Preparation method of high-activity humic acid biological fertilizer

Abstract

The invention relates to a preparation method of a high-activity humic acid bio-fertilizer, and belongs to the technical field of agricultural fertilizers, the high-activity humic acid bio-fertilizer comprises the following raw materials: 30-35 parts of livestock and poultry manure, 40-50 parts of an inorganic fertilizer, 15-20 parts of modified humic acid, 3-5 parts of compound beneficial bacteria, 1-3 parts of an auxiliary agent and 50-60 parts of deionized water; according to the technical scheme, the humic acid is intercalated into the organic clay to prepare the composite material, and the humic acid enhances the adsorption capacity of the organic clay; the modified composite material is prepared by grafting the composite material with the silane coupling agent, so that leaching of an organic part can be avoided, and the dispersity of the composite material is improved; maleic anhydride grafted lignin and a modified composite material are combined to prepare modified humic acid, the ion exchange capacity of the modified humic acid is enhanced, and the modified humic acid has good compatibility with microorganisms in soil; and the compound beneficial bacteria have relatively high viable count and relatively strong stress resistance, so that the biological activity of the fertilizer can be further improved, and the yield and quality of crops can be improved.

Description

Technical Field

[0001] The invention belongs to the technical field of agricultural fertilizers, and in particular relates to a method for preparing a high-activity humic acid biofertilizer. Background Art

[0002] As an important agricultural product, fertilizer plays a significant role in increasing crop yields and is an indispensable production factor in modern agriculture. People have been using inorganic fertilizers in large quantities for a long time, and improper use of fertilizers has resulted in low fertilizer efficiency, which has led to a large amount of fertilizer loss, soil and water pollution, and reduced crop resistance, which has seriously threatened the sustainable development of agriculture. In addition, the large-scale application of inorganic fertilizers can easily lead to a decrease in soil fertility, destroy the acid-base balance of the soil, and lead to problems such as a decrease in soil organic matter content and soil compaction. Humic acid is a type of organic substance formed and accumulated by the decomposition and transformation of animal and plant remains, mainly plant remains, and a series of geochemical processes. It is a non-uniform polymer condensation product, which can also be regarded as an amorphous polymer colloid with good physiological activity and absorption, complexation, exchange and other functions, which plays a role in improving soil structure. Humic acid biofertilizer can promote the absorption of nutrients by crops and reduce the amount of fertilizers used. At the same time, it produces a variety of physiologically active substances to stimulate and regulate plant growth and improve plant resistance.

[0003] At present, the preparation technology of humic acid bio-fertilizer is relatively simple, and the biological activity of humic acid is not high, so it is difficult to play the expected effect in production practice; although humic acid bio-fertilizer contains some microbial strains, there are many problems with unreasonable strain ratios, and most of them cannot form dominant bacterial communities in the soil, and cannot achieve comprehensive effects such as nitrogen fixation, phosphorus solubilization, and potassium solubilization; in addition, the different sources of organic waste, livestock and poultry manure and other materials used as raw materials in humic acid bio-fertilizer will lead to different nutrient contents and high water content, making the quality and effect of the produced bio-fertilizer unstable. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing a high-activity humic acid biofertilizer. A composite material is prepared by intercalating humic acid onto organic clay. Humic acid can expand the distance between organic clay layers, further enhance the adsorption capacity of organic clay, and improve its thermal stability. A modified composite material is prepared by grafting a silane coupling agent onto the composite material, which can avoid leaching of the organic part and improve the dispersibility of the composite material. At the same time, a carbon-carbon double bond is provided for subsequent combination with maleic anhydride grafted lignin. Modified humic acid is prepared by combining maleic anhydride grafted lignin with the modified composite material, which can improve the structure of the soil. , increase its cation exchange capacity, and have good compatibility with the microbial community in the soil; after the mixed bacterial liquid is inoculated into the culture medium for cultivation, it is adsorbed on the biochar to obtain a composite beneficial bacteria, which has a high number of viable bacteria, strong stress resistance, and enhanced The stability of the strain has further improved the soil quality; finally, the modified humic acid is mixed with livestock and poultry manure, inorganic fertilizer, adjuvant, composite beneficial bacteria and deionized water to obtain a high-activity humic acid bio-fertilizer, which generally improves the biological activity of the fertilizer, improves the utilization rate of the fertilizer, improves the soil structure, promotes the growth and development of crops, and increases the yield and quality of crops.

