CN111592403A - Method for preparing humic acid urea fertilizer by using ball milling technology - Google Patents
Method for preparing humic acid urea fertilizer by using ball milling technology Download PDFInfo
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- CN111592403A CN111592403A CN202010440822.7A CN202010440822A CN111592403A CN 111592403 A CN111592403 A CN 111592403A CN 202010440822 A CN202010440822 A CN 202010440822A CN 111592403 A CN111592403 A CN 111592403A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
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- 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
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
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- 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
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
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- 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
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
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- 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
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
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- 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
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/12—Granules or flakes
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Abstract
The invention relates to the field of functional fertilizers, and particularly discloses a method for preparing a humic acid urea fertilizer by using a ball milling technology. The method provided by the invention has the advantages that the ball milling technology is utilized to accelerate the carboxyl activation of humic acid, the humic acid and urea are subjected to rapid amidation reaction in a ball mill, and long-acting humic acid urea with different release periods is obtained by controlling the reaction conditions.
Description
Technical Field
The invention relates to the technical field of functional fertilizers, in particular to a method for preparing a humic acid urea fertilizer by utilizing a ball milling technology.
Background
Improving nitrogen utilization of nitrogen fertilizer, especially urea, is one of the research hotspots in the field of plant nutrition today. The urease inhibitors such as hydroquinone, diamminephenylphosphate and the like which are used in the prior art have good inhibitory effect on urease activity, but are difficult to popularize in a large area due to residue and high price. In recent years, people find that the utilization rate of nitrogen can be improved by 5-23% generally by using the urea humic acid prepared from the high-molecular humic acid, and the urea humic acid has the advantages of wide source, low price, no pollution to soil and the like, so the urea humic acid has wide application prospect.
Humic acid comes from soil, and feedback soil fertilizer comes from the intrinsic properties of humic acid. At present, aiming at safety problems of soil, fertilizer, grain, environment and the like, the development direction of the fertilizer industry must be adjusted timely to establish a new soil-fertilizer harmony relationship. And humic acid is a bridge tie for connecting soil-fertilizer-plant nutrition as an operation warehouse of soil nutrition. The humic acid is combined with the nitrogen fertilizer, so that the loss of the nitrogen fertilizer can be reduced, and the utilization rate of the nitrogen fertilizer is improved; humic acid is combined with phosphate fertilizer, so that phosphorus can be activated, and the utilization rate of the phosphate fertilizer in the season is improved; the humic acid is combined with the potash fertilizer, can activate potassium and promote the absorption of potassium by crops. Humic acid plays roles of storing, protecting and synergizing medium elements through the actions of adsorption, chelation, complexation, ion exchange and the like, reduces the fixation of medium nutrient elements in soil, improves the nutrient utilization rate and promotes the absorption of crops. However, the humic acid and the existing fertilizer are directly compounded to obtain the long-acting slow release effect, and the slow release period is difficult to control, so that the crops cannot obtain required fertility in each growth period, and the crop yield is reduced.
The humic acid urea long-acting fertilizer is a fertilizer with long-acting slow release performance obtained by compounding humic acid and urea, wherein urea is slowly released mainly through a chemical process, so that the long-acting purpose is achieved. At present, humic acid urea has two types of direct compound type and chemical reaction type, the direct compound is to add urea directly into humic acid and to use functional groups on humic acid to complex with urea, thereby achieving the purpose of slow release and long acting, but the humic acid urea directly compounded has limited slow release effect because of limited complexing ability of humic acid. The chemical reaction type is that functional groups on humic acid and urea are subjected to chemical reaction, and the urea is slowly hydrolyzed through the generation of chemical bonds, so that the slow release effect is achieved. Therefore, attention is paid to improvement of a method for producing urea humate.
