CN110950719A - Coated controlled release fertilizer and preparation method thereof - Google Patents
Coated controlled release fertilizer and preparation method thereof Download PDFInfo
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- CN110950719A CN110950719A CN201911038202.4A CN201911038202A CN110950719A CN 110950719 A CN110950719 A CN 110950719A CN 201911038202 A CN201911038202 A CN 201911038202A CN 110950719 A CN110950719 A CN 110950719A
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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
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/62—Carboxylic acid esters
- C12P7/625—Polyesters of hydroxy carboxylic acids
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Abstract
The invention belongs to the technical field of fertilizers, and particularly relates to a coated controlled-release fertilizer which comprises fertilizer particles and a coating coated on the surfaces of the fertilizer particles. The coated controlled-release fertilizer provided by the invention adopts the polyhydroxyalkanoate as the coating material, so that the coated controlled-release fertilizer has good biodegradability, biocompatibility and controlled-release effect. Moreover, the coated controlled-release fertilizer provided by the invention can also provide an organic carbon source for microorganisms in soil, improve the utilization rate of the fertilizer, and increase the fertility of the soil, thereby promoting the growth and development of plants.
Description
Technical Field
The invention belongs to the technical field of fertilizers, and particularly relates to a coated controlled-release fertilizer and a preparation method thereof.
Background
The coated controlled release fertilizer is an intelligent fertilizer capable of accurately controlling nutrient release. The fertilizer has flexible and changeable formula, and can regulate and control the dissolution and release of nutrients of the core fertilizer by adjusting the thickness and material properties of the coating, so that the fertilizer adapts to the nutrient characteristics of different plants, thereby achieving the purpose of improving the fertilizer efficiency. The invention and the utilization of the coated controlled release fertilizer not only improve the utilization rate of the fertilizer, but also reduce the pollution of chemical fertilizer to the environment.
The main components of the existing coating material come from petrochemical products, the high price of the petrochemical products causes the cost of the coated controlled-release fertilizer to be higher, and the coating material produced by the petrochemical products is not easy to degrade.
Polyhydroxyalkanoates (PHA) is a biopolymer material which has been developed rapidly for over 20 years. PHAs can be synthesized by microorganisms, are present in microbial cells, particularly bacterial cells, in large quantities, and serve as a storage material for carbon and energy within the body of the microorganisms. When the growth environment of the microorganism is lack of certain nutrient substances necessary for growth, such as nitrogen, phosphorus, magnesium and the like, and excessive carbon sources exist, the redox balance and energy and reducing equivalent balance in the bacteria body are unbalanced, and the bacteria need to store the excessive energy in the form of compounds, such as PHA; when the environment is deficient in a source of carbon and other nutrients are abundant, PHA can be degraded and reused as a source of carbon. PHA has biodegradability, biocompatibility, piezoelectricity, optical activity, and the like.
At present, the PHA industrialization variety has four generations. Typical representatives of the first generation of products are the homopolymer PHB (poly-3-hydroxybutyrate), the second generation of PHBV (poly-3-hydroxybutyrate/3-hydroxyvalerate copolymer), the third generation of PHBHHx (poly-3-hydroxybutyrate/3-hydroxyhexanoate copolymer), and the fourth generation of P34HB (poly-3-hydroxybutyrate/3-hydroxybutyrate copolymer).
Therefore, a coated controlled-release fertilizer with easily degradable residual membrane and good controlled-release effect is needed.
Disclosure of Invention
The invention aims to provide a coated controlled-release fertilizer with easily-degradable residual film and good controlled-release effect.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a coated controlled-release fertilizer comprising a fertilizer granule and a coating coated on the surface of the fertilizer granule, wherein the coating is made of a material comprising polyhydroxyalkanoate.
