WO2020093847A1 - 一种适于碱性土壤的含有腐植酸增效载体的磷铵制备方法 - Google Patents
一种适于碱性土壤的含有腐植酸增效载体的磷铵制备方法 Download PDFInfo
- Publication number
- WO2020093847A1 WO2020093847A1 PCT/CN2019/111586 CN2019111586W WO2020093847A1 WO 2020093847 A1 WO2020093847 A1 WO 2020093847A1 CN 2019111586 W CN2019111586 W CN 2019111586W WO 2020093847 A1 WO2020093847 A1 WO 2020093847A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- humic acid
- weight
- parts
- ammonium phosphate
- acid
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/45—Form not covered by groups C05G5/10 - C05G5/18, C05G5/20 - C05G5/27, C05G5/30 - C05G5/38 or C05G5/40, e.g. soluble or permeable packaging
Definitions
- the invention relates to the technical field of fertilizer production. More specifically, the present invention relates to a method for preparing ammonium phosphate containing humic acid synergistic carrier suitable for alkaline soil.
- the ways to reduce phosphorus fixation and improve the utilization rate of phosphorus fertilizer are mainly to adjust the soil pH, reduce the amount of phosphorus and metal ions in the soil, and promote crop absorption.
- Humic acid is rich in acidic functional groups such as carboxyl groups and phenolic hydroxyl groups, which can reduce phosphorus fixation to a certain extent and improve the effectiveness of phosphate fertilizers.
- the traditional humic acid extraction method is mainly to use inorganic hydroxides such as sodium hydroxide, potassium hydroxide, ammonia, etc. to form a water-soluble humate through a strong reaction. The original structure of humic acid is destroyed. Not suitable for application on alkaline soil.
- CN03274798A discloses a humic acid-enhanced ammonium phosphate and its preparation method. It extracts the weathered coal / lignite humic acid with dilute lye to prepare a humic acid-enhanced liquid, which is combined with the ammonium phosphate production process to produce Effective ammonium phosphate has the effect of inhibiting and reducing phosphorus fixation.
- a humic acid-enhanced ammonium phosphate extracts the weathered coal / lignite humic acid with dilute lye to prepare a humic acid-enhanced liquid, which is combined with the ammonium phosphate production process to produce Effective ammonium phosphate has the effect of inhibiting and reducing phosphorus fixation.
- ammonium humate phosphate suitable for alkaline soil.
- the present inventor has finally completed the present invention through a large number of experimental research and analysis work against the technical problems existing in the existing technology.
- the object of the present invention is to provide a preparation method of ammonium phosphate containing humic acid synergistic carrier suitable for alkaline soil.
- the present invention is achieved by the following technical solutions.
- the invention relates to a preparation method of ammonium phosphate containing humic acid synergistic carrier suitable for alkaline soil.
- step A Add 100 parts by weight of the humic acid mineral raw material to 800 to 1500 parts by weight of the humic acid organic extractant obtained in step A, and then gradually raise its temperature to 90 ° C under stirring, and keep it at this temperature for 40 to 60 minutes, Then cool to room temperature, centrifuge, and discard the precipitate to obtain the humic acid extract;
- the alcohol amine is one or more alcohol amines selected from monoethanolamine, diethanolamine, triethanolamine or N-methyldiethanolamine.
- step A the solution obtained by stirring and dissolving at a rotation speed of 60 to 180 rpm is cooled to a temperature of 35 ° C or lower.
- the rotation speed may specifically be 60, 100, 140 or 180 rpm;
- step A the weight ratio of alcoholamine, potassium citrate, potassium salicylate, ethylene glycol and water is 28-42: 6-9: 6-9: 6 ⁇ 9: 1200 ⁇ 1800.
- the weight part of the alcohol amine may be 30, 40 or 30-40 parts;
- the weight part of the potassium citrate may be 6, 8 or 6-8 parts;
- the weight part of the potassium salicylate may be 6, 8 or 6-8 parts;
- the weight part of the ethylene glycol may be 6, 8 or 6-8 parts;
- the weight part of the water may be 1400, 1600 or 1400-1600 parts;
- the humic acid mineral raw material is weathered coal or lignite, and the particle size of the humic acid mineral raw material is 150-300 mesh; specifically, 150, 200, 250 or 300 mesh;
- the weight parts of the organic extract of humic acid may specifically be 800, 1050, 1250, 1500 or 8000-1500 parts;
- centrifugal separation is performed at a rotational speed of 1000 to 5000 rpm for 5 to 30 min; the rotational speed may specifically be 1000, 1600, 2400, or 3000 rpm; the centrifugal separation time may specifically be 10, 26, 42 or 60min; more specifically, it can be centrifuged at 3000rpm for 10min or at 1000rpm for 60min or at 1600rpm for 42min or at 2400rpm Separation 26min;
- the benzene carboxylic acid is benzoic acid, phenylacetic acid, salicylic acid or acetylsalicylic acid.
- the sulfonic acid is benzenesulfonic acid, naphthalenesulfonic acid, methylsulfonic acid or aminoethanesulfonic acid.
