SU1640107A1 - Copper amminophosfate and method for its production - Google Patents

Description

The invention relates to new chemical compounds, to coordination compounds of copper with ammonia

The invention relates to new chemical compounds, more specifically to the coordination compounds of copper with ammonia in the solid state of the general, of the formula (Cu · (ΝΗ _$ ) _η (H ₂ 0) _t '] ₃ (P0 ₄ ) ₂ xH ₂ 0, where' η = G - 4, ta = 1 - 3, x = 1 - 2, and to the method of their preparation, which can be used as biologically active, microelement compositions in agriculture and as catalysts in organic synthesis.

The aim of the invention is to obtain compounds with biological activity.

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in the solid state, specifically to copper aminophosphate of the formula £ θιι (ΝΗ ₃ ) x x (H ₂ 0)] _e (P0 ₄ ) ₂ . (1-2) 1 ^ 0 and to the way they are received. This compound can be used as a biologically active substance or microelement composition in agriculture, as well as a catalyst in organic synthesis. In order to obtain solid crystalline copper aminophosphate with a high yield of an individual product, synthesis is carried out by salting out the compound with organic solvents (standard, acetone, etc.) from ammoniacal solutions of copper phosphate, followed by crystallization and drying. The yield of an individual copper aminophosphate of the composition [Cu (BN ₃ ) (H _g O) Z _e (PO ₄ ) ₂ 'H _g O can reach 99% for copper and phosphorus. The technology of obtaining environmentally friendly. 2 sec. f-ly, 4 tabl

Copper amminophosphate is prepared as follows.

As initial reagents, use is made of 'crystalline average copper phosphate of the general formula: Cu ₃ (P0 ₄ ) ^ x x (O - 3) H _g 0, aqueous ammonia solution and organic solvents (ethanol or acetone),

Synthesis is carried out in the following order. A portion of the average copper phosphate is dissolved completely in an aqueous solution of ammonia. To the resulting solution of copper phosphate tetraamminacate, painted in an intense blue color, to Γν А01ПН11 ТТС

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An organic solvent is added, for example ethanol or acetone. At the same time, the bottom phase is formed in the form of a dark blue oily film. The mixture, consisting of the bottom phase and the mother liquor, is held at 15-25 ° C until the beginning of the crystallization of the bottom phase. Then the mother liquor is separated and the solid product (copper phosphate copper aminophosphate) is dried to constant weight. A fine-crystalline polydisperse substance of green color is obtained, which corresponds to the gross formula CsiO · P ^ O ^ - 3ΝΗ ₃ x x (4 - 5) H _? 0. 15

Examples of capacity contribute 6 May o Cho crystalline Cu ₃ (PC> 4.) _G x 'x 2H ^ 0 (42.8% Cu), add 14 wt.h "(15 v _about 18 h) 18.1% , an aqueous solution of ammonia (100% of stoichiometry in 20

in the form of tetraamminacate ₍ nogra complex) and mixed until the starting phosphate is completely dissolved. To the resulting solution of intense blue color is added in 25

based on 1 wt.h. the initial copper phosphate 5.2 wt.h. (6.4 vol. ”H.) 97% ethanol solution and mix the mixture until an oily film is formed and an intense blue color, 39 The mixture consisting of the bottom phase and the mother liquor is kept at 15 - 25 ° C, until the beginning of the bottom phase crystallization . Then the mother liquor is drained and the precipitate is dried in air to constant weight "

As a result of the implementation of the described method, a polydisperse powder of green color is obtained, containing,%:

CuO 45.9; P ^ O ^ 28,5; ΝΗ ₃ 9.7; H ₂ 0. _4θ

15, -9. The gross formula of the substance is 2.9CiOx χ Ρ ₂ , Ο _5. · 2.9ΝΗ ₃ · 4H ₂ 0; molecular formula according to the complex of physicochemical studies £ Cu (ΝΗ _e ) x χ ( _ζ 0) ^ y (P0 ₄ ) g'1.4 H ₂ 0 "Exit ₄₅

product by CuO and 99.5%.

Example 2. In the capacity contribute 6 May "h <, crystalline Cu ₃ CPO ^) ^ x

χ 3NH ^ O (42.8% Cu), add 14 wt.h ”(15 vol.h) of an 18.1% aqueous solution of ammonia (100% of stoichiometry based on the formation of the tetraamine complex) and mix until the phosphate is completely dissolved. To the solution obtained is an intense blue, the colors are added per 1 wt.h. the original, copper phosphate 5.1 wt.h.

(6.4 ob.h) of an acetone solution and the mixture is stirred until an oily film of intense blue color is formed. The mixture consisting of the bottom phase and the mother liquor is kept at 15-25 ° C until the beginning of the crystallization of the bottom phase. Then the mother liquor is drained and dried in air to constant weight.

