RU2579378C2 - Method of producing compound metal-phosphate product (versions) - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to production of complex type phosphate compounds. Method of producing a complex metal phosphate product comprises dissolving iron (Fe) in form of iron shavings in 85 %-90 % orthophosphoric acid (H₃PO₄), then while stirring, gradually dissolving powdered aluminum hydroxide or bauxite or boehmite powder and iron oxide (Fe₂O₃) or a mixture thereof, while slowing down reaction heating to 90 °C-100 °C, after dissolution of components cooling solution to room temperature, further, while stirring, adding to the obtained solution a solution of chromium oxide, resulting paste of a complex iron-chromium-aluminophosphate product is dried and ground to obtain a powder of a complex metal phosphate gross product of formula $$M_{4-12}^{III}{(HP{O}_4)}_{6-18}{H}_{0-2},$$

where M^III denotes cations of trivalent metals (iron $$F{e}_{3-9}^{III},$$

chromium $$C{r}_{1-3}^{III},$$

aluminium $$A{l}_{0-3}^{III}$$

in different proportions). In another version, paste of iron-chromium-aluminophosphate complex compound, in order to reduce acidity, with constant stirring is mixed with oxide or mixture of oxides of divalent metals, or carbonates, dolomite, then resulting paste product metal phosphate complex is dried and ground to obtain a powder of metal phosphate complex gross product of formula $${М}_{\text{4-12}}^{\text{III}}{(HP{O}_4)}_m{(P{O}_4)}_n{M}_{1-4}^{II},$$

where M^III denotes ations of trivalent metals (iron $$F{e}_{3-7}^{III},$$

chromium $$C{r}_{1-2}^{III},$$

aluminium $$A{l}_{0-1}^{III}$$

in different ratios, M^II denotes cations of divalent metals (zinc, magnesium, copper, nickel, iron, and other in different proportions), m = 4… 16, n = 2… 8. In third version, obtained paste of iron-chromium-aluminophosphate complex compound, in order to reduce acidity, with constant stirring is mixed with 60-200 g of a mixture of divalent metal oxide or hydroxide, and carbonates of monovalent metals, and then resulting metal phosphate complex paste product is dried and pulverised to obtain a powder metal phosphate complex gross product of formula $$M_{4-12}^{III}{(HP{O}_4)}_m{(P{O}_4)}_n{M}_{1-4}^{II}{M}_{1-4}^I,$$

where M^III denotes cations of trivalent metals (iron $$F{e}_{3-7}^{III},$$

chromium $$C{r}_{1-2}^{III},$$

aluminium $$C{r}_{1-2}^{III}$$

in different ratios, M^II denotes cations of divalent metals (zinc, magnesium, copper, nickel, iron, and other in different ratios), M^I denotes cations of monovalent metals (potassium, sodium, and others) m = 3… 12, n = 3… 12.

EFFECT: invention enables production of industrial complex metal-phosphate product with low solubility in water, in form of paste or dry powder with high stability properties during storage, and wide range of application.

3 cl, 2 ex

Description

The invention relates to the field of production of complex-type phosphate compounds.

Known raw material mixture for producing a phosphate binder, disclosed in the description of the invention to copyright certificate No. 1728157, published on 04/23/1992 gist of the invention: the raw material mixture for producing a phosphate binder contains, wt. %: phosphoric acid 74-91, aluminum hydroxide 1-8, the departure of iron-aluminum catalyst 8-18. Orthophosphoric acid is poured into the binder synthesis tank, it is heated to 30-40 ° C, and catalyst production waste is introduced with constant stirring. After its dissolution, aluminum hydroxide is gradually introduced with stirring. The reaction mixture is brought to a boil, boiled for 30-40 minutes and cooled to room temperature. The result is a mixed phosphate of chromium, iron and aluminum in liquid form.

The disadvantage of this method is that as a result of the implementation of this energy-intensive method, only a liquid phosphate binder is obtained, which is extremely inconvenient to use. The resulting binder consists of mixed phosphates of chromium, iron and aluminum and this binder cannot be used as a hardener for water glass and mixtures, because quickly react with sodium silicate, and does not provide the necessary adhesive properties to silicate glass.