Chinese patent application No. 201210086696.5 discloses a humic acid urea and a preparation method thereof, which is prepared by firstly preparing a humic acid synergistic liquid, then adding the humic acid synergistic liquid into a urea melt liquid in the urea production process, and finally carrying out high tower cooling granulation on the mixture of the humic acid synergistic liquid and the urea melt liquid; the method has the advantages of complex process, high equipment requirement and troublesome post-drying treatment, and strong acid and strong alkali are needed for preparing the humic acid synergistic liquid, so that the damage to equipment is large. The Chinese patent application No. 201711319097.2 discloses a humic acid activation method and a device, the method comprises the steps of mixing a humic acid raw material with an activating agent, adding water, stirring, placing under high-temperature high-pressure saturated water vapor for steam curing, activating the humic acid by adopting a steam-pressing activation mode, achieving a good activation effect, alternately performing steam curing reaction, realizing continuous production of active humic acid, shortening the production period and improving the efficiency. But high temperature activation consumption and high equipment requirement.
In order to effectively improve the slow release effect of the urea humate, simplify the preparation process of the urea humate and promote the development and application of the urea humate, a novel preparation method of the urea humate is needed to be provided, and the aim of simply preparing the high-efficiency urea humate is further fulfilled.
Disclosure of Invention
Aiming at the problem of complicated process of the existing preparation process of the humic acid urea, the invention provides a method for preparing the humic acid urea fertilizer by using a ball milling technology, so that the controlled and sustained release effect of the humic acid urea is improved, the preparation process is simplified, and the preparation cost is reduced.
In order to solve the problems, the invention adopts the following technical scheme:
a method for preparing a humic acid urea fertilizer by utilizing a ball milling technology comprises the steps of mixing and grinding humic acid, a carboxyl activating agent and a grinding aid to obtain carboxyl activated humic acid, then adding urea and oxalic acid to grind to obtain a humic acid urea compound, and then spraying an adhesive to a disc granulator to granulate to obtain the humic acid urea fertilizer. The preparation method comprises the following steps:
(1) adding humic acid and a carboxyl activating agent into a planetary ball mill, then adding a grinding aid, and then carrying out grinding treatment to obtain carboxyl activated humic acid;
(2) adding urea into a planetary ball mill, mixing with carboxyl activated humic acid, carrying out ball milling treatment for a certain time, adding adipic acid, continuously grinding, and discharging to obtain a humic acid urea compound;
(3) adding the humic acid urea compound into a disc granulator, then spraying the adhesive through a spraying device and granulating to obtain the humic acid urea fertilizer, and realizing the preparation of the humic acid urea fertilizer by utilizing the ball milling technology.
Preferably, the carboxyl activating agent in step (1) is a mixture of N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
Further preferably, in the mixture, the mass ratio of the N-hydroxysuccinimide to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 1-2: 1-2.
Preferably, the grinding aid in the step (1) is one of medical stone and calcite; without removal, as part of the fertilizer.
Preferably, the rotation speed of the grinding treatment in the step (1) is 300-.
Preferably, in the step (1), in the preparation of the carboxyl activated humic acid, the mass ratio of the humic acid to the carboxyl activating agent to the grinding aid is 15-25: 0.5-1: 0.3-0.8.
Preferably, the rotation speed of the mixing ball mill in the step (2) is 300-.
Preferably, in the preparation of the humic acid-urea compound in the step (2), the mass ratio of urea to carboxyl activated humic acid to adipic acid is 10-20: 5-10: 1-2.
Preferably, the adhesive in the step (3) is polyvinyl alcohol glue solution with the mass concentration of 15%.
Preferably, in the preparation of the humic acid urea fertilizer in the step (3), the mass ratio of the humic acid urea compound to the adhesive is 5-10: 0.1-0.3.
Preferably, the particle size of the humic acid urea fertilizer in the step (3) is 2-4 mm.
In the known urea humate, the activity of urease in soil can be inhibited by the humic acid, the hydrolysis speed of the urea in the soil is reduced, the utilization rate of a nitrogen fertilizer is improved, and the fertilizer efficiency of the urea can be improved by the humic acid through improving the soil structure, so that the urea humate has a very wide application prospect. Wherein, the chemical reaction type humic acid urea has good sustained and controlled release effects, but the development and application are restricted due to the complex preparation process. The present invention utilizes ball milling process creatively to solve the above problems effectively.