- the weight part of the benzene carboxylic acid may be 13, 16, or 13-16 parts;
- the weight part of the sulfonic acid may be 6, 8 or 6-8 parts;
- the weight part of the polyethylene glycol may be 0.03, 0.04 or 0.03-0.04 parts;
- the weight part of the dicumyl peroxide may be 2.4, 2.8 or 2.4-2.8 parts;
- the weight part of the polyoxyethylene ether may be 4, 5 or 4-5 parts;
- the concentration of the superphosphate solution is 1 to 5 mol / L; specifically, it may be 1, 2, 4 or 5 mol / L;
- step C after adding polyoxyethylene ether, the solution is cooled to a temperature of 10-40 ° C; specifically, it may be 10 ° C, 20 ° C, 30 ° C, or 40 ° C;
- the invention relates to a preparation method of ammonium phosphate containing humic acid synergistic carrier suitable for alkaline soil.
- the alcohol amine used in the present invention is a compound that takes the nitrogen atom of ammonia as the core and the hydrogen atom of ammonia is replaced by an alcohol. It can chelate with calcium, magnesium, iron and other ions in the raw material of humic acid minerals to improve this raw material.
- the water solubility of humic acid helps to increase the extraction rate of humic acid from humic acid mineral raw materials.
- the alcoholamine used in the present invention is one or more alcoholamines selected from monoethanolamine, diethanolamine, triethanolamine or N-methyldiethanolamine.
- the alcohol amines mentioned are all products currently on the market, such as those sold by Shanghai Minchen Chemical Co., Ltd. under the trade name monoethanolamine (MEA), and Zouping Guoan Chemical Co., Ltd. under the trade name N-methyldiethanolamine (MDEA) products sold.
- MEA monoethanolamine
- MDEA N-methyldiethanolamine
- the basic function of potassium citrate in the preparation of humic acid organic extractant is to increase the humic acid COO - functional group and improve the extraction rate of humic acid.
- the potassium citrate used in the present invention is a product currently on the market, for example, the product sold by Xi'an Huibang Bioengineering Co., Ltd. under the trade name potassium citrate.
- the basic function of potassium salicylate in the preparation of humic acid organic extractant is to increase the carboxyl structure containing aromatic ring, so that the humic acid carrier has anti-stress performance.
- the potassium salicylate used in the present invention is a product currently on the market, for example, the product sold by Wuhan Belka Biomedical Co., Ltd. under the trade name potassium salicylate.
- Ethylene glycol can enhance the liquid stability and fluidity of humic acid organic extractant due to its good miscibility with water and low temperature resistance.
- the ethylene glycol used in the present invention is a product currently on the market, for example, the product sold by Zhengzhou Zhengsheng Chemical Products Co., Ltd. under the trade name ethylene glycol for antifreeze.
- the amount of alcohol amine when the amount of other raw materials is within the above-mentioned range, if the amount of alcohol amine is less than 20 parts by weight, the humic acid extraction rate will be reduced; if the amount of alcohol amine is more than 50 parts by weight, it will As a result, there are too many bubbles in the humic acid liquid, fine impurities are mixed in the humic acid liquid, and the purity of the extracted humic acid liquid is reduced; therefore, the amount of alcohol amine is 20-50 parts by weight is suitable, preferably 28-42 parts by weight It is more preferably 30 to 36 parts by weight.
- the amount of potassium citrate is less than 5 parts by weight, it will have no obvious effect on improving the extraction rate of humic acid; if the amount of potassium citrate is more than 10 parts by weight, then It will cause the humic acid organic extractant to be too alkaline; therefore, the amount of potassium citrate used is 5 to 10 parts by weight, preferably 6 to 9 parts by weight.
- the amount of potassium salicylate is less than 5 parts by weight, it will have a limited effect on enhancing the humic acid carrier; if the amount of potassium salicylate is more than 10 parts by weight, It will increase the alkalinity of the humic acid organic extractant and increase the cost; therefore, it is appropriate to use 5-10 parts by weight of potassium salicylate, preferably 6-9 parts by weight.
- the amount of other raw materials is within the stated range, if the amount of ethylene glycol is less than 5 parts by weight, the effect of improving the stability of the humic acid extract at low temperatures will be insignificant; if the amount of ethylene glycol is higher than 10 parts When the amount is high, the hydroxy acid may be precipitated as the storage time is extended; therefore, the amount of ethylene glycol is 5-10 parts by weight, preferably 6-9 parts by weight.
- the amount of water is suitable for 1000-2000 parts by weight, preferably 1200-1800 parts by weight Parts, more preferably 1400 to 1600 parts by weight.
- the weight ratio of alcohol amine, potassium citrate, potassium salicylate, ethylene glycol and water is 28-42: 6-9: 6-9: 6-9: 1200-1800.
- the solution obtained by stirring and dissolving at a rotation speed of 60 to 180 rpm is cooled to a temperature below 35 ° C, and its main purpose is to ensure the stability and quantitative preparation of the humic acid organic extractant.
- step A Add 100 parts by weight of the humic acid mineral raw material to 800 to 1500 parts by weight of the humic acid organic extractant obtained in step A, and then gradually raise its temperature to 90 ° C under stirring, and keep it at this temperature for 40 to 60 minutes, Next, it was cooled to room temperature, centrifuged, and the precipitate was discarded to obtain the humic acid extract.
- the humic acid mineral raw material is weathered coal or lignite.