[0005] The technical problems to be solved by the present invention are as follows: the preparation technology of humic acid biofertilizer is relatively simple, and the biological activity of humic acid is not high, so it is difficult to achieve the desired effect in production practice; although humic acid biofertilizer contains some microbial strains, there is often an unreasonable strain ratio problem, and most of them cannot form dominant bacterial communities in the soil, and cannot achieve the comprehensive effects of nitrogen fixation, phosphorus solubilization, potassium solubilization, etc.; in addition, the organic waste, livestock and poultry manure and other materials used as raw materials in humic acid biofertilizer have different sources, which will lead to different nutrient contents and high water content, making the quality and effect of the produced biofertilizer unstable.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A high-activity humic acid biofertilizer comprises the following raw materials in parts by weight: 30-35 parts of livestock and poultry manure, 40-50 parts of inorganic fertilizer, 15-20 parts of modified humic acid, 3-5 parts of composite beneficial bacteria, 1-3 parts of auxiliary agent and 50-60 parts of deionized water;

[0008] The modified humic acid is prepared by combining maleic anhydride grafted lignin with a modified composite material; the modified composite material is prepared by grafting a silane coupling agent onto a composite material; the composite material is prepared by intercalating humic acid onto organic clay; the composite beneficial bacteria is prepared by inoculating a mixed bacterial liquid into a culture medium for cultivation and then adsorbing it onto biochar.

[0009] Further, the modified humic acid is prepared by the following steps:

[0010] The maleic anhydride grafted lignin is dissolved in deionized water, and then the modified composite material is added, the mixture is stirred for 1-2 hours, and then an initiator is added, and the mixture is heated at 65-75°C for 3.5-4.5 hours. After the reaction is completed, the mixture is washed with deionized water and dried at 75-85°C to obtain modified humic acid, wherein the amount ratio of the maleic anhydride grafted lignin, the modified composite material and the initiator is 9.5-10.5g:4.5-5.5g:0.1-0.2g.

[0011] In the above reaction process, the maleic anhydride in the maleic anhydride grafted lignin has a carbon-carbon double bond after ring opening, and the modified composite material also has a carbon-carbon double bond. The carbon-carbon double bond in the maleic anhydride grafted lignin can be combined with the carbon-carbon double bond in the modified composite material through a free radical polymerization reaction, and the maleic anhydride grafted lignin and the modified composite material are combined together to finally obtain modified humic acid, thereby improving the activity of the humic acid.

[0012] Furthermore, the initiator is ammonium persulfate.

[0013] Furthermore, the maleic anhydride grafted lignin is prepared by the following steps:

[0014] 5 g of lignin, 1 g of maleic anhydride and 0.3 mL of 1-methylimidazole were dissolved in 35 mL of anhydrous tetrahydrofuran and refluxed at 60 °C under nitrogen atmosphere for 3 h, and then the solvent was collected by rotary evaporation and dried in vacuum at 70 °C to finally obtain modified lignin.

[0015] In the above reaction process, lignin has hydroxyl groups, and maleic anhydride has two carboxyl groups after ring opening. The hydroxyl groups on lignin and the carboxyl groups on maleic anhydride are combined together through esterification reaction to obtain modified lignin.

[0016] Furthermore, the modified composite material is prepared by the following steps:

[0017] The composite material is mixed with toluene, dispersed with ultrasound for 2-3 hours, and then a silane coupling agent is added. The mixture is refluxed at 95-105° C. for 22-24 hours. After filtering, the mixture is washed with acetone and finally dried at 55-65° C. for 22-24 hours to obtain a modified composite material, wherein the amount ratio of the composite material, toluene and silane coupling agent is 4.5-5.5 g: 40-60 mL: 0.5-1.5 g.

[0018] In the above reaction process, the composite material has hydroxyl groups, and the silane coupling agent has carbon-carbon double bonds and silicon-chlorine bonds. The silicon-chlorine bonds on the silane coupling agent can combine with the hydroxyl groups on the composite material, and the silane coupling agent is grafted onto the composite material to finally obtain a modified composite material.

[0019] Furthermore, the silane coupling agent is vinyltrichlorosilane.

[0020] Furthermore, the composite material is prepared by the following steps:

[0021] The organic clay is dispersed in deionized water, and then humic acid is added, and the pH value of the mixture is adjusted to 2-4, and then incubated at 85-95° C. for 19-21 hours, filtered, washed with deionized water until the pH value becomes 7-7.5, and then dried at 85-95° C., ground, and passed through a 190-210 mesh sieve to obtain a composite material, wherein the amount ratio of the organic clay to the humic acid is 14.5-15.5 g: 0.8-1.2 g.

