Method for producing organic bio-complex phosphorus fertilizer

Abstract

The application discloses a production method of organic biological compound phosphate fertilizer and belongs to the technical field of biological organic fertilizer preparation. The method comprises the following steps: constructing oxidized biomass charcoal by using biomass raw materials, oxidizing and treating the oxidized biomass charcoal combined with carboxymethyl chitosan to obtain aldehyde-based oxidized biomass charcoal, and cross-linking the aldehyde-based oxidized biomass charcoal with amino acids to form amino acid modified oxidized biomass charcoal. Finally, the amino acid modified oxidized biomass charcoal is mixed with superphosphate, water is added and stirred, and then drying is performed until a constant weight is obtained to obtain the organic biological compound phosphate fertilizer. The slow-release effect is realized, and the purpose of weakening the adsorption and combination of soil metal ions on the phosphate fertilizer and affecting the release and fertilizer efficiency of the phosphate fertilizer is achieved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of bio-organic fertilizer preparation, and particularly relates to a production method of an organic bio-complex phosphorus fertilizer. BACKGROUND

[0002] Fertilizers are used to improve soil quality and promote plant growth, and generally contain the nutrients required by plants, which play a crucial role in agricultural production by providing essential nutrients such as nitrogen, phosphorus, and potassium, helping crops to increase yield and improve quality. Fertilizers can be divided into several types, mainly including the following categories: (1) organic fertilizers: mainly made of natural substances such as plant and animal residues or manure, which not only provide the nutrients required by plants, but also improve soil structure and microbial activity. Common organic fertilizers include: compost (made from plant residues, animal manure, etc., rich in organic matter and various trace elements), green manure (by planting specific plants and turning them into the soil, increasing soil nitrogen content and organic matter), and animal manure (such as cow dung, chicken manure, etc., containing rich nutrients such as nitrogen, phosphorus, and potassium); (2) inorganic fertilizers: mainly refers to fertilizers synthesized by chemical synthesis or extracted from minerals, usually containing highly concentrated plant nutrients. Mainly includes: nitrogen fertilizer (such as urea, mainly used to provide nitrogen elements required by plants), phosphorus fertilizer (such as ammonium phosphate, mainly used to provide phosphorus elements, promote root growth), and potassium fertilizer (such as potassium chloride, potassium sulfate, etc., mainly used to improve plant resistance and fruit quality); (3) compound fertilizer: mainly mixed with multiple nutrients in a certain proportion, which can provide nitrogen, phosphorus, potassium and other nutrients; (4) trace element fertilizer: mainly used to supplement the trace elements required by plants during growth, such as zinc, iron, boron, etc., although the amount required is small, but it is essential for plant growth and development. However, with the rapid development of agriculture, the amount of fertilizer used has also increased year by year, which has had a significant impact on the environment. Phosphorus is one of the essential nutrients for crops, which is crucial for high and stable yield, but it is easily combined with some metal ions in the soil to form precipitates, which cannot be directly absorbed and utilized by crops, resulting in low utilization rate of phosphorus fertilizer in the season. To ensure high and stable yield, terminal growers will invest a large amount of phosphorus fertilizer in the process of agricultural production, which will further accumulate in the soil, reduce agricultural production efficiency, cause a series of environmental problems such as soil compaction and water eutrophication, and cause waste of phosphorus resources. To solve the problem of low utilization rate of traditional phosphorus fertilizer and cope with the challenges brought by the tight supply and demand of phosphorus ore to the phosphorus fertilizer industry, it is urgent to develop new types of phosphorus fertilizer products.

[0003] Patent CN117720382A discloses an agricultural composite phosphorus fertilizer and its preparation method. The invention uses super-aeration flotation on the extraction slurry obtained by extraction and crystallization in the wet-process phosphoric acid process. By super-aeration flotation, super-aeration micro-bubbles are introduced into the extraction slurry. After classification, the gas flotation layer slurry and the residual layer slurry are obtained. The gas flotation layer slurry is the base material, which does not need to be filtered directly and can be directly mixed with straw, coal slime, layered silicate, phosphate rock, and straw fast-rotting microbial agent to obtain an agricultural composite phosphorus fertilizer. The phosphate rock can use low-grade phosphate rock, achieving the purpose of comprehensive utilization of phosphogypsum waste and low-grade mineral resources. It can also further solve the technical problem of waste accumulation in the existing phosphoric acid production process. Patent CN115353429A discloses a method for preparing phosphorus fertilizer from phosphorus-containing iron tailings and the obtained phosphorus fertilizer. The invention uses high-energy grinding of the material to increase the content of effective phosphorus that can be directly absorbed by plants in the phosphorus-containing iron tailings through mechanical activation. After superfine grinding and activation, the crystal structure of the phosphorus-containing iron tailings changes, changing its reactivity and increasing its effective phosphorus content. This has an important role in improving the utilization rate of phosphorus resources. Patent CN114890842A discloses an environmentally friendly slow-release phosphorus fertilizer based on the value-added utilization of agricultural solid waste and its preparation method. The invention uses crop straw, wood ash, eggshells, and chicken feathers as raw materials to prepare an environmentally friendly modified porous biochar through microwave-assisted pyrolysis, activation, and hole expansion, and finally enriches the modified porous biochar with phosphorus-rich waste liquid to achieve the preparation of an environmentally friendly slow-release phosphorus fertilizer, achieving the slow release of phosphorus fertilizer and improving the utilization rate of phosphorus fertilizer.

