from an aqueous solution with a high yield, it is necessary to prepare an aqueous solution with a concentration of copper (II) salt above 0.5 mol / L and 1-hydroxyethane-1,1-diphosphonic acid above 2.0 mol / L. The upper limit of permissible concentrations of copper (II) salt is 2.0 mol / L and 1-hydroxyethane-1,1-diphosphonic acid 6.0 mol / L is limited by the solubility of substances in water, as well as the need to obtain a solution with a moderate viscosity.

To obtain bis (1-hydroxyethane-1,1-diphosphonate (1-)) copper (II) as liquid copper-containing waste from production, used solutions of various compositions containing copper (II) salts (simple or complex) in high concentrations can be used. It is advisable to use the waste of producing copper coatings by the electrochemical method — spent electrolytes of galvanic copper plating (GOST USSR 9.305-84. Metallic and nonmetallic inorganic coatings. Operations of technological processes for producing coatings. - M .: Iz Gosstandart, 1988, S. 61, 65. Guskov S.V., Kazakovtsev Yu.I., Bychkov V.F. // Exchange of industrial and technical experience, 1989, No. 5, P. 14), which have the composition, for example:

Copper (II) sulfate 100-190 g / l Sulphuric acid 40-110 g / l

or

Copper (II) sulfate 65-130 g / l Copper (II) Nitrate 80-120 g / l Sulphuric acid 40-110 g / l

waste from electronic production - spent solutions for etching printed circuit boards (Fedulova A.A., Ustinov Yu.A., Kotov E.P., Shustov V.P., Yavich E.R. Technology of multilayer printed circuit boards. - M .: Radio and communication , 1990, P.186. Dudko NK, Nikolaeva EM, Solovieva TG // Exchange of industrial and technical experience, 1988, No. 8, P.29), which have the composition, for example:

Copper (II) chloride 180-240 g / l Hydrogen chloride 30-85 g / l

wastes from the treatment of copper-containing wastewater from the production of galvanic coatings, printed circuit boards - eluates formed during the washing (regeneration) of ion-exchange resins with solutions of mineral acids (Proskuryakov V.A., Shmidt L.I. Wastewater treatment in the chemical industry. - L .: Chemistry, 1977, S. 169. Nadeau, T., Dejak M. // Plating and Surface Finishing, 1986, No. 4, P. 48. Flexible Automated Galvanic Lines. Handbook. - M .: Mechanical Engineering, 1989, S. 439. .I., Plohov S.V., Matasova I.G., Mikhalenko M.G. // Ecology and Industry in Russia, 1999, No. 5, P.35), which have a composition on Example:

Copper (II) sulfate 60-110 g / l Sulphuric acid 30-60 g / l

or

Copper (II) chloride 25-40 g / l Hydrogen chloride 40-60 g / l.

In addition to these liquid waste products for the production of bis (1-hydroxyethane-1,1-diphosphonate (1-)) copper (II), you can directly use other waste solutions containing copper (II) in concentrations from 0.5 to 2.0 mol / l, for example, spent copper-ammonia solution for the production of divinyl (Trunin A.S., Ktumanev A.N., Kosmynin A.S., Igontov V.G., Eremin Yu.A. RF patent No. 2164491 C2, Cl. 7 C 05 D 9/02, 11/00, A 01 N 59/20, publ. 2001).

To obtain bis (1-hydroxyethane-1,1-diphosphonate (1-)) copper (II), liquid copper-containing waste products containing a copper (II) salt in a concentration below 0.5 mol / L can also be used. Such solutions are pre-concentrated by known methods (evaporation at atmospheric pressure, vacuum evaporation, freezing of the solvent and others) to a concentration of copper (II) salt from 0.5 to 2.0 mol / L. Liquid copper-containing production wastes containing copper (II) salt in a concentration below 0.5 mol / l and mineral acids (sulfuric, hydrochloric, tetrafluoroboric) to increase the concentration of copper (II) salt and, as a result, to increase the yield of the target product, it is desirable pretreated with copper (II) oxide, hydroxide or hydroxocarbonate.

