Organic-inorganic polymeric water-retaining fertilizer and preparation method of the same

Abstract

Provided is an organic-inorganic polymeric water-retaining fertilizer, which is a co-polymer made by fusion and co-polymerization of an organic water-retaining monomer and an inorganic nutrient under action of a catalyst, a biological enzyme and a modifying agent. The co-polymer is of a three-dimensional mesh-like hydrophilic group structure. In a method for preparing the organic-inorganic polymeric water-retaining fertilizer, after obtaining a neutralized pre-polymer from the organic monomer with the catalyst, an initiator and a cross-linking agent are added; the inorganic nutrient and a metasilicate are added simultaneously, a solution is formed by stirring sufficiently; the biological enzyme is added for catalysis; a co-polymer is obtained after fusion and co-polymerization; and granulation and drying are carried out. Preferably, the catalyst is an inorganic alkaline solution. Preferably, the catalyst is selected from the group consisting of a sodium hydroxide solution, a potassium hydroxide solution, an ammonia water and a calcium hydroxide solution.

Claims

1. An organic-inorganic polymeric water-retaining fertilizer, wherein said organic-inorganic polymeric water-retaining fertilizer is a co-polymer, said co-polymer is made by fusion and co-polymerization of an organic water-retaining monomer, an inorganic nutrient, a biological enzyme and a modifying agent under action of a catalyst, a cross-linking agent and an initiator, and said co-polymer is of a three-dimensional mesh-like hydrophilic group structure, said organic-inorganic polymeric water-retaining fertilizer, weighed in parts by weight, comprises: 400-600 parts of acrylic acid, 8900-9600 parts of inorganic nutrient, 50-100 parts of modifying agent and 5-15 parts of biological enzyme.

2. The organic-inorganic polymeric water-retaining fertilizer according to claim 1, wherein said organic-inorganic polymeric water-retaining fertilizer is made by fusion and co-polymerization of the organic water-retaining monomer, the biological enzyme and the inorganic nutrient; and said monomer comprises one selected from the group consisting of an acrylic acid and a derivative of the same.

3. The organic-inorganic polymeric water-retaining fertilizer according to claim 1, wherein said inorganic nutrient comprises one or more selected from the group consisting of calcium magnesium nitrate, urea, monoammonium phosphate, potassium salt, calcium nitrate, magnesium sulfate, zinc sulfate, sodium silicate and sodium borate; and said potassium salt comprises one selected from the group consisting of a potassium sulfate and a potassium chloride.

4. The organic-inorganic polymeric water-retaining fertilizer according to claim 1, wherein said biological enzyme comprises one or more selected from the group consisting of protease, cellulase, lipase, pectinase and an enzyme from enzyme microorganisms.

5. The organic-inorganic polymeric water-retaining fertilizer according to claim 1, wherein said modifying agent comprises two or more selected from the group consisting of protein powder, cellulase powder, pectin, lipid, starch, fish meal and bone meal.

6. The organic-inorganic polymeric water-retaining fertilizer according to claim 1, wherein said inorganic nutrient comprises the following components in parts by weight: 1700-1800 parts of urea, 1500-1600 parts of monoammonium phosphate, 3500-3600 parts of potassium sulfate, 1000-1100 parts of calcium nitrate, 1000-1100 parts of magnesium sulfate, 150-250 parts of sodium silicate, 30-80 parts of zinc sulfate, and 30-80 parts of sodium borate.

7. The organic-inorganic polymeric water-retaining fertilizer according to claim 1, wherein said fertilizer has a pH of 3-8, a mass fraction of organic matter of more than 20%, a water absorbency of 10 g/g-20 g/g; the total content of nitrogen, phosphorous and potassium is 35%-40%; the total content of calcium, magnesium, silicon and sulfur is greater than 5%.

8. A method for preparing the organic-inorganic polymeric water-retaining fertilizer according to claim 1, wherein after obtaining a neutralized pre-polymer from the organic water-retaining monomer under the action of the catalyst, the inorganic nutrient is added; then an initiator and a cross-linking agent are added, a solution is formed by stirring sufficiently; the modifying agent and the biological enzyme are added; a co-polymer is obtained after fusion and co-polymerization; and granulation and drying are carried out; said catalyst is an inorganic alkaline solution.