[0004] Phosphorus fertilizer is easily combined with metal ions in the soil after application, resulting in ineffective utilization by plants. Therefore, increasing the amount of phosphorus fertilizer is a common practice. However, the increase in the amount of fertilizer can lead to an excessive concentration of phosphorus in the soil, affecting the acid-base balance of the soil and possibly causing soil acidification, which in turn affects crop growth. Excess phosphorus fertilizer can flow into rivers, lakes, and other water bodies during rainwater runoff or irrigation, leading to water eutrophication, promoting the proliferation of algae, causing water hypoxia, and affecting aquatic life.

[0005] Therefore, the design of an organic biological compound phosphorus fertilizer that can slow-release phosphorus fertilizer and weaken the adsorption and combination of metal ions in the soil on phosphorus fertilizer is of great significance in avoiding the negative effects of excessive phosphorus fertilizer application. SUMMARY

[0006] To address the shortcomings of existing technologies, this invention constructs oxidized biochar from biomass raw materials, combines it with carboxymethyl chitosan, and then oxidizes it to obtain aldehyde-modified oxidized biochar. This oxidized biochar is then cross-linked with amino acids to form amino acid-modified oxidized biochar. Finally, the amino acid-modified oxidized biochar is mixed with superphosphate, water is added and stirred, and then dried to constant weight to obtain an organic-bio-compound phosphate fertilizer. The organic-bio-compound phosphate fertilizer prepared through the above-described inventive concept and preparation method solves the technical problems mentioned in the background art. Specifically, the technical solution of this invention includes the following:

[0007] A method for producing an organic-biological compound phosphate fertilizer, the method comprising the following steps:

[0008] Biomass raw materials are carbonized at 500℃~600℃ for 2h~3h to obtain bio-based carbon materials;

[0009] The bio-based char material is subjected to oxidation and hydrogenation treatment to obtain oxidized biochar.

[0010] The oxidized biochar and carboxymethyl chitosan were dispersed in anhydrous dichloromethane to obtain a dispersion. An acid catalyst and a dehydrating agent were added to the dispersion, mixed, and heated to 40°C~50°C for 20h~24h. After filtration, carboxymethyl chitosan-modified oxidized biochar was obtained.

[0011] The carboxymethyl chitosan-modified oxidized biochar was subjected to oxidative treatment with an oxidant in the dark for 4-6 hours to obtain aldehyde-based oxidized biochar.

[0012] The aldehyde-modified oxidized biochar was dispersed in an amino acid aqueous solution and heated to 100℃~110℃ for 3h~5h to obtain amino acid-modified oxidized biochar.

[0013] The amino acid-modified oxidized biochar, water-soluble phosphate fertilizer, and water are mixed and stirred for 2-3 hours, and then dried to obtain the organic-bio compound phosphate fertilizer.

[0014] Furthermore, the biomass raw materials include straw, and peat moss may also be used.

[0015] Furthermore, the conditions for the hydrogen peroxide oxidation treatment include a hydrogen peroxide mass concentration of 30% to 40% and a treatment time of 3 to 4 hours.

[0016] Furthermore, the weight ratio of the oxidized biochar: carboxymethyl chitosan: anhydrous dichloromethane is 1:3~5:200~300.

[0017] Furthermore, the acid catalyst comprises 3-quinoline boric acid.

[0018] Furthermore, the absorbent comprises 13X molecular sieve.

[0019] Further, the weight ratio of the dispersion liquid: acid catalyst: water absorbent is 1: 0.08~0.1: 0.01~0.03.

[0020] Further, the oxidizing agent is sodium periodate.

[0021] Further, the weight ratio of the carboxymethyl chitosan modified oxidized biomass charcoal: oxidizing agent is 1: 0.5~0.7.

[0022] Further, the aqueous amino acid solution comprises an L-lysine aqueous solution with a mass concentration of 30% or an L-arginine aqueous solution with a mass concentration of 30%.

[0023] Further, the water-soluble phosphorus fertilizer comprises superphosphate or triple superphosphate.

[0024] Further, the weight ratio of the amino acid modified oxidized biomass charcoal: water-soluble phosphorus fertilizer: water is 1: 0.4~0.6: 300~500.

