Preparation method and application of modified yellow phosphorus slag

Abstract

The invention discloses a preparation method and application of modified yellow phosphorus slag, and relates to the technical field of chemical waste resource utilization and fertilizer synergism. The preparation method of the modified yellow phosphorus slag comprises the following steps: pretreating the yellow phosphorus slag with microorganisms or acid, adjusting the water content, crushing, and modifying with a modifier to obtain the modified yellow phosphorus slag. The yellow phosphorus slag is modified to be used for preparing the non-water-soluble medium element liquid fertilizer, the non-water-soluble medium element liquid fertilizer is obtained by performing wet grinding on the modified yellow phosphorus slag and then performing homogeneous mixing on the ground yellow phosphorus slag, the dispersing agent and the emulsifying agent, the liquid fertilizer has good compatibility with water, the sedimentation or layering phenomenon does not occur after the liquid fertilizer is placed for a long time, and the non-water-soluble medium element liquid fertilizer is obtained. The non-water-soluble medium element liquid fertilizer prepared from the modified yellow phosphorus slag has the advantages that the fertilizer efficiency can be improved, the non-water-soluble medium element liquid fertilizer is quick in effect and high in yield after being used, and the non-water-soluble medium element liquid fertilizer is suitable for popularization and application.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of chemical waste resource utilization and fertilizer efficiency enhancement, and particularly relates to a preparation method and application of modified yellow phosphorus slag. BACKGROUND

[0002] The main element components of medium element fertilizer are silicon, calcium, magnesium and the like. At present, the medium element fertilizer on the market mainly includes calcium magnesium nitrate, calcium ammonium nitrate, calcium chloride and the like, which is water-soluble fertilizer and can be completely and rapidly dissolved in water, is easy to be absorbed by crops, but is easy to be washed away by rainwater, resulting in rapid loss, low utilization rate, and containing acid radical ions, which can easily aggravate the degree of soil acidification in southern areas. The non-water-soluble medium element fertilizer has the characteristics of long-lasting fertilizer effect, not easy to be lost and leached away due to containing medium element mineral powder which is not soluble in ordinary water, and has a good development and application prospect.

[0003] Yellow phosphorus slag is a solid waste generated in the process of producing yellow phosphorus by an electric furnace method, and mainly contains calcium oxide (40-55%), silicon dioxide (25-35%) and a small amount of magnesium oxide, elemental phosphorus and the like, and can be used as a soil conditioner or a fertilizer raw material. Therefore, it is feasible to use the yellow phosphorus slag to prepare the non-water-soluble medium element fertilizer. However, there are the following problems in preparing the non-water-soluble medium element liquid fertilizer from the yellow phosphorus slag: the yellow phosphorus slag powder has poor compatibility with water, poor dispersity, is easy to be stratified, is not conducive to long-term preservation, and is easy to block the water pipe during use; the effectiveness of silicon, calcium and magnesium in the yellow phosphorus slag is not high enough, that is, the form which can be absorbed by crop roots is less, and the part which is difficult to utilize is high, and needs to be further improved.

[0004] The non-patent document "Preparation of Special Fertilizer for Rice in Yunnan-Guizhou-Sichuan Region by Using Modified Yellow Phosphorus Slag" (Wang Jie, Gu Shouyu, Hou Cuirong, et al. Preparation of Special Fertilizer for Rice in Yunnan-Guizhou-Sichuan Region by Using Modified Yellow Phosphorus Slag [J]. Inorganic Salt Industry, 2022, 54(12): 79-86) discloses that the raw material prepared by adding a nutrient element additive required by crops and the yellow phosphorus slag is treated at a high temperature (above 800 DEG C) to obtain modified yellow phosphorus slag, which can improve the effectiveness of silicon, calcium and magnesium in the yellow phosphorus slag, and has high fertilizer effect and good effect for rice. However, the modification method of the yellow phosphorus slag in the document is relatively complex, needs to be treated at a high temperature for a long time, and is not conducive to production and use. Therefore, there are problems of how to improve the fertilizer effect and how to improve the compatibility with water in the preparation of the non-water-soluble medium element liquid fertilizer from the yellow phosphorus slag. SUMMARY

[0005] In view of the above problems, the present application provides a preparation method and application of modified yellow phosphorus slag. The method can be used to prepare non-water-soluble medium element liquid fertilizer by modifying and activating the yellow phosphorus slag, improves the effectiveness of silicon, calcium and magnesium in the fertilizer, and improves the compatibility with water. The specific technical scheme is as follows. A preparation method of modified yellow phosphorus slag, comprising the following steps: (1) using microorganism or acid to pretreat yellow phosphorus slag, and adjusting the water content to be ≤1%, to obtain pretreated yellow phosphorus slag; (2) after crushing the pretreated yellow phosphorus slag to a particle size of 300-400 meshes, adding a modifier and mixing and stirring, to obtain modified yellow phosphorus slag.