Firstly, adding humic acid, a hydroxyl activating agent and a grinding aid into a ball mill for grinding to prepare carboxyl activated humic acid. The hydroxyl activating agent can activate carboxyl on humic acid, can perform amidation reaction with amino of urea at low temperature, and improves the slow release performance of the fertilizer. Meanwhile, when the ball milling process is used for activating the hydroxyl groups of humic acid, the interaction between the humic acid and the activating agent can be accelerated by the friction force and the extrusion force in the ball milling process, so that the hydroxyl activation is accelerated, the grinding effect of the humic acid and the activating agent can be further improved by adding grinding aids (medical stone and calcite) with high hardness, the grinding aids are mineral fertilizer raw materials, and the grinding aids are directly used in soil without being removed by a special process after being used, so that the preparation process is simplified.
Further, the carboxyl activated humic acid, urea and adipic acid are sequentially added into a ball mill for continuous grinding, the activated humic acid and the urea can carry out amidation and other complex chemical reactions in the ball mill by controlling the grinding speed and temperature, and the urea and the humic acid can rapidly react by extrusion and friction in the ball mill, so that the production period is shortened, and the process is simplified. The whole reaction process can avoid the introduction of water, and the prepared humic acid urea can be slowly hydrolyzed by the introduction of chemical bonds, so that the long-acting release is realized, and the good sustained and controlled release effect is realized. Meanwhile, by controlling the consumption of adipic acid, the content of amido bond in the urea humate can be effectively controlled, and the release period of the urea humate can be better controlled, so that the long-acting urea humate with different release periods can be obtained.
Furthermore, spraying the humic acid urea compound into a disc granulator for granulation. The polyvinyl alcohol is nontoxic and tasteless, has good water solubility and good biodegradability and adhesion, so that the polyvinyl alcohol is selected as a binding agent for granulation of the urea humic acid to obtain the urea humic acid compound fertilizer with a specific particle size. The reaction process and conditions of the whole preparation process are simple and feasible, and the raw materials are easy to obtain, so that the aim of preparing the urea humate by using the simple process is fulfilled.
The application of the existing humic acid urea is limited due to the problem of complicated preparation process. In view of the above, the invention provides a method for preparing humic acid urea fertilizer by using a ball milling technology, which comprises the steps of adding humic acid and a carboxyl activating agent into a planetary ball mill, continuously adding a grinding aid, and carrying out grinding treatment to obtain carboxyl activated humic acid; adding urea into a planetary ball mill, mixing the urea with carboxyl activated humic acid, ball-milling for a certain time, and continuously adding adipic acid for grinding to obtain a humic acid urea compound; adding the humic acid urea compound into a disc granulator, spraying an adhesive through a spraying device for granulation, and obtaining the humic acid urea fertilizer. The method provided by the invention has the advantages that the ball milling technology is utilized to accelerate the carboxyl activation of humic acid, the humic acid and urea are subjected to rapid amidation reaction in a ball mill, and long-acting humic acid urea with different release periods is obtained by controlling the reaction conditions.
Compared with the prior art, the invention provides a method for preparing the humic acid urea fertilizer by utilizing the ball milling technology, which has the outstanding characteristics and excellent effects that:
1. according to the invention, the activation of carboxyl in humic acid by a carboxyl activating agent is accelerated by utilizing a ball milling technology, the amidation reaction is carried out on the carboxyl and urea in a ball mill, and the urea and the humic acid are quickly reacted by extrusion and friction force in the ball mill, so that the production period is reduced, the process is simplified, and the long-acting humic acid urea with different release periods is obtained by controlling the reaction conditions.
2. According to the invention, the activated carboxyl on humic acid and the amino of urea are subjected to amidation reaction at low temperature, so that the obtained humic acid urea can be released for a long time, and meanwhile, the content of amido bond in the humic acid urea can be effectively controlled by controlling the consumption of adipic acid, thereby better controlling the release period of the compound fertilizer.