[0025] Compared with the prior art, the present application has the following beneficial effects:

[0026] The present application takes biomass raw material as carrier raw material, obtains biomass charcoal-based material through high-temperature carbonization, then obtains oxygen-containing active groups such as hydroxyl and carboxyl on the surface through oxidation treatment, and then obtains oxidized biomass charcoal. Then the oxidized biomass charcoal and carboxymethyl chitosan are mixed and ultrasonically dispersed in anhydrous dichloromethane, then a catalyst 3-quinoline boronic acid and a water absorbent HX-113 molecular sieve are added to obtain carboxymethyl chitosan modified oxidized biomass charcoal. Then the carboxymethyl chitosan modified oxidized biomass charcoal is treated with an oxidizing agent to break the ortho-dihydroxy group on the structure of carboxymethyl chitosan to produce aldehyde group, and then aldehyde group oxidized biomass charcoal is obtained. The aldehyde group oxidized biomass charcoal is dispersed in an amino acid aqueous solution, then heated to promote crosslinking of the aldehyde group and the amino group on the structure of the amino acid to form amino acid modified oxidized biomass charcoal. The amino acid modified oxidized biomass charcoal is mixed with water-soluble phosphate fertilizer, then stirred with water, and then dried to constant weight to obtain organic bio-composite phosphate fertilizer. The present application utilizes the adsorption of biomass charcoal-based material, and obtains oxidized biomass charcoal through oxidation treatment. The oxidized biomass charcoal can occur amide condensation between the oxygen-containing active group carboxyl after oxidation and the amino group on the carboxymethyl chitosan, and then carboxymethyl chitosan is introduced into the oxidized biomass to obtain carboxymethyl chitosan modified oxidized biomass charcoal. The carboxymethyl chitosan can form a slow-release structure through crosslinking to achieve the slow-release effect of phosphate fertilizer. Then the carboxymethyl chitosan modified oxidized biomass charcoal is oxidized to obtain functional groups aldehyde group, and then the aldehyde group oxidized biomass charcoal is modified with amino acid. The polar hydrophilic effect of the amino acid can increase the water absorption and retention of the fertilizer, and improve the utilization efficiency of the fertilizer. Finally, the amino acid modified oxidized biomass charcoal is mixed with water-soluble phosphate fertilizer and stirred with water. On the one hand, the phosphate fertilizer is adsorbed to the amino acid modified oxidized biomass charcoal through the physical adsorption of the biomass charcoal. On the other hand, the amino acid modified oxidized biomass charcoal contains a large amount of oxygen-containing groups, which can form coordination bonding with the metal ions on the structure of the water-soluble phosphate fertilizer to further combine the phosphorus element to the amino acid modified oxidized biomass charcoal, thereby increasing the load of phosphorus element. This not only helps to improve the utilization efficiency of the fertilizer, but also has a positive effect on reducing the adverse effects of environmental pollution and damage caused by excessive use of phosphate fertilizer. DETAILED DESCRIPTION

[0027] The technical solutions of the present application will be described clearly and completely through the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application.

[0028] Unless otherwise specified, the raw materials and reagents used in the present application are commercially available or can be prepared by known methods.

[0029] 3-Quinoline Boronic Acid was purchased from Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0030] 13X molecular sieve was purchased from Dalian Haixin Chemical Co., Ltd. Example 1

[0031] A production method of an organic biological compound phosphate fertilizer, specifically comprising the following processes:

[0032] After the biomass raw material straw is cleaned to remove surface impurities, it is placed in a blast drying machine to dry the surface moisture at a temperature of 80°C until the weight is constant. The dried straw is cut into small pieces and then placed in a pulverizer for crushing, and then passed through a 50-mesh screen to obtain fine particles. The fine particles are placed in a tube furnace and heated at a rate of 5°C / min to 500°C, and then carbonized at this temperature for 2h, and then naturally cooled to room temperature to obtain a biomass-based carbon material;

[0033] 10 parts by weight of biomass carbon material is placed in a container, then 300 parts by weight of 30% hydrogen peroxide solution is added, then it is sealed and oxidized in the dark for 3h. After the oxidation treatment is completed, the solid particles are collected by filtration, and the solid particles are washed with distilled water until the pH of the leaching water reaches neutral, and then the washed solid particles are placed in a vacuum drying oven at 60°C to dry to constant weight to obtain oxidized biomass carbon;

[0034] 1 part by weight of oxidized biomass carbon and 3 parts by weight of carboxymethyl chitosan are added to 200 parts by weight of anhydrous dichloromethane solution, and then placed in an ultrasonic disperser, and ultrasonic treated at a power of 300W for 20min to obtain a dispersion liquid. 0.08 times the weight of the dispersion liquid of 3-quinoline boronic acid catalyst is added to the dispersion liquid, and 0.01 times the weight of the dispersion liquid of 13X molecular sieve water absorbent is added to the dispersion liquid containing 3-quinoline boronic acid and mixed, and stirred at a speed of 400r / min, then placed in a temperature environment of 40°C for timed reaction for 20h, and the stirring state needs to be maintained during the reaction. After the reaction is completed, the solution and the water absorbent are removed by filtration, and the carbon particles are collected, then the carbon particles are washed with anhydrous ethanol, and then washed with deionized water until the pH of the leaching water is neutral, and then the washed carbon particles are placed in a vacuum drying oven at 60°C to dry to constant weight to obtain carboxymethyl chitosan modified oxidized biomass carbon;