To obtain bis (1-hydroxyethane-1,1-diphosphonate (1-)) copper (II), you can use 1-hydroxyethane-1,1-diphosphonic acid grade "h", manufactured by the chemical industry, for example, according to TU 6-09- 713-84, TU 6-09-5372-87, TU 6-09-20-174-90, or 1-hydroxyethane-1,1-diphosphonic acid monohydrate, which is obtained by recrystallization of the reagent grade “h” from an aqueous solution of acetic acid (Afonin E.G., Pechurova N.I. // Journal of General Chemistry, 1987, V. 57, No. 3, S.538). To reduce the material costs of obtaining bis (1-hydroxyethane-1,1-diphosphonate (1-)) copper (II), technical grade 1-hydroxyethane-1,1-diphosphonic acid, concentrated aqueous solution or aqueous suspension can be used instead of a commercial reagent 1-hydroxyethane-1,1-diphosphonic acid, as well as a mixture of 1-hydroxyethane-1,1-diphosphonic acid with acetic acid or a mixture of 1-hydroxyethane-1,1-diphosphonic acid with acetic acid and water, formed at various stages of industrial production of 1-hydroxyethane-1,1-diphosphonic acid (Pa nfilov V.Ya., Efremov A.I., Shevnitsyn L.S., Abramov I.A., Kasimov R.G., Danilov S.D., Vinogradov E.A., Golyakin N.P., Gradov V. A., Nikitinsky VD Auth. St. USSR No. 1065418, Cl. 07 F 9/38, published 1984; Suchkov A.V., Wise F.V., Milgotin I.M., Bolshova I. V., Bogach E.V., Kuznetsov A.A., Badmaev A.V., Komova S.N., Kostryukova M.N. RF Patent No. 2173321 C1, Cl. C 07 F 9/38, publ. 2001 ; Badmaev A.V., Wise F.V., Suchkov A.V., Milgotin I.M., Bogach E.V., Kuznetsov A.A., Bolshova I.V. RF patent No. 2178793 C1, Cl. C 07 F 9/38, publ. 2002). The yield and quality of the resulting target product remain high (see examples 7.8).

Since bis (1-hydroxyethane-1,1-diphosphonate (1-)) of copper (II) is formed in solution as a result of the equilibrium process

CuX ₂ + 2C ₂ H ₈ O ₇ P ₂ ↔ Cu (C ₂ H ₇ O ₇ P ₂ ) ₂ + 2HX,

where X is the mineral acid anion, then the shift of the reaction equilibrium towards the formation of the target product is promoted not only by high concentrations of reagents in the solution, but also by the creation of a certain molar excess of 1-hydroxyethane-1,1-diphosphonic acid in the solution. The lower limit of the desired molar ratio of copper (II): 1-hydroxyethane-1,1-diphosphonic acid 1.0: 1.8 is determined by the need to obtain the target product with a yield of at least 30% from solutions with a high concentration of copper (II). The upper limit of the desired molar ratio of copper (II): 1-hydroxyethane-1,1-diphosphonic acid 1.0: 4.0 is determined by the need to obtain the target product with a yield of at least 30% from solutions with a low concentration of copper (II).

Example 1

20.0 ml of spent electrolyte of copper plating with concentrations of copper (II) sulfate 141 g / l, sulfuric acid 50 g / l is evaporated by heating to a volume of 10.0 ml and 11.0 g of 1-hydroxyethane-1.1 are added with stirring diphosphonic acid TU 6-09-713-84 brand "h". A crystalline seed is introduced Cu (C ₂ H ₇ O ₇ P ₂ ) ₂ · 4H ₂ O. The solution is left to crystallize for 4 days at a temperature of 18-20 ° C. The precipitate is filtered off on a POR 100 glass filter under reduced pressure, the filter cake is washed first with a 50% aqueous solution of ethanol (three portions of 1 ml), then ethanol (three portions of 1 ml). The precipitate is dried in air at room temperature to constant weight. Copper (II) yield 94%.

Found,%: C - 8.6; H - 3.9; P - 22.4; Cu - 11.6.

Calculated for Cu (C ₂ H ₇ O ₇ P ₂ ) ₂ · 4H ₂ O,%: C - 8.80; H - 4.06; P - 22.71; Cu - 11.65.