A known method of producing iron hydrogen phosphates disclosed in the description of the invention to copyright certificate No. 1549916 published March 15, 1990. Iron hydrogen phosphates are obtained by treating iron hydroxide with concentrated phosphoric acid at 40-60 ° C and a molar ratio of F ₂ O ₃ : P ₂ O ₅ , equal to 1: (3-6), the resulting reaction mixture is cooled, an organic solvent in the amount of 40-0% of the volume of the reaction mixture is introduced, the product precipitate is crystallized for 15-20 hours, it is separated from the mother liquor by filtration, washed and dried. It is advisable to maintain the concentration of phosphoric acid in the reaction mixture equal to 35-65% P ₂ O ₅ , to cool to 18-25 ° C, to use ethyl alcohol or acetone as an organic solvent. When the concentration of phosphoric acid is less than 58% P ₂ O ₅ , trihydro iron phosphate hydrate is obtained, and when the concentration of phosphoric acid is 58-65% P ₂ O ₅ , iron dihydrogen phosphate is obtained.

The disadvantage of this method is that its implementation requires high energy costs, long crystallization and complex technological operations, the resulting substance is not used for curing liquid silicate glass.

A known method for producing acidic chromium-containing metal phosphates, taken as a prototype disclosed in the description of the invention to copyright certificate No. 814851, published 03/23/1981, a Method for producing acidic chromium-containing metal phosphates, includes the interaction of chromic anhydride or chromates and metal compounds with phosphoric acid, and before the introduction of compounds metal, a mixture of an acid with a chromium-containing compound is heated to a temperature of 160-220 ° C, and maintained at this temperature for 0.5-2.0 hours, stir vigorously st.

The disadvantage of this method is that as a result of the implementation of this energy-intensive method, only liquid aluminum-chromophosphate, chromium-aluminum-phosphate or chromium-zinc phosphate binders are obtained, which is extremely inconvenient to use, and these binders cannot be used as a hardener for liquid glass and mixtures, since quickly react with sodium silicate, and do not provide the necessary adhesive properties to silicate glass.

The aim of the invention is the creation of an energy-efficient and simple method for producing a complex metal phosphate product, without using organic compounds for the recovery of chromium, sparingly soluble in water in the form of a dry powder, with high adhesive properties to silicate glass, capable of curing liquid silicate glass in 3-4 hours.

The technical result of the claimed invention is the possibility of industrial production of a complex metal phosphate product with low solubility in water, in the form of a paste or dry powder, with high stability during storage, and a wide range of applications.

, где M^III - катионы трехвалентных металлов - железа $$F{e}_{3-9}^{III}$$

, хрома $$C{r}_{1-3}^{III}$$

, алюминия $$A{l}_{0-3}^{III}$$

в разных соотношениях;Due to the fact that the method for producing a complex metal phosphate product involves the interaction of phosphoric acid with metal compounds, according to the invention according to claim 1, in the range of 820-1700 g of 85% -90% phosphoric acid (H ₃ PO ₄ ), 62-130 g of iron is dissolved ( Fe) in the form of cast-iron shavings, then, with stirring, powdery aluminum hydroxide 60-130 g or boehmite or bauxite and 160-500 g of powdered iron oxide (Fe ₂ O ₃ ) or a mixture of them are gradually dissolved, and the reaction is heated to 90 ° C -100 ° C, after dissolving the components, the solution is cooled to room temperature, then with stirring, 95-200 g of chromium oxide is added to the resulting solution, the resulting paste of the complex iron-chromium-phosphate product is dried and ground to obtain a powder of the complex metal phosphate product of the gross formula $$M_{\text{4-12}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_{6-\mathrm{eighteen}}{H}_{0-2}$$

where M ^III - cations of trivalent metals - iron $$F{e}_{3-9}^{III}$$

chrome $$C{r}_{\mathrm{one}-3}^{III}$$

aluminum $$A{l}_{0-3}^{III}$$

in different ratios;

, где M^III - катионы трехвалентных металлов - железа $$F{e}_{3-9}^{III}$$

, хрома $$C{r}_{1-3}^{III}$$

, алюминия $$A{l}_{0-3}^{III}$$

в разных соотношениях, M^II - катионы двухвалентных металлов, m=4…16, n=2…8;according to the invention according to claim 2, in 820-1700 g of 85% -90% phosphoric acid (H ₃ PO ₄ ), 62-130 g of iron (Fe) is dissolved in the form of cast-iron shavings, then, with stirring, the powdery aluminum hydroxide is gradually dissolved 60-130 g or boehmite or bauxite and 160-500 g of powdered iron oxide (Fe ₂ O ₃ ) or a mixture thereof, when the reaction is slowed down, they are heated to 90 ° C-100 ° C, after the components are dissolved, the solution is cooled to room temperature, then with stirring in the resulting the solution is added 95-200 g of chromium oxide, then in the resulting complex iron paste omalyumofosfatnogo compound to reduce acidity with constant stirring 40-250 g of oxide or mixture of oxides of divalent metals, or carbonates, dolomite, then the resulting metal phosphate complex pasta product is dried and pulverized to obtain a powder metal phosphate complex gross product of formula $$M_{\text{4-12}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_m{(P{O}_{\mathrm{four}})}_n{M}_{\mathrm{one}-\mathrm{four}}^{II}$$

where M ^III - cations of trivalent metals - iron $$F{e}_{3-9}^{III}$$

chrome $$C{r}_{\mathrm{one}-3}^{III}$$

aluminum $$A{l}_{0-3}^{III}$$

in different ratios, M ^II - divalent metal cations, m = 4 ... 16, n = 2 ... 8;

