CN1793066B - Competitive Complex Production Method of High Concentration Microelement Foliar Fertilizer - Google Patents

Abstract

Competitive complexation production method of high-concentration trace element foliar fertilizer: use ethylenediaminetetraacetic acid to react with one or more oxides or carbonates of zinc, manganese and magnesium, etc., to generate EDTA-Zn, EDTA-Mn and EDTA-Mg complexes, and use borax, ammonium molybdate, and boric acid to control the pH of the medium; add ferrous sulfate and copper sulfate, and compete with EDTA-Zn, EDTA-Mn, and EDTA-Mg for complexation react to form EDTA-Fe and EDTA-Cu water-soluble complexes, and finally dry to obtain 100% water-soluble high-concentration trace element leaves containing boron, manganese, copper, zinc, molybdenum and iron with a total content of 16-24%. surface fertilizer. The invention can prepare trace element foliar fertilizers of various uses and types and trace element companions of multi-element compound fertilizers according to the abundance and deficiency of soil trace elements in my country and the requirements of plant growth and development.

Description

Competitive Complex Production Method of High Concentration Microelement Foliar Fertilizer

technical field

The invention relates to a production method of leaf fertilizer, in particular to a competitive complex production method of high-concentration trace element foliage fertilizer.

Background technique

Modern agriculture, horticulture, orchards, protected cultivation and hydroponics require the supply of highly concentrated fertilizers to facilitate automated fertilization and save costs. Standards issued by the Ministry of Agriculture: The total content of active ingredients of six trace elements such as boron, manganese, copper, zinc, molybdenum and iron in the trace element foliar fertilizer should be ≥10%, and the water-insoluble matter should be ≤5%. (2002 "Guidelines for Fertilizer Registration" issued by the Fertilizer and Drug Administration Office of the Ministry of Agriculture, page 83, China Agricultural Press, 2002). However, the trace element fertilizer prepared by the general method complexing agent and sulphate has high inactive ingredient content, which often does not meet the active ingredient content standard issued by the Ministry of Agriculture; at the same time, the water quality requirement for leaf fertilizer is improved. And prepare with trace element complex pure product, then process is complicated, and cost is high.

Contents of the invention

For the above-mentioned deficiencies in the prior art, the purpose of this invention is to provide a kind of competitive complexation production method of high-concentration trace element foliage fertilizer, the high-concentration trace element foliage fertilizer produced by the method can reach boron, manganese, copper, The total content of active ingredients of six trace elements such as zinc, molybdenum and iron is ≥10%, and the water-insoluble matter is ≤5%. The production method should have simple process, less equipment, less energy consumption and no waste. The product is 100% water-soluble and has a high concentration, which can exceed 1.6 to 2.4 times the ministerial standard, and can develop multi-element compound fertilizers with high concentrations of trace elements and macroelements N, P, K, etc. At the same time, the impurity SO ₄ ^2- root is reduced, which also reduces the water quality requirement for dissolved leaf fertilizer. The finished product is directly used as leaf fertilizer, or as a fertilizer companion for preparing fertilizer.

The technical scheme of completing the above-mentioned invention task is: the competitive complexation production method of new high-concentration trace element foliar fertilizer: apply EDTA (ethylenediaminetetraacetic acid) and zinc, manganese and magnesium etc. in the oxide or carbonate One or more reactions, one-step method to generate one or more of EDTA-Zn, EDTA-Mn and EDTA-Mg complexes, and use borax, ammonium molybdate and boric acid to control the pH of the medium; add sulfurous acid Iron (FeSO ₄ 7H ₂ O) and copper sulfate (CaSO ₄ 5H ₂ O) undergo competitive complexation reactions with EDTA-Zn, EDTA-Mn, and EDTA-Mg to form EDTA-Fe and EDTA-Cu complexes , to ensure the completion of the competitive complexation reaction and the formation of water-soluble complexes, and finally dry at 105°C to obtain high-concentration trace elements containing boron, manganese, copper, zinc, molybdenum and iron with a total content of 16-24%, 100% water-soluble Foliar fertilizer.

The ratio of each component in the above scheme is determined according to the ratio requirements of the produced leaf fertilizer, and the ratio of various types of leaf fertilizer has been finalized in the prior art and is well known to those skilled in the art.