[0022] In the above reaction process, the organoclay has hydroxyl groups, and the humic acid has hydroxyl groups and carboxyl groups. The hydroxyl groups on the organoclay can combine with the carboxyl groups on the humic acid to intercalate the humic acid between the layers of the organoclay, and finally a composite material is obtained. The humic acid is inserted between the layers of the organoclay, which can expand the interlayer distance of the organoclay.

[0023] Furthermore, the organoclay is bentonite or kaolinite.

[0024] Furthermore, the composite beneficial bacteria is prepared by the following steps:

[0025] A1: Inoculate the mixed bacterial solution into the sterilized slant culture medium and culture it aerobically at 30-40°C for 10-30 hours to obtain activated strains;

[0026] A2: Disperse the biochar in a phosphate buffered saline solution, then add the activated bacteria, incubate under shaking at room temperature for 2-3 hours, centrifuge for 15-20 minutes, wash with deionized water, and vacuum dry at room temperature to obtain composite beneficial bacteria, wherein the dosage ratio of biochar, phosphate buffered saline solution and activated bacteria is 4-6 mg:8-12 mL:4-7 mg.

[0027] Furthermore, the mixed bacterial liquid is obtained by uniformly mixing Bacillus amyloliquefaciens, Bacillus thuringiensis and Bacillus subtilis in a volume ratio of 1:1:9.

[0028] Furthermore, the number of viable Bacillus subtilis is 5×10 8 CFU / mL-4×10 9 CFU / mL, the number of viable Bacillus thuringiensis is 1×10 10 CFU / mL-5×10 10 CFU / mL, the number of viable bacteria of Bacillus amyloliquefaciens is 1×10 11 CFU / mL-3×10 11 CFU / mL.

[0029] Furthermore, the components of the slant culture medium include: 1-5 g beef extract, 5-15 g peptone, 2-10 g sodium chloride, 10-30 g agar and 900-1100 mL deionized water, and the pH value is 7.2-7.5.

[0030] A method for preparing a high-activity humic acid biofertilizer comprises the following steps:

[0031] The livestock and poultry manure, inorganic fertilizer and modified humic acid are mixed evenly, and then the additives and deionized water are added, and stirred for 5-10 minutes, and then the compound beneficial bacteria are added, and stirring is continued for 20-30 minutes. After extrusion granulation, it is dried at 60-80°C to finally obtain a high-activity humic acid biofertilizer.

[0032] Furthermore, the livestock and poultry manure is one or more of sheep manure, cow manure and pig manure.

[0033] Furthermore, the inorganic fertilizer is one or more of ammonium sulfate, monoammonium phosphate, ammonium chloride and potassium sulfate.

[0034] Furthermore, the auxiliary agent is one or more of polyoxyethylene carboxylate, polyoxyethylene alkyl ether, sodium dodecylbenzene sulfonate, and sodium dodecyl sulfate.

[0035] Beneficial effects of the present invention:

[0036] (1) In the technical scheme of the present invention, a composite material is prepared by intercalating humic acid onto organic clay. The organic clay has good adsorption performance and can effectively adsorb ammonium ions in the soil to reduce the volatilization of nitrogen. Humic acid has good ion exchange, complexation and adsorption functions. When humic acid is combined with organic clay, humic acid can be intercalated into the interlayer of organic clay to expand the interlayer distance, further enhance the adsorption capacity of organic clay, and improve its thermal stability. The composite material can also be used as a nitrogen fertilizer synergist to improve the utilization rate of nitrogen. , and humic acid is not simply adsorbed between the layers of organic clay, but a chemical reaction occurs, which further increases the activity of humic acid; a modified composite material is prepared by grafting a silane coupling agent onto the composite material, and the silane coupling agent is grafted onto the composite material. By avoiding the leaching of the organic part, the organic clay has greater stability to the aqueous medium. The silane coupling agent can also improve the dispersibility of the composite material, and at the same time provide a carbon-carbon double bond for the subsequent combination with maleic anhydride grafted lignin, thereby increasing the binding force between the composite material and the maleic anhydride grafted lignin.