, где M^III - катионы трехвалентных металлов - железа $$F{e}_{3-7}^{III}$$

, хрома $$C{r}_{1-2}^{III}$$

, алюминия $$A{l}_{0-1}^{III}$$

, в разных соотношениях, M^II - катионы двухвалентных металлов, M^I - катионы одновалентных металлов - калия, натрия, m=3…12, n=3…12, появляется возможность промышленного изготовления комплексного металлофосфатного продукта с низкой растворимостью в воде, в виде пасты или сухого порошка, с высокой стабильностью свойств при хранении, и широким спектром применения.according to the invention according to claim 3, in 820-1700 g of 85% -90% phosphoric acid (H ₃ PO ₄ ), 62-130 g of iron (Fe) is dissolved in the form of cast-iron shavings, then, with stirring, the powdery aluminum hydroxide is gradually dissolved 60-130 g or boehmite or bauxite and 160-500 g of powdered iron oxide (Fe ₂ O ₃ ) or a mixture thereof, when the reaction is slowed down, they are heated to 90 ° C-100 ° C, after the components are dissolved, the solution is cooled to room temperature, then with stirring in the resulting the solution is added 95-200 g of chromium oxide, then in the obtained paste complex iron malyumofosfatnogo compound to reduce acidity with constant stirring 60-200 g of a mixture of oxides of divalent metals and 60-200 g hydroxides or carbonates of monovalent metals - potassium, sodium, and then the resulting metal phosphate complex pasta product is dried and pulverized to obtain a powder metal phosphate complex gross product of formula $$M_{\text{4-12}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_m{(P{O}_{\mathrm{four}})}_n{M}_{\mathrm{one}-\mathrm{four}}^{II}{\text{M}}_{\text{1-4}}^{\text{I}}$$

where M ^III - cations of trivalent metals - iron $$F{e}_{3-7}^{III}$$

chrome $$C{r}_{\mathrm{one}-2}^{III}$$

aluminum $$A{l}_{0-\mathrm{one}}^{III}$$

, in different ratios, M ^II - cations of divalent metals, M ^I - cations of monovalent metals - potassium, sodium, m = 3 ... 12, n = 3 ... 12, it becomes possible to industrial complex metallophosphate product with low solubility in water, in the form paste or dry powder, with high stability of storage properties, and a wide range of applications.

The invention can be widely used as an astringent for curing liquid silicate glass; in the manufacture of enamels, glazes for products subjected to heat treatment; in the manufacture of abrasive products with a bunch of liquid silicate glass; in the manufacture of flasks; in the manufacture of waterproof concrete products; to accelerate the curing of bakelite phenol-formaldehyde resin; as a phosphate fertilizer.

The invention can be implemented on standard equipment of industrial enterprises.

In the claimed method for the production of ferrous phosphate, a redox reaction is used, in which the oxidation of part of the iron atoms occurs due to another part of the atoms of the same element, as well as due to hydrogen, which in this method is almost not released in gaseous form, but enters in reaction with oxygen to form water.

This method of producing ferrous acid phosphate (Fe (H ₂ PO ₄ ) ₂ ) was applied for the first time. The existing laboratory method for producing ferrous phosphate is energy-intensive and allows you to get it only in small quantities. The obtained ferrous acid phosphate is used in a redox reaction in which Fe ^II is oxidized to Fe ^III , and Cr ^{VI is} reduced to Cr ^III , and three Fe ^II ions are expended to produce one Cr ^III ion. The developed method for producing ferrous phosphate allows it to be obtained in industrial production in the required amount for the production of a complex metal phosphate product.

