RU2579107C1 - Method of producing copper phosphate monohydrate (+2)-ammonium from production wastes - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method of producing copper phosphate(+2)-ammonium involves preparation of a reactive aqueous solution containing copper(+2), phosphate and ammonium, precipitation of copper phosphate monohydrate(+2)-ammonium and its separation from the solution. Source of copper(+2) is used as liquid production wastes selected from a group consisting of spent solution from printed-circuit board etching, spent solution from the first printed-circuit board washing after etching, spent solution from printed-circuit board copper plating, spent solution from copper etching in mineral acids taken separately or in any combination. Reduced extraction of 99.9% copper(+2) from spent solutions.

EFFECT: reduced cost of the product and extraction copper(+2) from spent solutions.

12 cl, 2 dwg, 8 ex

Description

The invention relates to the chemical technology of inorganic substances and industrial ecology, in particular to methods for producing copper phosphates (+2) and methods for processing toxic liquid copper wastes (+2), which are formed upon receipt of copper coatings, surface treatment of copper parts, printing circuit boards. Solutions containing copper (+2) in high concentration are toxic waste of many technological processes. In large quantities, they are formed in the manufacture of printed circuit boards, the production of copper coatings, the surface treatment of copper and its alloys, the synthesis of organic substances and the production of copper-ammonia fibers. Copper is a valuable non-ferrous metal, therefore, it is necessary to extract copper (+2) from spent solutions either in the form of a metal or in the form of some chemical compound in order to return an expensive and scarce component of production waste into economic circulation.

Several methods are known in the art for producing a double salt of copper phosphate (+2) ammonium, which crystallizes from an aqueous solution in the form of a monohydrate of the composition состава ₄ CuΡΟ ₄ · H ₂ H.

A method of obtaining phosphate monohydrate, copper (+2) ammonium, which comprises treating with water at 35 ° C compound (NH _{4) 4} [Cu (NH _{3) 2]} (PO _{4) 2} · 7H ₂ O (Syntheses of inorganic compounds (ed Jolly W.). T. 2. M.: Mir. 1967. S. 209). The disadvantage of this method is its complexity and the need for reagent costs (the starting compound is obtained using copper oxide (+2), ammonia, phosphoric acid).

A known method of producing copper phosphate monohydrate (+2) -ammonium, including dissolving copper oxide (+2) in excess phosphoric acid by heating, followed by neutralization of the solution with gaseous ammonia (Turaev Z., Khakimova V.K., Tukhtaev C. Interaction of copper oxide with ammonium phosphates // Uzbek Chemical Chemistry Journal 1985. No. 4. P. 43-45). The disadvantage of this method is the need for costs for reagents and for heating the solution.

A known method of producing copper phosphate monohydrate (+2) -ammonium, including the preparation of a reaction aqueous solution containing copper (+2), phosphate and ammonium, in which the reaction aqueous solution is prepared by the reaction of powdered metallic copper with ammonium carbonate in an aqueous medium, followed by addition phosphoric acid solution (Kopilevich V.A., Voitenko L.V., Shchegrov L.N., Panchuk T.K. Method for producing copper-ammonium phosphate monohydrate. RF Patent No. 2051089. Publ. 1995). The disadvantage of this method is the need for costs for reagents and for heating the solution.

A known method for producing copper phosphate monohydrate (+2) -ammonium, including the preparation of a reaction aqueous solution containing copper (+2), phosphate and ammonium, in which the source of copper (+2) is copper sulfate, the source of ammonia is ammonia, and the source of phosphate - a solution obtained by alkaline hydrolysis of an off-grade pesticidal preparation O, O-dimethyl-S (N-methylcarbamoylmethyldithiophosphate) (Ransky A.P., Petruk R.V. Povniy pond hydrolysis of non-pesticidal pesticide drugNAU. 2012. No. 1. P. 258-265). The method allows to utilize sodium phosphate formed during the hydrolysis of substandard pesticide. The disadvantage of this method is the need for material costs for copper sulfate (+2). The method does not provide for the disposal of liquid copper waste (+2).