The polyhydroxyalkanoates currently commercially available can be used as a coating material for preparing the coated controlled release fertilizer of the present invention. Considering the degradation time of the coating, the present invention selects a polyhydroxylated lipid having a relatively short degradation timeThe monomer of the polyhydroxy fatty acid ester can be C3-C5Or an ester thereof. Through C3-C5The polyhydroxy fatty acid ester formed by polymerization of the fatty acid or the ester thereof is short-chain polyhydroxy fatty acid ester, and is more easily degraded by microorganisms. The degradation time required is short. The molecular weight of the polyhydroxyalkanoate is 5 x 104-2×107Da。
The polyhydroxyalkanoate of the present invention can be obtained by those skilled in the art through existing routes, and the present invention is not particularly limited herein. In view of the manufacturing cost, environmental protection and environmental friendliness of the coated controlled-release fertilizer, the polyhydroxyalkanoate may be cultured in municipal sludge by microorganisms to produce Polyhydroxyalkanoate (PHA), and the PHA is obtained after extraction. Specifically, the polyhydroxyalkanoate is prepared by a method comprising the following steps:
enriching and activating flora in aerobic activated sludge (obtained from aeration tank) by abundance-hunger mode, culturing at constant temperature of 150r/min and 35 deg.C with shaking table, and performing COD treatment<100mg/L is used as a mark for entering a hungry period, the time ratio of the abundant period to the hungry period is controlled to be 1:2-4, for example, 1:3, enriched seed liquid is obtained, the enriched seed liquid is centrifuged after each round is finished, and the flora obtained by centrifugation is used as the next round of inoculated strains; when the time of reaching the hunger stage and the COD change are stable for at least two periods, the flora is stable, and the domesticated flora is collected; the culture medium comprises the following components: 20mM sodium acetate; 4mM NH4Cl；0.33mM KH2PO4；0.2mM K2HPO4；0.4mM MgSO4；0.4mM CaCl2(ii) a 1ml/L trace element liquid and 20mg/L thiourea.
The pre-dehydrated sludge enters a thermal hydrolysis reaction system, and plate-frame dehydration is carried out to obtain filtrate;
taking the filtrate as a culture medium, inoculating the domesticated flora to the culture medium, and fermenting in a PHA fermentation system under the fermentation condition that the temperature is 30-40 ℃ and the ammonia nitrogen and Volatile Fatty Acid (VFAs) concentration in the culture medium is 8000-12000mg COD/L to obtain fermentation liquor;
extracting the Polyhydroxyalkanoate (PHA) from the fermentation broth, and grinding into PHA powder for later use.
In the present invention, the material for making the coating further comprises an emulsifier and a coating agent. The emulsifier is BS-12 and/or OP-10. The coating agent is at least one of dichloromethane, ethyl acetate and ethanol.
The amount of the polyhydroxyalkanoate can be selected by one skilled in the art depending on the desired release time of the coated controlled release fertilizer. Preferably, the mass ratio of the polyhydroxyalkanoate to the fertilizer granules is 1: 15-25. The release amount of nutrient substances required for the growth of crops is met.
The fertilizer granules in the coated controlled-release fertilizer provided by the invention can be any commercially available fertilizer granules, and preferably organic fertilizer granules. The nature and function of the fertilizer granules are not particularly limited in the present invention. Preferably, the fertilizer granules are prepared by dehydrating, granulating and drying urban domestic sludge subjected to anaerobic digestion. More preferably, the anaerobically digested municipal sewage sludge after PHA extraction is dewatered, granulated, and dried. When the urban domestic sludge is used as a fertilizer, the fertilizer contains rich nutrient resources such as nitrogen, phosphorus, potassium and the like, and has high nutrient salt content, so that the fertilizer is beneficial to plant growth, the coating can prevent the nutrient salt content in the urban domestic sludge from being rapidly released after the urban domestic sludge is directly applied to soil as the fertilizer and meets water, and risks such as groundwater pollution caused by seedling burning and excessive nutrient migration are avoided for plants with small body sizes such as flowers and plants.
In the manufacturing process of the fertilizer granules, the dehydration can adopt filtration dehydration or plate-and-frame dehydration.
In a second aspect, the present invention provides a method for preparing the above coated controlled release fertilizer, comprising the steps of:
mixing the polyhydroxyalkanoate, the emulsifier and a coating agent to form an emulsion;
and spraying the emulsion on the fertilizer particles, and drying to prepare the coated controlled-release fertilizer.