[0037] (2) In the technical scheme of the present invention, modified humic acid is prepared by combining maleic anhydride grafted lignin with a modified composite material. The carbon-carbon double bonds generated after maleic anhydride grafted lignin can be combined with the carbon-carbon double bonds on the modified composite material through free radical polymerization. The modified composite material is combined with maleic anhydride grafted lignin, that is, humic acid, organic clay and lignin are combined together. The three different components can be used as a soil conditioner to improve the structure of the soil and increase its cation exchange capacity. It also has good compatibility with the microbial community in the soil; the mixed bacterial liquid is inoculated into the culture medium for cultivation, and then adsorbed onto the biochar to obtain the composite beneficial bacteria, Bacillus amyloliquefaciens. When the three strains of Bacillus, Bacillus thuringiensis and Bacillus subtilis are mixed in a certain proportion, they have a higher number of live bacteria and stronger stress resistance. Bacillus amyloliquefaciens and Bacillus thuringiensis also have insecticidal activity, which further improves soil quality. The mixed strains are adsorbed onto biochar to enhance the stability of the strains. At the same time, the composite beneficial bacteria also have the effects of nitrogen fixation, phosphorus solubilization and potassium solubilization, and have a certain synergistic effect with modified humic acid, which further improves the stability of the biological fertilizer. Finally, the raw materials are mixed to obtain high-activity humic acid biofertilizer. The modified humic acid has good biological activity, which can effectively improve the utilization rate of fertilizer, promote crop growth, increase production and improve quality.

[0038] (3) In the technical scheme of the present invention, humic acid is intercalated onto organoclay, then grafted with a silane coupling agent, and then combined with maleic anhydride grafted with lignin to obtain modified humic acid, which is finally mixed with livestock and poultry manure, inorganic fertilizer, adjuvant, composite beneficial bacteria and deionized water to obtain a high-activity humic acid biofertilizer. The prepared high-activity humic acid biofertilizer not only has high biological activity, but also improves the utilization rate of fertilizer, improves soil structure, reduces pest and disease damage, promotes the growth and development of crops, and enhances their stress resistance. DETAILED DESCRIPTION

[0039] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0040] The specific parameters of the raw materials used in the present invention are as follows:

[0041] The deposit number of Bacillus amyloliquefaciens is CCTCC NO: M2013086; Bacillus subtilis is from Guangdong Microbiological Culture Collection Center and is numbered: GI M1.271; Bacillus thuringiensis is deposited in the General Microbiological Center of China Microbiological Culture Collection Administration and is deposited with CGMCC No.20588.

[0042] The mixed bacterial solution used in the following examples and comparative examples is obtained by uniformly mixing Bacillus amyloliquefaciens, Bacillus thuringiensis, and Bacillus subtilis in a volume ratio of 1:1:9;

[0043] The number of viable Bacillus subtilis used was 5×10 8 CFU / mL, the number of viable Bacillus thuringiensis is 1×10 10 CFU / mL, the number of viable bacteria of Bacillus amyloliquefaciens is 1×10 11 CFU / mL;

[0044] The components of the slant culture medium used include: 3 g beef extract, 10 g peptone, 6 g sodium chloride, 20 g agar and 1000 mL deionized water, with a pH value of 7.3.

[0045] Maleic anhydride grafted lignin is prepared by the following steps:

[0046] 5 g of lignin, 1 g of maleic anhydride and 0.3 mL of 1-methylimidazole were dissolved in 35 mL of anhydrous tetrahydrofuran and refluxed at 60 °C under nitrogen atmosphere for 3 h, and then the solvent was collected by rotary evaporation and dried in vacuum at 70 °C to finally obtain modified lignin.

[0047] Example 1

[0048] The composite material is prepared by the following steps:

[0049] 14.5 g of kaolinite was dispersed in 90 mL of deionized water, and then 0.8 g of humic acid was added, and the pH value of the mixture was adjusted to 2, and then incubated at 85 ° C for 19 h. After filtering, it was washed with deionized water until the pH value became 7, and then dried at 85 ° C. After grinding, it was passed through a 190-mesh sieve to obtain a composite material.

[0050] Example 2

[0051] The composite material is prepared by the following steps:

[0052] 15 g of bentonite was dispersed in 100 mL of deionized water, and then 1 g of humic acid was added, and the pH value of the mixture was adjusted to 3, and then incubated at 90 ° C for 20 h. After filtering, it was washed with deionized water until the pH value became 7.3, and then dried at 90 ° C. After grinding, it was passed through a 200-mesh sieve to obtain a composite material.