Example 2

10.0 ml of spent electrolyte of copper plating with concentrations of copper (II) sulfate 128 g / l, sulfuric acid 39 g / l is evaporated by heating to a volume of 5.0 ml and 4.2 g of 1-hydroxyethane-1,1 are added with stirring diphosphonic acid TU 6-09-713-84 brand "h". After cooling to room temperature, crystalline seed Cu (C ₂ H ₇ O ₇ P ₂ ) ₂ · 4H ₂ O is introduced into the solution. The solution is left to crystallize for 1 day at a temperature of (-4) - (- 6) ° C. The precipitate is filtered off on a POR 100 glass filter under reduced pressure, washed on the filter with ethanol (two 2 ml portions) and dried in air at room temperature to constant weight. Copper (II) yield 85%.

Found,%: C - 8.5; H - 3.8; P - 22.4; Cu - 11.3.

Example 3

In 20.0 ml of spent electrolyte of electroplating copper plating with concentrations of copper (II) sulfate 152 g / l, sulfuric acid 98 g / l with stirring, dissolve 1.59 g of copper oxide (II) GOST 16539-79 brand “h”, heat the resulting a solution to a temperature of 60-70 ° C and 20.6 g of 1-hydroxyethane-1,1-diphosphonic acid TU 6-09-713-84 of the grade "h" are dissolved in it. After cooling to room temperature, crystalline seed Cu (C ₂ H ₇ O ₇ P ₂ ) ₂ · 4H ₂ O is introduced into the solution. The solution is left to crystallize for 6 days at room temperature. The precipitate is filtered off on a POR 40 glass filter under reduced pressure, washed on the filter with an 80% aqueous ethanol solution (three portions of 3 ml) and dried in air at room temperature to constant weight. The yield of copper (II) 82%.

Found,%: C - 8.5; H - 4.1; P - 22.0; Cu - 11.8.

Example 4

In 20.0 ml of spent electrolyte of galvanic copper plating with concentrations of copper (II) sulfate 148 g / l, sulfuric acid 51 g / l, 0.83 g of copper (II) oxide GOST 16539-79 grade “h” is dissolved, then 18, 2 g of 1-hydroxyethane-1,1-diphosphonic acid TU 6-09-713-84 brand "h". Evaporate the solution by heating to a volume of 20.0 ml. After cooling to room temperature, crystalline seed Cu (C ₂ H ₇ O ₇ P ₂ ) ₂ · 4H ₂ O is introduced into the solution. The solution is left to crystallize for 4 days at room temperature. The precipitate is filtered off on a POR 40 glass filter under reduced pressure, washed on the filter with a 60% aqueous ethanol solution (three portions of 2 ml each), then with ethanol (three 2 ml portions) and dried in air at room temperature to constant weight. Copper (II) yield 97%.

Found,%: C - 8.9; H - 3.9; P - 22.5; Cu - 11.5.

Example 5

In 10.0 ml of the spent etching solution for printed circuit boards with copper (II) chloride concentrations of 136 g / l, 82 g / l of hydrogen chloride is first dissolved 0.87 g of copper (II) oxide GOST 16539-79 brand "h", then 18, 0 g of 1-hydroxyethane-1,1-diphosphonic acid TU 6-09-713-84 brand "h". A crystalline seed of Cu (C ₂ H ₇ O ₇ P ₂ ) ₂ · 4H ₂ O is introduced into the solution. The solution is left to crystallize for 3 days at a temperature of 20-22 ° C. The precipitate is filtered on a POR 40 glass filter under reduced pressure, washed on the filter with ethanol (four portions of 2 ml) and dried in air at room temperature to constant weight. Copper (II) yield 85%.

Found,%: C - 8.6; H - 3.9; P - 22.4; Cu - 11.4.

Example 6

10.0 ml of the eluate of ion-exchange wastewater treatment of copper (II) ions with copper (II) sulfate concentrations of 80 g / l, sulfuric acid 59 g / l is heated to 70-80 ° C, 1.48 g of oxide is added first with stirring copper (II) GOST 16539-79 grade "h", then 14.9 g of 1-hydroxyethane-1,1-diphosphonic acid TU 6-09-713-84 brand "h". After cooling to room temperature, crystalline seeds are introduced with Cu (C ₂ H ₇ O ₇ P ₂ ) ₂ · 4H ₂ O and the solution is left to crystallize for 3 days at room temperature. The precipitate is filtered off on a POR 16 glass filter under reduced pressure, washed on the filter with ethanol (three portions of 3 ml) and dried in air at room temperature to constant weight. The yield of copper (II) is 96%.