, где M^III - катионы трехвалентных металлов (железа Fe^III, хрома Cr^III, алюминия Al^III) находится в вершинах, а HPO₄ находится по ребрам; в форме треугольной призмы $${\text{M}}_{\text{6}}^{\text{III}}{(HP{O}_4)}_9$$

; в форме четырехугольной призмы $${\text{M}}_{\text{8}}^{\text{III}}{(HP{O}_4)}_{12}$$

; в форме пятиугольной призмы $${\text{M}}_{\text{10}}^{\text{III}}{(HP{O}_4)}_{15}$$

; в форме шестиугольной призмы $${\text{M}}_{\text{12}}^{\text{III}}{(HP{O}_4)}_{18}$$

.From the point of view of crystal chemistry, it is possible to obtain five types of crystals of metal phosphate compounds - a tetrahedral form $${\text{M}}_{\text{four}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_6$$

where M ^III - cations of trivalent metals (iron Fe ^III , chromium Cr ^III , aluminum Al ^III ) is located at the vertices, and HPO ₄ is located along the edges; triangular prism $${\text{M}}_{\text{6}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_9$$

; quadrangular prism $${\text{M}}_{\text{8}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_{12}$$

; pentagonal prism $${\text{M}}_{\text{10}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_{\mathrm{fifteen}}$$

; hexagonal prism $${\text{M}}_{\text{12}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_{\mathrm{eighteen}}$$

.

The method is as follows. In 820-1700 g of 85% -90% orthophosphoric acid (H ₃ PO ₄ ) 62-130 g of iron (Fe) are added in the form of cast-iron shavings, the shavings can be crushed for faster dissolution. Then, while stirring in small portions (30-50 g each), powdered aluminum hydroxide 60-130 g or boehmite or bauxite is gradually dissolved in the same amount and 160-500 g of powdered iron oxide (Fe ₂ O ₃ ) or a mixture thereof, each subsequent portion add after dissolving the previous portion. To implement the method, powdered iron oxide can be used, which is captured by air purification filters in the production of metal at ferrous metallurgy enterprises. The reaction mass must be constantly mixed, the reaction proceeds with the release of heat, when the reaction slows down (after adding the entire amount of powdered iron oxide to the reaction mass), the reaction mass is additionally heated to 90 ° C-100 ° C. It is kept until the iron chips dissolve (about 1-1.5 hours) and then cooled to room temperature. The result is a solution of a mixture of ferric acid phosphate (Fe ^II (H ₂ PO ₄ ) ₂ ) and iron-aluminum phosphate.

, где M^III - катионы трехвалентных металлов - железа $$F{e}_{3-9}^{III}$$

, хрома $$C{r}_{1-3}^{III}$$

, алюминия $$A{l}_{0-3}^{III}$$

в разных соотношениях.Then, with stirring, 95-200 g of chromium oxide is added to the resulting solution (it is possible to add a solution of chromium oxide, for which 95-200 g of chromium oxide (CrO ₃ ) is dissolved in 60-120 g of water), in this reaction hexavalent chromium is reduced by ferrous ions to ferric chromium, and ferrous iron is oxidized to ferric iron. The result is 1255-2780 g of iron-chromophosphate product in the form of a green paste containing 21-24.5% of water, 0.5-0.7% of impurities and 78.5-74.8% of a complex gross-chromium phosphate compound of the formula $$M_{\text{4-12}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_{6-\mathrm{eighteen}}{H}_{0-2}$$

where M ^III - cations of trivalent metals - iron $$F{e}_{3-9}^{III}$$

chrome $$C{r}_{\mathrm{one}-3}^{III}$$

aluminum $$A{l}_{0-3}^{III}$$

in different ratios.

, где M^III - катионы трехвалентных металлов - железа $$F{e}_{3-9}^{III}$$

, хрома $$C{r}_{1-3}^{III}$$

, алюминия $$A{l}_{0-3}^{III}$$

в разных соотношениях, M^II - катионы двухвалентных металлов, m=4…16, n=2…8.Further, according to claim 2, in the resulting paste of a complex iron-chromium-phosphate compound to reduce acidity with constant stirring, add 40-250 g of an oxide or mixture of oxides of divalent metals or their carbon salts, dolomite. Replacing one oxide with another can only affect their adhesion properties to silicate glass, the greatest adhesion to silicate glass of copper ions. The result is 1295-3030 g of paste containing 27.5-17.3% of water, 0.5-0.7% of impurities and 72-82% of a complex metal phosphate gross product of the formula $$M_{\text{4-12}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_m{(P{O}_{\mathrm{four}})}_n{M}_{\mathrm{one}-\mathrm{four}}^{II}$$

where M ^III - cations of trivalent metals - iron $$F{e}_{3-9}^{III}$$

chrome $$C{r}_{\mathrm{one}-3}^{III}$$

aluminum $$A{l}_{0-3}^{III}$$

in different ratios, M ^II - cations of divalent metals, m = 4 ... 16, n = 2 ... 8.