[0006] Further, in step (1), the pretreatment of the yellow phosphorus slag by using microorganism is as follows: after adjusting the water content of the yellow phosphorus slag to 50-60%, adding 0.5-1.5% of soluble carbon source, 0.05-0.3% of nitrogen source and 1-2% of phosphate buffer by weight of the yellow phosphorus slag, mixing and stirring uniformly to obtain a mixture, inoculating 2-5% of Bacillus mucilaginosus and 1-3% of Aspergillus niger by weight of the mixture into the mixture, and treating at 28-35℃ for 20-30 days, to obtain the pretreated yellow phosphorus slag.

[0007] Further, the soluble carbon source is sugarcane molasses, and the nitrogen source is urea.

[0008] Further, in step (1), the pretreatment of the yellow phosphorus slag by using acid is as follows: soaking the yellow phosphorus slag in a dilute acid solution for 3-5h, taking out and drying to a water content of 30-40%, to obtain the pretreated yellow phosphorus slag; the dilute acid solution is prepared by mixing citric acid, acetic acid and water in a volume ratio of (5-12):(1-4):100.

[0009] Further, in step (2), the modifier comprises hydrophilic calcium carbonate or hydrophilic magnesium carbonate. The preparation method of the hydrophilic calcium carbonate is as follows: mixing titanate with an equal amount of anhydrous ethanol uniformly to obtain a mixed solution; slowly dropping the mixed solution into calcium carbonate powder, the amount of addition being 0.5-1.0% of the mass of the calcium carbonate powder, continuously mixing and stirring at a rotation speed of 1500-2000r / min for 15-30min, and drying, to obtain the hydrophilic calcium carbonate. The preparation method of the hydrophilic magnesium carbonate is as follows: mixing titanate with an equal amount of anhydrous ethanol uniformly to obtain a mixed solution; slowly dropping the mixed solution into magnesium carbonate powder, the amount of addition being 0.8-1.5% of the mass of the calcium carbonate powder, continuously mixing and stirring at a rotation speed of 1500-2000r / min for 15-30min, and drying, to obtain the hydrophilic magnesium carbonate.

[0010] Further, in step (2), the amount of addition of the modifier is 1-3% of the weight of the yellow phosphorus slag.

[0011] The application further provides a use of the modified yellow phosphorus slag in the preparation of a non-water-soluble medium element liquid fertilizer.

[0012] The application further provides a non-water-soluble trace element liquid fertilizer containing the modified yellow phosphorus slag, and a preparation method of the non-water-soluble trace element liquid fertilizer. After wet grinding the modified yellow phosphorus slag with water to a particle size of 3-8 um, adding 0.1-0.5% of a dispersing agent and 1-2% of an emulsifying agent by weight of the modified yellow phosphorus slag, and uniformly mixing, the non-water-soluble trace element liquid fertilizer is obtained.

[0013] Further, the weight ratio of the modified yellow phosphorus slag to water is 1: (1-1.5).

[0014] Further, the dispersing agent is acrylic acid homopolymer sodium salt, and the emulsifying agent is Tween-80 or alkyl glycoside.

[0015] The non-water-soluble trace element liquid fertilizer can be applied to increase the yield and improve the quality of fruits and vegetables.

[0016] Compared with the prior art, the application has the following beneficial effects: 1. The modified yellow phosphorus slag is used to prepare a non-water-soluble trace element liquid fertilizer, and the non-water-soluble trace element and water in the liquid fertilizer have good compatibility, and do not settle or stratify after long storage. When diluted with water, the liquid fertilizer can be quickly dispersed in water to form a suspension state without agglomeration. The liquid fertilizer can be used for long-term water-fertilizer integration without causing pipe blockage. In addition, the liquid fertilizer has high fertilizer efficiency and fast effect after use, and is suitable for popularization and application.