3. The production process is simple, and the obtained humic acid urea can be released in a long-acting manner and is suitable for large-scale production.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Adding 20kg of humic acid and 0.8kg of carboxyl activating agent into a planetary ball mill, wherein the carboxyl activating agent is N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride according to the mass ratio of 1: 1, adding 0.6kg of medical stone, and then grinding at 350rpm for 2.5h to obtain carboxyl activated humic acid;
(2) adding 15kg of urea into a planetary ball mill, mixing and ball-milling with 7.5kg of carboxyl activated humic acid for 2h, adding 1.5kg of adipic acid, continuously grinding at the rotation speed of 350rpm of the mixing and ball-milling and the grinding temperature of 18 ℃, continuously grinding for 1h, and discharging to obtain a humic acid-urea compound;
(3) adding 8kg of humic acid urea compound into a disc granulator, then spraying 0.2kg of polyvinyl alcohol glue solution with the mass concentration of 15% through a spraying device, and granulating to obtain the humic acid urea fertilizer, wherein the average particle size is 3mm, and the preparation of the humic acid urea fertilizer by using a ball milling technology is realized.
Example 2
(1) Adding 22kg of humic acid and 0.6kg of carboxyl activating agent into a planetary ball mill, wherein the carboxyl activating agent is N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride according to the mass ratio of 1.2: 1.8, adding 0.4kg of calcite into the mixture, and then carrying out grinding treatment at the rotating speed of 320rpm for 3h to obtain carboxyl activated humic acid;
(2) adding 18kg of urea into a planetary ball mill, mixing and ball-milling the urea with 6kg of carboxyl activated humic acid for 2 hours, adding 1.2kg of adipic acid, continuously grinding at the rotation speed of 320rpm of the mixing and ball-milling, at the grinding temperature of 15 ℃, continuously grinding for 1 hour, and discharging to obtain a humic acid urea compound;
(3) adding 9kg of humic acid urea compound into a disc granulator, then spraying 0.15kg of polyvinyl alcohol glue solution with the mass concentration of 15% through a spraying device, and granulating to obtain the humic acid urea fertilizer, wherein the average particle size is 2.5mm, and the preparation of the humic acid urea fertilizer by using a ball milling technology is realized.
Example 3
(1) Adding 18kg of humic acid and 0.9kg of carboxyl activating agent into a planetary ball mill, wherein the carboxyl activating agent is N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride according to the mass ratio of 1.8: 1.2, adding 0.7kg of medical stone into the mixture, and then carrying out grinding treatment at the rotating speed of 380rpm for 2h to obtain carboxyl activated humic acid;
(2) adding 12kg of urea into a planetary ball mill, mixing and ball-milling with 9kg of carboxyl activated humic acid for 2h, adding 1.8kg of adipic acid, continuously grinding at the rotation speed of 380rpm of mixed ball milling and the grinding temperature of 20 ℃, continuously grinding for 0.5h, and discharging to obtain a humic acid-urea compound;
(3) adding 6kg of humic acid urea compound into a disc granulator, then spraying 0.15kg of polyvinyl alcohol glue solution with the mass concentration of 15% through a spraying device, and granulating to obtain the humic acid urea fertilizer, wherein the average particle size is 3.5mm, and the preparation of the humic acid urea fertilizer by using a ball milling technology is realized.
Example 4
(1) Adding 25kg of humic acid and 0.5kg of carboxyl activating agent into a planetary ball mill, wherein the carboxyl activating agent is N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride according to the mass ratio of 1: 2, adding 0.3kg of medical stone and calcite into the mixture, and then carrying out grinding treatment at the rotating speed of 300rpm for 3 hours to obtain carboxyl activated humic acid;
(2) adding 20kg of urea into a planetary ball mill, mixing and ball-milling the urea with 5kg of carboxyl activated humic acid for 2 hours, adding 1kg of adipic acid, continuously grinding at the rotation speed of 300rpm of mixing and ball-milling and the grinding temperature of 10 ℃, continuously grinding for 1 hour, and discharging to obtain a humic acid urea compound;
(3) adding 10kg of humic acid urea compound into a disc granulator, then spraying 0.1kg of polyvinyl alcohol glue solution with the mass concentration of 15% through a spraying device, and granulating to obtain the humic acid urea fertilizer, wherein the average particle size is 2mm, and the preparation of the humic acid urea fertilizer by using a ball milling technology is realized.