- Weathered coal is the product of the surface or shallow layer of lignite, bituminous coal and anthracite coal which has been subjected to a combination of atmospheric, sunlight, rain and snow, groundwater and mineral erosion for a long time.
- the total content of weathered coal humic acid is generally 30 to 70%, and the highest can reach more than 80%.
- Lignite is the mineral coal with the lowest coalification degree, a brownish black, dull low-grade coal between peat and bituminous coal.
- weathered coal or lignite is crushed by using existing conventional crushing equipment, and humic acid mineral raw materials with a particle size of 150 to 300 mesh are collected to prepare a humic acid extract.
- the humic acid mineral raw material is 100 parts by weight
- the amount of the humic acid organic extractant is less than 800 parts by weight, it will cause the liquid to be thick and it is difficult to perform subsequent centrifugal treatment; if the amount of the humic acid organic extractant is higher than 1500 The part by weight will lead to high water content of the humic acid extract, which will affect the application of the humic acid synergistic carrier in urea. Therefore, it is appropriate that the amount of humic acid organic extractant is 800-1500 parts by weight.
- the temperature of the mixture of the humic acid mineral raw material and the humic acid organic extractant is gradually raised to 90 ° C with stirring at a rotation speed of 100 to 200 rpm, and maintained at this temperature for 40 to 60 min. It is undesirable that the extraction temperature and extraction time exceed the above range. If the extraction time is shorter than 40min, the extraction of humic acid is incomplete, resulting in loss of humic acid; if the extraction time exceeds 60min, the energy consumption and cost of humic acid extraction increase. Therefore, the extraction time of humic acid is 40 ⁇ 60min is feasible.
- the extract cooled to room temperature is centrifuged at a rotation speed of 1000 to 5000 rpm for 5 to 30 minutes using a centrifuge.
- the centrifuge is a product currently on the market, for example, a product sold by Shanghai Centrifuge Machinery Research Institute Co., Ltd. under the trade name of two-phase separation decanter sedimentation centrifuge.
- benzene carboxylic acid undergoes a grafting reaction with the humic acid in the humic acid extract obtained in step B, so further Increasing the type and number of acidic functional groups of humic acid, its purpose is to react with the amino group in the ammonium phosphate molecule to bind more tightly and delay the decomposition rate of ammonium phosphate in the soil.
- the benzene carboxylic acid is benzoic acid, phenylacetic acid, salicylic acid or acetylsalicylic acid; they are all products currently on the market, for example, sold by Jiangsu Shunfeng Chemical Co., Ltd. under the trade name of benzoic acid Products, products sold by Shandong Xinhua Longxin Chemical Co., Ltd. under the trade name of industrial salicylic acid, and products sold by Zhengzhou Jiahong Chemical Co., Ltd. under the trade name of acetylsalicylic acid.
- Sulfonic acid is a type of organic compound formed by the connection of sulfo groups and hydrocarbon groups (including aryl groups). It can enhance the water solubility of humic acid and its chelating ability with metal ions.
- the sulfonic acid is benzenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid or aminoethanesulfonic acid, which are all products currently on the market, for example, sold by Shanghai Yihe Biotechnology Co., Ltd. under the trade name benzenesulfonic acid Products, products sold by Shanghai Gaoming Chemical Co., Ltd. under the trade name of 2-naphthalenesulfonic acid, products sold by Wuhan Hyde Chemical Development Co., Ltd. under the trade name of methanesulfonic acid, and products sold by Jiangsu Caiwei Biological Technology Co., Ltd. The product sold under the name ⁇ -aminoethanesulfonic acid.
- the amount of other raw materials when the amount of other raw materials is within the range, if the amount of benzene carboxylic acid is less than 10 parts by weight, the increase of benzene carboxyl functional group will be low; if the amount of benzene carboxylic acid is more than 20 parts by weight, it will cause Partial humic acid precipitation; therefore, it is appropriate to use 10 to 20 parts by weight of benzenecarboxylic acid;
- the amount of other raw materials is within the range, if the amount of sulfonic acid is less than 5 parts by weight, the effect of increasing the water solubility of humic acid will be insignificant; if the amount of sulfonic acid is more than 10 parts by weight, the cost will increase too much; therefore ,
- the amount of benzene carboxylic acid is suitable for 5 to 10 parts by weight;
- the amount of other raw materials is within the range, if the amount of polyethylene glycol is less than 0.02 parts by weight, the grafting effect is not ideal due to low dispersibility; if the amount of polyethylene glycol is more than 0.05 parts by weight, it will affect Grafting effect; therefore, it is feasible to use benzenecarboxylic acid in an amount of 0.02 to 0.05 parts by weight;
- the amount of other raw materials is within the range, if the amount of dicumyl peroxide is less than 2 parts by weight, it will result in low grafting efficiency; if the amount of dicumyl peroxide is more than 3 parts by weight, it will cause reaction Too fast; therefore, the amount of dicumyl peroxide is 2 to 3 parts by weight is appropriate;
- This reaction is carried out at a temperature of 100 ° C for 60 to 120 min. If the reaction time is shorter than 60 min, the stability of the combination of benzene carboxylic acid, sulfonic acid and humic acid is insufficient; if the reaction time is longer than 120 min, the energy consumption increases significantly. Therefore, the reaction time of 60 ⁇ 120min is feasible.