In a preferred embodiment of the present invention, the method further comprises: heating the emulsion to improve the solubility of PHA, accelerate the dissolution rate and improve the dissolution effect; the heating temperature is not higher than 40 ℃.
In the process of spraying the emulsion on the fertilizer granules, the emulsion can be sprayed and stirred at the same time, so that the fertilizer granules are uniformly coated by the emulsion, and uniform coatings are formed on the surfaces of the fertilizer granules.
The emulsifier can make the polyhydroxyalkanoate form a uniform emulsion in the emulsifier, so that the polyhydroxyalkanoate in the emulsifier is uniformly attached to the surface of the fertilizer granules, namely the surface of the fertilizer granules is coated with the polyhydroxyalkanoate, and the controlled release performance of the coated controlled release fertilizer is ensured. The emulsifier is BS-12 and/or OP-10.
The coating agent is not particularly limited in the present invention, and the polyhydroxyalkanoate is dissolved as much as possible to coat the surface of the fertilizer granule with polyhydroxyalkanoate uniformly. Preferably, the coating agent is at least one of dichloromethane, ethyl acetate and ethanol. More preferably, the coating agent is dichloromethane.
In a preferred embodiment of the present invention, the drying process is room temperature ventilation, or drying. And in the drying process, turning or shaking the fertilizer particles sprayed with the emulsion at preset time intervals, such as 3-5 minutes, wherein the turning and shaking particle size is mainly used in the turning and shaking process, so that the fertilizer particles are prevented from being crushed, and the release control performance of the coated controlled release fertilizer is ensured.
And (3) cooling the prepared coated controlled release fertilizer to room temperature, weighing, packaging and storing.
The coated controlled-release fertilizer provided by the invention adopts the polyhydroxyalkanoate as the coating material, so that the coated controlled-release fertilizer has good biodegradability, biocompatibility and controlled-release effect. Moreover, the coated controlled-release fertilizer provided by the invention can also provide an organic carbon source for microorganisms in soil, improve the utilization rate of the fertilizer, and increase the fertility of the soil, thereby promoting the growth and development of plants.
The coated controlled release fertilizer provided by the invention can be fully degraded by microorganisms, the controlled release performance completely conforms to the fertilizer requirement rule of plants, and the cost is low.
The coated controlled-release fertilizer provided by the invention adopts the municipal domestic sludge or the anaerobically digested municipal domestic sludge to prepare fertilizer granules, so that the environmental pollution is reduced, and the resource recycling is realized.
The method for coating the controlled release fertilizer is simple, has low cost and is beneficial to recycling resources.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
Preparation example 1
This preparation provides fertilizer granules. And (3) dehydrating, granulating and drying the anaerobic digestion product of the municipal domestic sludge by using a plate frame to prepare fertilizer granules.
Preparation example 2
The present preparation provides PHA. The process for producing PHA comprises the steps of:
enrichment and activation are carried out on flora by adopting a flourishing-hungry mode for strain domestication. Inoculating aerobic activated sludge from aeration tank into culture medium comprising carbon source, NP nutrition, microelement and thiourea, performing shake culture at constant temperature of 35 deg.C at 150r/min, and performing COD treatment<100mg/L is used as a mark for entering a hungry period, the time ratio of the abundant period to the hungry period is controlled to be 1:3, enriched seed liquid is obtained, the enriched seed liquid is centrifuged after each round is finished, and thalli obtained by centrifugation are used as the next round of inoculated strains; when the time to reach the starvation stage and the change of COD were stable for at least two cycles, the flora was considered to be stable and collected as the species for PHA batch experiments. The culture medium comprises the following components: 20mM sodium acetate; 4mM NH4Cl；0.33mM KH2PO4；0.2mM K2HPO4；0.4mMMgSO4；0.4mM CaCl2(ii) a 1ml/L trace element liquid, 20mg/L thiourea.
And (4) allowing the pre-dewatered sludge to enter a thermal hydrolysis reaction system, and performing plate-frame dewatering to obtain filtrate.