Example 5
(1) Adding 15kg of humic acid and 1kg of carboxyl activating agent into a planetary ball mill, wherein the carboxyl activating agent is N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride according to the mass ratio of 2: 1, adding 0.8kg of medical stone, and then grinding at the rotation speed of 400rpm for 2h to obtain carboxyl activated humic acid;
(2) adding 10kg of urea into a planetary ball mill, mixing and ball-milling with 10kg of carboxyl activated humic acid for 2h, adding 2kg of adipic acid, continuously grinding at the rotation speed of 400rpm of mixing and ball-milling and the grinding temperature of 25 ℃, continuously grinding for 0.5h, and discharging to obtain a humic acid-urea compound;
(3) adding 5kg of humic acid urea compound into a disc granulator, then spraying 0.3kg of polyvinyl alcohol glue solution with the mass concentration of 15% through a spraying device, and granulating to obtain the humic acid urea fertilizer, wherein the average particle size is 4mm, and the preparation of the humic acid urea fertilizer by using a ball milling technology is realized.
Comparative example 1
(1) Adding 20kg of humic acid and 0.1kg of carboxyl activating agent into a planetary ball mill, wherein the carboxyl activating agent is N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride according to the mass ratio of 1: 1, adding 0.6kg of medical stone, and then grinding at 350rpm for 2.5h to obtain carboxyl activated humic acid;
(2) adding 15kg of urea into a planetary ball mill, mixing and ball-milling with 7.5kg of carboxyl activated humic acid for 2h, adding 1.5kg of adipic acid, continuously grinding at the rotation speed of 350rpm of the mixing and ball-milling and the grinding temperature of 18 ℃, continuously grinding for 1h, and discharging to obtain a humic acid-urea compound;
(3) adding 8kg of humic acid urea compound into a disc granulator, then spraying 0.2kg of polyvinyl alcohol glue solution with the mass concentration of 15% through a spraying device, and granulating to obtain the humic acid urea fertilizer, wherein the average particle size is 3mm, and the preparation of the humic acid urea fertilizer by using a ball milling technology is realized.
Comparative example 1 the amount of the carboxyl activating agent was reduced to have an effect on the activation of humic acid and thus on the rapid amidation of urea, and the fertilizer was poor in the long-lasting type.
Comparative example 2
(1) Adding 20kg of humic acid and 0.8kg of carboxyl activating agent into a planetary ball mill, wherein the carboxyl activating agent is N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride according to the mass ratio of 1: 1, adding 0.6kg of medical stone, and then grinding at a rotation speed of 100rpm for 30min to obtain carboxyl activated humic acid;
(2) adding 15kg of urea into a planetary ball mill, mixing and ball-milling with 7.5kg of carboxyl activated humic acid for 2h, adding 1.5kg of adipic acid, continuously grinding at the rotation speed of 350rpm of the mixing and ball-milling and the grinding temperature of 18 ℃, continuously grinding for 1h, and discharging to obtain a humic acid-urea compound;
(3) adding 8kg of humic acid urea compound into a disc granulator, then spraying 0.2kg of polyvinyl alcohol glue solution with the mass concentration of 15% through a spraying device, and granulating to obtain the humic acid urea fertilizer, wherein the average particle size is 3mm, and the preparation of the humic acid urea fertilizer by using a ball milling technology is realized.
Comparative example 2 the ball milling speed and the ball milling time were reduced, and the activation effect was also affected.
Testing the slow release performance of the humic acid urea fertilizer:
testing the slow release performance: the fertilizers of examples 1-5 and comparative examples 1-2 were tested for sustained release performance with reference to the method and requirements of national Standard for sustained release fertilizers (GB/T23348-2009). The specific method comprises the following steps: 10g of the fertilizer obtained in the examples and the comparative examples are respectively taken and put into small bags made of 100-mesh nylon gauze, after sealing, the small bags are respectively placed into 250mL glass bottles, 200 mL of water is added, the bottles are covered and sealed, the cultivation is carried out in a constant temperature incubator at 25 ℃, the sampling time is 1d, 3d, 5d, 7d, 14d, 28d and 42d, the upper part and the lower part are inverted three times during sampling, after the nitrogen content is determined by sampling each time, 200 mL of distilled water is added into the original glass bottle again, the bottles are covered and sealed, then the cultivation is carried out in a biochemical incubator, and then the nitrogen release content is determined by using a boric acid solution and a sulfuric acid standard titration solution. The test results are shown in table 1;
table 1:
as can be seen from Table 1, the humic acid urea prepared by activating humic acid and urea in the comparative example has good slow release effect, and the process is simpler and more efficient. However, the urea humate obtained in the comparative examples 1-2 still has a slow release effect, and the test results show that the urea release amount in the early stage is high, and the sustained release time is short.