[0053] Example 3

[0054] The composite material is prepared by the following steps:

[0055] 15.5 g of kaolinite was dispersed in 110 mL of deionized water, and then 1.2 g of humic acid was added, and the pH value of the mixture was adjusted to 4, and then incubated at 95 °C for 21 h. After filtering, it was washed with deionized water until the pH value became 7.5, and then dried at 95 °C, ground, and passed through a 210 mesh sieve to obtain a composite material.

[0056] Example 4

[0057] The modified composite material is prepared by the following steps:

[0058] 4.5 g of the composite material prepared in Example 1 was mixed with 40 mL of toluene, and after ultrasonic dispersion for 2 h (ultrasonic power of 150 W, frequency of 20 kHz), 0.5 g of vinyltrichlorosilane was added, and refluxed at 95 ° C for 22 h. After filtering, it was washed with 50 mL of acetone and finally dried at 55 ° C for 22 h to obtain a modified composite material.

[0059] Example 5

[0060] The modified composite material is prepared by the following steps:

[0061] 5 g of the composite material prepared in Example 2 was mixed with 50 mL of toluene, and after ultrasonic dispersion for 2.5 h (ultrasonic power of 150 W, frequency of 20 kHz), 1 g of vinyltrichlorosilane was added, and refluxed at 100 ° C for 23 h. After filtering, it was washed with 50 mL of acetone and finally dried at 60 ° C for 23 h to obtain a modified composite material.

[0062] Example 6

[0063] The modified composite material is prepared by the following steps:

[0064] 5.5 g of the composite material prepared in Example 3 was mixed with 60 mL of toluene, and after ultrasonic dispersion for 3 h (ultrasonic power of 150 W, frequency of 20 kHz), 1.5 g of vinyltrichlorosilane was added, and refluxed at 105 ° C for 24 h. After filtering, it was washed with 50 mL of acetone and finally dried at 65 ° C for 24 h to obtain a modified composite material.

[0065] Comparative Example 1

[0066] The difference between this comparative example and Example 6 is that the composite material prepared in Example 3 is replaced by kaolinite in equal mass, and the remaining steps and raw materials are the same as those in Example 6.

[0067] Comparative Example 2

[0068] The difference between this comparative example and Example 6 is that the mass of the composite material prepared in Example 3 is replaced by humic acid, and the remaining steps and raw materials are the same as those in Example 6.

[0069] Example 7

[0070] Modified humic acid is prepared by the following steps:

[0071] 9.5 g of maleic anhydride grafted lignin was dissolved in 40 mL of deionized water, and then 4.5 g of the modified composite material prepared in Example 4 was added. The mixture was stirred for 1 h, and then 0.1 g of ammonium persulfate was added and heated at 65 ° C for 3.5 h. After the reaction was completed, it was washed with 50 mL of deionized water and dried at 75 ° C to finally obtain modified humic acid.

[0072] Example 8

[0073] Modified humic acid is prepared by the following steps:

[0074] 10 g of maleic anhydride grafted lignin was dissolved in 50 mL of deionized water, and then 5 g of the modified composite material prepared in Example 5 was added, the mixture was stirred for 1.5 h, and then 0.15 g of ammonium persulfate was added and heated at 70 ° C for 4 h. After the reaction was completed, it was washed with 50 mL of deionized water and dried at 80 ° C to finally obtain modified humic acid.

[0075] Example 9

[0076] Modified humic acid is prepared by the following steps:

[0077] 10.5 g of maleic anhydride grafted lignin was dissolved in 60 mL of deionized water, and then 5.5 g of the modified composite material prepared in Example 6 was added. The mixture was stirred for 2 h, and then 0.2 g of ammonium persulfate was added and heated at 75 ° C for 4.5 h. After the reaction was completed, it was washed with 50 mL of deionized water and dried at 85 ° C to finally obtain modified humic acid.

[0078] Comparative Example 3

[0079] The difference between this comparative example and Example 9 is that the modified composite material prepared in Example 6 is replaced by the material prepared in Comparative Example 1, and the remaining steps and raw materials are the same as in Example 9.

[0080] Comparative Example 4

[0081] The difference between this comparative example and Example 9 is that the modified composite material prepared in Example 6 is replaced by the material prepared in Comparative Example 2, and the remaining steps and raw materials are the same as in Example 9.

[0082] Comparative Example 5

[0083] The difference between this comparative example and Example 9 is that the modified composite material prepared in Example 6 is replaced by the composite material prepared in Example 3, and the remaining steps and raw materials are the same as in Example 9.