More specifically, the competitive complex production method of high-concentration microelement foliar fertilizer comprises the following steps:

One, two or three of elements such as magnesium, zinc and manganese are complexed and dissolved with ethylenediaminetetraacetic acid (EDTA), and elements such as magnesium, zinc and manganese are added by using their oxides or carbonic acid Salt, one-step method to generate complexes such as EDTA-Mg, EDTA-Zn and EDTA-Mn;

Add the above EDTA-Mg, EDTA-Zn and EDTA-Mn complexes into a certain medium, then add ferrous sulfate (FeSO ₄ 7H ₂ O) and copper sulfate (CaSO ₄ 5H ₂ O);

Using the complexation stability constant (logκ value) of iron and copper in EDTA, which is greater than the logκ value of magnesium, zinc, manganese, etc., EDTA and ferrous sulfate (FeSO ₄ 7H ₂ O) and copper sulfate in these complexes (CaSO ₄ 5H ₂ O) undergoes a competitive complexation reaction to generate water-soluble complexes such as EDTA-Fe and EDTA-Cu;

In the previous step, borax, ammonium molybdate and boric acid and other trace element agents are used to control the pH of the medium to ensure the completion of the competitive complexation reaction and the formation of water-soluble complexes;

Finally, it is dried at 105°C to produce a yellow-green powdery finished product.

The finished product is 100% water-soluble, ultra-high concentration trace element foliar fertilizer.

The "certain medium" in the above scheme refers to two or three kinds of mediums such as borax, ammonium molybdate and boric acid.

The specific method of trace element agents such as borax, ammonium molybdate and boric acid in the above scheme to control the pH of the medium is: after oxides or carbonates such as magnesium, zinc and manganese are ground and dissolved, add the above-mentioned borax, ammonium molybdate and boric acid Wait for the grinding to dissolve, and control the pH of the medium. When the medium is acidic, ammonium molybdate or borax can be added; when the medium is alkaline, boric acid can be added. The method and amount of addition are the same as the method for adjusting the pH value of the solution.

The finished product is directly used as leaf fertilizer, or as a fertilizer companion for preparing fertilizer.

More optimized and more specifically, the concrete steps of production method of the present invention are:

First use EDTA and oxides or carbonates of magnesium, zinc and manganese, etc., add water to grind, dissolve, and generate complexes such as EDTA-Mg, EDTA-Zn and EDTA-Mn in one-step method; the weight ratio of each reactant, Add according to the needs of various formulations of leaf fertilizer in the prior art.

In the above-mentioned certain medium, using the complexation stability constant (logκ value) of iron and copper in EDTA, which is greater than the logκ value of magnesium, zinc, manganese, etc., EDTA in the complex will react with ferrous sulfate and copper sulfate. Competitive complexation reaction to generate water-soluble complexes such as EDTA-Fe and EDTA-Cu; the proportion of water added in the reaction, because Cu ²⁺ and Fe ²⁺ ions are both complexed and concealed, even at concentrated and dry temperatures , and Cu ²⁺ ions will not catalyze the oxidation of Fe ²⁺ to generate ferric precipitates, and the reaction can be carried out in a supersaturated solution. The amount of water added, including the water for washing utensils, and the weight ratio of water to materials can be controlled at 5:1-6:1; to ensure that the supersaturated solution changes to the true solution in the early stage of concentration and evaporation, which can save energy.

In the above steps, borax, ammonium molybdate and boric acid and other trace element agents are used to control the pH of the medium to ensure the completion of the competitive complexation reaction and the formation of water-soluble complexes; finally, it is dried at 105°C to become a solid and made into a powdery product; The finished product is 100% water-soluble, ultra-high concentration trace element foliar fertilizer.

The process of the invention is simple and convenient, low in energy consumption and cost, and produces no waste.

The present invention can prepare trace element foliar fertilizers of various uses and models and trace element companions of multi-element compound fertilizers according to the abundance and deficiency of soil trace elements in my country and the needs of plant growth and development. This patent also has the following advantages:

First, the use of competitive complexation prevents the catalytic reaction of copper plasma, which not only reduces the impurity SO ₄ ^2- content, but also reduces energy consumption.

Second, using EDTA to complex dissolve ZnO, MgO and MnCO ₃ also greatly reduces the impurity content, and this method can also be used to prepare pure complexes of these ions.

Third, although the SO ₄ ^2- root S is also a fertilizer (but not a micro-fertilizer), but the SO ₄ ^2- in the leaf fertilizer is reduced, and the water quality requirement for dissolving the leaf fertilizer can be reduced. Groundwater in northern China contains a lot of calcium ions, some of which are hard water; SO ₄ ^2- and calcium in the water will cause CaSO ₄ to precipitate and block the nozzle. There is less SO ₄ ^2- in the leaf fertilizer of the patent, which can reduce the water quality requirement for dissolving the leaf fertilizer.