A known method of producing copper phosphate monohydrate (+2) -ammonium, including the preparation of a reaction aqueous solution containing copper (+2), phosphate and ammonium, the formation of a precipitate of copper phosphate monohydrate (+2) -ammonium and its separation from a solution in which copper (+2) is copper sulfate, and the source of phosphate and ammonium is ammonium hydrogen phosphate, taken in a molar ratio of 1.0: (3.5-4.0). The reaction is carried out at 60-80 ° C for 1 h (Kopilevich V.A., Shchegrov L.N., Panchuk T.K., Fomenko V.V. Auth. Svid. SSSR No. 1742207. Publ. 1992). The disadvantage of this method is the need for costs of copper sulfate and for heating the solution.

A known method of producing copper phosphate monohydrate (+2) -ammonium, including the preparation of a reaction aqueous solution containing copper (+2), phosphate and ammonium, the formation of a precipitate of copper phosphate (+2) -ammonium and its separation from a solution in which the reagents are Copper chloride (+2) and ammonium hydrogen phosphate taken in large excess (Bassett H., Bedwell WL Studies of phosphates. I. Ammonium magnesium phosphate and related compounds // J. Chem. Soc. 1933. P. 854-871. Lapina L.M. Metallammonium phosphates and new fields of their application // Advances in Chemistry. 1968. V. 37. No. 9. S. 1626-1641). The disadvantage of this method is the need for material costs for copper chloride (+2). The method does not provide for the disposal of liquid copper waste (+2).

Also known is a method of producing copper phosphate (+2) -ammonium monohydrate, comprising preparing a reaction aqueous solution containing copper (+2), phosphate and ammonium, the formation of a precipitate of copper (+2) -ammonium phosphate monohydrate and its separation from a solution in which the source of copper (+2) is a compound of copper (+2) soluble in phosphoric acid (oxide, hydroxide, carbonate, chloride, sulfate, nitrate, silicate) (Salutsky ML, Lee FS, Bridger GL Process for preparing metal ammonium phosphates. US Patent No. 3126254, publ. 1964). The copper compound (+2) is dissolved in phosphoric acid in an aqueous medium, then an ammonia solution is added to pH 7, the solution with the precipitate is kept for several days, after which the precipitate is separated from the solution by filtration, washed with water and dried at room temperature. The disadvantage of this method is the need for material costs for the connection of copper (+2). The method does not provide for the disposal of liquid copper waste (+2).

Closest to the claimed is a method of producing copper phosphate (+2) -ammonium monohydrate, including the preparation of a reaction aqueous solution containing copper (+2), phosphate and ammonium, the formation of a precipitate of copper (+2) -ammonium phosphate monohydrate and its separation from the solution , in which the source of copper (+2) is copper sulfate, and the source of phosphate and ammonium is ammonium hydrogen phosphate (Kopilevich V.A., Shchegrov L.I., Panchuk T.K. On the conditions for the formation of CuNH ₄ PO ₄ · H ₂ O // Journal of Inorganic Chemistry. 1991.Vol. 36. No. 7. P. 1654-1657). In the prototype method for producing copper (+2) -ammonium phosphate monohydrate in a reaction aqueous solution, copper (+2) and ammonium hydrogen phosphate are taken in a molar ratio of 1.0: 4.0. The disadvantage of this method is the need for material costs for copper sulfate (+2). The method does not provide for the disposal of liquid copper waste (+2).

The aim of the claimed invention is to reduce the material costs of obtaining pure copper phosphate (+2) -ammonium, expand the arsenal of methods for processing liquid waste containing copper (+2), reduce material costs to protect the environment from the negative effects of copper (+2).