9. The method according to claim 8, wherein said method comprises steps of: 1) mixing an acrylic acid and the catalyst, which react for 15-20 minutes to obtain the neutralized pre-polymer; 2) sequentially adding the inorganic nutrients, the cross-linking agent and the initiator into the neutralized pre-polymer, which react for 15-25 minutes under a temperature controlled at 65 C.-70 C.; and lowering the temperature to 35 C.-55 C.; 3) stirring the mixture obtained in step 2) to form a solution; adding into the solution the modifying agent and the biological enzyme, which are stirred for 10-20 minutes to obtain the co-polymer; and 4) making said co-polymer into granules by drying, grinding and sieving.

10. A method for preparing the organic-inorganic polymeric water-retaining fertilizer according to claim 2, wherein after obtaining a neutralized pre-polymer from the organic water-retaining monomer under the action of the catalyst, the inorganic nutrient is added; then an initiator and a cross-linking agent are added, a solution is formed by stirring sufficiently; the modifying agent and the biological enzyme are added; a co-polymer is obtained after fusion and co-polymerization; and granulation and drying are carried out; said catalyst is an inorganic alkaline solution.

11. A method for preparing the organic-inorganic polymeric water-retaining fertilizer according to claim 3, wherein after obtaining a neutralized pre-polymer from the organic water-retaining monomer under the action of the catalyst, the inorganic nutrient is added; then an initiator and a cross-linking agent are added, a solution is formed by stirring sufficiently; the modifying agent and the biological enzyme are added; a co-polymer is obtained after fusion and co-polymerization; and granulation and drying are carried out; said catalyst is an inorganic alkaline solution.

12. A method for preparing the organic-inorganic polymeric water-retaining fertilizer according to claim 4, wherein after obtaining a neutralized pre-polymer from the organic water-retaining monomer under the action of the catalyst, the inorganic nutrient is added; then an initiator and a cross-linking agent are added, a solution is formed by stirring sufficiently; the modifying agent and the biological enzyme are added; a co-polymer is obtained after fusion and co-polymerization; and granulation and drying are carried out; said catalyst is an inorganic alkaline solution.

13. A method for preparing the organic-inorganic polymeric water-retaining fertilizer according to claim 5, wherein after obtaining a neutralized pre-polymer from the organic water-retaining monomer under the action of the catalyst, the inorganic nutrient is added; then an initiator and a cross-linking agent are added, a solution is formed by stirring sufficiently; the modifying agent and the biological enzyme are added; a co-polymer is obtained after fusion and co-polymerization; and granulation and drying are carried out; said catalyst is an inorganic alkaline solution.

14. A method for preparing the organic-inorganic polymeric water-retaining fertilizer according to claim 6, wherein after obtaining a neutralized pre-polymer from the organic water-retaining monomer under the action of the catalyst, the inorganic nutrient is added; then an initiator and a cross-linking agent are added, a solution is formed by stirring sufficiently; the modifying agent and the biological enzyme are added; a co-polymer is obtained after fusion and co-polymerization; and granulation and drying are carried out; said catalyst is an inorganic alkaline solution.

15. A method for preparing the organic-inorganic polymeric water-retaining fertilizer according to claim 7, wherein after obtaining a neutralized pre-polymer from the organic water-retaining monomer under the action of the catalyst, the inorganic nutrient is added; then an initiator and a cross-linking agent are added, a solution is formed by stirring sufficiently; the modifying agent and the biological enzyme are added; a co-polymer is obtained after fusion and co-polymerization; and granulation and drying are carried out; said catalyst is an inorganic alkaline solution.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) In order to more clearly illustrate the technical solutions in the examples of the present invention or in the prior art, drawings needed to be used in the description of the examples or in the prior art are briefly discussed below.

(2) FIG. 1 is a schematic flow of production for the organic-inorganic polymeric water-retaining fertilizer of the present invention;

(3) FIG. 2 shows leaching characteristics of the organic-inorganic polymeric water-retaining fertilizer of the present invention in a soil column;

(4) FIG. 3 shows a comparison of the number of microorganisms in the soil between the organic-inorganic polymeric water-retaining fertilizer of the present invention and an ordinary chemical fertilizer after being applied for three years.