[0035] 1 part by weight of carboxymethyl chitosan modified oxidized biomass charcoal is dispersed in deionized water, then 0.5 parts by weight of sodium periodate is added and mixed and stirred, then it is shielded from light and stirred at a speed of 100 r / min at room temperature for 4 h. After the sodium periodate oxidation treatment is completed, 1 part by weight of ethylene glycol is added and mixed and stirred for 1 h, then the solid particles are collected by filtration, the solid particles are rinsed with anhydrous ethanol and then with deionized water until the rinsing water reaches neutral pH, and then the rinsed solid particles are placed in a vacuum drying oven at 60°C until a constant weight is obtained to obtain aldehyde group modified oxidized biomass charcoal;

[0036] 10 parts by weight of aldehyde group modified oxidized biomass charcoal is dispersed in 200 parts by weight of a 30% mass concentration L-lysine aqueous solution, and dispersed at an ultrasonic power of 300 W for 10 min. Then stirring is carried out at a speed of 100 r / min, and then the temperature is raised to 100°C for reflux reaction for 3 h. After the reflux reaction is completed, the solid is collected by suction filtration and dried in a vacuum drying oven at 60°C to obtain amino acid modified oxidized biomass charcoal;

[0037] 0.4 parts by weight of water-soluble phosphate fertilizer superphosphate is added to 300 parts by weight of water and stirred to dissolve, then 1 part by weight of amino acid modified oxidized biomass charcoal is added to the superphosphate solution and mixed and stirred for 2 h, and then evaporative drying is carried out to remove water to obtain an organic biological compound phosphate fertilizer. Example 2

[0038] A production method of an organic biological compound phosphate fertilizer, specifically comprising the following processes:

[0039] After the biomass raw material straw is cleaned to remove surface impurities, it is placed in a forced air drying machine to dry the surface moisture at a temperature of 80°C until the weight is constant. The dried straw is cut into small pieces and then placed in a pulverizer to break, and then a 50-mesh screen is used to obtain fine particles, and the fine particles are placed in a tube furnace and heated to 550°C at a heating rate of 5°C / min, and then carbonized at this temperature for 2.5 h, and then naturally cooled to room temperature to obtain a bio-based carbon material;

[0040] 10 parts by weight of biomass carbon material is placed in a container, then 300 parts by weight of 34% mass concentration hydrogen peroxide solution is added, then it is sealed and oxidized in the dark for 3 h. After the oxidation treatment is completed, the solid particles are collected by filtration, the solid particles are rinsed with distilled water until the rinsing water reaches neutral pH, and then the rinsed solid particles are placed in a vacuum drying oven at 60°C until a constant weight is obtained to obtain oxidized biomass charcoal;

[0041] Take 1 part by weight of oxidized biomass charcoal and 4 parts by weight of carboxymethyl chitosan into 240 parts by weight of anhydrous dichloromethane solution, and then place it in an ultrasonic disperser, and ultrasonic treatment is carried out at an ultrasonic power of 300 W for 20 min to obtain a dispersion liquid. Take 0.09 times the weight of the dispersion liquid of 3-quinolinine boronic acid catalyst and add it to the dispersion liquid, and then take 0.02 times the weight of the dispersion liquid of 13X molecular sieve water absorbent and add it to the dispersion liquid containing 3-quinolinine boronic acid, and mix it at a stirring speed of 400 r / min, and then place it in a temperature environment of 45℃ for timed reaction for 20 h, and the stirring state needs to be maintained during the reaction. After the reaction is completed, the solution and the water absorbent are removed by filtration, the charcoal particles are collected, and then the charcoal particles are rinsed with anhydrous ethanol, and then rinsed with deionized water until the pH of the rinsing water is neutral, and then the rinsed charcoal particles are placed in a vacuum drying oven at 60℃ for drying to constant weight to obtain carboxymethyl chitosan modified oxidized biomass charcoal;

[0042] Disperse 1 part by weight of carboxymethyl chitosan modified oxidized biomass charcoal in deionized water, then add 0.6 parts by weight of sodium periodate and mix and stir, then perform light shielding treatment, and stir at a stirring speed of 100 r / min in a room temperature environment for 5 h. After the sodium periodate oxidation treatment is completed, 1 part by weight of ethylene glycol is added and mixed and stirred for 1 h, and then the solid particles are collected by filtration, rinsed with anhydrous ethanol, and then rinsed with deionized water until the pH of the rinsing water reaches neutral, and then the rinsed solid particles are placed in a vacuum drying oven at 60℃ for drying to constant weight to obtain aldehyde-oxidized biomass charcoal;

[0043] Take 10 parts by weight of aldehyde-oxidized biomass charcoal and disperse it in 240 parts by weight of a 30% mass concentration L-lysine aqueous solution, and disperse it at an ultrasonic power of 300 W for 10 min. Then stir at a stirring speed of 100 r / min, and then heat to 100℃ for reflux reaction for 4 h. After the reflux reaction is completed, the solid is collected by filtration and dried in a vacuum drying oven at 60℃ to obtain amino acid modified oxidized biomass charcoal;

[0044] Take 0.5 parts by weight of water-soluble phosphate fertilizer superphosphate and add it to 400 parts by weight of water and stir to dissolve, then take 1 part by weight of amino acid modified oxidized biomass charcoal and add it to the superphosphate solution and mix and stir for 2 h, and then evaporate and dry to remove water to obtain an organic biological compound phosphate fertilizer. Example 3