[0084] Example 10

[0085] The compound beneficial bacteria is prepared by the following steps:

[0086] A1: Inoculate the mixed bacterial solution into the sterilized slant culture medium and culture it aerobically at 30°C for 10 hours until colonies grow to obtain activated strains, wherein the inoculation amount of the mixed bacterial solution is 5%;

[0087] A2: Disperse 4 mg of biochar in 8 mL of 0.1 mol / L phosphate buffered saline solution, then add 4 mg of activated bacteria, incubate with shaking at room temperature for 2 h, centrifuge at 9000 rpm for 15 min, wash with 50 mL of deionized water, and vacuum dry at room temperature for 24 h to obtain composite beneficial bacteria.

[0088] Embodiment 11

[0089] The compound beneficial bacteria is prepared by the following steps:

[0090] A1: Inoculate the mixed bacterial solution into the sterilized slant culture medium and culture it aerobically at 37°C for 18 hours until colonies grow to obtain activated strains, wherein the inoculation amount of the mixed bacterial solution is 5%;

[0091] A2: Disperse 5 mg of biochar in 10 mL of phosphate buffered saline solution, then add 5.5 mg of activated bacteria, incubate with shaking at room temperature for 2.5 h, centrifuge at 9500 rpm for 18 min, wash with 50 mL of deionized water, and vacuum dry at room temperature for 24 h to obtain composite beneficial bacteria.

[0092] Example 12

[0093] The compound beneficial bacteria is prepared by the following steps:

[0094] A1: Inoculate the mixed bacterial solution into the sterilized slant culture medium and culture it aerobically at 40°C for 30 hours until colonies grow to obtain activated strains, wherein the inoculation amount of the mixed bacterial solution is 5%;

[0095] A2: 6 mg of biochar was dispersed in 12 mL of phosphate buffered saline solution, and then 7 mg of activated bacteria was added. After incubation under shaking at room temperature for 3 h, the mixture was centrifuged at 10,000 rpm for 20 min, washed with 50 mL of deionized water, and vacuum dried at room temperature for 24 h to obtain composite beneficial bacteria.

[0096] Embodiment 13

[0097] A high-activity humic acid biofertilizer comprises the following raw materials in parts by weight: 30 parts of sheep manure, 40 parts of ammonium sulfate, 15 parts of modified humic acid prepared in Example 7, 3 parts of composite beneficial bacteria prepared in Example 10, 1 part of polyoxyethylene carboxylate and 50 parts of deionized water.

[0098] The following steps are involved:

[0099] Sheep manure, ammonium sulfate and the modified humic acid prepared in Example 7 were mixed evenly, and then polyoxyethylene carboxylate and deionized water were added, and stirred for 5 minutes. The composite beneficial bacteria prepared in Example 10 were added, and stirring was continued for 20 minutes. After extrusion granulation, it was dried at 60° C. to finally obtain a high-activity humic acid biofertilizer.

[0100] Embodiment 14

[0101] A high-activity humic acid biofertilizer comprises the following raw materials in parts by weight: 33 parts of pig manure, 45 parts of monoammonium phosphate, 18 parts of modified humic acid prepared in Example 8, 4 parts of composite beneficial bacteria prepared in Example 11, 2 parts of sodium dodecylbenzene sulfonate and 55 parts of deionized water.

[0102] The following steps are involved:

[0103] Pig manure, monoammonium phosphate and the modified humic acid prepared in Example 8 were mixed evenly, and then sodium dodecylbenzene sulfonate and deionized water were added, and stirred for 8 minutes. The composite beneficial bacteria prepared in Example 11 were added, and stirring was continued for 25 minutes. After extrusion granulation, it was dried at 70° C. to finally obtain a high-activity humic acid biofertilizer.

[0104] Embodiment 15

[0105] A high-activity humic acid biofertilizer comprises the following raw materials in parts by weight: 35 parts of cow dung, 50 parts of potassium sulfate, 20 parts of modified humic acid prepared in Example 9, 5 parts of composite beneficial bacteria prepared in Example 12, 3 parts of sodium dodecyl sulfate and 60 parts of deionized water.

[0106] The following steps are involved:

[0107] Cow dung, potassium sulfate, and the modified humic acid prepared in Example 9 were mixed evenly, and then sodium dodecyl sulfate and deionized water were added and stirred for 10 minutes. The composite beneficial bacteria prepared in Example 12 were added and stirred for 30 minutes. After extrusion granulation, the mixture was dried at 80° C. to obtain a high-activity humic acid biofertilizer.