- Polyoxyethylene ether has both resin and nonionic surfactant properties in the present invention. It can be used as a stationary phase to further slow down and reduce the contact between metal ions and ammonium phosphate in the soil solution.
- Superphosphoric acid is a mineral acid containing phosphoric acid and several polyphosphoric acids. It has a strong chelating ability to impurity metal ions. Therefore, it can not only adjust the pH of the system, but also chelate the calcium and Magnesium plasma enhances the stability of the humic acid synergistic carrier.
- the amount of polyoxyethylene ether is 2 to 6 parts by weight. If the amount of polyoxyethylene ether is less than 2 parts by weight, the dispersion and penetration properties are not obvious; if the amount of polyoxyethylene ether is higher than 6 parts by weight, the viscosity of the synergistic carrier is too high; therefore, the amount of polyoxyethylene ether is 2 to 6 parts by weight is appropriate.
- the solution is cooled to a temperature of 10-40 ° C.
- the concentration of the superphosphate solution is 1 to 5 mol / L.
- the existing production process of ammonium phosphate and the equipment used can be referred to "Modern Phosphorus Chemical Technology and Application", 2013, Chemical Industry Press.
- the amount of the humic acid synergistic carrier is 10 to 100 parts by weight. If this amount is less than 10 parts by weight, the effect of reducing phosphorus fixation is not significant; if this amount is higher than 100 parts by weight, the water content of the ammonium phosphate is too high, increasing drying Process pressure.
- ammonium phosphate prepared according to the method for preparing ammonium phosphate provided by the present invention described above and the application of the ammonium phosphate in any of the following and products containing the ammonium phosphate also belong to the protection scope of the present invention:
- the crops may be various crops, such as wheat.
- the product may specifically be fertilizer.
- the present invention is further described below in conjunction with specific embodiments, but the present invention is not limited to the following embodiments.
- the methods are conventional methods unless otherwise specified.
- the raw materials can be obtained from open commercial sources.
- the humic acid mineral raw material in the following examples is weathered coal or lignite.
- Weathered coal is the product of the surface or shallow layer of lignite, bituminous coal and anthracite coal which has been subjected to a combination of atmospheric, sunlight, rain and snow, groundwater and mineral erosion for a long time.
- the total content of weathered coal humic acid is generally 30 to 70%, and the highest can reach more than 80%.
- Lignite is the mineral coal with the lowest coalification degree, a brownish black, dull low-grade coal between peat and bituminous coal.
- Example 1 Preparation of ammonium phosphate containing humic acid synergistic carrier suitable for alkaline soil
- Step A Add 100 parts by weight of weathered coal humic acid mineral raw material with a particle size of 150 mesh to 1250 parts by weight of the organic extract of humic acid obtained in Step A, and then gradually raise its temperature to 90 ° C under stirring at 100 rpm, and Maintain at this temperature for 40 min, then cool to room temperature, centrifuge at 3000 rpm for 10 min, discard the precipitate, and obtain the humic acid extract;
- step C 70 parts by weight of the humic acid synergistic carrier obtained in step C is added to 1000 parts by weight of phosphoric acid washing solution, and reacted with liquid ammonia in a tubular reactor to obtain the humic acid-containing Ammonium phosphate as a synergistic carrier.
- Example 2 Preparation of ammonium phosphate containing humic acid synergistic carrier suitable for alkaline soil
- step A Add 100 parts by weight of lignite humic acid mineral raw material with a particle size of 200 mesh to 800 parts by weight of the humic acid organic extractant obtained in step A, and then gradually raise its temperature to 90 ° C under stirring at a rotation speed of 130 rpm. Maintain the temperature for 48 min, then cool to room temperature, centrifuge at 1000 rpm for 60 min, discard the precipitate, and obtain the humic acid extract;
- humic acid synergistic carrier obtained in step C 10 parts by weight of the humic acid synergistic carrier obtained in step C is added to 1000 parts by weight of phosphoric acid washing solution, and reacted with liquid ammonia in a tubular reactor to obtain the humic acid Ammonium phosphate as a synergistic carrier.
- Example 3 Preparation of ammonium phosphate containing humic acid synergistic carrier suitable for alkaline soil
- step A Add 100 parts by weight of lignite humic acid mineral raw material with a particle size of 250 mesh to 1500 parts by weight of the organic extract of humic acid obtained in step A, and then gradually increase its temperature to 90 ° C under stirring at 180 rpm, and Maintain the temperature for 60 min, then cool to room temperature, centrifuge at 1600 rpm for 42 min, discard the precipitate, and obtain the humic acid extract;
- humic acid synergistic carrier obtained in step C 100 parts by weight of the humic acid synergistic carrier obtained in step C is added to 1000 parts by weight of phosphoric acid washing solution, and reacted with liquid ammonia in a tubular reactor to obtain the humic acid-containing Ammonium phosphate as a synergistic carrier.