[0045] A production method of an organic biological compound phosphate fertilizer, specifically comprising the following processes:

[0046] The biomass raw material straw is cleaned to remove surface impurities, then placed in a blast drying machine to dry the surface moisture at a temperature of 80°C until the weight is constant. The dried straw is cut into small pieces and then placed in a pulverizer for crushing, then passed through a 50-mesh screen to obtain fine particles. The fine particles are placed in a tube furnace and heated at a rate of 5°C / min to 550°C. The carbonization treatment is carried out at this temperature for 3h, and then naturally cooled to room temperature to obtain a bio-based carbon material;

[0047] 10 parts by weight of biomass carbon material are placed in a container, then 300 parts by weight of 38% hydrogen peroxide solution are added, then sealed and oxidized in the dark for 4h. After the oxidation treatment is completed, the solid particles are collected by filtration, washed with distilled water until the pH of the washing water reaches neutral, then the washed solid particles are placed in a vacuum drying oven at 60°C and dried to constant weight to obtain an oxidized biomass carbon;

[0048] 1 part by weight of oxidized biomass carbon and 5 parts by weight of carboxymethyl chitosan are added to 280 parts by weight of anhydrous dichloromethane solution, then placed in an ultrasonic disperser, and ultrasonic treated at a power of 300W for 20min to obtain a dispersion liquid. 0.1 times the weight of 3-quinolinol borate catalyst is added to the dispersion liquid, and 0.03 times the weight of 13X molecular sieve water absorbent is added to the dispersion liquid containing 3-quinolinol borate, and stirred at a speed of 400r / min. Then, it is placed in a temperature environment of 45°C for timed reaction for 22h, and the stirring state needs to be maintained during the reaction. After the reaction is completed, the solution and the water absorbent are removed by filtration, and the carbon particles are collected, then washed with anhydrous ethanol, and then with deionized water until the pH of the washing water is neutral. Then, the washed carbon particles are placed in a vacuum drying oven at 60°C and dried to constant weight to obtain carboxymethyl chitosan modified oxidized biomass carbon;

[0049] 1 part by weight of carboxymethyl chitosan modified oxidized biomass carbon is dispersed in deionized water, then 0.7 parts by weight of sodium periodate is added and stirred, then shielded from light and stirred at a speed of 100r / min at room temperature for 6h. After the sodium periodate oxidation treatment is completed, 1 part by weight of ethylene glycol is added and stirred for 2h, then the solid particles are collected by filtration, washed with anhydrous ethanol, and then with deionized water until the pH of the washing water is neutral. Then, the washed solid particles are placed in a vacuum drying oven at 60°C and dried to constant weight to obtain an aldehyde-oxidized biomass carbon;

[0050] Take 10 parts by weight of aldehyde-based oxidized biomass charcoal dispersed in 280 parts by weight of 30% mass concentration L-arginine aqueous solution, disperse for 10 min at 300 W ultrasonic power. Then stir at 100 r / min speed, and then warm up to 110℃ to reflux for 4 h. After the reflux reaction is completed, collect the solid by suction filtration and dry in a vacuum drying oven at 60℃ to obtain amino acid modified oxidized biomass charcoal;

[0051] Take 0.6 parts by weight of water-soluble phosphate fertilizer superphosphate and add to 450 parts by weight of water to stir and dissolve, then take 1 part by weight of amino acid modified oxidized biomass charcoal and add to the superphosphate solution to mix and stir for 3 h, then evaporate and dry to remove water to obtain organic biological compound phosphate fertilizer. Example 4

[0052] A method for producing an organic biological compound phosphate fertilizer, specifically comprising the following processes:

[0053] After the biomass raw material straw is cleaned to remove surface impurities, it is placed in a forced air drying machine to dry the surface moisture at a temperature of 80℃ until the weight is constant. The dried straw is cut into small pieces and then placed in a pulverizer for crushing, and then passed through a 50 mesh screen to obtain fine particles. The fine particles are placed in a tube furnace and heated to 600℃ at a heating rate of 5℃ / min, and then naturally cooled to room temperature to obtain a biomass-based carbon material;

[0054] Take 10 parts by weight of biomass carbon material and place it in a container, then add 300 parts by weight of 40% mass concentration hydrogen peroxide solution, then seal and oxidize in the dark for 4 h. After the oxidation treatment is completed, filter and collect the solid particles, rinse the solid particles with distilled water until the pH of the rinsing water reaches neutral, then place the rinsed solid particles in a 60℃ vacuum drying oven and dry to constant weight to obtain oxidized biomass charcoal;