DETAILED DESCRIPTION OF EMBODIMENTS

(5) The embodiments of the present invention will be described in detail below in combination with the examples, but persons of skill in the art will understand that the examples are only used for illustration of the invention, and shall not be considered as limiting the scope of the present invention. Those for which a specific condition is not indicated in the examples are performed under conventional conditions or under the conditions suggested by the manufacturers. Those agents or instruments for which the manufacturer is not indicated are conventional available products that can be purchased on the market.

(6) The calcium magnesium nitrate is a pure white crystal, which has a neutral pH, can be completely dissolved in water, and is easy to obtain. The fertilizer of the calcium magnesium nitrate is a total nitrate nitrogen type hydrosoluble fertilizer which supplies calcium and magnesium for crops.

(7) The enzyme from enzyme microorganisms is a mixture of multiple biological enzymes generated from enzyme microorganism, which has a relatively strong catalytic activity and a function of promoting biochemical reactions. The enzyme microorganism is a beneficial microbial population which is used widely in fields of food processing, livestock and poultry production, pharmaceutical chemicals, etc., and the enzyme microorganism includes one or more selected from the group consisting of nitrogen-fixing bacteria, phosphorus bacteria, potassium bacteria, saccharomycetes, bacilli, photosynthetic bacteria, lactobacillus, etc.

Example 1

(8) The following raw materials were prepared in parts by weight:

(9) 400 parts of acrylic acid;

(10) an aqueous solution of sodium hydroxide as a catalyst, with a pH=8.5;

(11) 10 parts of potassium persulfate as an initiator;

(12) 20 parts of glycol as a cross-linking agent;

(13) 1700 parts of urea, 1500 parts of monoammonium phosphate, 3500 parts of potassium sulfate, 1000 parts of calcium nitrate, 1000 parts of magnesium sulfate, 150 parts of sodium silicate, 30 parts of zinc sulfate and 30 parts of sodium borate as inorganic nutrients;

(14) 5 parts of biological enzymes (2 parts of protease and 3 parts of cellulase);

(15) 25 parts of protein powder and 25 parts of cellulase powder.

(16) The fertilizer was prepared in accordance with the steps of:

(17) 1) mixing acrylic acid and the catalyst, which react for 15 minutes to obtain a neutralized pre-polymer, followed by adding the inorganic nutrients into the reaction system;

(18) 2) sequentially adding the inorganic nutrients, the cross-linking agent and the initiator into the neutralized pre-polymer, which react for 15 minutes in the reaction system under a temperature controlled at 65 C.-68 C. with a rotational speed of stirring set at 70 revolutions; and lowering the temperature to 35 C.;

(19) 3) stirring the mixture obtained in step 2) to form a solution; adding into the solution the modifying agent and the biological enzymes, which are stirred for 10 minutes to obtain a co-polymer;

(20) 4) introducing the co-polymer into a granulating dryer to obtain an finished product of granular fertilizer.

(21) Detected by the laboratory based on the enterprise's standard, the fertilizer prepared in accordance with the formulation has a pH of 6.5, a content of the organic matter of 20.5%, a water absorbency of 16.5 g/g; the total content of nitrogen, phosphorus and potassium is 37%, in which the content of nitrogen is 9.9%, of phosphorus pentoxide is 9.6%, of potassium oxide is 17.8%; the total content of calcium, magnesium, silicon and sulfur is 17.9%, in which calcium oxide is 2.1%, magnesium oxide is 1.5%, silicon dioxide is 0.02%, and sulfur dioxide is 14.3%; and the release rate of nutrients at the initial stage is 8.3%.

Example 2

(22) The following raw materials were prepared in parts by weight:

(23) 600 parts of acrylic acid;

(24) an aqueous solution of sodium hydroxide as a catalyst, with a pH=11.7;

(25) 20 parts of potassium persulfate as an initiator;

(26) 30 parts of glycol as a cross-linking agent;

(27) 1800 parts of urea, 1600 parts of monoammonium phosphate, 3600 parts of potassium sulfate, 1100 parts of calcium nitrate, 1100 parts of magnesium sulfate, 250 parts of sodium silicate, 80 parts of zinc sulfate and 80 parts of sodium borate as inorganic nutrients;

(28) 15 parts of biological enzymes (5 parts of lipase, 5 parts of pectinase and 5 parts of enzyme from enzyme microorganisms);

(29) 25 parts of lipid, 25 parts of pectin and 30 parts of starch.