- Example 4 Preparation of ammonium phosphate containing humic acid synergistic carrier suitable for alkaline soil
- step A Add 100 parts by weight of weathered coal humic acid mineral raw material with a particle size of 300 mesh to 1050 parts by weight of the organic extract of humic acid obtained in step A, and then gradually increase its temperature to 90 ° C under stirring at 200 rpm, and Maintain it at this temperature for 55 minutes, then cool to room temperature, centrifuge at 2400 rpm for 26 minutes, and discard the precipitate to obtain the humic acid extract;
- step C 40 parts by weight of the humic acid synergistic carrier obtained in step C is added to 1000 parts by weight of phosphoric acid washing solution, and reacted with liquid ammonia in a tubular reactor to obtain the humic acid-containing Ammonium phosphate as a synergistic carrier.
- Test Example 1 Comparison of soil pH and available phosphorus of humic acid ammonium phosphate fertilizer in the present invention with commercially available ammonium phosphate
- humic acid ammonium phosphate a commercially available ammonium phosphate (manufactured by Guizhou Kai Phosphorus Group, P 2 O 5 content 46%) was treated in the same manner to obtain a cubic sample of ammonium phosphate.
- Test procedure Place the control sample P of tetrahedral ammonium phosphate and the square ammonium humic acid ammonium phosphate A, B and C in calcareous Chao soil (Dezhou, Shandong) with a water content of 18% by weight, and compact the soil to a bulk density of 1.3, Incubate at a temperature of 25 ⁇ 2 ° C for 12 hours. After the cultivation is completed, cut the soil 1.5-2.0cm, 1.0-1.5cm, 0.5-1.0cm, 0-0.5cm from the edge of the cube of ammonium phosphate with a blade. According to (Lu Rukun. "Analysis Methods of Soil Agricultural Chemistry". Beijing: China Agricultural Science and Technology Press, 2000.) standard analysis method, test the pH and available phosphorus content in the ammonium phosphate fertilizer soil. The test results are listed in Table 1.
- Table 1 Test results of soil pH and available phosphorus content in the fertilizer soil of ammonium humate of the present invention and commercially available ammonium phosphate
- Fertilization is the initial stage of fertilizer conversion and determines the later fixation process of ammonium phosphate.
- the test results show that the humic acid synergistic carrier prepared by the present invention can significantly reduce the soil pH of the ammonium phosphate fertilizer, especially the soil pH within 1 cm of the fertilizer, and the reduction range is 0.3 to 1.4 pH units, that is, the The H + concentration is increased by 3 to 14 times; the available phosphorus content in the soil within 2 cm of the fertilization is significantly higher than the commercially available ammonium phosphate treatment by 56.3%, indicating that the fixing rate of ammonium humate phosphate of the present invention is significantly slowed down.
- Test Example 2 Effect of the ammonium humate phosphate of the present invention on the form of soil inorganic phosphorus
- Example 1 Put the humic acid ammonium phosphate prepared in Example 1 and the commercially available ammonium phosphate on the principle of equal-quantity fertilizer phosphorus (P 2 O 5 0.30g / kg air-dried soil) into the principle design test, and test fertilizers (U, A, B, C) They were mixed with 100g of air-dried test soil (calcareous Chao soil, Dezhou, Shandong) that had passed through a 2mm sieve, and filled into plastic culture cups. Each treatment was repeated 4 times, and the water content of the soil was adjusted to 20% by weight using a water weighing method. The culture cup was sealed and placed in an artificial climate box at a temperature of 25 ° C to maintain humidity.
- Table 2 Inorganic phosphorus content of various forms in the soil on the 3rd, 42th and 97th days of cultivation
- Ca 2 -P stands for available phosphorus
- Ca 8 -P stands for potential available phosphorus pool, which means soil phosphorus supply capacity
- Al-P stands for phosphorus combined with aluminum
- Fe-P stands for phosphorus combined with iron
- Ca 10 -P stands for Phosphorus that is difficult to release from the soil.
- the Ca 2 -P of the humic acid ammonium phosphate-treated soil of the present invention is increased by 19%, 29% and 22% on average compared to the commercially available ammonium phosphate; Ca 8 -P increased by an average of 8%, 24%, and 14%, respectively. It can be seen from this that the ammonium humate phosphate of the present invention can not only reduce phosphorus fixation and increase the effective phosphorus content in the soil, but also supplement the effective phosphorus storage in the soil.
- Test Example 3 Effect of the ammonium humate phosphate of the present invention on wheat root growth and vigor
- Example 2 Using the ammonium humate phosphate prepared in Example 1, Example 2 and Example 4, a sand culture test was used to study the effect of the humic acid synergistic carrier of the present invention on the growth and vitality of wheat roots.
- the addition amount of these humic acid ammonium phosphates in Hogeland's nutrient solution was 0.2g / L, which were recorded as A, B, and C, respectively, and the control was 0g / L.
- Table 3 Effect of ammonium humate phosphate of the present invention on wheat root growth and vigor
- the absorption capacity of the crop root system is an important factor that determines the fertilizer utilization rate. From the results listed in Table 3, it can be seen that the fresh weight and vitality of the wheat root system treated with ammonium humate A, B, and C of the present invention are increased by 46.5% and 35.2%, respectively, on average compared with the control.
- Test Example 4 Effect of the present invention on ammonium humate phosphate on wheat yield and utilization rate of phosphate fertilizer
- test fertilizers were humic acid ammonium phosphate A, humic acid ammonium phosphate B and humic acid ammonium phosphate C prepared in Example 1, Example 2 and Example 4.