Found,%: C - 8.7; H - 4.1; P - 22.8; Cu - 11.8.

Example 7

5.0 g of copper (II) sulfate pentahydrate GOST 4165-78 grade “h” and 13.6 g of technical 1-hydroxyethane-1,1-diphosphonic acid are dissolved in 10.0 ml of water when heated to a temperature of 60-80 ° C. (the content of 1-hydroxyethane-1,1-diphosphonic acid is 91%, phosphorous acid 2%, acetic acid 3%, water 4%). The solution was left to crystallize for 1 day at room temperature. The precipitate is filtered off on a POR 40 glass filter under reduced pressure, washed on the filter with a 70% aqueous ethanol solution (three portions of 1 ml each), then with ethanol (two 2 ml portions) and dried in air at room temperature to constant weight. Copper (II) yield 91%.

Found,%: C - 8.5; H - 3.6; P - 22.3; Cu - 11.6.

Example 8

To 10.0 ml of spent electrolyte of galvanic copper plating with concentrations of copper (II) sulfate 140 g / l, sulfuric acid 50 g / l, 1.50 g of copper (II) hydroxocarbonate are first added with stirring, then 21.0 g of intermediate 1- hydroxyethane-1,1-diphosphonic acid containing 67 wt.% 1-hydroxyethane-1,1-diphosphonic acid, 16 wt.% water, 17 wt.% acetic acid and heated at a temperature of 40-50 ° C until the substances are dissolved. The solution was left to crystallize for 1 day at room temperature. The precipitate is filtered off on a POR 40 glass filter under reduced pressure, washed on the filter with a 70% aqueous solution of acetic acid (three portions of 2 ml), then acetone (two portions of 2 ml). The substance is dried in air at room temperature to constant weight. Copper (II) yield 95%.

Found,%: C - 8.6; H - 3.8; P - 22.5; Cu - 11.7.

Obtained in examples 1-8 bis (1-hydroxyethane-1,1-diphosphonate (1-)) of copper (II) is a crystalline substance of blue color. The substance is highly soluble in water, alkalis, aqueous solutions of ammonia and mineral acids, poorly soluble in ethanol, acetic acid, acetone, chloroform, carbon tetrachloride, hexane, benzene. The substance is stable when stored in air at room temperature.

According to elemental analysis (see examples) and powder x-ray (see table), the claimed method allows to obtain a well-crystallized single-phase bis (1-hydroxyethane-1,1-diphosphonate (1-)) of copper (II) copper (II) composition Cu (C ₂ H ₇ O ₇ P ₂ ) ₂ · 4H ₂ O with high yield. The reduction of material costs in obtaining the target product in the claimed method is achieved by using liquid copper-containing production waste as a source of copper (II), in particular spent electrolyte of galvanic copper plating, spent solution for etching printed circuit boards, eluate of ion-exchange wastewater treatment from copper ions, instead of used in the method according to the prototype of the purchased reagents - salts of copper (II), and also due to the use of technical 1-gi as a source of 1-hydroxyethane-1,1-diphosphonic acid droxyethane-1,1-diphosphonic acid or intermediates of industrial production of this substance, in particular mixtures of 1-hydroxyethane-1,1-diphosphonic acid with acetic acid and other substances. Liquid copper-containing production wastes pose a serious environmental problem, since they contain copper (II) toxic to humans and animals in high concentrations in the form of various simple and complex compounds. To neutralize them, significant material costs are required. Utilization of liquid copper-containing industrial wastes in the technological process for producing bis (1-hydroxyethane-1,1-diphosphonate (1-)) copper (II) can reduce environmental costs. The use of copper-containing production waste makes it possible to expand the range of materials and the raw material base for producing bis (1-hydroxy-ethane-1,1-diphosphonate (1-)) copper (II) while maintaining a high yield of the target product and its high quality.