As a result of the implementation of the described method, a polydisperse powder of green color is obtained, containing,

%: CuO 46.4; Р ₂ 0д- 28,5; ШЦ 9,5;

H ^ O 15.6. The gross formula of substance 2.9SiO> P _g 0 _? 2.8 4 · 4, 3N ₂ 0; molecular formula tTdankm complex physico-chemical studies: ['si (LN ₃ ) (H ^ O) 3 ₃ (P0 ₄ ) ₂ 1.3 H ^ O.

Yield of the product according to CuO and Ρ ₂ 0 _? 99.8%

Example 6 wt »h of crystalline Cu ₃ (P0 ₄ ) ₂ x x 2.7 H ^ O (44.7% of Cu) are introduced into the tank, 20.9 wt.h. (19 parts by volume) of a 22.5% aqueous solution of ammonia (150% of stoichiometry calculated on the formation of the tetraammine complex) and stirred until complete dissolution of the phosphate. To the resulting solution of intense blue color is added to the calculation. On 1 part by weight of the initial copper phosphate 10.3 wt. "H" (12 _O 8 vol.h,) of a 97% aqueous solution of ethanol and the mixture is stirred until an oily film is formed. of blue color. The mixture consisting of the bottom phase and the mother liquor is kept at 15-25 ° C until the beginning of the crystallization of the bottom phase. Then the mother liquor is drained and the precipitate is dried in air to constant weight "

As a result of the implementation of the proposed method, polydispers is obtained! ny green powder containing,%: CuO 46,9; Ρ ₂ θ5-28,2; ΝΗ ₃ 10.1;

H _g 0 14,8. The gross formula of substance 3, OSiO P ₂ 0 ₅ > 3.0ΝΗ ₃ · 4.1N ₂ 0; molecular formula according to the complex physicochemical studies, ["Cu x x (MH ₃ ) (H _g 0P _l (P0 ₄ ) _g 1.1 H ₂ 0. The product yield for Cu and P ₂ 0d is 99.0%. ·

Π p and me 4. 6 wt.h ”of crystalline Cu ₃ (P0 ₄ ) ₂ x x 3N ₂ 0 (42.8% Cu) are added to the tank, 20.9 wt.h. (19 ob.ch.) Of a 22.5% aqueous solution of ammonia (150% of stoichiometry based on the formation of the tetraammine complex) and stirred until complete dissolution of the phosphate. To the resulting solution of intense blue color is added in the calculation of

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1 wt.h. copper source phosphate

10.1 wt.h. (12.8 parts by volume) of an acetone solution and the mixture is stirred until an oily film of intense blue color is formed. The mixture consisting of the bottom phase and the mother liquor is kept at 15-25 ° C until the beginning of the crystallization of the bottom phase. Then the mother liquor is drained and the precipitate is dried in air to constant weight.

As a result of the implementation of the described method, a polydisperse powder of green color is obtained, containing,

%: CuO 47.0; P ^ 28.2; ΝΗ ₃ 10.7;

H ₂ 0 14.2. The gross formula of a substance is 3.0Ci0 · P _g 0 ₅ · 3.2ΝΗ _} · 4.0 Bimolecular formula according to the complex of physico-chemical studies [Si (LH ₃ ) x χίΗ ^ Ο) ^ ( P0 <|) ₂ . 1.0 H ₂ 0. The yield of the product according to CuO and P2O5 is 99.3%.

The effect of the nature of the salting out agent on the duration of the process of the formation of copper aminophosphate crystals is shown in Table. one.

Conducting synthesis using other organic solvents significantly slows down the crystallization of the bottom phase, which reduces the performance of the method.

The completeness of copper deposition from an ammonia solution of copper phosphate, depending on the conditions of dissolution of the initial substance and the amount of the salting out agent, is given in Table 2.

The increase in the yield of the target product, as can be judged by the completeness of copper deposition from the mother liquor (Table 2), is observed as the concentration of the initial aqueous ammonia solution increases from 4.9 to 18.1%. At the same time, the best performance is achieved with a dose of ammonia of 85-100% of stoichiometry (based on the formation of copper in the tetraammine solution) and the consumption of the salting out agent (standard) 6.4 - 12.8 ml per 1 g of the initial copper phosphate. The same trend is observed when using acetone as a salting out agent.

The stoichiometry of the coordination sphere of copper aminophosphate (by which one can judge the individuality of the substance) is determined by the integer molar ratio of Cu:: ₃ . For example, Cu: ΝΗ ₃ = 1: 1 for [Cu (NH ₃ ) 2 ^{g +} , Cu: ΝΗ ₃ = 1: 2 for

[Si (UN _e ) _g ] **, etc. Considering that

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In the experiment, the average copper phosphate with a gross formula of 2.9CiO x x P ^ Oy'3.1 N ₂ O is used; in the final product of the synthesis, the molar fraction of CuO must be within 2.9 + 0.1, which fits within the limits of chemical accuracy. analysis of the composition of copper aminophosphate.