- Commercially available ammonium phosphate (produced by Guizhou Kaipho Group, P 2 O 5 content 46%, denoted as P) was used as a control sample.
- the experiment adopts the soil column cultivation method, selects PVC pipes with an inner diameter of 25cm and a height of 100cm, and buries the pipes in the soil.
- the upper mouth is 2cm higher than the ground to prevent the inflow of rainfall and runoff, and the bottom is not sealed. .
- Each soil column is filled with 55kg of soil.
- ammonium humate phosphate and commercially available ammonium phosphate of the present invention are designed with different phosphorus application levels based on the principle of equal total phosphorus input, and all are evenly mixed in the soil column of 0-30 cm; the nitrogen fertilizer and potassium fertilizer are designed according to the principle of sufficient supply, and the nitrogen fertilizer is urea ,
- the application rate is N0.2g / kg soil, potassium fertilizer is potassium sulfate, the application rate is K 2 O 0.3g / kg soil.
- Nitrogen fertilizer, phosphate fertilizer and potassium fertilizer are all mixed into the soil of 0-30 cm at one time as base fertilizer.
- the phosphorus application level was P 2 O 5 0.10 g / kg, with 8 repeats per treatment. Choose full and uniform seeds, sow 30 wheat seeds per column, and interplant seedlings at the seedling stage, leaving 12 plants per pot at the end.
- Phosphate fertilizer utilization rate (phosphorus treatment phosphorus absorption amount-non-phosphorus treatment phosphorus absorption amount) / phosphorus application amount ⁇ 100%].
- ammonium phosphate containing the humic acid synergistic carrier prepared by the present invention can significantly slow the fixation of ammonium phosphate in alkaline soil by affecting the pH of the fertilizer interface, improve the effectiveness of phosphorus, and can also supplement the soil effective phosphorus reservoir.
- the ammonium phosphate containing the humic acid synergistic carrier prepared by the invention can promote the growth of the crop root system, improve the root system vitality, and improve the utilization rate of phosphate fertilizer by enhancing nutrient absorption.
- ammonium phosphate product containing humic acid synergistic carrier of the present invention is rich in organic acidic functional groups, which can reduce the pH of granular ammonium phosphate fertilizer fertilizer by 0.3 to 1.4 units, and enhance the buffering property of the fertilizer fertilizer soil.
- the ammonium phosphate product containing the humic acid synergistic carrier of the present invention can reduce the fixation of phosphorus in the soil, the soil calcium diphosphorus and calcium octaphosphorus are increased by 23% and 16%, respectively, and activate the phosphorus and medium trace elements in the soil.
- the ammonium phosphate product containing the humic acid synergistic carrier of the present invention can increase the wheat root activity by more than 35%. Compared with the commercially available ammonium phosphate, the yield of the wheat treated with the humic acid ammonium phosphate of the present invention is increased by 12% compared with the commercially available ammonium phosphate Above, the utilization rate of phosphate fertilizer increased by 9 percentage points.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Fertilizers (AREA)