, где M^III - катионы трехвалентных металлов - железа $$F{e}_{3-7}^{III}$$

, хрома $$C{r}_{1-2}^{III}$$

, алюминия $$A{l}_{0-1}^{III}$$

, в разных соотношениях, M^II - катионы двухвалентных металлов, M^I - катионы одновалентных металлов - калия, натрия, m=3…12, n=3…12.Or according to claim 3, in the resulting paste of a complex iron-chromium-phosphate compound to reduce acidity with constant stirring, 60-200 g of a mixture of oxides of divalent metals and 60-200 g of hydroxide or carbonic salts of monovalent metals - potassium, sodium are added. The result is 1375-3180 g of paste containing 29.5-17.3% water, 0.5-0.7% impurities and 70-82% of the complex metal phosphate gross product of the formula $$M_{\text{4-12}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_m{(P{O}_{\mathrm{four}})}_n{M}_{\mathrm{one}-\mathrm{four}}^{II}{\text{M}}_{\text{1-4}}^{\text{I}}$$

where M ^III - cations of trivalent metals - iron $$F{e}_{3-7}^{III}$$

chrome $$C{r}_{\mathrm{one}-2}^{III}$$

aluminum $$A{l}_{0-\mathrm{one}}^{III}$$

, in different ratios, M ^II - cations of divalent metals, M ^I - cations of monovalent metals - potassium, sodium, m = 3 ... 12, n = 3 ... 12.

If necessary, to obtain a complex metal phosphate product in the form of a dry powder, the resulting paste is dried, for example, in a heating cabinet at a temperature of up to 100 ° C, as a result, a complex metal phosphate product is obtained in the form of a powder and small crystals, which are ground to a fine powder by any method.

Example 1

In 820 g of 85% -90% orthophosphoric acid (H ₃ PO ₄ ) add 62 g of iron (Fe) in the form of cast-iron shavings, shavings can be crushed for faster dissolution. Then, while stirring in small portions (30-50 g each), 60 g of powdered aluminum hydroxide or boehmite or bauxite and 160 g of powdered iron oxide (Fe ₂ O ₃ ) or a mixture thereof are gradually dissolved, each subsequent portion is added after the previous portion has been dissolved. To implement the method, powdered iron oxide can be used, which is captured by air purification filters in the production of metal at ferrous metallurgy enterprises. The reaction mass must be constantly mixed, the reaction proceeds with the release of heat, when the reaction slows down (after adding the entire amount of powdered iron oxide to the reaction mass), the reaction mass is additionally heated to 90 ° C-100 ° C. It is kept until the iron chips dissolve (about 1-1.5 hours) and then cooled to room temperature. The result is a solution of a mixture of ferric acid phosphate (Fe ^II (H ₂ PO ₄ ) ₂ ) and iron-aluminum phosphate.

, где M^III - катионы трехвалентных металлов - железа $$F{e}_{3-9}^{III}$$

, хрома $$C{r}_{1-3}^{III}$$

, алюминия $$A{l}_{0-3}^{III}$$

в разных соотношениях.Then, with stirring, 95 g of chromium oxide is added to the resulting solution (possibly in the form of a solution, 95 g of chromium oxide (CrO ₃ ) is dissolved in 60 g of water to obtain a solution of chromium oxide), in this reaction hexavalent chromium is reduced by ferrous ions to ferric chromium, and ferrous iron is oxidized to ferric iron. The result is 1255 g of iron-chromophosphate product in the form of a green paste containing 21-24.5% of water, 0.5-0.7% of impurities and 78.5-74.8% of a complex gross-chromium phosphate compound of the formula $$M_{\text{4-12}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_{6-\mathrm{eighteen}}{H}_{0-2}$$

where M ^III - cations of trivalent metals - iron $$F{e}_{3-9}^{III}$$

chrome $$C{r}_{\mathrm{one}-3}^{III}$$

aluminum $$A{l}_{0-3}^{III}$$

in different ratios.