[0017] 2. The yellow phosphorus slag is pretreated, then crushed to 300-400 mesh, modified by adding a modifier, and wet ground to a particle size of 3-8 um. The pretreatment can increase the number of hydrophilic sites on the surface of the yellow phosphorus slag particles, improve the affinity of the yellow phosphorus slag to water, and prevent agglomeration or stratification.

[0018] 3. When the yellow phosphorus slag is modified, the yellow phosphorus slag is pretreated by Bacillus mucilaginosus and Aspergillus niger or pretreated by a dilute acid solution. Under the action of the microorganisms or the dilute acid solution, the yellow phosphorus slag releases a large amount of effective silicon, calcium and magnesium, and converts the parts of silicon, calcium and magnesium that are difficult to be utilized into forms that can be easily absorbed by plant roots, thereby improving the effectiveness of silicon, calcium and magnesium and the fertilizer efficiency. BRIEF DESCRIPTION OF DRAWINGS

[0019] In order to more clearly illustrate the technical solutions of the embodiments of the application, the following will briefly introduce the drawings needed to be used in the embodiment description.

[0020] Figure 1 A schematic diagram of the liquid fertilizer prepared in Example 1 quickly dispersed in water; Figure 2 A state diagram of the liquid fertilizer prepared in Example 1 after being dispersed in water and standing for 10 hours. DETAILED DESCRIPTION

[0021] The specific embodiments of the present application are described in detail below, but the scope of protection of the present application is not limited by the specific embodiments.

[0022] Example 1 A preparation method of modified yellow phosphorus slag, comprising the following steps: (1) Yellow phosphorus slag pretreatment: after adjusting the water content of the yellow phosphorus slag to 50%, 0.5% of the weight of the yellow phosphorus slag of sugarcane molasses, 0.05% of urea, and 1% of phosphate buffer are added and uniformly mixed and stirred to obtain a mixture, 2% of the weight of the mixture of Bacillus mucilaginosus CGMCC1.211 (from the China General Microbiological Culture Collection Center, hereinafter the same) and 1% of Aspergillus niger CGMCC3.17612 (from the China General Microbiological Culture Collection Center, hereinafter the same) are inoculated into the mixture, and the mixture is treated at 28°C for 20 days to obtain the modified yellow phosphorus slag.

[0023] (2) Preparation of modified yellow phosphorus slag: after adjusting the water content of the pretreated yellow phosphorus slag to 0.5%, the yellow phosphorus slag is crushed to a particle size of 300 mesh to obtain a yellow phosphorus slag powder, 1% of the weight of the yellow phosphorus slag powder of hydrophilic calcium carbonate is added to the yellow phosphorus slag powder, and the mixture is stirred at a speed of 2000 r / min for 20 min to obtain the modified yellow phosphorus slag. The preparation method of the hydrophilic calcium carbonate is as follows: titanium ester is uniformly mixed with an equal amount of anhydrous ethanol to obtain a mixed solution; the mixed solution is slowly dropped into calcium carbonate powder, the amount of the mixed solution added is 0.5% of the mass of the calcium carbonate powder, and the mixture is continuously stirred at a speed of 1500 r / min for 15 min, and then dried to obtain the hydrophilic calcium carbonate.

[0024] A method for preparing a non-aqueous medium element liquid fertilizer from the modified yellow phosphorus slag: the modified yellow phosphorus slag is wet ground with water to a particle size of 3 um at a weight ratio of 1:1, 0.1% of the weight of the modified yellow phosphorus slag of a dispersant acrylic acid homopolymer sodium salt and 1% of the weight of the modified yellow phosphorus slag of an emulsifying agent Tween-80 are added, and the mixture is uniformly stirred and mixed to obtain the non-aqueous medium element liquid fertilizer.

[0025] Example 2 A preparation method of modified yellow phosphorus slag, comprising the following steps: (1) Yellow phosphorus slag pretreatment: after adjusting the water content of the yellow phosphorus slag to 60%, 1.5% of the weight of the yellow phosphorus slag of sugarcane molasses, 0.3% of urea, and 2% of phosphate buffer are added and uniformly mixed and stirred to obtain a mixture, 5% of the weight of the mixture of Bacillus mucilaginosus and 3% of the weight of the mixture of Aspergillus niger are inoculated into the mixture, and the mixture is treated at 35°C for 30 days to obtain the modified yellow phosphorus slag.