(30) The fertilizer was prepared in accordance with the steps of:

(31) 1) mixing acrylic acid and the catalyst, which react for 20 minutes to obtain a neutralized pre-polymer, followed by adding the inorganic nutrients into the reaction system;

(32) 2) sequentially adding the inorganic nutrients, the cross-linking agent and the initiator into the neutralized pre-polymer, which react for 25 minutes in the reaction system under a temperature controlled at 66 C.-70 C. with a rotational speed of stirring set at 80 revolutions; and lowering the temperature to 55 C.;

(33) 3) stirring the mixture obtained in step 2) to form a solution; adding into the solution the modifying agent and the biological enzymes, which are stirred for 20 minutes to obtain a co-polymer;

(34) 4) introducing the co-polymer into a granulating dryer to obtain an finished product of granular fertilizer.

(35) Detected by the laboratory based on the enterprise's standard, the fertilizer prepared in accordance with the formulation has a pH of 6.9, a content of the organic matter of 24.1%, a water absorbency of 19.6 g/g; the total content of nitrogen, phosphorus and potassium is 39.4%, in which the content of nitrogen is 10.9%, of phosphorus pentoxide is 9.8%, of potassium oxide is 18.7%; the total content of calcium, magnesium, silicon and sulfur is 20.5%, in which calcium oxide is 2.1%, magnesium oxide is 1.9%, silicon dioxide is 0.05%, sulfur dioxide is 16.4%; and the release rate of the nutrients at the initial stage is 5.1%

Example 3

(36) The following raw materials were prepared in parts by weight:

(37) 500 parts of acrylic acid;

(38) an aqueous solution of sodium hydroxide as a catalyst, with a pH=9.5;

(39) 15 parts of potassium persulfate as an initiator;

(40) 25 parts of glycol as a cross-linking agent;

(41) 1750 parts of urea, 1550 parts of monoammonium phosphate, 3550 parts of potassium sulfate, 1050 parts of calcium nitrate, 1050 parts of magnesium sulfate, 200 parts of sodium silicate, 50 parts of zinc sulfate and 50 parts of sodium borate as inorganic nutrients;

(42) 10 parts of biological enzyme (10 parts of protease);

(43) 75 parts of protein powder.

(44) The fertilizer was prepared in accordance with the steps of:

(45) 1) mixing acrylic acid and the catalyst, which react for 20 minutes to obtain a neutralized pre-polymer, followed by adding the inorganic nutrients into the reaction system;

(46) 2) sequentially adding the inorganic nutrients, the cross-linking agent and the initiator into the neutralized pre-polymer, which react for 20 minutes in the reaction system under a temperature controlled at 66 C.-70 C. with a rotational speed of stirring set at 80 revolutions; and lowering the temperature to 50 C.;

(47) 3) stirring the mixture obtained in step 2) to form a solution; adding into the solution the biological enzyme, which are stirred for 15 minutes to obtain a co-polymer;

(48) 4) introducing the co-polymer into a granulating dryer to obtain an finished product of granular fertilizer.

(49) Detected by the laboratory based on the enterprise's standard, the fertilizer prepared in accordance with the formulation has a pH of 6.8, a content of the organic matter of 22.3%, a water absorbency of 17.3 g/g; the total content of nitrogen, phosphorus and potassium is 35.9%, in which the content of nitrogen is 9.2%, of phosphorus pentoxide is 9.4%, of potassium oxide is 17.3%; the total content of calcium, magnesium, silicon and sulfur is 17.9%, in which calcium oxide is 1.9%, magnesium oxide is 1.4%, silicon dioxide is 0.04%, sulfur dioxide is 15.2%; and the release rate of the nutrients at the initial stage is 7.2%

Example 4

(50) The following raw materials were prepared in parts by weight:

(51) 400 parts of acrylic acid;

(52) an aqueous solution of sodium hydroxide as a catalyst, with a pH=8.5;