The goal is achieved in that the method of producing copper phosphate monohydrate (+2) -ammonium from waste products includes the preparation of a reaction aqueous solution containing copper (+2), phosphate and ammonium, the formation of a precipitate of copper phosphate monohydrate (+2) -ammonium and its separation from the solution. New in the claimed method is that as a source of copper (+2) use a liquid waste product selected from the group consisting of a spent solution of etching printed circuit boards, a spent solution of the first washing of printed circuit boards after etching, a spent solution of galvanic copper plating of used circuit boards a solution of etching copper in mineral acids, and the liquid waste products are taken individually or in combination with each other. As a spent solution for etching printed circuit boards, it is desirable to use a spent copper-ammonia solution for etching printed circuit boards, spent acidic or ammonia copper-sulfate solutions for etching printed circuit boards, spent acidic copper-chloride solution for etching printed circuit boards, spent sulfuric acid or ammonia peroxodisulfate solutions for etching printed circuit boards. In addition, as a source of copper (+2), it is desirable to use a spent solution of galvanic copper plating of printed circuit boards containing copper sulfate (+2), sulfuric acid as the main components, as well as a spent solution of copper etching in mineral acids, containing as main components copper (+2), sulfuric acid, nitric acid. It is desirable to use phosphoric acid or ammonium phosphate, or ammonium hydrogen phosphate, or ammonium dihydrogen phosphate, or ammophos and / or diammophos mineral fertilizers as a source of phosphate for preparing the reaction aqueous solution, and it is desirable to use ammonium phosphates and / or ammonia as a source of ammonium.

The claimed method for producing copper phosphate monohydrate (+2) -ammonium consists in preparing a reaction aqueous solution containing copper (+2), phosphate ions and ammonium cations as main components. The said aqueous reaction solution is prepared by mixing a liquid waste containing copper (+2), which can be a spent solution of etching the printed circuit boards, a spent solution of the first washing of the printed circuit boards after etching, a spent solution of galvanic copper plating of the printed circuit boards, a spent solution of etching copper in mineral acids, moreover, these solutions containing copper (+2) solutions can be taken either individually or in combination with each other, with reagents that are a source of phosphate ions and cation Ammonium s. Various chemicals can serve as these reagents: phosphoric acid H ₃ PO ₄ and its aqueous solutions, ammonium phosphates (ammonium phosphate (NH ₄ ) ₃ PO ₄ , ammonium hydrogen phosphate (ΝΗ ₄ ) ₂ ΗΡ O ₄ , ammonium dihydrogen phosphate ΝΗ ₄ Η ₂ ΡΟ ₄ ), taken individually or in various combinations, as well as ammophos mineral fertilizers (contains 85-90% ammonium dihydrogen phosphate and 5-7% ammonium hydrogen phosphate) and / or diammophos (contains mainly ammonium hydrogen phosphate), gaseous ammonia and its aqueous solutions. Another source of phosphate ions and ammonium cations in the reaction aqueous solution may be a mixture of sodium phosphates and ammonium salts (chloride, sulfate, nitrate). The source of sufficient amounts of ammonium cation can often be the waste solution of the etching of printed circuit boards, containing free ammonia and / or ammonia, complexed with copper (+2), and / or an ammonium salt (chloride, carbonate, sulfate, peroxodisulfate). If necessary, the pH of the reaction aqueous solution is adjusted by adding mineral acid (preferably phosphoric acid) or a base (preferably ammonia solution). A precipitate of copper (+2) -ammonium copper phosphate monohydrate precipitates from the resulting reaction aqueous solution. If necessary, the suspension is maintained for a time sufficient to form a crystalline precipitate of copper phosphate monohydrate (+2) -ammonium, which quickly settles and takes up a small volume. The precipitate is separated from the solution by one of the known methods. If necessary, the precipitate is washed with water, ethanol, acetone or another suitable solvent and dried at ordinary or elevated temperature in air.

The method for producing copper phosphate (+2) -ammonium monohydrate is based on chemical reactions, for example:

In contrast to low-toxic reagents, which are a source of phosphate ions and ammonium cations, the copper source (+2) -ammonium used in the claimed method for producing copper phosphate monohydrate (+2) is a toxic waste of industrial production (Harmful chemicals. Inorganic compounds of elements I-IV groups (under the editorship of V. Filov). L.: Chemistry. 1988. P. 61. Some questions of the toxicity of metal ions (under the editorship of Siegel X., Siegel Α.). Μ .: Mir. 1993 P. 49. Vinogradov SS Ecologically safe galvanic production.M .: Globus. 200 2. S. 26) primarily due to the high concentration of copper (+2). Such production waste can be, for example, spent solutions for etching printed circuit boards (copper (+2) 60-140 g / l, hydrogen chloride 10-50 g / l, ammonium chloride 50-150 g / l or copper (+2) 50- 120 g / l, ammonia 50-100 g / l, ammonium chloride 50-150 g / l, or copper (+2) 50-130 g / l, ammonia 30-120 g / l, ammonium chloride 5-50 g / l, ammonium carbonate 20-400 g / l, or copper (+2) 40-100 g / l, ammonia 50-130 g / l, ammonium sulfate 40-100 g / l, or copper (+2) 9-45 g / l, sulfuric acid 10-40 g / l, ammonium peroxodisulfate 20-200 g / l, ammonium sulfate 25-130 g / l, or copper (+2) 9-22 g / l, ammonia 60-75 g / l, ammonium peroxodisulfate 10-55 g / l, ammonium sulfate 40-110 g / l), waste solution of the first washing of printed circuit boards after etching (copper (+2) 2-5 g / l, ammonia 2-6 g / l, ammonium chloride 0-290 g / l, ammonium carbonate 0-30 g / l), spent solution copper plating of printed circuit boards (copper (+2) 25-60 g / l, sulfuric acid 60-240 g / l), spent solution of copper etching in mineral acids (copper (+2) 15-30 g / l, sulfuric acid 500 -900 g / l, nitric acid 50-400 g / l, sodium chloride 1-10 g / l or copper (+2) 20-30 g / l, sulfuric acid 800-1000 g / l, sodium nitrate or ammonium nitrate 200-290 g / l).

Thus, the claimed method allows to obtain copper phosphate monohydrate (+2) -ammonium using inexpensive, non-deficient reagents and at the same time to utilize various types of toxic liquid copper waste (+2).

For the production of copper phosphate (+2) -ammonium should not be used as a source of copper (+2) the spent solution of etching printed circuit boards based on iron chloride (+3), since when adding ammonium phosphates to it, in addition to the target product, precipitate iron phosphate (+3) and iron phosphates (+2), as well as a spent solution for etching printed circuit boards based on chromium trioxide and sulfuric acid, because the latter always contains chromium sulfate (+3), which, when ammonium phosphates are added to it, gives a precipitate of chromium phosphate (+3). The spent solutions for etching printed circuit boards (sulfate and ammonia) containing a strong oxidizing agent, ammonium peroxodisulfate, can be successfully used to produce copper phosphate (+2) -ammonium by the claimed method, because the used reagents ammonium and phosphate are resistant to the oxidative action of peroxodisulfate.

Examples of the preparation of copper (+2) -ammonium phosphate monohydrate from spent solutions of various compositions.

Example 1

Mix 50 ml of the spent solution of galvanic copper plating of printed circuit boards with copper (+2) concentrations of 0.42 mol / l, sulfuric acid 2.4 mol / l with a solution of 8.3 g of “chda” grade ammonium hydrogen phosphate in 30 ml of water and with stirring 25% ammonia solution was added dropwise until a pH of 7.0 was reached. The solution was left to stand, periodically shaking, at room temperature until the sediment particles coarsened significantly and sedimentation rate increased, after which the precipitate was filtered on a POR 40 glass filter under reduced pressure (pH of the filtrate 5.7), washed 2 times with water and ethanol and dried in air at room temperature to constant weight. Copper yield (+2) 99.8%. Found,%: Cu - 33.0; N - 7.0; Ρ - 16.1. For NH ₄ CuPO ₄ · H ₂ O calculated,%: Cu - 32.66; N, 7.20; Ρ - 15.92.