[0108] Comparative Example 6

[0109] The difference between this comparative example and Example 15 is that the modified humic acid prepared in Example 9 is replaced by the substance prepared in Comparative Example 3, and the remaining steps and raw materials are the same as those in Example 15.

[0110] Comparative Example 7

[0111] The difference between this comparative example and Example 15 is that the modified humic acid prepared in Example 9 is replaced by the substance prepared in Comparative Example 4, and the remaining steps and raw materials are the same as in Example 15.

[0112] Comparative Example 8

[0113] The difference between this comparative example and Example 15 is that the modified humic acid prepared in Example 9 is replaced by the substance prepared in Comparative Example 5, and the remaining steps and raw materials are the same as Example 15.

[0114] Comparative Example 9

[0115] The difference between this comparative example and Example 15 is that the modified humic acid prepared in Example 9 is replaced by the modified composite material prepared in Example 6, and the remaining steps and raw materials are the same as in Example 15.

[0116] Comparative Example 10

[0117] The difference between this comparative example and Example 15 is that the composite beneficial bacteria prepared in Example 12 are not added in this comparative example, and the remaining steps and raw materials are the same as those in Example 15.

[0118] Comparative Example 11

[0119] The difference between this comparative example and Example 15 is that the modified humic acid prepared in Example 9 is not added in this comparative example, and the remaining steps and raw materials are the same as Example 15.

[0120] The performance of the high-activity humic acid biofertilizer prepared in Examples 13-15 and Comparative Examples 6-11 was tested. The test treatment was: 40 kg / mu (1.49 kg / plot) of compound fertilizer, 40 kg / mu (1.49 kg / plot) of high-activity humic acid biofertilizer prepared in Examples 13-15 and Comparative Examples 6-11, and the fertilizer was applied on the inner side of the potato sowing furrow, and the plot area was 24.75 m 2(3.3×7.5m), 3 replicates per treatment, randomly arranged, the potato yield after applying compound fertilizer was 3423±466 (kg / mu). The experiment was conducted in May 2013 at the test site of the Jungar Rainwater Collection and Irrigation Experiment Station in Inner Mongolia. Basic soil properties: pH 7.8, organic matter 10.2mg / kg, total nitrogen 0.095g / kg, available phosphorus 5.78mg / kg, available potassium 98.72mg / kg. The test results are shown in the following table:

[0121] Table 1

[0122] project Potato yield (kg / mu) Relative compound fertilizer yield increase (%) Embodiment 13 5167±435 33.8 Embodiment 14 5206±223 34.2 Embodiment 15 5094±158 32.8 Comparative Example 6 4618±239 25.9 Comparative Example 7 4792±186 28.6 Comparative Example 8 4713±367 27.4 Comparative Example 9 4326±164 20.9 Comparative Example 10 3814±209 10.3 Comparative Example 11 3561±312 3.9

[0123] As can be seen from the data in Table 1 above, by comparing Comparative Examples 6-7 with Example 15, it can be seen that the composite material is prepared using only organic clay or only humic acid, and its test results are worse than those of Example 15, indicating that intercalating humic acid into the interlayer of organic clay can expand the interlayer distance of organic clay, enhance the adsorption capacity of organic clay, further improve the activity of humic acid biofertilizer, and increase the utilization efficiency of fertilizer;

[0124] From the comparison between Comparative Example 8 and Example 15, it can be seen that the composite material without the addition of silane coupling agent is used to prepare the high-activity humic acid bio-fertilizer, which indicates that the silane coupling agent is grafted onto the composite material to form a modified composite material, which can not only improve the dispersibility of the composite material, but also avoid the leaching of the organic part, so that the organic clay has greater stability to the aqueous medium, and further improves the utilization rate of the humic acid bio-fertilizer;

[0125] From the comparison between Comparative Example 9 and Example 15, it can be seen that the modified composite material without maleic anhydride grafted lignin is used to prepare the high-activity humic acid biofertilizer, which shows that the combination of maleic anhydride grafted lignin and the modified composite material can further increase the compatibility between the fertilizer and the soil microbial community, while enhancing the water retention capacity and ion exchange capacity of the fertilizer, improving the utilization rate of the biofertilizer, and increasing the yield of crops;

[0126] By comparing Comparative Examples 10-11 with Example 15, it can be seen that the yield of crops when high-activity humic acid bio-fertilizer is prepared without adding composite beneficial bacteria or modified humic acid is poorer than that in Example 15, indicating that the addition of composite beneficial bacteria and modified humic acid has a certain synergistic effect, which can further improve the activity of humic acid bio-fertilizer, increase its fertilizer utilization rate, and increase the yield of crops.