Abstract
Description
处理 | 籽粒产量(g/pot) | 磷肥利用率(%) |
P | 71.82 | 27.06 |
A | 78.54 | 33.42 |
B | 83.00 | 41.67 |
C | 81.09 | 34.12 |
Claims (14)
- 一种适于碱性土壤的含有腐植酸增效载体的磷铵制备方法,其特征在于该制备方法的步骤如下:A、腐植酸有机提取剂制备将20~50重量份醇胺、5~10重量份柠檬酸钾、5~10重量份水杨酸钾与5~10重量份乙二醇加到1000~2000重量份温度为60~70℃的水中,搅拌溶解,冷却,得到所述的腐植酸有机提取剂;B、腐植酸提取液制备将100重量份腐植酸矿物原料添加到800~1500重量份在步骤A得到的腐植酸有机提取剂中,然后在搅拌下将其温度逐渐升至90℃,并在这个温度下保持40~60min,接着冷却至室温,离心分离,沉淀物弃去,得到所述的腐植酸提取液;C、腐植酸增效载体制备将10~20重量份苯羧酸、5~10重量份磺酸和0.02~0.05重量份聚乙二醇加入到100重量份在步骤B得到的腐植酸提取液中,加热至温度50℃,再加入2~3重量份过氧化二异丙苯,接着加热至温度100℃,在这个温度下反应60~120min,再加入2~6重量份聚氧乙烯醚,冷却,用过磷酸水溶液将其pH值调节至4.5~5.5,得到一种腐植酸增效载体;D、含腐植酸增效载体的磷铵制备在现有磷铵生产过程中,将10~100重量份步骤C得到的腐植酸增效载体加入到1000重量份磷酸洗涤液中,经在管式反应器中与液氨反应,得到所述含腐植酸增效载体的磷铵。
- 根据权利要求1所述的磷铵制备方法,其特征在于在步骤A中,所述的醇胺是一种或多种选自一乙醇胺、二乙醇胺、三乙醇胺或N-甲基二乙醇胺的醇胺。
- 根据权利要求1所述的磷铵制备方法,其特征在于在步骤A中,将在 转速60~180rpm的条件下搅拌溶解得到的溶液冷却至温度35℃以下。
- 根据权利要求1所述的磷铵制备方法,其特征在于在步骤A中,醇胺、柠檬酸钾、水杨酸钾、乙二醇与水的重量比是28~42:6~9:6~9:6~9:1200~1800。
- 根据权利要求1所述的磷铵制备方法,其特征在于在步骤B中,所述的腐植酸矿物原料是风化煤或褐煤,所述腐植酸矿物原料的粒度为150~300目。
- 根据权利要求1所述的磷铵制备方法,其特征在于在步骤B中,在转速1000~5000rpm的条件下离心分离5~30min。
- 根据权利要求1所述的磷铵制备方法,其特征在于在步骤C中,所述的苯羧酸是苯甲酸、苯乙酸、水杨酸或乙酰水杨酸。
- 根据权利要求1所述的磷铵制备方法,其特征在于在步骤C中,所述的磺酸是苯磺酸、萘磺酸、甲基磺酸或氨基乙磺酸。
- 根据权利要求1所述的磷铵制备方法,其特征在于在步骤C中,所述过磷酸水溶液的浓度是1~5mol/L。
- 根据权利要求1所述的磷铵制备方法,其特征在于在步骤C中,加入聚氧乙烯醚后将其溶液冷却至温度10~40℃。
- 权利要求1-10任一所述磷铵制备方法制备得到的磷铵。
- 权利要求11所述磷铵在如下任意一种中的应用:a、降低颗粒磷铵肥际pH值;b、增强肥际土壤的缓冲性;c、减少磷在土壤中的固定;d、活化土壤中的磷及中微量元素;e、提高土壤中钙二磷和钙八磷的含量;f、提高农作物小麦根系活力;g、提高农作物产量;h、提高磷肥利用率。
- 根据权利要求12所述的应用,其特征在于所述农作物为小麦。
- 含有权利要求11所述磷铵的产品。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2019376123A AU2019376123A1 (en) | 2018-11-09 | 2019-10-17 | Preparation method for ammonium phosphate containing humic acid synergistic carrier suitable for alkaline soil |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811328610.9 | 2018-11-09 | ||
CN201811328610.9A CN109438029A (zh) | 2018-11-09 | 2018-11-09 | 一种适于碱性土壤的含有腐植酸增效载体的磷铵制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020093847A1 true WO2020093847A1 (zh) | 2020-05-14 |
Family
ID=65552064
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2019/111586 WO2020093847A1 (zh) | 2018-11-09 | 2019-10-17 | 一种适于碱性土壤的含有腐植酸增效载体的磷铵制备方法 |
Country Status (3)
Country | Link |
---|---|
CN (1) | CN109438029A (zh) |
AU (2) | AU2019101744A4 (zh) |
WO (1) | WO2020093847A1 (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109438029A (zh) * | 2018-11-09 | 2019-03-08 | 中国农业科学院农业资源与农业区划研究所 | 一种适于碱性土壤的含有腐植酸增效载体的磷铵制备方法 |
CN117567197A (zh) * | 2023-11-03 | 2024-02-20 | 中化化肥有限公司 | 增效磷酸二铵及其制备方法 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS49123849A (zh) * | 1973-04-13 | 1974-11-27 | ||
CN1434006A (zh) * | 2002-01-21 | 2003-08-06 | 中国科学院山西煤炭化学研究所 | 一种长效腐植酸磷肥及其制备方法 |
CN101104667A (zh) * | 2007-06-14 | 2008-01-16 | 胜利油田长安控股集团有限公司 | 丙烯酸、腐殖酸与凹凸棒土共聚制备保水剂的方法 |
CN101328088A (zh) * | 2008-07-02 | 2008-12-24 | 缪应松 | 大颗粒腐植复混肥料、以及该肥料的制备方法 |
CN102701868A (zh) * | 2012-06-27 | 2012-10-03 | 中国农业科学院农业资源与农业区划研究所 | 一种改性腐植酸肥料增效剂及其生产方法与用途 |
CN103274798A (zh) * | 2013-06-17 | 2013-09-04 | 中国农业科学院农业资源与农业区划研究所 | 一种腐植酸增效磷铵及其制备方法 |
CN109369225A (zh) * | 2018-11-09 | 2019-02-22 | 中国农业科学院农业资源与农业区划研究所 | 一种适于碱性土壤的磷铵用腐植酸增效载体制备方法 |
CN109369291A (zh) * | 2018-11-09 | 2019-02-22 | 中国农业科学院农业资源与农业区划研究所 | 一种用于冬小麦或春玉米基肥的含有腐植酸增效载体的磷铵制备方法 |