Example 2

To 100 ml of washing water of the first washing of the printed circuit boards after etching with concentrations of copper (+2) 0.036 mol / l, ammonia 0.30 mol / l, in which 8.4 g of “chda” grade ammonium hydrogen phosphate are pre-dissolved, first add with stirring 50 ml of the spent solution etching printed circuit boards with concentrations of copper (+2) 0.25 mol / L, sulfuric acid 0.30 mol / L, ammonium sulfate 0.82 mol / L, ammonium peroxodisulfate 0.23 mol / L, and then 25% ammonia solution until a pH of 7.5 is reached. The solution with the precipitate is left to stand at room temperature for 30 days. The solution is drained, the crystals are washed 3 times with water, squeezed on a paper filter and dried in air at room temperature to constant weight. Copper yield (+2) 99.7%. Found,%: Cu - 32.0; N, 6.9; Ρ - 15.9. For NH ₄ CuPO ₄ · Н ₂ О calculated,%: Cu - 32.66; N - 7.20; Ρ - 15.92.

Example 3

Dilute with water 10 ml of spent etching solution for printed circuit boards with copper (+2) concentrations of 1.7 mol / L, ammonia 7.2 mol / L, ammonium chloride 1.3 mol / L, ammonium carbonate 0.3 mol / L to total a volume of 50 ml, and with stirring, an 85% phosphoric acid solution is added dropwise until a pH of 7.0 is reached. The solution is left to stand, periodically mixing it with the precipitate, at room temperature for 15 days. The precipitate is filtered off on a POR 40 glass filter under reduced pressure (pH of the filtrate is 6.4), washed first 3 times with water, then 2 times with ethanol and dried in air at room temperature to constant weight. Copper yield (+2) 99.9%. Found,%: Cu - 33.5; N, 7.3; Ρ - 16.3. For NH ₄ CuPO ₄ · H ₂ O calculated,%: Cu - 32.66; N - 7.20; Ρ - 15.92.

Example 4

In 50 ml of the spent solution for etching printed circuit boards with concentrations of copper (+2) 0.18 mol / L, sulfuric acid 0.35 mol / L, ammonium sulfate 0.95 mol / L, ammonium peroxodisulfate 0.05 mol / L is dissolved 4 75 g of the "chda" grade ammonium hydrogen phosphate and, with stirring, a 25% ammonia solution is added dropwise until a pH of 6.5 is reached. A crystalline seed of copper phosphate monohydrate (+2) -ammonium is introduced. The suspension is left to stand, periodically shaking, at room temperature until the initially formed loose precipitate is transformed into a compactly precipitated monodisperse crystalline precipitate. The precipitate is filtered off on a POR 16 glass filter under reduced pressure (pH of the filtrate is 5.8), washed first 4 times with water, then 2 times with ethanol and dried in air at room temperature to constant weight. Copper yield (+2) 99.8%. Found,%: Cu - 32.2; N - 7.0; Ρ - 15.7. For NH ₄ CuPO ₄ · H ₂ O calculated,%: Cu - 32.66; N - 7.20; Ρ - 15.92.

Example 5

100 ml of washing water of the first washing of the printed circuit boards after etching are mixed with concentrations of copper (+2) 0.036 mol / l, ammonia 0.30 mol / l with a solution of 2.1 g of grade "ammonium dihydrogen phosphate" in 10 ml of water and with stirring 25% ammonia solution was added dropwise until a pH of 8.2 was reached. The solution with the precipitate is left to stand at room temperature for 45 days. The precipitate was filtered on a POR 16 glass filter under reduced pressure, washed 2 times with water and ethanol, and dried in air at room temperature to constant weight. Copper yield (+2) 96.5%. Found,%: Cu - 33.3; N, 6.9; Ρ - 16.0. For NH ₄ CuPO ₄ · H ₂ O calculated,%: Cu - 32.66; N, 7.20; Ρ - 15.92.