[0127] As can be seen from Table 1 above, the high-activity humic acid biofertilizer prepared in Examples 13-15 is compared with Comparative Examples 6-11. The modified humic acid is prepared by intercalating humic acid onto organic clay, then grafting a silane coupling agent, and then combining it with maleic anhydride grafted lignin, and finally mixing it with livestock and poultry manure, inorganic fertilizer, adjuvant, composite beneficial bacteria and deionized water to obtain a high-activity humic acid biofertilizer, which improves the utilization rate of the biofertilizer, increases the yield of crops, and meets the test performance requirements. The high-activity humic acid biofertilizer prepared in Comparative Examples 6-11 did not meet the performance requirements, indicating that the high-activity humic acid biofertilizer prepared by the present invention has higher biological activity, improves the utilization efficiency of fertilizers, increases the yield of crops, and improves the structure of the soil.

[0128] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0129] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A high-activity humic acid biofertilizer, characterized in that: The raw materials include the following parts by weight: 30-35 parts of livestock and poultry manure, 40-50 parts of inorganic fertilizer, 15-20 parts of modified humic acid, 3-5 parts of compound beneficial bacteria, 1-3 parts of auxiliary agent and 50-60 parts of deionized water; The modified humic acid is prepared by combining maleic anhydride grafted lignin with a modified composite material; the modified composite material is prepared by grafting a silane coupling agent onto a composite material; the composite material is prepared by intercalating humic acid onto organic clay; the composite beneficial bacteria is prepared by inoculating a mixed bacterial liquid into a culture medium for cultivation and then adsorbing it onto biochar.

2. A high-activity humic acid biofertilizer according to claim 1, characterized in that: The modified humic acid is prepared by the following steps: The maleic anhydride grafted lignin is dissolved in deionized water, and then the modified composite material is added, the mixture is stirred for 1-2 hours, and then an initiator is added, and heated at 65-75°C for 3.5-4.5 hours. After the reaction is completed, it is washed with deionized water and dried at 75-85°C to finally obtain modified humic acid.

3. A high-activity humic acid biofertilizer according to claim 2, characterized in that: The dosage ratio of maleic anhydride grafted lignin, modified composite material and initiator is 9.5-10.5g:4.5-5.5g:0.1-0.2g.

4. A high-activity humic acid biofertilizer according to claim 2, characterized in that: The modified composite material is prepared by the following steps: The composite material is mixed with toluene, dispersed by ultrasonic for 2-3 hours, and then a silane coupling agent is added. The mixture is refluxed at 95-105° C. for 22-24 hours. After filtering, the mixture is washed with acetone and finally dried at 55-65° C. for 22-24 hours to obtain a modified composite material.

5. A high-activity humic acid biofertilizer according to claim 4, characterized in that: The usage ratio of the composite material, toluene and silane coupling agent is 4.5-5.5 g: 40-60 mL: 0.5-1.5 g.

6. A high-activity humic acid biofertilizer according to claim 4, characterized in that: The silane coupling agent is vinyltrichlorosilane.

7. A high-activity humic acid biofertilizer according to claim 4, characterized in that: The composite material is prepared by the following steps: The organic clay is dispersed in deionized water, and then humic acid is added, and the pH value of the mixture is adjusted to 2-4, and then incubated at 85-95° C. for 19-21 hours, filtered, washed with deionized water until the pH value becomes 7-7.5, and then dried at 85-95° C., ground, and passed through a 190-210 mesh sieve to obtain a composite material.

8. The high-activity humic acid biofertilizer according to claim 7, characterized in that: The dosage ratio of organic clay and humic acid is 14.5-15.5g:0.8-1.2g.

9. The high-activity humic acid biofertilizer according to claim 7, characterized in that: The organoclay is bentonite or kaolinite.

10. A method for preparing a high-activity humic acid biofertilizer according to any one of claims 1 to 9, characterized in that: The following steps are involved: The livestock and poultry manure, inorganic fertilizer and modified humic acid are mixed evenly, and then the additives and deionized water are added, and stirred for 5-10 minutes, and then the compound beneficial bacteria are added, and stirring is continued for 20-30 minutes. After extrusion granulation, it is dried at 60-80°C to finally obtain a high-activity humic acid biofertilizer.