Taking the filtrate as a culture medium, inoculating the domesticated flora to the culture medium, and fermenting in a PHA fermentation system under the fermentation condition of 35 ℃ and the concentration of ammonia nitrogen and Volatile Fatty Acids (VFAs) in the culture medium of 10000mg COD/L to obtain fermentation liquor; extracting PHA product from fermentation liquor, grinding it into PHA powder for stand-by.
Example 1
This example provides a method of preparing a coated controlled release fertilizer. The method comprises the following steps:
3.000g of PHA powder prepared in preparation example 2, 18.00ml of methylene chloride and BS-122.00ml were weighed and placed in a beaker and stirred at 40 ℃ until homogeneous to form an emulsion.
60.00g of the fertilizer granules prepared in preparation example 1 were placed in a tumbler, the emulsion was sprayed on the fertilizer granules and baked in an oven at (40. + -. 1) ℃ C. and the tumbler was shaken every 3 minutes for 30 seconds until drying, which took about 10-15 minutes, to produce a coated controlled release fertilizer.
Example 2
This example provides a method of preparing a coated controlled release fertilizer. The method comprises the following steps:
3.00g of PHA powder prepared in preparation example 2, 18.00ml of methylene chloride and BS-122.00ml were weighed and placed in a beaker and stirred at 40 ℃ until homogeneous to form an emulsion.
45.00g of the fertilizer granules prepared in preparation example 1 were placed in a tumbler, the emulsion was sprayed onto the fertilizer granules and baked in an oven at (40. + -. 1) ℃ C. and the tumbler was shaken every 3 minutes for 30 seconds until drying, which took about 10-15 minutes, to produce a coated controlled release fertilizer.
Example 3
This example provides a method of preparing a coated controlled release fertilizer. The method comprises the following steps:
3.00g of PHA powder prepared in preparation example 2, 18.00ml of methylene chloride and BS-122.00ml were weighed and placed in a beaker and stirred at 40 ℃ until homogeneous to form an emulsion.
75.00g of the fertilizer granules prepared in preparation example 1 were placed in a tumbler, the emulsion was sprayed on the fertilizer granules and baked in an oven at (40. + -. 1) ℃ C. and the tumbler was shaken every 3 minutes for 30 seconds until drying, which took about 10-15 minutes, to prepare a coated controlled release fertilizer.
Test example
The coated controlled release fertilizer prepared in example 1 and the fertilizer granules prepared in preparation example 1 were subjected to a comparative test of phosphorus dissolution rate in water at 25 ℃ with a test period of 56 days, and specific test data are shown in table 1:
TABLE 1 phosphorus dissolution rates for coated and uncoated granules as a function of time
As can be seen from table 1, the coated controlled-release fertilizer prepared in example 1 has a significantly lower phosphorus dissolution rate than the fertilizer granules prepared in preparation example 1. It can be seen that the coating made of PHA has a release controlling effect on the dissolution of the material in the fertilizer granule. And organoleptically, after 28 days, the particles of the coated controlled release fertilizer are obviously broken, which shows that PHA is degraded in a large area, and therefore, the coated controlled release fertilizer provided by the invention has excellent biodegradability.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A coated controlled release fertilizer comprising fertilizer granules and a coating on the surface of said fertilizer granules, wherein the material from which said coating is made comprises polyhydroxyalkanoate.
2. The coated controlled-release fertilizer of claim 1, wherein the monomer of the polyhydroxyalkanoate is C3-C5Or an ester thereof.
