CN110218121B - Controlled release fertilizer and preparation method and application thereof - Google Patents
Controlled release fertilizer and preparation method and application thereof Download PDFInfo
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- CN110218121B CN110218121B CN201910560991.1A CN201910560991A CN110218121B CN 110218121 B CN110218121 B CN 110218121B CN 201910560991 A CN201910560991 A CN 201910560991A CN 110218121 B CN110218121 B CN 110218121B
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- release fertilizer
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01C—PLANTING; SOWING; FERTILISING
- A01C21/00—Methods of fertilising, sowing or planting
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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
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
- C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer
Abstract
The invention provides a controlled release fertilizer and a preparation method and application thereof, wherein the controlled release fertilizer comprises a polyurethane coating material and an inorganic fertilizer, and the mass ratio of the polyurethane coating material to the inorganic fertilizer is (1-6): 1000; the polyurethane coating material takes modified castor oil and diisocyanate as main reaction raw materials, the mechanical property and the processing property of a film layer are improved by adding a chain extender, an auxiliary agent and a catalyst, the formed polyurethane film layer has higher strength and good toughness, the controlled release performance is obviously improved, the processing process is slightly influenced by the adhesion process, continuous coating production can be continuously and stably carried out, the initial dissolution rate is generally below 2%, the differential dissolution rate can be as low as about 0.83%, the maximum release period can be more than 70 days, and compared with the existing controlled release fertilizer, the polyurethane coating material has better mechanical property and no adhesion phenomenon and is beneficial to market application.
Description
Technical Field
The invention belongs to the field of fertilizers, and relates to a controlled release fertilizer, and a preparation method and application thereof.
Background
The polyurethane coated controlled release fertilizer is prepared by directly mixing and reacting reactants such as polyol, isocyanate and the like on the surface of fertilizer particles, and relates to a plurality of technologies such as polyurethane reaction materials, film forming reaction processes, equipment and the like. As the coating material, currently, castor oil type polyol and isocyanate are mainly used as the coating material.
Hansen filed a patent for preparing a controlled release fertilizer by using a polymerization reaction of a polyol and an isocyanate in 1961 and 1965, and a technical system using polyurethane as a coating material began to develop an important direction for producing the controlled release fertilizer. However, until 1994, when Alice p.hudson prepared a polyurethane coated controlled release fertilizer in a 355mm diameter disc coating apparatus using isocyanate (DOW PAPI 94) and hydrogenated castor oil (Union Camp Cenwax G), a coated controlled release fertilizer releasing about 20% in 7 days could be obtained, and this technology was not put into commercial use. Based on Alice P.Hudson invention, in a patent applied in 2000, compared the influence of paraffin addition on the performance of coated controlled release fertilizer, the invention considers that: in the preparation of the coated fertilizer, isocyanate is firstly utilized to react with polyol to form a film, and then organic wax is coated, so that the performance of the controlled release fertilizer can be greatly improved. Such a process allows the production of coated fertilizers at reduced cost, making possible the mass application of coated fertilizers, on the basis of which Agrium corporation developed "ESN○R"series coated urea. Yasuhiro Hirano et al, 1999, used disc equipment to spray 4.1g of MDI (Sumidule 44V10, Bayer) and 5.3g of castor oil (Sumifen TM, Bayer) and 0.1g of 2,4, 6-tris (dimethylaminoethyl) phenol catalyst on the surface of fertilizer particles under the process conditions of 20-30 rpm and 75 ℃ temperature to prepare a controlled release fertilizer with a total coating rate of 8%; the release period can reach about 6 months.
CN101006032A discloses a method and apparatus for producing coated articles, which will contain 18% C30+6.7g (1.2+5.5) of wax castor oil mixture and 2.3g of PAPI are simultaneously dripped on the fertilizer, single operation can be completed in 6 minutes, and the operation is repeated for 3 times, so that the polyurethane coated controlled release fertilizer with the release period reaching 6 months can be prepared; in addition, the preheated mixture of the castor oil and the wax is ultrasonically mixed with the isocyanate, and then the coating operation is carried out, so that the release period is better.