[0026] (2) Preparation of modified yellow phosphorus slag: the pretreated yellow phosphorus slag is crushed to a particle size of 400 mesh after adjusting the moisture content to 0.8%, and yellow phosphorus slag powder is obtained. 3% of hydrophilic calcium carbonate by weight of the yellow phosphorus slag powder is added to the yellow phosphorus slag powder, and mixed and stirred at a speed of 2500 r / min for 30 min to obtain modified yellow phosphorus slag. The preparation method of the hydrophilic calcium carbonate is as follows: titanium ester is uniformly mixed with an equal amount of anhydrous ethanol to obtain a mixed solution; the mixed solution is slowly dropped into calcium carbonate powder, and the amount added is 1.0% of the mass of the calcium carbonate powder; the mixture is continuously stirred at a speed of 2000 r / min for 0 min; and then dried to obtain the hydrophilic calcium carbonate.

[0027] The method for preparing a non-aqueous medium element liquid fertilizer by using the modified yellow phosphorus slag is as follows: the modified yellow phosphorus slag is wet ground with water in a weight ratio of 1:1.5 to a particle size of 8 um, and then 0.5% of a dispersant acrylic homopolymer sodium salt and 2% of an emulsifier Tween-80 by weight of the modified yellow phosphorus slag are added and uniformly stirred to obtain the non-aqueous medium element liquid fertilizer.

[0028] Example 3 A method for preparing modified yellow phosphorus slag comprises the following steps: (1) Yellow phosphorus slag pretreatment: after adjusting the moisture content of the yellow phosphorus slag to 55%, 1% of sugarcane molasses, 0.2% of urea, and 1.2% of phosphate buffer by weight of the yellow phosphorus slag are added and uniformly mixed and stirred to obtain a mixture; 3% of Bacillus mucilaginosus and 2% of Aspergillus niger by weight of the mixture are inoculated into the mixture, and the mixture is treated at 32°C for 25 days to obtain the pretreated yellow phosphorus slag.

[0029] (2) Preparation of modified yellow phosphorus slag: the pretreated yellow phosphorus slag is crushed to a particle size of 400 mesh after adjusting the moisture content to 1%, and yellow phosphorus slag powder is obtained. 2% of hydrophilic magnesium carbonate by weight of the yellow phosphorus slag powder is added to the yellow phosphorus slag powder, and mixed and stirred at a speed of 2200 r / min for 25 min to obtain modified yellow phosphorus slag. The preparation method of the hydrophilic magnesium carbonate is as follows: titanium ester is uniformly mixed with an equal amount of anhydrous ethanol to obtain a mixed solution; the mixed solution is slowly dropped into magnesium carbonate powder, and the amount added is 1% of the mass of the calcium carbonate powder; the mixture is continuously stirred at a speed of 1800 r / min for 20 min; and then dried to obtain the hydrophilic magnesium carbonate.

[0030] The method for preparing a non-aqueous medium element liquid fertilizer by using the modified yellow phosphorus slag is as follows: the modified yellow phosphorus slag is wet ground with water in a weight ratio of 1:1.5 to a particle size of 6 um, and then 0.3% of a dispersant acrylic homopolymer sodium salt and 1.5% of an emulsifier alkyl glycoside by weight of the modified yellow phosphorus slag are added and uniformly stirred to obtain the non-aqueous medium element liquid fertilizer.

[0031] Example 4 A method for preparing modified yellow phosphorus slag, comprising the following steps: (1) Yellow phosphorus slag pretreatment: soak the yellow phosphorus slag in a dilute acid solution for 4 hours, take it out, and dry it to a water content of 35%, and obtain it; the dilute acid solution is prepared by mixing citric acid, acetic acid and water in a volume ratio of 9:2:100.

[0032] (2) Preparation of modified yellow phosphorus slag: after adjusting the water content of the pretreated yellow phosphorus slag to 0.5%, it is crushed to a particle size of 400 mesh to obtain yellow phosphorus slag powder, and 2% of hydrophilic magnesium carbonate by weight of the yellow phosphorus slag powder is added to the yellow phosphorus slag powder, and mixed and stirred at a speed of 2200 r / min for 30 minutes to obtain the modified yellow phosphorus slag. The preparation method of the hydrophilic magnesium carbonate is as follows: mix titanate with an equal amount of anhydrous ethanol to obtain a mixed solution; slowly drop the mixed solution into the magnesium carbonate powder, the amount of addition is 1% of the mass of the calcium carbonate powder, continuously mix and stir at a speed of 1800 r / min for 20 minutes, and dry to obtain the hydrophilic magnesium carbonate.