, где M^III - катионы трехвалентных металлов - железа $$F{e}_{3-9}^{III}$$

, хрома $$C{r}_{1-3}^{III}$$

, алюминия $$A{l}_{0-3}^{III}$$

в разных соотношениях, M^II - катионы двухвалентных металлов, например, цинка, магния, меди, никеля, железа в разных соотношениях, m=4…16, n=2…8.Further, according to claim 2, in the resulting paste of a complex iron-chromium-phosphate compound to reduce acidity with constant stirring, an oxide or a mixture of oxides of divalent metals, for example zinc, magnesium, copper, nickel or their carbonic salts, dolomite, for example is added: a) 40 g of magnesium oxide ; b) 80 g of zinc oxide; c) 80 g of copper oxide; g) 70 g of nickel oxide; d) 70 g of cobalt oxide; e) 70 g of a mixture of nickel oxide and cobalt in any ratio; g) 80 g of dolomite; h) 80 g of a mixture of zinc oxide and copper oxide in any ratio; i) a mixture of 40 g of magnesium oxide, 80 g of zinc oxide and 80 g of copper oxide. Replacing one oxide with another can only affect their adhesion properties to silicate glass, the greatest adhesion to silicate glass of copper ions. The result is a paste containing 27.5-17.3% water, 0.5-0.7% impurities and 72-82% complex metal phosphate gross product of the formula $$M_{\text{4-12}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_m{(P{O}_{\mathrm{four}})}_n{M}_{\mathrm{one}-\mathrm{four}}^{II}$$

where M ^III - cations of trivalent metals - iron $$F{e}_{3-9}^{III}$$

chrome $$C{r}_{\mathrm{one}-3}^{III}$$

aluminum $$A{l}_{0-3}^{III}$$

in different ratios, M ^II - cations of divalent metals, for example, zinc, magnesium, copper, nickel, iron in different ratios, m = 4 ... 16, n = 2 ... 8.

, где M^III - катионы трехвалентных металлов - железа $$F{e}_{3-7}^{III}$$

, хрома $$C{r}_{1-2}^{III}$$

, алюминия $$A{l}_{0-1}^{III}$$

, в разных соотношениях, M^II - катионы двухвалентных металлов, например, цинка, магния, меди, никеля, железа в разных соотношениях, M^I - катионы одновалентных металлов - калия, натрия, m=3…12, n=3…12.Or according to claim 3, a mixture of oxides of divalent metals, for example zinc, magnesium, copper, manganese, cobalt, is added to the resulting paste of a complex iron-chromium-phosphate compound with constant stirring: a) 60 g from a mixture of 30 g of zinc oxide and 30 g of oxide copper; b) 140 g of a mixture of 60 g of magnesium oxide, 40 g of zinc oxide, 40 g of copper oxide; c) 180 g of a mixture of 60 g of magnesium oxide, 40 g of zinc oxide, 40 g of copper oxide and 40 g of cobalt oxide; g) 200 g of a mixture of 60 g of magnesium oxide, 40 g of zinc oxide, 30 g of copper oxide, 30 g of manganese oxide and 30 g of cobalt oxide) and 60 g of hydroxide or carbonic salts of monovalent metals - potassium, sodium, for example: a) 60 g of potassium carbonate; b) 60 g of potassium hydroxide; c) 40 g of potassium carbonate and 20 g of sodium carbonate). The result is a paste containing 29.5-17.3% of water, 0.5-0.7% of impurities and 70-82% of a complex metal phosphate gross product of the formula $$M_{\text{4-12}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_m{(P{O}_{\mathrm{four}})}_n{M}_{\mathrm{one}-\mathrm{four}}^{II}{\text{M}}_{\text{1-4}}^{\text{I}}$$

where M ^III - cations of trivalent metals - iron $$F{e}_{3-7}^{III}$$

chrome $$C{r}_{\mathrm{one}-2}^{III}$$

aluminum $$A{l}_{0-\mathrm{one}}^{III}$$

, in different ratios, M ^II - cations of divalent metals, for example, zinc, magnesium, copper, nickel, iron in different ratios, M ^I - cations of monovalent metals - potassium, sodium, m = 3 ... 12, n = 3 ... 12.

If necessary, to obtain a complex metal phosphate product in the form of a dry powder, the resulting paste is dried, for example, in a heating cabinet at a temperature of up to 100 ° C, as a result, a complex metal phosphate product is obtained in the form of a powder and small crystals, which are ground to a fine powder by any method.

Example 2

The method is as follows. In 1700 g of 85% -90% orthophosphoric acid (H ₃ PO ₄ ) 130 g of iron (Fe) are added in the form of cast-iron shavings, the shavings can be crushed for faster dissolution. Then, while stirring in small portions (30-50 g each), 130 g of powdered aluminum hydroxide or boehmite or bauxite and 500 g of powdered iron oxide (Fe ₂ O ₃ ) or a mixture thereof are gradually dissolved, each subsequent portion is added after the previous portion has been dissolved. To implement the method, powdered iron oxide can be used, which is captured by air purification filters in the production of metal at ferrous metallurgy enterprises. The reaction mass must be constantly mixed, the reaction proceeds with the release of heat, when the reaction slows down (after adding the entire amount of powdered iron oxide to the reaction mass), the reaction mass is additionally heated to 90 ° C-100 ° C. It is kept until the iron chips dissolve (about 1-1.5 hours) and then cooled to room temperature. The result is a solution of a mixture of ferric acid phosphate (Fe ^II (H ₂ PO ₄ ) ₂ ) and iron-aluminum phosphate.