[0055] Take 1 part by weight of oxidized biomass charcoal and 5 parts by weight of carboxymethyl chitosan and add to 300 parts by weight of anhydrous dichloromethane solution, then place in an ultrasonic disperser and ultrasonic treat at 300 W for 20 min to obtain a dispersion liquid. Take 0.1 times the weight of the dispersion liquid of 3-quinolinol borate catalyst and add to the dispersion liquid, then take 0.03 times the weight of the dispersion liquid of 13X molecular sieve water absorbent and add to the dispersion liquid containing 3-quinolinol borate, mix and stir at 400 r / min speed, then place in a 50℃ temperature environment for timed reaction for 24 h, and the stirring state needs to be maintained during the reaction. After the reaction is completed, remove the solution and water absorbent by filtration, collect the carbon particles, then rinse the carbon particles with anhydrous ethanol, then rinse with deionized water until the pH of the rinsing water is neutral, then place the rinsed carbon particles in a 60℃ vacuum drying oven and dry to constant weight to obtain carboxymethyl chitosan modified oxidized biomass charcoal;

[0056] 1 part by weight of carboxymethyl chitosan modified oxidized biomass charcoal was dispersed in deionized water, then 0.7 parts by weight of sodium periodate was added and mixed and stirred, then it was shielded from light and stirred at a speed of 100 r / min at room temperature for 6 h. After the sodium periodate oxidation treatment was completed, 1 part by weight of ethylene glycol was added and mixed and stirred for 2 h, then the solid particles were collected by filtration, the solid particles were rinsed with anhydrous ethanol and then with deionized water until the pH of the rinsing water reached neutral, and then the rinsed solid particles were placed in a vacuum drying oven at 60°C to dry to constant weight to obtain aldehyde-oxidized biomass charcoal;

[0057] 10 parts by weight of aldehyde-oxidized biomass charcoal was dispersed in 300 parts by weight of a 30% mass concentration L-arginine aqueous solution, and dispersed at an ultrasonic power of 300 W for 10 min. Then it was stirred at a speed of 100 r / min, and then heated to 110°C and refluxed for 5 h. After the reflux reaction was completed, the solid was collected by suction filtration and dried in a vacuum drying oven at 60°C to obtain amino acid modified oxidized biomass charcoal;

[0058] 0.6 parts by weight of water-soluble phosphate fertilizer superphosphate was added to 500 parts by weight of water and stirred to dissolve, then 1 part by weight of amino acid modified oxidized biomass charcoal was added to the superphosphate solution and mixed and stirred for 3 h, then evaporated and dried to remove water to obtain an organic biological compound phosphate fertilizer.

[0059] Comparative Example 1:

[0060] A production method of an organic biological compound phosphate fertilizer, specifically including the following processes:

[0061] After the biomass raw material straw was cleaned to remove surface impurities, it was placed in a forced air drying machine and dried at a temperature of 80°C until the surface moisture was constant. The dried straw was cut into small pieces and then placed in a pulverizer to break up, then passed through a 50 mesh screen to obtain fine particles, and then the fine particles were placed in a tube furnace and heated at a rate of 5°C / min to 700°C, and then carbonized at this temperature for 4 h, and then naturally cooled to room temperature to obtain a bio-based carbon material; the remaining processes were consistent with Example 4.

[0062] Comparative Example 2:

[0063] A production method of an organic biological compound phosphate fertilizer, specifically including the following processes:

[0064] The biomass raw material straw is cleaned to remove surface impurities, then put into a blast drying machine to dry the surface moisture at a temperature of 80°C until the weight is constant. The dried straw is cut into small pieces and put into a pulverizer for crushing, then passed through a 50-mesh screen to obtain fine particles. The fine particles are put into a tube furnace and heated to 600°C at a heating rate of 5°C / min. The carbonization treatment is carried out at this temperature for 3h, and then naturally cooled to room temperature to obtain a bio-based carbon material;

[0065] 10 parts by weight of biomass carbon material is put into a container, then 300 parts by weight of hydrogen peroxide solution with a mass concentration of 50% is added, then sealed and oxidized in the dark environment for 5h. After the oxidation treatment is completed, the solid particles are collected by filtration, and the solid particles are washed with distilled water until the pH of the washing water reaches neutral, then the washed solid particles are put into a vacuum drying oven at 60°C and dried to constant weight to obtain oxidized biomass carbon; the rest of the process remains the same as example 4.

[0066] Comparative example 3:

[0067] A production method of an organic biological compound phosphate fertilizer, specifically including the following processes:

[0068] The carboxymethyl chitosan in example 4 is replaced by chitosan, and the rest of the process remains the same as example 4.

[0069] Comparative example 4:

[0070] A production method of an organic biological compound phosphate fertilizer, specifically including the following processes:

[0071] The biomass raw material straw is cleaned to remove surface impurities, then put into a blast drying machine to dry the surface moisture at a temperature of 80°C until the weight is constant. The dried straw is cut into small pieces and put into a pulverizer for crushing, then passed through a 50-mesh screen to obtain fine particles. The fine particles are put into a tube furnace and heated to 600°C at a heating rate of 5°C / min. The carbonization treatment is carried out at this temperature for 3h, and then naturally cooled to room temperature to obtain a bio-based carbon material;