Detailed ways

Embodiment 1: Trace element foliage fertilizer based on iron (formulation product code number 3120, the same below)

A, trace element composition (element weight %)

Fe 10.96% Zn 5.48%;

Mn 5.48% Cu 1.1%;

B 1.1% Mo 0.1%;

S 6.89%

When excluding S, the total amount of trace elements is 24.22%.

The production process includes the following steps:

In a non-metal container with a grinder, first weigh 21 parts of EDTA (ethylenediaminetetraacetic acid) (weight unit, the same hereinafter), then weigh 3.2 parts of zinc oxide ZnO and 5.7 parts of manganese carbonate MnCO ₃ . First dry grind and mix, then add water to grind until no bubbles are produced. Add 4.4 parts of borax (Na ₂ B ₄ O ₇ 10H ₂ O), 0.1 part of ammonium molybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ 4H ₂ O], grind and dissolve; then add high-quality ferrous sulfate sequentially 25 parts of (FeSO ₄ ·7H ₂ O) and 2 parts of copper sulfate (CuSO ₄ ·5H ₂ O) were ground and dissolved successively to complete the competitive complexation reaction. Finally, it is dried at 105°C or sprayed with powder to obtain a high-concentration trace element foliar fertilizer with a total amount of six trace elements of boron, manganese, copper, zinc, molybdenum and iron reaching 24%.

Fertilizer Characteristics

①The dry matter is 100% water-soluble, and its 0.1% aqueous solution in water has a pH of 3.7±0.2.

②When using, dilute 3000-5000 times with water, spray, and top-dress the roots of plants.

Embodiment 2, iron-based trace element foliar fertilizer companion (formulation product code 3124, the same below).

formula

42 parts of EDTA CuSO ₄ 5H ₂ O 2 parts

ZnO 3.15 parts Na ₂ B ₄ O ₇ ·10H ₂ O 2.2 parts

MnCO ₃ 5.7 parts H ₃ BO ₃ 1.5 parts

MgO 4.15 parts (NH ₄ ) ₆ Mo ₇ O ₂₄ 4H ₂ O 0.1 parts

FeSO ₄ ·7H ₂ o 25 parts

craft

With embodiment 1.

Fertilizer Characteristics

① The total concentration of trace elements is 16.15%, and if including Mg element, its content is 19.81%.

② Composition of trace elements:

Fe 7.31% Mg 3.655%

Zn 3.655% B 0.73%

Mn 3.655 Mo 0.073%

Cu 0.73% S 4.5%

Total trace elements excluding S and Mg: 19.81%

③The obtained fertilizer is 100% soluble in water, and the pH value of its 0.1% aqueous solution is 3.8±0.2.

④ Metal cations and trace elements are all complexes, which can be used as trace element companions for multi-element fertilizers.

Embodiment 3, the trace element foliar fertilizer companion formula (formulation product code 424, the same below) based on zinc and boron.

formula

1. EDTA 22 parts 6. CuSO ₄ 5H ₂ O 1.8 parts

2.MgO 0.95 parts 7.Na ₂ B ₄ O ₇ ·10H ₂ O 8 parts

3.ZnO 4.5 parts 8.H ₃ BO ₃ 5.21 parts

4.MnCO ₃ 1.95 parts 9.(NH ₄ ) ₆ Mo ₇ O ₂₄ ·4H ₂ 0 0.85% parts

5. FeSO ₄ ·7H ₂ O 4.55 parts

Technology is with embodiment 1.

feature

① The total amount of trace elements boron, manganese, copper, zinc, molybdenum and iron is 20.20%, and when magnesium is included, it is 21.62%.

② Composition of trace elements:

Zn 8.95% Mg 1.42%

Fe 2.26% B 4.5%

Mn 2.26% Mo 1.13%

Cu 1.1% S 1.87%

③The fertilizer is 100% soluble in water, and the pH value of its 0.1% aqueous solution is 3.5±0.2.

④The trace elements are all in complex state, which can be used not only as foliar fertilizer, but also as trace element companion of multi-component compound fertilizer.

Multi-element compound fertilizer preparation:

The products of Example 2 and Example 3 can be mixed with domestic N, P, and K macronutrient fertilizers to prepare multi-element compound fertilizers. Examples are as follows:

(I) (N ₂₀ -P ₂₀ -K ₂₀ -T _E 0.27. Total active ingredient 60.27% general-purpose multi-element compound fertilizer. N is calculated as pure N, P is calculated as P ₂ O ₅ , K is calculated as K ₂ O and _TE It is the % concentration of the total amount of trace elements (the same below).