Yu Gross formula of copper aminophosphates, obtained by using an 18.1% solution of ammonia in the synthesis, are given in the table.

From the data table. 3 it follows that

15 A product of stoichiometric composition, corresponding to the presence of a complex ion [si (ΝΗ,)] ²⁴ in a substance, is best formed when it is salted out of an 18-22.5% ammonia solution, taking 100-150% of the stoichiometric dose ( calculation for the formation of copper tetraamminacate in solution), if a salting out agent (ethanol or acetone) is introduced in an amount

25 6.4 -12.8 ml per 1 g of the initial average copper phosphate. Taking into account the data of Table 2, the optimal dose of the ammonia solution in the synthesis should be considered 100% of the stoichiometric amount.

The content of the ingredients in the copper aminophosphate, obtained by the proposed method, the following (in terms of oxides), wt.%:

SIO 45.78

P ^ O *. 28.18

ΝΗ _er 9.99

NDO Rest.

According to X-ray diffraction data, the synthesized copper aminophosphate is represented by one phase, i.e. is an individual product with the following lattice unit cell parameters: a _o = 15.417

OS '

• b = 13.523 _K A; c = 11.291 A; ν =

45

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= 2354.05 A. The lattice type is rhombic.

The complex of physicochemical methods has confirmed that the composition of the copper aminophosphate synthesized can be expressed by the formula [Ίθυ (^) (H ₂ 0 G] x x (Ρ0 ₄ ) ^ · _ζ 0.

The synthesized ammonium phosphate of copper contains nutrients useful for plants (copper, nitrogen and phosphorus) and can be used as a fertilizer or biologically active compound.

Table 4 shows the results of agrochemical tests of the action of Am7

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copper minophosphate on the development of winter wheat.

The studies were carried out in comparison with the use of copper sulfate supplements in agricultural practice with intensive nitrogen nutrition of plants. It has been established that copper aminophosphate increases seed germination by 6–15%, their energy, θ germination by 7–12%, and the weight of seedlings by 8%. Table 4). Such an effect of copper aminophosphate on plants is due to the fact that there are three batteries in the compound molecule at the same time, and its structure is 2θ

corresponds to the structure of chelate substances that are biologically active against plants.

The product of the proposed composition is obtained by salting out with ethanol or 25 with acetone from an ammoniacal solution of copper phosphate. In a known substance, cobalt (III) ammonium phosphate is obtained from a mixture of ammonia solutions of CoCl ₂ and Na2_HPO4 * 12H ^ 0 by the oxidizing effect of H ₂ p ₂ at room temperature. By a known method, copper aminophosphate cannot be obtained.

In a known method, reagents are used that give waste in the form of C1 ~ ~, IA * ions, and in the proposed method they are not. In the proposed method, it is possible to obtain an individual compound of the composition (^ Cu (LH ₃ ) (H ^ Od e x x H ^ O, which is not guaranteed

in a known way.

Claims (1)