(53) 10 parts of potassium persulfate as an initiator;

(54) 20 parts of glycol as a cross-linking agent;

(55) 1780 parts of urea, 1580 parts of monoammonium phosphate, 3580 parts of potassium sulfate, 1088 parts of calcium nitrate, 1088 parts of magnesium sulfate, 200 parts of sodium silicate, 50 parts of zinc sulfate and 50 parts of sodium borate as inorganic nutrients;

(56) 10 parts of biological enzymes (5 parts of protease, 3 parts of cellulase and 2 parts of enzyme from enzyme microorganisms);

(57) 30 parts of hydrolyzed protein powder of soybean, 20 parts of fish meal, and 10 parts of bone meal.

(58) The fertilizer was prepared in accordance with the steps of:

(59) 1) mixing acrylic acid and the catalyst, which react for 15 minutes to obtain a neutralized pre-polymer, followed by adding the inorganic nutrients into the reaction system;

(60) 2) sequentially adding the inorganic nutrients, the cross-linking agent and the initiator into the neutralized pre-polymer, which react for 15 minutes in the reaction system under a temperature controlled at 66 C.-68 C. with a rotational speed of stirring set at 70 revolutions; and lowering the temperature to 50 C.;

(61) 3) stirring the mixture obtained in step 2) to form a solution; adding into the solution the biological enzymes and heating them to 45 C., and stirring the same for 10 minutes to obtain a co-polymer;

(62) 4) introducing the co-polymer into a granulating dryer to obtain an finished product of granular fertilizer.

(63) Detected by the laboratory based on the enterprise's standard, the fertilizer prepared in accordance with the formulation has a pH of 6.5, a content of the organic matter of 21%, a water absorbency of 17.5 g/g; the total content of nitrogen, phosphorus and potassium is 40%, in which the content of nitrogen is 10.9%, of phosphorus pentoxide is 10.3%, of potassium oxide is 18.8%; the total content of calcium, magnesium, silicon and sulfur is 20.8%, in which calcium oxide is 2.6%, magnesium oxide is 1.9%, silicon dioxide is 0.04%, sulfur dioxide is 16.3%; and the release rate of nutrients at the initial stage is 7.8%

Experimental Example 1

(64) Under a culture condition of soil column leaching, the sustained release period of the nutrients for the organic-inorganic polymeric water-retaining fertilizer prepared by the method of Example 4 is 80 days, and the characteristic curve for the sustained release property of the total nutrients of the combined fertilizer presents an S shape (see FIG. 2). The release characteristic of the fertilizer in the soil presents a long-lasting sustained release property, which indicates that the application of the fertilizer in the soil is benefit to the stability and sustained release of the nutrients.

(65) The fertilizer was measured by a method for measuring a water absorbency of organic-inorganic polymeric water-retaining fertilizers according to the enterprise's standard Q/370203XYD 001-2016 and the industrial standard NY 886-2010 set forth in Agro-Forestry Water-retaining Agent, it can be known, the range of the water absorbency of the fertilizer is 10.21 g/g-19.33 g/g, with an average being 17.5 g/g; the range of the absorbency for 0.9% NaCl solution of the fertilizer is 14.06 g/g-18.32 g/g, with an average being 16.56 g/g. In production practice, a water-retaining capacity of more than 5 g/g water absorbency would be valuable in actual applications.

(66) The organic-inorganic polymeric water-retaining fertilizer prepared by the method of Example 4 as well as an ordinary fertilizer (without a biological enzyme) were applied to a soil. The number of microorganisms in the soil were counted and compared three years later. See FIG. 3 for the results.

(67) In comparison to the conventional chemical fertilizer, after applying the above-mentioned organic-inorganic polymeric water-retaining fertilizer for three years continuously, the number of bacteria in the soil is increased to 17.69 times; the number of actinomyces is increased to 2.16 times, and the number of fungi decreased by . The benignant microbes in the soil are mainly bacteria and actinomyces, and the pathogenic microbes in the soil are mainly fungi.

(68) Although the present invention has been illustrated and described with specific examples, it should be noted, however, that many other variations and modifications can be made without departing from the spirit and scope of the present invention. Therefore, the accompanying claims encompass all of these variations and modifications which belong to the scope of the present invention.