Formulation (weight%)

①.NH ₄ H ₂ PO ₄ 32.78％

②.KNO ₃ 43.73%

③.(NH ₂ ) ₂ CO 21.91％

4. formula product code number 3124 (the product of embodiment 2) 1.4%

craft

Powder ④ firstly mixed with ② mechanically, then add ① and then add ③ to mix step by step (mix in a hammer mixer).

feature

①N 20%, P ₂ O ₅ 20%, K ₂ O 20%, total 60%.

② Composition of trace elements:

Fe 0.1% Zn 0.05%

Mn 0.05% Mg 0.05%

Cu 0.01% B 0.01%

Mo 0.001% S 0.096%

③The fertilizer is 100% soluble in water, and the pH value of its 1% aqueous solution is 4.77; when Ca ²⁺ 300ppm is added, the pH value is 4.64, a clear liquid.

(II) N18-P18-K18-T _E 2.0 is a multi-element compound fertilizer with 56% total effective ingredients and more iron content.

formula:

①.NH ₄ H ₂ PO ₄ 29.51％

②.KNO ₃ 39.35%

③.(NH ₂ ) ₂ CO 19.71％

④. formula product code 3124 (the product of embodiment 2) 11.4%

Total 99.97%

Technology is identical with preparation example (I). The product is packaged in a double plastic bag.

feature

①The fertilizer is 100% soluble in water, and its 1% aqueous solution has a pH value of 4.1; when Ca ²⁺ 300ppm is added, the pH value is 4.01, a clear liquid.

②N 18% P ₂ O ₅ 18% K ₂ O 18%.

③Trace elements: Fe 0.738% Cu 0.073%;

Zn 0.369% B 0.073%

Mn 0.369% Mo 0.007%

Mg 0.369%; Total 1.998%

(III) N25-P10-K20-T _E 1.0 A multi-element compound fertilizer with 56% total active ingredients and more iron content.

formula

①, KH ₂ PO ₄ 19.4%

②, _KNO3 29.3%

③, (NH ₂ ) ₂ CO 45.7%

④, formula product code number 3124 (the product of embodiment 2) 5.07%

A total of 99.47%.

Technology is identical with preparation example (I). The product is packaged in a double plastic bag.

feature

① Fertilizer is 100% water soluble, 1% aqueous solution pH3.81; when Ca ²⁺ 300ppm is added, it is pH3.76, clear liquid.

②N 25% P ₂ O ₅ 10% K ₂ O 20%, total 55%.

③Trace element composition:

Fe 0.37% Cu 0.037%

Zn 0.18% B 0.037%

Mn 0.18% Mo 0.0035%

Mg 0.18% S 0.225%

(IV) N18-P18-K18-T _E 2.0 is a multi-element compound fertilizer with 56% total active ingredients and more zinc and boron content.

Formulation (weight%)

①, NH ₄ H ₂ PO ₄ 29.51%

②, _KNO3 39.35%

③, (NH ₂ ) ₂ CO 19.71%

④, formula product code number 424 (the product of embodiment 3) 10.08%

A total of 98.65%.

Technology is identical with preparation example (I). The product is packaged in a double plastic bag.

feature

①The fertilizer is 100% water-soluble, and the pH of 1% aqueous solution is 4.54; when Ca ²⁺ 300ppm is added, the pH is 4.50, a clear liquid.

②N 18% P ₂ O ₅ 18% K ₂ O 18%, total 54%.

③Trace element composition:

Zn 0.88% Cu 0.11%

Fe 0.22% B 0.44%

Mn 0.22% Mo 0.11%

Mg 0.14% S 0.173%

(V), N25-P10-K20-T _E 1.0 The total active ingredients are 56%, and the multi-element compound fertilizer contains more zinc and boron.

Formulation (weight%)

①KH ₂ PO ₄ 19.4%

② _KNO3 29.3%

③(NH ₂ ) ₂ CO 45.7%

4. formula product code number 424 (the product of embodiment 3) 5.1%

Total 99.5%

Technology is identical with preparation example (I). The product is packaged in a double plastic bag.

Fertilizer Characteristics

①The fertilizer is 100% water-soluble, and the pH of 1% aqueous solution is 3.97; when Ca ²⁺ 300ppm is added, the pH is 3.91, a clear liquid.

②Trace elements 1.0%:

Zn 0.44% Cu 0.05%

Mn 0.11% B 0.22%;

Mg 0.07% Mo 0.05%;

Fe 0.11% S 0.09%

③A large number of elements:

N 25%, P ₂ O ₅ 10%, K ₂ O 20%, total 55%.