Table 1
X-ray identification of bis (1-hydroxyethane-1,1-diphosphonate (1-)) copper (II) h k one The calculated values Experimental values d, E I,% Example 1 Example 8 d, E I,% d, E I,% one one 0 8,582 10 8.57 7 8.56 four -one one one 8,114 81 8.11 45 8.12 40 2 0 0 6,572 one hundred 6.57 one hundred 6.58 one hundred one one one 5,928 23 5.92 22 5.93 17 -2 0 2 5,811 10 5.80 10 5.81 9 0 2 0 5,666 47 5.66 35 5.67 thirty 0 0 2 5,507 63 5.50 fifty 5.51 45 -one one 2 5,480 36 -3 one one 4,553 10 4,55 9 4,55 9 -2 2 one 4,504 5 4,50 four 4,51 3 2 2 0 4,291 5 4.29 four 4.29 four one one 2 4,089 39 4.09 thirty 4.09 28 -2 2 2 4,057 5 -3 one 3 3,666 6 3,668 four 3,663 four -one 3 one 3,592 21 3,591 16 3,596 17 2 0 2 3,478 6 3,477 6 3,485 four 3- one one 3,371 10 3,373 9 3,372 eleven -one 3 2 3,234 5 3,233 3 3,234 5 -four 2 2 3,105 32 3,106 27 3,106 25 one one 3 3,048 10 3,048 7 3,048 7 -3 one four 2,985 23 2,985 16 2,984 fifteen -four 0 four 2,906 6 2,898 twenty 2,899 19 -5 one 2 2,897 19 one 3 2 2,862 6 2,860 5 2,867 5 four 2 0 2,842 eighteen 2,841 twenty 2,840 19 0 four 0 2,833 fifteen -one 3 3 2,771 7 2,771 7 2,772 5 0 0 four 2,753 12 2,750 10 2,752 12 0 four one 2,744 6 -four 2 four 2,585 17 2,585 12 2,588 10 2 2 3 2,438 10 2,438 9 2,441 8 four 0 2 2,366 7 2,364 7 2,369 7 -5 3 2 2,347 5 2,346 5 2,348 5 -5 3 one 2,295 8 2,295 7 2,297 8 3 one 3 2,271 8 2,271 6 2,271 8 -3 one 6 2,053 5 2,052 four 2,053 four 2 2 four 2,044 5 2,043 10 2,046 9 6 2 0 2,043 7 -5 one 6 1,998 8 1,998 6 1,998 5 Legend: d is the interplanar distance, I is the relative intensity of the reflections on the x-ray powder.

Claims (9)

1. The method of obtaining bis (1-hydroxyethane-1,1-diphosphonate (1-)) copper (II) from waste products, including the preparation of an aqueous solution with a concentration of copper (II) salt from 0.5 to 2.0 mol / l and a concentration of 1-hydroxyethane-1,1-diphosphonic acid from 2.0 to 6.0 mol / l, crystallization of the target product, separation of the crystals from the solution and their drying, characterized in that the liquid salt is used as a source of copper (II) a copper-containing waste product and / or as a source of 1-hydroxyethane-1,1-diphosphonic acid, an intermediate product is used 1-hydroxyethane-1,1-diphosphonic acid. 2. The method according to claim 1, characterized in that the spent copper-containing electrolyte is used as liquid copper-containing production waste. 3. The method according to claim 1, characterized in that as the liquid copper-containing waste products used exhaust solution of etching of printed circuit boards. 4. The method according to claim 1, characterized in that the eluate of ion-exchange wastewater treatment from copper (II) ions is used as liquid copper-containing production waste. 5. The method according to claim 1, characterized in that the liquid copper-containing waste product is pre-concentrated or diluted with water. 6. The method according to claim 1, characterized in that a substance selected from the group consisting of oxide, hydroxide, copper (II) hydroxocarbonate is preliminarily added to the liquid copper-containing waste product. 7. The method according to claim 1, characterized in that the intermediate product of the production of 1-hydroxyethane-1,1-diphosphonic acid contains, as main components, 1-hydroxyethane-1,1-diphosphonic acid, water or 1-hydroxyethane-1,1- diphosphonic acid, acetic acid or 1-hydroxyethane-1,1-diphosphonic acid, water, acetic acid. 8. The method according to claim 1, characterized in that technical intermediate 1-hydroxyethane-1,1-diphosphonic acid with a basic substance content of above 85% is used as an intermediate product of the production of 1-hydroxyethane-1,1-diphosphonic acid. 9. The method according to claim 1, characterized in that an aqueous solution is prepared containing a salt of copper (II) and 1-hydroxyethane-1,1-diphosphonic acid in a molar ratio of 1.0: (1.8-4.0).