[0072] 10 parts by weight of biomass carbon material is put into a container, then 300 parts by weight of hydrogen peroxide solution with a mass concentration of 40% is added, then sealed and oxidized in the dark environment for 4h. After the oxidation treatment is completed, the solid particles are collected by filtration, and the solid particles are washed with distilled water until the pH of the washing water reaches neutral, then the washed solid particles are put into a vacuum drying oven at 60°C and dried to constant weight to obtain oxidized biomass carbon;

[0073] 1 part by weight of oxidized biomass charcoal and 5 parts by weight of carboxymethyl chitosan were added to 300 parts by weight of anhydrous dichloromethane solution, and then placed in an ultrasonic disperser to be ultrasonically treated at an ultrasonic power of 300 W for 20 min to obtain a dispersion liquid. 0.1 times the weight of the dispersion liquid of 3-quinolinine boronic acid catalyst was added to the dispersion liquid, and 0.03 times the weight of the dispersion liquid of 13X molecular sieve water absorbent was added to the dispersion liquid containing 3-quinolinine boronic acid and mixed, and stirred at a speed of 400 r / min, and then placed in a temperature environment of 50°C for timed reaction for 24 h, and stirring was required during the reaction. After the reaction was completed, the solution and the water absorbent were removed by filtration, the charcoal particles were collected, and then the charcoal particles were washed with anhydrous ethanol, and then washed with deionized water until the pH of the washing water was neutral, and then the washed charcoal particles were placed in a vacuum drying oven at 60°C for drying to constant weight to obtain carboxymethyl chitosan modified oxidized biomass charcoal;

[0074] 1 part by weight of carboxymethyl chitosan modified oxidized biomass charcoal was dispersed in deionized water, then 0.7 parts by weight of sodium periodate was added and mixed and stirred, then light shielding treatment was performed, and stirring was performed at a speed of 100 r / min at room temperature for 6 h. After the sodium periodate oxidation treatment was completed, 1 part by weight of ethylene glycol was added and mixed and stirred for 2 h, and then the solid particles were collected by filtration, and then the solid particles were washed with anhydrous ethanol and then washed with deionized water until the pH of the washing water was neutral, and then the washed solid particles were placed in a vacuum drying oven at 60°C for drying to constant weight to obtain aldehyde-oxidized biomass charcoal.

[0075] 0.6 parts by weight of water-soluble phosphate fertilizer triple superphosphate was added to 500 parts by weight of water and stirred and dissolved, and then 1 part by weight of aldehyde-oxidized biomass charcoal was added to the triple superphosphate solution and mixed and stirred for 3 h, and then evaporative drying was performed to remove water to obtain an organic biological compound phosphate fertilizer.

[0076] Total phosphorus content determination:

[0077] According to the standard of “GB / T 17767.2-2010 Determination of organic-inorganic compound fertilizers Part 2: Total phosphorus content”, 1 g of the organic biological compound phosphate fertilizer obtained in Examples 1-4 and Comparative Examples 1-4 was respectively weighed, and the total phosphorus content was determined according to the sulfuric acid-hydrogen peroxide digestion method, and the results are shown in Table 1 below.

[0078]

[0079] Slow-release performance test:

[0080] 1.0 g of the organic bio-composite phosphorus fertilizer obtained in Examples 1-4 and Comparative Examples 1-4 was respectively packed in a 100-mesh nylon bag, the nylon bag was immersed in a plastic bottle containing 250 mL of distilled water, and the bottle was sealed and placed in a constant temperature incubator at 25°C. On the 28th day, 50 mL of the solution was taken from the bottle and placed in a centrifuge tube with a cap, and the cumulative release rate of phosphorus content was measured. The results are shown in Table 2 below.

[0081]

[0082] Water retention performance test:

[0083] 1.0 g of the organic bio-composite phosphorus fertilizer obtained in Examples 1-4 and Comparative Examples 1-4 was respectively mixed with 50 g of soil (passed through a 30-mesh sieve) and placed in a 200-mL glass beaker. Then 50 mL of tap water was slowly added to the beaker and placed in a constant temperature incubator at 30±5°C, and then the remaining weight was weighed on the 7th day. The results are shown in Table 3 below.

[0084]

[0085] From the test results in Tables 1-3 above, the following conclusions can be drawn:

[0086] (1) From Examples 1-4, it can be found that the biomass raw material is used to construct oxidized biomass charcoal, which is combined with carboxymethyl chitosan and then oxidized to obtain aldehyde-based oxidized biomass charcoal, which is then cross-linked with amino acids to form amino acid-modified oxidized biomass charcoal. Finally, the amino acid-modified oxidized biomass charcoal is mixed with superphosphoric acid and stirred with water, and then dried to constant weight to obtain an organic bio-composite phosphorus fertilizer, which has good performance in loading phosphorus fertilizer, and good slow-release performance and water retention performance.

[0087] (2) From Comparative Example 1, it can be found that although high-temperature carbonization can increase the specific surface area of the biomass-based carbon material, and the increase in specific surface area can increase the adsorption capacity, but in this system, high-temperature carbonization at too high a temperature and for too long a time can cause the structure of the biomass-based carbon material to collapse, which can actually reduce the adsorption capacity of the phosphorus fertilizer, resulting in the organic bio-composite phosphorus fertilizer prepared finally having a low total phosphorus content, poor phosphorus loading performance, and the collapse of the structure of the biomass-based carbon material, resulting in poor slow-release effect and water retention performance.