Example 6

To 10 ml of spent etching solution for printed circuit boards with copper (+2) concentrations of about 1.7 mol / L, ammonia about 6.7 mol / L, ammonium chloride about 1.1 mol / L, ammonium carbonate about 0.40 mol / with stirring, the spent solution for etching printed circuit boards with copper concentrations (+2) of about 1.3 mol / l, ammonium chloride about 2.0 mol / l, hydrogen chloride about 0.30 mol / l in such a quantity that the initially precipitated is added in portions the precipitate dissolved and the solution had a pH of 3.5. After cooling, the crystalline precipitate precipitated from the solution is dissolved by adding a minimal amount of water. In the resulting solution, which is a mixture of two spent etching solutions of printed circuit boards of various compositions, determine the concentration of copper (+2). An aqueous solution of “chda” grade ammonium hydrogen phosphate is prepared, which contains 4 mol of phosphate per 1 mol of copper (+2), and with stirring, a mixture of spent solutions for etching printed circuit boards prepared as described above is poured into it. The resulting solution was left to stand, periodically mixing it with the precipitate, for 6 days at room temperature. The precipitate is filtered on a glass filter POR 40 (pH of the filtrate 6.4), washed 5 times with water, 2 times with ethanol and dried in air at room temperature to constant weight. Copper yield (+2) 99.9%. Found,%: Cu - 32.6; N, 7.1; Ρ - 15.7. For NH ₄ CuPO ₄ · H ₂ O calculated,%: Cu - 32.66; Ν - 7.20; Ρ - 15.92.

Example 7

Mix 100 ml of the spent solution of etching the printed circuit boards with concentrations of copper (+2) 0.20 mol / L, ammonia 3.9 mol / L, ammonium sulfate 0.32 mol / L, ammonium peroxodisulfate 0.18 mol / L and solution 4 6 g of ammonium dihydrogen phosphate in 15 ml of water. An 85% phosphoric acid solution was added dropwise to the resulting solution with stirring until a pH of 7.8 was reached. The solution is left to stand, periodically mixing it with the precipitate, for 5 days at room temperature. The precipitate is filtered off on a POR 40 glass filter (pH of the filtrate 8.0), washed 5 times with water, 4 times with ethanol and dried in air at room temperature to constant weight. Copper yield (+2) 95.0%. Found,%: Cu - 32.6; N - 7.0; Ρ - 16.1. For NH ₄ CuPO ₄ · H ₂ O calculated,%: Cu - 32.66; N, 7.20; Ρ - 15.92.

Example 8

Mix 20.0 ml of the spent solution etching printed circuit boards with concentrations of copper (+2) 0.20 mol / L, ammonia 3.9 mol / L, ammonium sulfate 0.40 mol / L, ammonium peroxodisulfate 0.10 mol / L and 10.0 ml of spent etching solution for printed circuit boards with concentrations of copper (+2) 0.25 mol / L, sulfuric acid 0.30 mol / L, ammonium sulfate 0.65 mol / L, ammonium peroxodisulfate 0.35 mol / L. Dissolve 3.4 g of grade "ammonium chloride" ammonium hydrogen phosphate in 10 ml of water and pour with it a mixture of two spent solutions of etching printed circuit boards, prepared as described above. The solution with the precipitate is left to stand for 3 days at room temperature. The precipitate was filtered on a POR 40 glass filter, washed 4 times with water and dried in air at room temperature to constant weight. Copper yield (+2) 99.8%. Found,%: Cu - 32.6; Ν - 7.1; Ρ - 15.8. For NH ₄ CuPO ₄ · H ₂ O Calculated,%: Cu - 32,66; Ν - 7.20; Ρ - 15.92.

The obtained copper phosphate monohydrate (+2) -ammonium NH ₄ CuPO ₄ · H ₂ O is a bright blue crystalline substance of various dispersion (Fig. 1, 2), which depends on the composition of the solution and the conditions for the formation of precipitate; the color intensity of a substance varies markedly depending on the size of its crystals. The salt is poorly soluble in water, ethyl and isopropyl alcohols, ethylene glycol, glycerin, ethyl acetate and butyl acetate, dimethylformamide, dimethyl sulfoxide, chloroform, carbon tetrachloride, hexane, benzene. The substance is soluble in dilute mineral acids (hydrochloric, sulfuric, nitric, phosphoric), soluble in a 20% aqueous solution of acetic acid, slightly soluble, followed by decomposition in glacial acetic acid, soluble in 5% aqueous solutions of malonic, succinic, citric acids. Copper (+2) -ammonium phosphate monohydrate passes into solution in suspensions of aminotriacetic, ethylenediaminetetraacetic and diethylenetriaminepentaacetic acids, and also dissolves in aqueous solutions of ammonia, ethylenediamine, diethylenetriamine, diethanoethylamine, diethanolamine, diethanolamine potassium - substances that bind a copper cation (+2) to strong complexes. The NH ₄ CuPO ₄ · H ₂ O salt in an aqueous suspension is very slowly hydrolyzed at room temperature (and faster when boiled) to form average copper phosphate (+2). In a 1 M sodium hydroxide solution, even at room temperature, the salt gradually turns into copper hydroxide (+2). NH ₄ CuPO ₄ · H ₂ O is not hygroscopic and does not lose crystallization water or ammonia when the substance is stored in air at room temperature and with moderate heating.