Claim 1. Copper amminophosphate of the formula GSP (MN ₃ ) (n _g O) 3 s (P0 ₄ ) ₂ <(1-2) H ₂ 0, used in agriculture as a biologically active trace element compound. ι 2. A method of producing copper aminophosphate, which consists in the fact that, in order to form a biologically active compound, the product is obtained by dissolving crystalline Cu ^ PO ^) ^ x (0-3) H ^ O in 18-22.5% aqueous ammonia solution, followed by adding to the mixture of ethanol or acetone, taken from the calculation of 6.4 - 12.8 ml per 1 g of the initial phosphate, crystallization, separation of the bottom phase and its further drying at ambient temperature. Table 1 Solvent (precipitator * ^- *) Presence of bottom solvent phase the process until the crystallization of the bottom phase, Xsut Acetone there is u-go Ethanol _ eleven _ 3 - 15 Butanol _ H _ Crystallization does not occur within 4550 days. n-propanol Also Isopropanol _ and _ ~ 11 - Chloroform _ and _ ~ and _ Benzene _ eleven _ ^{, r} - Na ^ NRA 4, (solution) * Not Crystallization of the target product is not observed Ν3 _ε ΗΡ0 ₄ + Η ^ 0 _χ ** _ η _ Also • K-) Within the specified limits, the duration of the process depends on the concentration and dose of ammonia. To *) By a known method. 9 1640107 U table 2 The concentration of the original aqueous solution of ammonia, X The dose of the solution, X from stoichiometry in the calculation of the formation of tetraammoniaThe volume of ethanol, ml per 1 g of the original copper phosphate The completeness of copper deposition from the mother liquor to the final product, X that copper 18.1 150 3.2 96.6 18.1 150 6.4 98.6 18.1 150 12.8 99.0 18.1 150 16,0 99.2 18.1 100 3.2 98.9 18.1 100 6.4 99.5 18.1 100 12.8 99.9 18.1 85 3.2 98.9 18.1 85 6.4 99.7 18.1 85 12.8 99.9 9.6 150 6.4 69.3 9.6 150 12.8 93.3 4.9 150 6.4 52.4 4.9 .150 12.8 67.5 4.9 150 16,0 75.8 Table 3 Ammonia solution dose, X from stoichiometry based on the formation of tetraamyakata. copper The volume of the salting out agent, MP per 1 g of the original copper phosphate Gross formula product The ratio of Cu: ΝΗ ₃ in the product synthesis one 2 3 four Ethanol precipitation 150 3.2 g.ESiO ^ P ^ O ^ 2 7ΝΗ, - 4.9Η _έ Ο 1.1 150 6.4 2.8SiO'R _g 0 ₅ .3 om ’ 4.6H _g 0 0.9 150 12.8 2.9СиОР _г О ₅ -2 8ΝΗ 4,4N _g About 1.0 150 16,0 2.8Си0.Р _g 05--2 9ΝΗ, 4,4N _g About 1.0 100 3.2 2.9SiO-P ₂ 0 _y · 2 7ΝΗ, 4.1N _g 0 1.1 100 6.4 2.8SiO <R _and O5--2 7ΝΗ, 4.4H ₂ 0 1.0 100 12.8 2.9SiO.R _g O5-'2 8ΝΗ, 4,511 ^ 0 1.0 .100 16,0 2,9CiO · P ^. 2 7ΝΗ, 4.4Η ^ Ο 1.1 85 3.2 2.9SiO "P _g O ₅ g ^, 3 6№Ц 5.2N _x 0 0.8 85 6.4 2,90υΟ.Ρ ₂ θ5- · 2 7M _? 4.6H ₂ O 1.1 85 12.8 2.9Ci0 · Ρ ₂ 05 · -2 6ΝΗ, 4.4H _g 0 1.1 85 ^ 16,0 2.9Ci0.R ₂ O5-'2 6ΝΗ ₃ 4,4N _g About 1.1 150 * 12.8 Precipitation 3,0 СиО.Р _and О ₅ * 3 with acetone. 0M _? 4.1N _g 0 1.0 150 3.2 2.9SiO.R ₂ Oh _? .2 5ΝΗ ₈ 4.8H ₂ 0 1.2 150 6.4 2.9SiO.R _g Oh, _- 2 5ΝΒ, 4.311.0 1.2 150 12.8 2.9SiO · P _g 0 y 3 0ΝΗ ₃ 4.5 _ng about 1.0 150 16,0 2.9SiO · R _g Ou · 3 1ΝΗ, 4? Κ _ζ 0 0.9 100 3.2 2.9SiO.R * Ou.Z 6ΝΗ, 5, 3N ₂ 0. 0.8 eleven 1640107 g 3 12 Continuation of table. 3 - G ”V 100 6.4 2.9ΟυΟ.Ρ _ζ Ο _? 3.2ΝΗ ₃ · 5.7Н ₂ 0 0.9 yo 12.8 2.9SiO "P _g O _g -2.8I11 ,, 4.4" N _g 0 1.0 100 16,0 2.8SiO · P ^ Oy · 2.8ΝΗ ^ “4.9N /) 1.0 85 6.4 2.8Ci0 · P /) ^ · 3,2ΝΗ ₃ "4,6N ₂ 0 0.9 85 12.8 2,9SiO "P _z 0 _y:. 3,1ΝΗ _5" 4,6N _± O 0.9 85 16,0 2.9SiO »P ₂ 0 £ · 3,1ΝΗ ₃ · 4,711 ^ 0 0.9 # ") In the synthesis of used Cu ^ (PO ^ · ЗН ₂ 0 and an ammonia solution of 22.5% concentration. Table 4 Additive The concentration of the composition for feeding on medN'H Collection, protein with grain yield, kg / ha Protein content l grain! 2 Gluten content in grain, X Gluten quality * idk Elasticity Extensibility No additive Sulfate 0 859 12.9 29.2 85-95 Satisfactory Long copper 0.25 905 13.3 30.2 90-80 _- ”- “>” - Amminophos 0.10 942 13.5 30.6 85-95 - ι * - _m ”l copper veil 0.25 956 14.0 32.1 80-85 - one' - g- "- 0.10 1006 14.3 32.9 75-80 .Good Average 0.01 995 14.3 32,8 80-85 - · - * The quality of gluten is higher with lower IDC values, better elasticity and less extensibility.