CN101648837A discloses a polyurethane coated controlled release fertilizer and a preparation method thereof, 1) the granulated fertilizer is placed in a horizontal rotary drum with a plurality of shoveling plates for preheating; 2) dripping or injecting raw materials a) or b) for forming the polyurethane coating liquid onto the surface of the fertilizer through a nozzle to form a precoating layer; 3) coating the raw materials for forming the polyurethane coating liquid on a precoating layer of the granular fertilizer at the same time, and repeatedly coating for 2-10 times after the polyurethane coating liquid is cured to obtain the polyurethane coated controlled-release fertilizer; the raw materials for forming the polyurethane coating liquid are a) and b), wherein a) comprises alcohol containing 2-6 hydroxyl groups, and b) is isocyanate containing at least two isocyanate groups. By introducing the pre-coating layer, the nutrient controlled-release period of the coated fertilizer is prolonged; meanwhile, the pre-coating layer is made of one of the raw materials of the polyurethane coating liquid, so that the process operation is simplified. According to the method, the castor oil is used as a main reactant to prepare the polyurethane coated fertilizer, and researches show that the castor oil is used as a precoating layer to help improve the controlled release performance.
CN105111402A discloses a preparation method of a vegetable oil-based polyurethane coated fertilizer with improved water resistance, which comprises the following steps: (1) modification treatment of vegetable oil polyol: adding hydrolysis stabilizer into vegetable oil polyalcohol, wherein the addition amount of the hydrolysis stabilizer is 0.2-5 wt%, and stirring at high temperature to obtain modified vegetable oil polyalcohol; (2) preparing a polyurethane coated urea slow-release fertilizer: weighing large-particle urea, heating to 78-80 ℃, preserving heat, respectively and fully mixing the modified vegetable oil polyol prepared in the step (1) with a lubricant in a coating mode, then quickly mixing the mixed solution with isocyanate resin solution, uniformly coating the mixed solution on the surface of urea particles, fully mixing the urea particles with coating solution in a rotary drum, and gradually crosslinking and curing the coating solution to finally form the polyurethane coated urea slow-release fertilizer. The vegetable oil-based polyurethane coated urea prepared by the method is subjected to a water resistance test, so that a good result is obtained, or the water resistance of the material is improved, so that the controlled release performance is improved.
In addition to the basic reaction of polyurethane of castor oil and isocyanate, the method disclosed at present particularly emphasizes the addition of auxiliary agents such as paraffin and the like to improve the release performance of the coated controlled-release fertilizer. It is believed that the uneven or damaged coating in the conventional coating process is a problem of poor controlled release performance of the coating layer. In addition to solving the problem of uniform coating and preventing the adhesion damage of the film layer from the aspect of optimizing the process, the material formula can be optimized, and the auxiliary agent can be added to promote uniform coating and reduce the curing and bonding effect.
In summary, the polyurethane coated controlled release fertilizer is mainly based on a material system of castor oil and diphenylmethane diisocyanate (MDI), but this system has some disadvantages: the castor oil hydroxyl value and the performance of one of the main materials of the reactant are relatively stable, the mechanical property of the polyurethane film layer produced by the reaction is represented by insufficient strength, in addition, the reaction speed is slow, and the adhesion problem in the film coating process is more prominent.
Therefore, how to develop a fertilizer capable of improving the coating processability and the controlled release performance of the thin film controlled release fertilizer has important significance and value.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims at a controlled release fertilizer and a preparation method and application thereof, so as to solve the problems of poor controlled release effect and poor coating processability of the existing coated fertilizer.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a controlled release fertilizer, which comprises a polyurethane coating material and an inorganic fertilizer, wherein the mass ratio of the polyurethane coating material to the inorganic fertilizer is (1-6): 1000.
The controlled release fertilizer provided by the invention has excellent controlled release performance, the initial dissolution rate is generally below 2%, the minimum differential dissolution rate can reach about 0.83%, the maximum release period can reach more than 70 days, and the controlled release fertilizer has better mechanical property and no adhesion phenomenon compared with the existing controlled release fertilizer.
The mass ratio of the polyurethane coating material to the inorganic fertilizer can be 1:1000, 1:500, 3:1000, 1:250, 1:200, or 3:500, and the like.
Preferably, the polyurethane coating material comprises the following components:
the component A comprises polyalcohol, a catalyst, a chain extender and an auxiliary agent; component B comprises a diisocyanate.
In the invention, the polyurethane coating material takes modified castor oil and diisocyanate as main reaction raw materials, and the mechanical property and the processing property of the coating are improved by adding the chain extender, the auxiliary agent and the catalyst, compared with the existing coating reaction material based on castor oil and diisocyanate, the formed polyurethane coating has higher strength, good toughness, obviously improved controlled release property, small influence of an adhesion process on the processing process, and continuous and stable coating production can be continuously carried out.