As can be seen from the description of the invention and the above examples, the claimed method allows to obtain copper phosphate monohydrate (+2) -ammonium with the minimum cost using waste materials for copper coatings, pickling printed circuit boards, pickling copper with different chemical composition, recover 99.9 % copper (+2) from spent solutions. The chemical product obtained by the claimed method is of high purity, can be used for the production of catalysts for the synthesis of organic substances, as a pigment for paints, a pigment and a filler for plastics, a component of phosphors, copper microfertilizer and fungicide in agriculture, additives in pet food, as well as starting material for the preparation of other copper compounds.

Claims (12)

1. The method of producing copper phosphate monohydrate (+2) -ammonium, including the preparation of a reaction aqueous solution containing copper (+2), phosphate and ammonium, the formation of a precipitate of copper phosphate monohydrate (+2) -ammonium and its separation from the solution, characterized in that as a source of copper (+2) use a liquid waste product selected from the group consisting of a spent solution for etching printed circuit boards, an spent solution of the first washing of printed circuit boards after etching, an spent solution of galvanic copper plating of printed circuit boards, from a worked solution of etching copper in mineral acids, moreover, the liquid waste products can be used individually or in combination with each other. 2. The method according to p. 1, characterized in that the spent solution for etching printed circuit boards is a spent copper-ammonia solution for etching printed circuit boards containing copper (+2), ammonia, ammonium chloride or containing copper (+2 as main components) as the main components ), ammonia, ammonium chloride, ammonium carbonate. 3. The method according to claim 1, characterized in that the spent solution for etching the printed circuit boards is a spent acidic copper sulphate solution for etching the printed circuit boards containing copper (+2), sulfuric acid, ammonium sulfate as the main components. 4. The method according to p. 1, characterized in that the spent solution for etching printed circuit boards is a spent ammonia copper sulphate solution for etching printed circuit boards containing copper (+2), ammonia, ammonium sulfate as main components. 5. The method according to p. 1, characterized in that the spent solution for etching printed circuit boards is a spent acidic copper chloride solution for etching printed circuit boards containing copper (+2), hydrochloric acid, ammonium chloride as the main components. 6. The method according to p. 1, characterized in that the spent solution for etching printed circuit boards is a spent sulfate peroxodisulfate solution for etching printed circuit boards containing as main components copper (+2), sulfuric acid, ammonium sulfate, ammonium peroxodisulfate. 7. The method according to p. 1, characterized in that the spent solution for the etching of printed circuit boards is a spent ammonia peroxodisulfate solution for etching printed circuit boards containing as the main components copper (+2), ammonia, ammonium sulfate, ammonium peroxodisulfate. 8. The method according to p. 1, characterized in that they use a spent solution of galvanic copper plating of printed circuit boards containing copper sulfate (+2), sulfuric acid as the main components. 9. The method according to p. 1, characterized in that they use a spent solution of copper etching in mineral acids, containing copper (+2), sulfuric acid, nitric acid as the main components. 10. The method according to p. 1, characterized in that the source of phosphate is phosphoric acid or ammonium phosphate, or ammonium hydrogen phosphate, or ammonium dihydrogen phosphate. 11. The method according to claim 1, characterized in that ammophos and / or diammophos fertilizers are used as a phosphate source. 12. The method according to p. 1, characterized in that as a source of ammonium ammonium phosphates and / or ammonia are used.

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