, где M^III - катионы трехвалентных металлов - железа $$F{e}_{3-9}^{III}$$

, хрома $$C{r}_{1-3}^{III}$$

, алюминия $$A{l}_{0-3}^{III}$$

в разных соотношениях.Then, with stirring, 200 g of chromium oxide is added to the resulting solution (possibly in the form of a solution, 200 g of chromium oxide (CrO ₃ ) is dissolved in 120 g of water to obtain a solution of chromium oxide), in this reaction hexavalent chromium is reduced by ferrous ions to ferric chromium, and ferrous iron is oxidized to ferric iron. The result is 2780 g of iron-chromophosphate product in the form of a green paste containing 21-24.5% of water, 0.5-0.7% of impurities and 78.5-74.8% of a complex gross-chromium phosphate compound of the formula $$M_{\text{4-12}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_{6-\mathrm{eighteen}}{H}_{0-2}$$

where M ^III - cations of trivalent metals - iron $$F{e}_{3-9}^{III}$$

chrome $$C{r}_{\mathrm{one}-3}^{III}$$

aluminum $$A{l}_{0-3}^{III}$$

in different ratios.

, где M^III - катионы трехвалентных металлов - железа $$F{e}_{3-9}^{III}$$

, хрома $$C{r}_{1-3}^{III}$$

, алюминия $$A{l}_{0-3}^{III}$$

в разных соотношениях, M^II - катионы двухвалентных металлов, например цинка, магния, меди, никеля, железа в разных соотношениях, m=4…16, n=2…8.Further, according to claim 2, in the resulting paste of a complex iron-chromium-phosphate compound to reduce acidity with constant stirring, add an oxide or a mixture of oxides of divalent metals such as zinc, magnesium, copper, nickel or their carbonic salts, dolomite, for example: a) 80 g of magnesium oxide; b) 160 g of zinc oxide; c) 150 g of copper oxide; g) 150 g of nickel oxide; d) 150 g of cobalt oxide; f) 150 g of a mixture of nickel oxide and cobalt in any ratio; g) 100 g of dolomite; h) 150 g of a mixture of zinc oxide and copper oxide in any ratio; i) a mixture of 60 g of magnesium oxide, 90 g of zinc oxide and 100 g of copper oxide. Replacing one oxide with another can only affect their adhesion properties to silicate glass, the greatest adhesion to silicate glass of copper ions. The result is a paste containing 27.5-17.3% of water, 0.5-0.7% of impurities and 72-82% of a complex metal phosphate gross product of the formula $$M_{\text{4-12}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_m{(P{O}_{\mathrm{four}})}_n{M}_{\mathrm{one}-\mathrm{four}}^{II}$$

where M ^III - cations of trivalent metals - iron $$F{e}_{3-9}^{III}$$

chrome $$C{r}_{\mathrm{one}-3}^{III}$$

aluminum $$A{l}_{0-3}^{III}$$

in different ratios, M ^II - cations of divalent metals, for example zinc, magnesium, copper, nickel, iron in different ratios, m = 4 ... 16, n = 2 ... 8.

, где M^III - катионы трехвалентных металлов - железа $$F{e}_{3-7}^{III}$$

, хрома $$C{r}_{1-2}^{III}$$

, алюминия $$A{l}_{0-1}^{III}$$

, в разных соотношениях, M^II - катионы двухвалентных металлов - цинка, магния, меди, никеля, железа в разных соотношениях, M^I - катионы одновалентных металлов - калия, натрия, m=3…12, n=3…12.Or according to claim 3, a mixture of oxides of divalent metals, for example zinc, magnesium, copper, manganese, cobalt, is added to the resulting paste of a complex iron-chromium-phosphate compound with constant stirring: a) 200 g of a mixture of 60 g of magnesium oxide, 50 g of oxide zinc, 50 g of copper oxide and 40 g of cobalt oxide; b) 200 g of a mixture of 60 g of magnesium oxide, 50 g of zinc oxide, 30 g of copper oxide, 30 g of manganese oxide and 30 g of cobalt oxide and 200 g of hydroxide or carbonic salts of monovalent metals - potassium, sodium, for example: a) 200 g potassium carbonate; b) 170 g of potassium hydroxide; c) 120 g of potassium carbonate and 80 g of sodium carbonate. The result is a paste containing 29.5-17.3% of water, 0.5-0.7% of impurities and 70-82% of a complex metal phosphate gross product of the formula $$M_{\text{4-12}}^{\text{III}}{(HP{O}_{\mathrm{four}})}_m{(P{O}_{\mathrm{four}})}_n{M}_{\mathrm{one}-\mathrm{four}}^{II}{\text{M}}_{\text{1-4}}^{\text{I}}$$