[0033] A method for preparing non-aqueous medium element liquid fertilizer using modified yellow phosphorus slag: wet grinding the modified yellow phosphorus slag with water to a particle size of 8 um in a weight ratio of 1:1, adding 0.1% of the dispersant acrylic acid homopolymer sodium salt and 1% of the emulsifying agent Tween-80 by weight of the modified yellow phosphorus slag, and uniformly stirring to obtain the non-aqueous medium element liquid fertilizer.

[0034] Example 5 A method for preparing modified yellow phosphorus slag, comprising the following steps: (1) Preparation of modified yellow phosphorus slag: after adjusting the water content of the pretreated yellow phosphorus slag to 0.5%, it is crushed to a particle size of 400 mesh to obtain yellow phosphorus slag powder, and 2% of hydrophilic magnesium carbonate by weight of the yellow phosphorus slag powder is added to the yellow phosphorus slag powder, and mixed and stirred at a speed of 2200 r / min for 30 minutes to obtain the modified yellow phosphorus slag. The preparation method of the hydrophilic magnesium carbonate is as follows: mix titanate with an equal amount of anhydrous ethanol to obtain a mixed solution; slowly drop the mixed solution into the magnesium carbonate powder, the amount of addition is 1% of the mass of the calcium carbonate powder, continuously mix and stir at a speed of 1800 r / min for 20 minutes, and dry to obtain the hydrophilic magnesium carbonate.

[0035] A method for preparing non-aqueous medium element liquid fertilizer using modified yellow phosphorus slag: wet grinding the modified yellow phosphorus slag with water to a particle size of 8 um in a weight ratio of 1:1, adding 0.1% of the dispersant acrylic acid homopolymer sodium salt and 1% of the emulsifying agent Tween-80 by weight of the modified yellow phosphorus slag, and uniformly stirring to obtain the non-aqueous medium element liquid fertilizer.

[0036] Fertilizer effect detection: The content of the medium elements in the liquid fertilizer prepared in each example was determined; the content of the medium elements in the yellow phosphorus slag after being ground to 400 meshes (control 1) was determined; the content of the medium elements in the yellow phosphorus slag after being pretreated by the acid solution and ground to 400 meshes (control 2) was determined; the content of the medium elements in the yellow phosphorus slag after being pretreated by the microorganism and ground to 400 meshes (control 3) was determined, and the availability of the medium elements in each group was calculated, wherein the availability of the element (%) = C / T x 100%; C is the effective mass of the element; and T is the total mass of the element. The results are shown in Table 1.

[0037] The content of the available silicon dioxide was detected by the weight method according to NY-T-797-2004 “Silicon Fertilizer”; the content of the available calcium oxide and the available magnesium oxide was detected by the EDTA complexometric titration method.

[0038] Table 1: Availability of the medium elements in each group Table 1 shows that the availability of silicon, calcium and magnesium in the medium element liquid fertilizer prepared from the yellow phosphorus slag is high, and the fertilizer can be basically absorbed and utilized by plants, and the effect is fast. At the same time, from each example and the control example, it can be seen that the availability of silicon, calcium and magnesium in the fertilizer can be improved by pretreating the yellow phosphorus slag by the microorganism or the acid solution.

[0039] Dispersion detection: Comparative example 1: without modification by the modifier, and other steps are the same as those in example 1.

[0040] Comparative example 2: without wet grinding, and other steps are the same as those in example 1.

[0041] Comparative example 3: wet grinding to a particle size of 2-4 um, and other steps are the same as those in example 1.

[0042] Comparative example 4: wet grinding to a particle size of 10-15 um, and other steps are the same as those in example 1.

[0043] The liquid fertilizer prepared in example 1 to example 3 and comparative example 1 to comparative example 4 was observed for the dispersion state after being placed for 3 days; the liquid fertilizer prepared in example 1 to example 3 and comparative example 1 to comparative example 4 was dropped into water (5 mL of the fertilizer was dropped into 100 mL of water), and the time required for complete dispersion was counted, and whether the sedimentation occurred after 10 h of dispersion was observed, and the results are shown in Table 2.

[0044] Table 2: Comparison of the dispersion of each group Table 2 shows that the non-aqueous medium element liquid fertilizer of the present application has good compatibility with water, is in a suspended state, does not settle or stratify after long storage, and can quickly disperse in water when diluted with water (see Figure 1 ), without agglomeration, and remains in a suspended state after 10 hours of dispersion in water (see Figure 2 ).