CN109400347A (zh) * | 2018-11-09 | 2019-03-01 | 中国农业科学院农业资源与农业区划研究所 | 一种适于冬小麦或春玉米基肥的磷铵用腐植酸增效载体制备方法 |
CN109438029A (zh) * | 2018-11-09 | 2019-03-08 | 中国农业科学院农业资源与农业区划研究所 | 一种适于碱性土壤的含有腐植酸增效载体的磷铵制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108503430A (zh) * | 2018-04-24 | 2018-09-07 | 吴刚 | 一种腐殖酸系悬浮型液体肥料的制备方法 |
-
2018
- 2018-11-09 CN CN201811328610.9A patent/CN109438029A/zh not_active Withdrawn
-
2019
- 2019-10-17 WO PCT/CN2019/111586 patent/WO2020093847A1/zh active Application Filing
- 2019-10-17 AU AU2019101744A patent/AU2019101744A4/en not_active Ceased
- 2019-10-17 AU AU2019376123A patent/AU2019376123A1/en active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS49123849A (zh) * | 1973-04-13 | 1974-11-27 | ||
CN1434006A (zh) * | 2002-01-21 | 2003-08-06 | 中国科学院山西煤炭化学研究所 | 一种长效腐植酸磷肥及其制备方法 |
CN101104667A (zh) * | 2007-06-14 | 2008-01-16 | 胜利油田长安控股集团有限公司 | 丙烯酸、腐殖酸与凹凸棒土共聚制备保水剂的方法 |
CN101328088A (zh) * | 2008-07-02 | 2008-12-24 | 缪应松 | 大颗粒腐植复混肥料、以及该肥料的制备方法 |
CN102701868A (zh) * | 2012-06-27 | 2012-10-03 | 中国农业科学院农业资源与农业区划研究所 | 一种改性腐植酸肥料增效剂及其生产方法与用途 |
CN103274798A (zh) * | 2013-06-17 | 2013-09-04 | 中国农业科学院农业资源与农业区划研究所 | 一种腐植酸增效磷铵及其制备方法 |
CN109369225A (zh) * | 2018-11-09 | 2019-02-22 | 中国农业科学院农业资源与农业区划研究所 | 一种适于碱性土壤的磷铵用腐植酸增效载体制备方法 |
CN109369291A (zh) * | 2018-11-09 | 2019-02-22 | 中国农业科学院农业资源与农业区划研究所 | 一种用于冬小麦或春玉米基肥的含有腐植酸增效载体的磷铵制备方法 |
CN109400347A (zh) * | 2018-11-09 | 2019-03-01 | 中国农业科学院农业资源与农业区划研究所 | 一种适于冬小麦或春玉米基肥的磷铵用腐植酸增效载体制备方法 |
CN109438029A (zh) * | 2018-11-09 | 2019-03-08 | 中国农业科学院农业资源与农业区划研究所 | 一种适于碱性土壤的含有腐植酸增效载体的磷铵制备方法 |
Also Published As
Publication number | Publication date |
---|---|
AU2019376123A1 (en) | 2020-08-06 |
CN109438029A (zh) | 2019-03-08 |
AU2019101744A4 (en) | 2020-10-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2020093847A1 (zh) | 一种适于碱性土壤的含有腐植酸增效载体的磷铵制备方法 | |
CN106116926A (zh) | 一种瓜蒌育苗专用营养土及其制备方法 | |
CN109354546A (zh) | 一种改良盐碱地土壤的调理肥及其制备方法与应用 | |
CN111377780A (zh) | 一种天然钠基膨润土土壤改良剂及其制备方法 | |
CN112088607A (zh) | 一种盐碱地土壤的改良方法及其应用 | |
CN105237299A (zh) | 一种绿色环保水稻氮肥及其制备方法 | |
CN102511278A (zh) | 微生物肥沙生植物专用肥治沙技术 | |
CN106478300B (zh) | 一种降低水稻大米中镉含量的酸性土壤改良降镉肥 | |
CN105503332A (zh) | 一种双羧基耦合钙多肽及其制备方法和在延长草莓产果期方面的应用 | |
WO2020093893A1 (zh) | 一种具有减缓尿素转化的海藻酸增效载体的制备方法 | |
CN109180393A (zh) | 一种适于玉米追肥的含有海藻酸增效载体的颗粒尿素制备方法 | |
CN1807550A (zh) | 土壤保水剂及其制备方法 | |
CN104824621A (zh) | 一种中重度碱性硫酸盐盐碱地海芦笋中低钾植物盐的提取方法 | |
CN109369225A (zh) | 一种适于碱性土壤的磷铵用腐植酸增效载体制备方法 | |
CN111559938A (zh) | 一种用于干旱地区提高松树成活率的营养液及制备方法 | |
CN109180387A (zh) | 一种适于水稻追肥的含有海藻酸增效载体的颗粒尿素制备方法 | |
AU2020100430A4 (en) | Method for preparing synergistic carrier with alginic acid for slowing urea conversion | |
CN109354543A (zh) | 一种水溶性纳米生物炭基肥及其制备方法和应用 | |
CN109384586A (zh) | 一种适于玉米追肥的尿素用海藻酸增效载体制备方法 | |
CN109336684A (zh) | 一种适于玉米追肥的尿素用腐植酸增效载体制备方法 | |
CN109320379A (zh) | 一种适于碱性土壤的含有海藻酸增效载体的磷铵制备方法 | |
CN109336681A (zh) | 一种适于玉米追肥的含有腐植酸增效载体的颗粒尿素制备方法 | |
CN109180394A (zh) | 一种适于冬小麦追肥的含有海藻酸增效载体的颗粒尿素制备方法 | |
WO2020093977A1 (zh) | 一种促进尿素转化的腐植酸增效载体的制备方法 | |
CN109369291A (zh) | 一种用于冬小麦或春玉米基肥的含有腐植酸增效载体的磷铵制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19882949 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2019376123 Country of ref document: AU Date of ref document: 20191017 Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 19882949 Country of ref document: EP Kind code of ref document: A1 |