where M ^III - cations of trivalent metals - iron $$F{e}_{3-7}^{III}$$

chrome $$C{r}_{\mathrm{one}-2}^{III}$$

aluminum $$A{l}_{0-\mathrm{one}}^{III}$$

, in different ratios, M ^II - cations of divalent metals - zinc, magnesium, copper, nickel, iron in different ratios, M ^I - cations of monovalent metals - potassium, sodium, m = 3 ... 12, n = 3 ... 12.

If necessary, to obtain a complex metal phosphate product in the form of a dry powder, the resulting paste is dried, for example, in a heating cabinet at a temperature of up to 100 ° C, as a result, a complex metal phosphate product is obtained in the form of a powder and small crystals, which are ground to a fine powder by any method.

Claims (3)

1. A method of obtaining a complex metal phosphate product, comprising the interaction of phosphoric acid with metal compounds, characterized in that in 820-1700 g of 85% -90% of phosphoric acid (H ₃ PO ₄ ) 62-130 g of iron (Fe) is dissolved in the form of cast iron shavings, then, with stirring, gradually dissolve 60-130 g of powdered aluminum hydroxide or boehmite or bauxite and 160-500 g of powdered iron oxide (Fe ₂ O ₃ ) or a mixture thereof, while slowing down the reaction, they are heated to 90 ° C-100 ° C, after dissolving the components, the solution is cooled to room temperature rats, then, with stirring, 95-200 g of chromium oxide is added to the resulting solution, the resulting paste of the complex iron-chromium-phosphate product is dried and crushed to obtain a powder of the complex metal phosphate gross product of the formula

where M ^III - cations of trivalent metals - iron

chrome

aluminum

in different ratios. 2. A method of obtaining a complex metal phosphate product, comprising the interaction of phosphoric acid with metal compounds, characterized in that in 820-1700 g of 85% -90% of phosphoric acid (H ₃ PO ₄ ) 62-130 g of iron (Fe) is dissolved in the form of cast iron shavings, then, with stirring, gradually dissolve 60-130 g of powdered aluminum hydroxide or boehmite or bauxite and 160-500 g of powdered iron oxide (Fe ₂ O ₃ ) or a mixture thereof, while slowing down the reaction, they are heated to 90 ° C-100 ° C, after dissolving the components, the solution is cooled to room temperature rats, then with stirring, 95-200 g of chromium oxide is added to the resulting solution, then 40-250 g of oxide or a mixture of oxides of divalent metals or their carbonic salts, dolomite are added to the resulting paste of a complex iron-chromium-phosphate compound with constant stirring, then the resulting paste the complex metal phosphate product is dried and ground to obtain a powder of the complex metal phosphate product gross of the formula

where M ^III - cations of trivalent metals - iron

chrome

aluminum

in different ratios, M ^II - cations of divalent metals, m = 4 ... 16, n = 2 ... 8. 3. A method of obtaining a complex metal phosphate product, comprising the interaction of phosphoric acid with metal compounds, characterized in that in 820-1700 g of 85% -90% of phosphoric acid (H ₃ PO ₄ ) 62-130 g of iron (Fe) is dissolved in the form of cast iron shavings, then, with stirring, gradually dissolve 60-130 g of powdered aluminum hydroxide or boehmite or bauxite and 160-500 g of powdered iron oxide (Fe ₂ O ₃ ) or a mixture thereof, while slowing down the reaction, they are heated to 90 ° C-100 ° C, after dissolving the components, the solution is cooled to room temperature rats, then with stirring, 95-200 g of chromium oxide is added to the resulting solution, then 60-200 g of a mixture of oxides of divalent metals and 60-200 g of hydroxide or carbonic salts of monovalent metals are added to the resulting paste of a complex iron-chromium-phosphate compound with constant stirring - potassium, sodium, then the resulting paste of the complex metal phosphate product is dried and crushed, obtaining a powder of the complex metal phosphate product gross of the formula

where M ^III - cations of trivalent metals - iron

chrome

aluminum

in different ratios, M ^II - cations of divalent metals, M ^I - cations of monovalent metals - potassium, sodium, m = 3 ... 12, n = 3 ... 12.