[0045] Field test: To test the application effect of the non-aqueous medium element liquid fertilizer produced by the present application on citrus, the applicant conducted a citrus fertilizer application test in Lingchuan County, Guangxi in 2023. The specific test conditions are as follows: 1.1 Test soil The test soil is water and soil, the soil name is Yuchao mud field, the soil texture is sandy loam, the terrain is flat, the fertility is medium and uniform, the drainage is convenient, and no fertilizer test has been done in recent years. The soil nutrients in the plough layer are: organic matter 26.4 g / kg, total nitrogen 1.83 g / kg, available phosphorus (P0) 24.7 mg / kg, available potassium (K0) 66.0 mg / kg, and pH value 5.5. The test crop is citrus, the variety is: sand sugar orange, the tree age is 6 years, the planting specification is 2.5*3.0 m, and 89 are planted per mu.

[0046] 1.2 Test method The test has 7 treatments, 3 repetitions, and is arranged randomly in blocks, with a total of 21 fruit trees (1 tree per repetition), and the test treatments are as follows: Treatment 1: Conventional fertilization + application of non-aqueous medium element liquid fertilizer prepared by Example 1. Apply the non-aqueous medium element liquid fertilizer prepared by Example 1 once during the fruit enlargement period, taking 10 kg / mu as topdressing.

[0047] Treatment 2: Conventional fertilization + application of non-aqueous medium element liquid fertilizer prepared by Example 2. Apply the non-aqueous medium element liquid fertilizer prepared by Example 2 once during the fruit enlargement period, taking 10 kg / mu as topdressing.

[0048] Treatment 3: Conventional fertilization + application of non-aqueous medium element liquid fertilizer prepared by Example 3. Apply the non-aqueous medium element liquid fertilizer prepared by Example 3 once during the fruit enlargement period, taking 10 kg / mu as topdressing.

[0049] Treatment 4: Conventional fertilization + application of non-aqueous medium element liquid fertilizer prepared by Example 4. Apply the non-aqueous medium element liquid fertilizer prepared by Example 4 once during the fruit enlargement period, taking 10 kg / mu as topdressing.

[0050] Treatment 5: Conventional fertilization + application of non-aqueous medium element liquid fertilizer prepared by Example 5. Apply the non-aqueous medium element liquid fertilizer prepared by Example 5 once during the fruit enlargement period, taking 10 kg / mu as topdressing.

[0051] Treatment 6: blank control: no fertilizer is applied.

[0052] Treatment 7: conventional fertilization: 45% compound fertilizer 95 kg and potassium sulfate 20 kg per mu are applied during the fruit expansion period.

[0053] Conventional fertilization method: base fertilizer is applied in February: compound fertilizer 45 kg; the first topdressing is applied in May: each treatment is applied with compound fertilizer 25 kg per mu; the second topdressing is applied in July: each treatment is applied with compound fertilizer 25 kg per mu; and the third topdressing is applied in September: each treatment is applied with potassium sulfate 20 kg per mu. Except for different test fertilization, other fertilization, pest control and other factors of farm operation are consistent in each treatment of the test.

[0054] All the plots are harvested in December, and the yield of each treatment plot is separately harvested and counted. Before harvesting, 2 plants are randomly and continuously taken for each treatment to investigate the biological characteristics of the sugar orange.

[0055] 1.3 Effect of different treatments on the biological characteristics of sugar orange Table 3 Effect of different treatments on the yield and biological characteristics of sugar orange As shown in Table 3, compared with conventional fertilization (treatment 7), the leaf color is darker, the disease and pest incidence is lower, the yield is higher (increased by 6.9%-9.5%), and the quality is better (soluble solids increased by 0.8%-1.6%) when the non-water-soluble medium element liquid fertilizer prepared by the application is topdressed (treatments 1 to 5). Meanwhile, from the leaf color change time of treatments 1 to 5, it can be seen that when the yellow phosphorus slag is modified by the application, the yellow phosphorus slag is pretreated by Bacillus mucilaginosus and Aspergillus niger or the yellow phosphorus slag is pretreated by a dilute acid solution, the effectiveness of silicon, calcium and magnesium can be improved, and thus the fertilizer efficiency is improved, and the effect is faster after use (treatments 1 to 4 are faster than treatment 5).