Embodiment 4 is basically the same as the above-mentioned embodiment, but has the following changes:

1. Zn and Mg are ZnCO ₃ and MgCO ₃ respectively; Mn is MnO.

2. After adding water and grinding, add boric acid while adding borax and ammonium molybdate.

Embodiment 5 is basically the same as the above-mentioned embodiment, but has the following changes:

EDTA is only ground with ZnO in a non-metallic container with a grinder.

Embodiment 6 is basically the same as the foregoing embodiment, but has the following changes:

EDTA is only ground with MnO in a non-metallic container with a grinder.

Embodiment 7 is basically the same as the foregoing embodiment, but has the following changes:

EDTA is only ground with MgO in a non-metallic container with a grinder.

Embodiment 8 is basically the same as the above-mentioned embodiment, but has the following changes:

EDTA is only ground with _ZnCO3 in a non-metallic container with a grinder.

Embodiment 9 is basically the same as the above-mentioned embodiment, but has the following changes:

EDTA is only ground with _MnCO3 in a non-metal container with a grinder.

Embodiment 10 is basically the same as the above-mentioned embodiment, but has the following changes:

EDTA is only ground with _MgCO3 in a non-metallic container with a grinder.

Embodiment 11 is basically the same as the above-mentioned embodiment, but has the following changes:

EDTA was ground with ZnCO ₃ , MgCO ₃ in a non-metallic container with a grinder.

Embodiment 12 is basically the same as the above-mentioned embodiment, but has the following changes:

EDTA is ground with MnO, MgCO ₃ in a non-metallic container with a grinder.

Claims (2)

1. the process for competition coordination producing of a high concentration trace elements leaf fertilizer: use ethylene dinitrilotetra-acetic acid respectively with the oxide compound or the carbonate of zinc and magnesium, and in the carbonate of manganese one or more, adding water grinds, dissolving, reaction, single stage method generates one or more in EDTA-Zn, EDTA-Mn, the EDTA-Mg complex compound, with borax, ammonium molybdate or boric acid control agent potential of hydrogen; Add ferrous sulfate and copper sulfate again, with EDTA-Zn, EDTA-Mn, EDTA-Mg competition coordination takes place, generate EDTA-Fe and EDTA-Cu water soluble complex, last drying makes water-soluble high concentration trace elements leaf fertilizer or fertilizer companion;

The ratio of each component wherein is to determine according to the proportion requirement of the typing model of production leaf fertilizer;

1. the formulation product code name 3120

21 parts of (NH of EDTA ₄) ₆Mo ₇O ₂₄4H ₂0.1 part of O

3.2 parts of FeSO of ZnO ₄7H ₂25 parts of O

MnCO ₃5.7 part CuSO ₄5H ₂2 parts of O

Na ₂B ₄O ₇10H ₂4.4 parts of O;

2. the formulation product code name 3124

42 parts of CuSO of EDTA ₄5H ₂02 parts

3.15 parts of Na of ZnO ₂B ₄O ₇10H ₂2.2 parts of O

MnCO ₃5.7 part H ₃BO ₃1.5 part

4.15 parts of (NH of MgO ₄) ₆Mo ₇O ₂₄4H ₂0.1 part of O

FeSO ₄7H ₂25 parts of o

3. the formulation product code name 424

22 parts of CuSO of EDTA ₄5H ₂0 1.8 parts

0.95 part of Na of MgO ₂B ₄O ₇10H ₂08 parts

4.5 parts of H of ZnO ₃BO ₃5.21 part

MnCO ₃1.95 part (NH ₄) ₆Mo ₇O ₂₄4H ₂0 0.85 parts

FeSO ₄7H ₂0 4.55 parts;

Amount of water in the reaction comprises ware washing water, and water and weight of material ratio were controlled at 5: 1～6: 1.

2. the process for competition coordination producing of high concentration trace elements leaf fertilizer according to claim 1 is characterized in that, may further comprise the steps:

With a kind of, the two or three usefulness ethylene dinitrilotetra-acetic acid complexing in magnesium, zinc and the manganese element, dissolving, the adding mode of magnesium, zinc and manganese element is to adopt its oxide compound or carbonate, and single stage method generates one or more in EDTA-Mg, EDTA-Zn and the EDTA-Mn complex compound;

Above-mentioned EDTA-Mg, EDTA-Zn and EDTA-Mn complex compound are joined in the medium, add ferrous sulfate and copper sulfate again;

After 105 ℃ of dryings are made yellow-green colour powdery finished product,

Described medium is meant two kinds or three kind in borax, ammonium molybdate and the boric acid,

Described finished product is directly as leaf fertilizer, perhaps as the fertilizer companion who prepares fertilizer.