[0088] (3) Through the comparative example 2, it can be found that although the hydrogen peroxide oxidation treatment of the biomass charcoal material can increase the number of surface oxygen-containing active groups, so as to increase the reactivity of the biomass charcoal material, but in the present system, it is found that the total phosphorus content contained in the finally prepared organic biological compound phosphorus fertilizer is low, the phosphorus loading performance is poor, and the slow-release effect and water retention performance are poor, which may be due to the fact that the high concentration of hydrogen peroxide and the long time of oxidation treatment may cause the structure of the biomass charcoal material to be damaged, which in turn makes the prepared organic biological compound phosphorus fertilizer perform poorly.

[0089] (4) Through the comparative example 3, it can be found that although chitosan also has amino and ortho-dihydroxy structures, which can undergo subsequent condensation reaction and oxidation reaction, but in the present system, it is found that the total phosphorus content of the prepared organic biological compound phosphorus fertilizer is poor, and the water retention performance is general, which may be due to the fact that chitosan has extremely poor solubility and poor hygroscopicity, which in turn leads to poor performance of the organic biological compound phosphorus fertilizer.

[0090] (5) Through the comparative example 4, it can be found that although the prepared organic biological compound phosphorus fertilizer has good total phosphorus content, it performs poorly in water retention, which may be due to the fact that although carboxymethyl chitosan has good hydrophilic properties, during the oxidation process, the carbon chain structure is partially destroyed, which may in turn weaken the hydrophilicity, leading to poor water retention performance, and if not improved, it may lead to poor fertilizer efficiency.

[0091] The above-described examples have detailed the technical solutions and beneficial effects of the present application, it should be understood that the above-described only for the specific embodiments of the present application, and is not used to limit the present application. Without departing from the spirit and scope of the present application, the present application will have various changes and improvements, these changes and improvements all fall within the scope of the claimed present application.

Claims

1. A method for producing an organic bio-complex phosphatic fertilizer, characterized in that, The production method comprises the following steps: The biomass raw material is treated by high-temperature carbonization at 500-600 DEG C for 2-3 hours to obtain a bio-based carbon material; The bio-based carbon material is treated by hydrogen peroxide oxidation to obtain an oxidized biomass carbon; The oxidized biomass carbon and carboxymethyl chitosan are dispersed in anhydrous dichloromethane to obtain a dispersion liquid, an acid catalyst and a water absorbent are added into the dispersion liquid and mixed, heated to 40-50 DEG C and reacted for 20-24 hours, and then filtered to obtain carboxymethyl chitosan modified oxidized biomass carbon; The carboxymethyl chitosan modified oxidized biomass carbon is treated by light-shielded oxidation with an oxidizing agent for 4-6 hours to obtain an aldehyde group oxidized biomass carbon; The aldehyde group oxidized biomass carbon is dispersed in an amino acid aqueous solution and heated to 100-110 DEG C and reacted for 3-5 hours to obtain an amino acid modified oxidized biomass carbon; The amino acid modified oxidized biomass carbon, a water-soluble phosphorus fertilizer and water are mixed and stirred for 2-3 hours, and then dried to obtain the organic bio-composite phosphorus fertilizer. The amino acid aqueous solution comprises an L-lysine aqueous solution with a mass concentration of 30% or an L-arginine aqueous solution with a mass concentration of 30%.

2. The method of producing organic bio-composted phosphatic fertilizer according to claim 1, characterized in that, The hydrogen peroxide oxidation treatment conditions include a hydrogen peroxide mass concentration of 30-40% and a treatment time of 3-4 hours.

3. The method of producing organic bio-composted phosphatic fertilizer according to claim 1, characterized in that, The weight ratio of the oxidized biomass carbon: carboxymethyl chitosan: anhydrous dichloromethane is 1:3-5:200-300.

4. The method of producing organic bio-composted phosphatic fertilizer according to claim 1, characterized in that, The acid catalyst comprises 3-quinoline boronic acid.

5. The method of producing organic bio-composted phosphatic fertilizer according to claim 1, characterized in that, The water absorbent comprises 13X molecular sieve.

6. The method of producing organic bio-composted phosphatic fertilizer according to claim 1, characterized in that, The weight ratio of the dispersion liquid: acid catalyst: water absorbent is 1:0.08-0.1:0.01-0.

03.

7. The method of producing organic bio-composted phosphatic fertilizer according to claim 1, characterized in that, The weight ratio of the carboxymethyl chitosan modified oxidized biomass carbon: oxidizing agent is 1:0.5-0.

7.

8. The method of producing organic bio-composted phosphatic fertilizer according to claim 1, characterized in that, The water-soluble phosphorus fertilizer comprises superphosphate or triple superphosphate.

9. The method of producing organic bio-composted phosphatic fertilizer according to claim 1, characterized in that, The weight ratio of the amino acid modified oxidized biomass carbon: water-soluble phosphorus fertilizer: water is 1:0.4-0.6:300-500.

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