[0056] In order to test the application effect of the non-water-soluble medium element liquid fertilizer produced by the application on vegetables, the applicant carried out a celery fertilizer efficiency test in Xinyi City, Jiangsu Province in 2023, and the specific test conditions are as follows: 1.1 Test time: June 22, 2023 to October 12, 2023.

[0057] 1.2 Test site: Xinyuan Village, Gangtou Town, Xinyi City, Jiangsu Province.

[0058] 1.3 Type of test soil: Table 4 Soil physical and chemical properties 1.4 Test variety and cultivation method: celery (variety: French Queen), middle shed cultivation.

[0059] 1.5 Test method: Test design: three treatments, 3 times of repetition, 9 test plots in total, plot area 30 square meters, each plot is randomly arranged, sowing on June 22, harvesting on October 12, with protective rows.

[0060] Treatment 1: conventional fertilization; Treatment 2: conventional fertilization + fertilizer prepared in Example 3; Treatment 3 (CK): conventional fertilization + spraying the same amount of water as the test fertilizer at the same time.

[0061] Cultivation specifications: 6-meter-wide middle shed, 4 furrows, 0.3-meter-wide middle 3 aisles, net furrow width 1.2 meters, every 5 meters make a plot: celery average row spacing 12.5 cm, average plant spacing 8 cm, 60,000 plants per mu on average.

[0062] Fertilization method: ① Conventional fertilization: base fertilizer mainly with organic fertilizer, equivalent to 3,000 kg per mu, compound fertilizer (nitrogen, phosphorus and potassium content is 15-10-20) equivalent to 50 kg per mu. After 30 days and 60 days, respectively, 10 kg per mu of water-soluble fertilizer (nitrogen, phosphorus and potassium content is 15-20-15) is applied.

[0063] ② Spray the fertilizer prepared in Example 3: 10 days after celery transplanting and survival, spray 100 mL of the fertilizer prepared in Example 3 per mu per time, diluted with 300 times water, every 15 days once, continuously spray 2 times.

[0064] ③ Spray the same amount of water: 10 days after celery transplanting and survival, spray the same amount of water as the test fertilizer at the same time, every 15 days once, continuously spray 2 times.

[0065] The rest of the field management of the three treatments is consistent.

[0066] 1.6 Test results Table 5 Biological characteristics of celery The test shows that spraying the fertilizer prepared in the application on the leaves of celery significantly improves the biological characteristics of celery, the plant is strong, the plant height, stem diameter, stem leaf number and leaf color are improved to different degrees. Compared with the water control, the plant height of treatment 2 increases by 1.1 cm, the stem diameter increases by 0.4 cm, the stem petiole number increases by 0.5, and the leaf color is obviously green. The commodity property is improved.

[0067] On October 12, each treatment was harvested separately for yield counting, and the results are shown in Table 6: Table 6 Yield statistics of celery As shown in Table 6, the yield of treatment 2 (fertilizer of the present application) is increased by 5166.7 kg / hm2 compared with the water control (CK), and the yield increase rate is 9.02%.

[0068] The benefit analysis of each treatment is shown in Table 7. Table 7 Benefit analysis table The fertilizer (treatment 2) prepared by the present application is calculated at 10 yuan / 100 mL, and the fertilizer cost per hm2 is 300 yuan, and the labor cost per hectare is 600 yuan. The pure income of celery sprayed with the fertilizer of the present application is increased by 14600.1 yuan / hm2 compared with the water control (CK), and the input-output ratio is 1:16.22.

[0069] In summary, the yellow phosphorus slag is modified and used to prepare the non-water-soluble medium element liquid fertilizer, the liquid fertilizer has good compatibility with water, is in a suspension state, and does not occur subsidence or stratification after long storage, can be quickly dispersed in water without agglomeration when diluted with water, and does not cause pipe blockage when used for long-term water and fertilizer integration. At the same time, the modified yellow phosphorus slag is used to prepare the non-water-soluble medium element liquid fertilizer, which can improve the fertilizer efficiency, has a quick effect after use, and has high output.

[0070] The foregoing description of specific exemplary embodiments of the present application is intended for purposes of illustration and example only. These descriptions are not intended to limit the application to the precise form disclosed, and obviously many changes and modifications can be suggested to one skilled in the art without departing from the spirit or scope of the application. It is chosen and described exemplary embodiments in order to explain the particular principles of the application and its practical application, so that those skilled in the art can implement and utilize the various exemplary embodiments of the present application and various different choices and changes. The scope of the present application is intended to be defined by the claims and their equivalents.