Claims (10)
1. A method for preparing a humic acid urea fertilizer by utilizing a ball milling technology is characterized in that the preparation method of the humic acid urea fertilizer is that humic acid, a carboxyl activating agent and a grinding aid are mixed and ground to obtain carboxyl activated humic acid, then urea and oxalic acid are added to be ground to obtain a humic acid urea compound, and then an adhesive is sprayed in a disc granulator to granulate to obtain the humic acid urea fertilizer; the preparation method comprises the following steps:
(1) adding humic acid and a carboxyl activating agent into a planetary ball mill, then adding a grinding aid, and then carrying out grinding treatment to obtain carboxyl activated humic acid;
(2) adding urea into a planetary ball mill, mixing with carboxyl activated humic acid, carrying out ball milling treatment for a certain time, adding adipic acid, continuously grinding, and discharging to obtain a humic acid urea compound;
(3) adding the humic acid urea compound into a disc granulator, then spraying the adhesive through a spraying device and granulating to obtain the humic acid urea fertilizer, and realizing the preparation of the humic acid urea fertilizer by utilizing the ball milling technology.
2. The method for preparing the humic acid urea fertilizer by using the ball milling technology as claimed in claim 1, wherein the carboxyl activating agent in the step (1) is a mixture of N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, and the mass ratio of the N-hydroxysuccinimide to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in the mixture is 1-2: 1-2.
3. The method for preparing the urea humate fertilizer by using the ball milling technology as claimed in claim 1, wherein the grinding aid in the step (1) is one of medical stone and calcite.
4. The method for preparing urea humate fertilizer by ball milling technique as claimed in claim 1, wherein the rotation speed of the grinding treatment in step (1) is 300-400rpm, and the grinding time is controlled to be 2-3 h.
5. The method for preparing the humic acid urea fertilizer by using the ball milling technology as claimed in claim 1, wherein in the step (1) of preparing the carboxyl activated humic acid, the mass ratio of the humic acid to the carboxyl activating agent to the grinding aid is 15-25: 0.5-1: 0.3-0.8.
6. The method for preparing urea humate fertilizer by ball milling technique as claimed in claim 1, wherein the rotation speed of the mixing ball milling in step (2) is 300-400rpm, the milling temperature is 10-25 ℃, the oxalic acid is added after 1-3h of milling, and the milling is continued for 0.5-1 h.
7. The method for preparing the urea humate fertilizer by using the ball milling technology as claimed in claim 1, wherein in the preparation of the urea humate compound in the step (2), the mass ratio of urea to carboxyl-activated humic acid to adipic acid is 10-20: 5-10: 1-2.
8. The method for preparing the urea humate fertilizer by using the ball milling technology as claimed in claim 1, wherein the binder in the step (3) is a polyvinyl alcohol glue solution with a mass concentration of 15%.
9. The method for preparing the urea humate fertilizer by using the ball milling technology as claimed in claim 1, wherein in the step (3), the mass ratio of the urea humate compound to the binder is 5-10: 0.1-0.3.
10. The method for preparing the urea humate fertilizer by using the ball milling technology as claimed in claim 1, wherein the particle size of the urea humate fertilizer in the step (3) is 2-4 mm.
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| CN202010440822.7A CN111592403A (en) | 2020-05-22 | 2020-05-22 | Method for preparing humic acid urea fertilizer by using ball milling technology |
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| CN202010440822.7A CN111592403A (en) | 2020-05-22 | 2020-05-22 | Method for preparing humic acid urea fertilizer by using ball milling technology |
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2020
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Application publication date: 20200828 |