3. The coated controlled release fertilizer of claim 1, wherein the polyhydroxyalkanoate is prepared by a process comprising:
inoculating aerobic activated sludge taken from an aeration tank into a culture medium consisting of a carbon source, NP nutrition, trace elements and thiourea, carrying out shake culture at constant temperature of 35 ℃ at 150r/min, taking COD (chemical oxygen demand) of less than 100mg/L as a mark for entering a hungry period, controlling the time ratio of the abundance period to the hungry period to be 1:2-4 to obtain enriched seed liquid, centrifuging the enriched seed liquid after each round is finished, and taking a flora obtained by centrifugation as a next round of inoculated strains; when the time of reaching the hunger stage and the COD change are stable for at least two periods, the flora is stable, and the domesticated flora is collected;
the pre-dehydrated sludge enters a thermal hydrolysis reaction system, and plate-frame dehydration is carried out to obtain filtrate;
taking the filtrate as a culture medium, inoculating the domesticated flora to the culture medium, and fermenting in a PHA fermentation system under the fermentation condition that the temperature is 30-40 ℃ and the concentration of ammonia nitrogen and volatile fatty acid in the culture medium is 8000-12000mg COD/L to obtain fermentation liquor;
extracting the polyhydroxyalkanoate from the fermentation broth.
4. The coated controlled release fertilizer of claim 1, wherein the coating is made of a material further comprising an emulsifier and a coating agent.
5. The coated controlled release fertilizer of claim 4, the emulsifier is BS-12 and/or OP-10;
the coating agent is at least one of dichloromethane, ethyl acetate and ethanol.
6. The coated controlled-release fertilizer according to claim 1, wherein the mass ratio of the polyhydroxyalkanoate to the fertilizer granules is 1: 15-25.
7. The coated controlled-release fertilizer according to claim 1, wherein the fertilizer granules are prepared from city domestic sludge subjected to anaerobic digestion by dewatering, granulating and drying.
8. A method of making the coated controlled release fertilizer of any one of claims 1-7, comprising the steps of:
mixing the polyhydroxyalkanoate, the emulsifier and a coating agent to form an emulsion;
and spraying the emulsion on the fertilizer particles, and drying to prepare the coated controlled-release fertilizer.
9. The method of claim 8, further comprising: heating the emulsion; the heating temperature is not higher than 40 ℃.
10. The method of claim 8, wherein the drying process is room temperature ventilation or oven drying.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112592233A (en) * | 2020-12-30 | 2021-04-02 | 宜宾市云洁农业综合开发有限公司 | Soil testing formula fertilizer and preparation method thereof |
| CN113083144A (en) * | 2021-04-22 | 2021-07-09 | 邯郸市沃启生物科技有限公司 | Novel quantitative bacterium adding method for organic fertilizer-in-oil |
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| CN108530149A (en) * | 2017-03-05 | 2018-09-14 | 庆阳敦博科技发展有限公司 | Potato Controlled Release Fertilizer and its preparation process |
| CN109368945A (en) * | 2018-12-18 | 2019-02-22 | 江苏科技大学 | Sewage from Ships processing and recovery of nitrogen and phosphorus integral system and method based on sea water magnesia source |
| CN110331175A (en) * | 2019-07-04 | 2019-10-15 | 北京工业大学 | Mixed bacterial is using odd-carbon fatty acid as the method for substrate synthesizing polyhydroxyalkanoateby |
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- 2019-10-29 CN CN201911038202.4A patent/CN110950719A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102874974A (en) * | 2011-07-15 | 2013-01-16 | 天津市裕川置业集团有限公司 | Advanced treatment and comprehensive utilization process for sewage and sludge in sewage treatment plant |
| CN108530149A (en) * | 2017-03-05 | 2018-09-14 | 庆阳敦博科技发展有限公司 | Potato Controlled Release Fertilizer and its preparation process |
| CN109368945A (en) * | 2018-12-18 | 2019-02-22 | 江苏科技大学 | Sewage from Ships processing and recovery of nitrogen and phosphorus integral system and method based on sea water magnesia source |
| CN110331175A (en) * | 2019-07-04 | 2019-10-15 | 北京工业大学 | Mixed bacterial is using odd-carbon fatty acid as the method for substrate synthesizing polyhydroxyalkanoateby |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112592233A (en) * | 2020-12-30 | 2021-04-02 | 宜宾市云洁农业综合开发有限公司 | Soil testing formula fertilizer and preparation method thereof |
| CN113083144A (en) * | 2021-04-22 | 2021-07-09 | 邯郸市沃启生物科技有限公司 | Novel quantitative bacterium adding method for organic fertilizer-in-oil |
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Application publication date: 20200403 |