Claims

1. A method for preparing a modified yellow phosphorus slag, characterized by, It comprises the following steps: (1) using microorganisms or acid to pretreat yellow phosphorus slag, and adjusting the water content to ≤1%, to obtain pretreated yellow phosphorus slag; (2) crushing the pretreated yellow phosphorus slag to a particle size of 300-400 meshes, then adding a modifier and mixing and stirring, to obtain modified yellow phosphorus slag.

2. The method for preparing a modified yellow phosphorus slag according to claim 1, characterized in that, In step (1), the pretreatment of the yellow phosphorus slag with microorganisms is as follows: after adjusting the water content of the yellow phosphorus slag to 50-60%, adding 0.5-1.5% of the weight of the yellow phosphorus slag of soluble carbon source, 0.05-0.3% of nitrogen source, and 1-2% of phosphate buffer, and mixing and stirring uniformly, to obtain a mixture, inoculating 2-5% of the weight of the mixture of Bacillus mucilaginosus and 1-3% of Aspergillus niger into the mixture, and treating at 28-35°C for 20-30 days, to obtain the pretreated yellow phosphorus slag.

3. The method of claim 2, wherein the modified yellow phosphorus slag is prepared by adding a modifier to the yellow phosphorus slag, and then heating the yellow phosphorus slag at a temperature of 1,000°C or higher in an inert gas atmosphere. The soluble carbon source is sugarcane molasses, and the nitrogen source is urea.

4. The method of claim 1, wherein the modified yellow phosphorus slag is prepared by adding a modifier to the yellow phosphorus slag. In step (1), the pretreatment of the yellow phosphorus slag with acid is as follows: soaking the yellow phosphorus slag in a dilute acid solution for 3-5 h, taking out, and drying to a water content of 30-40%, to obtain the pretreated yellow phosphorus slag; the dilute acid solution is prepared by mixing citric acid, acetic acid, and water in a volume ratio of (5-12):(1-4):

100.

5. The method of claim 1, wherein the modified yellow phosphorus slag is prepared by adding a modifier to the yellow phosphorus slag, and then heating the yellow phosphorus slag at a temperature of 1,000°C or higher in an inert gas atmosphere. In step (2), the modifier comprises hydrophilic calcium carbonate or hydrophilic magnesium carbonate. The preparation method of the hydrophilic calcium carbonate is as follows: mixing titanate with an equal amount of anhydrous ethanol uniformly to obtain a mixed solution; slowly dropping the mixed solution into calcium carbonate powder at an amount of 0.5-1.0% of the mass of the calcium carbonate powder, continuously mixing and stirring at a rotation speed of 1500-2000 r / min for 15-30 min, and drying, to obtain the hydrophilic calcium carbonate. The preparation method of the hydrophilic magnesium carbonate is as follows: mixing titanate with an equal amount of anhydrous ethanol uniformly to obtain a mixed solution; slowly dropping the mixed solution into magnesium carbonate powder at an amount of 0.8-1.5% of the mass of the calcium carbonate powder, continuously mixing and stirring at a rotation speed of 1500-2000 r / min for 15-30 min, and drying, to obtain the hydrophilic magnesium carbonate.

6. The method of claim 1, wherein the modified yellow phosphorus slag is prepared by adding a modifier to the yellow phosphorus slag. In step (2), the amount of the modifier added is 1-3% of the weight of the yellow phosphorus slag.

7. The use of the modified yellow phosphorus slag prepared by the method of any one of claims 1 to 6 in the preparation of a non-aqueous medium element liquid fertilizer.

8. A non-aqueous liquid microelement fertilizer, characterized by comprising: It contains the modified yellow phosphorus slag prepared by the method of any one of claims 1 to 6, and the preparation method of the non-aqueous medium element liquid fertilizer comprises the following steps: After wet grinding the modified yellow phosphorus slag to a particle size of 3-8 um, adding 0.1-0.5% of the weight of the modified yellow phosphorus slag of dispersant and 1-2% of emulsifier, and mixing uniformly, to obtain the non-aqueous medium element liquid fertilizer.

9. The non-aqueous liquid microelement fertilizer according to claim 8, characterized in that, The weight ratio of the modified yellow phosphorus slag to water is 1:(1-1.5).

10. The non-aqueous liquid microelement fertilizer according to claim 8, characterized in that, The dispersant is acrylic acid homopolymer sodium salt, and the emulsifier is Tween-80 or alkyl glycoside.

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