Preferably, the polyol is a modified castor oil.
Preferably, the diisocyanate is any one of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or hexamethylene diisocyanate or a combination of at least two of the diphenylmethane diisocyanate, the toluene diisocyanate, the isophorone diisocyanate, the dicyclohexylmethane diisocyanate or the hexamethylene diisocyanate; diphenylmethane diisocyanate is preferred.
The molar ratio of isocyanate groups in the diisocyanate to hydroxyl groups in the polyol is preferably (1.05 to 2: 1), and may be, for example, 1.05:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2: 1.
Preferably, the catalyst is stannous octoate.
The amount of the catalyst used is preferably 0.01% to 0.5%, for example, 0.01%, 0.02%, 0.04%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, or 0.5%, based on 100% by mass of the polyurethane coating material.
Preferably, the chain extender comprises any one of 1, 3-Propanediol (PDO), 1, 4-Butanediol (BDO), or Trimethylolpropane (TMP), or a combination of at least two thereof.
In the invention, the addition of the chain extender has certain influence on the controlled release performance, and the influence of different types of chain extenders is different. The polyurethane coating material added with 1, 3-propylene glycol or 1, 4-butanediol can remarkably improve the controlled release performance of the fertilizer, the differential dissolution rate in 28 days can reach below 1.3 percent, and the release period can reach 72 days at the longest. The fertilizer is suitable for long-term controlled release. The fertilizer added with the trimethylolpropane shows better initial dissolution rate, the initial dissolution rate can reach 1.13%, but the dissolution rate is increased along with the passage of time, the differential dissolution rate of 28 days is 3.45%, and the release period is only 24 days. Such fertilizers may be particularly suitable for short term controlled release.
The molar ratio of the hydroxyl groups in the polyol to the hydroxyl groups in the chain extender is preferably (0.1 to 10: 1), and may be, for example, 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1, preferably (5 to 9: 1), and more preferably 9: 1.
In the invention, the proportion of the polyol and the chain extender can also generate obvious influence on the controlled release performance, the mole percentage content of the hydroxyl groups of the chain extender and the polyol is gradually increased from 5 percent to 95 percent, 10 percent to 90 percent, 15 percent to 85 percent, the performance is gradually improved, the optimal effect of the comprehensive controlled release performance can be achieved when the hydroxyl groups of the chain extender and the polyol are 10 percent to 90 percent, and the release days can be more than 70 days at most. Therefore, the best effect is obtained when the molar ratio of hydroxyl groups in the polyol to hydroxyl groups in the chain extender is 9: 1.
Preferably, the auxiliary agent is paraffin and/or fumed silica.
Preferably, the adjuvant is a combination of paraffin wax and fumed silica.
In the invention, the addition of the auxiliary agent helps to improve the performance of the controlled release fertilizer. The release performance of the controlled-release fertilizer can be improved by adding paraffin or fumed silica, and the effect can be mutually promoted by adding paraffin and fumed silica, so that the release performance of the coated controlled-release fertilizer can be further improved.
Preferably, the mass ratio of the paraffin wax to the fumed silica is 1: 1.
Preferably, the amount of the auxiliary agent is 1% to 2%, for example, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, or the like, based on 100% by mass of the polyurethane coating material.
Preferably, the preparation method of the polyurethane coating material comprises the following steps:
preheating polyol, and mixing the preheated polyol with a chain extender, a catalyst and an auxiliary agent to obtain a component A; then, after the diisocyanate is preheated, the diisocyanate is mixed with the component A to obtain the polyurethane coating material.
Preferably, the temperature to which the polyol is preheated is 50 to 70 ℃, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃.
Preferably, after mixing to obtain component A, the temperature of component A is raised to 75-90 deg.C, such as 75 deg.C, 78 deg.C, 80 deg.C, 82 deg.C, 85 deg.C, 86 deg.C, 88 deg.C or 90 deg.C.
Preferably, the diisocyanate is preheated to 75 to 90 ℃, for example, 75 ℃, 76 ℃, 79 ℃, 80 ℃, 82 ℃, 83 ℃, 85 ℃, 87 ℃, 89 ℃ or 90 ℃.
Preferably, the inorganic fertilizer comprises any one of ammonia water, ammonium bicarbonate, ammonium sulfate, ammonium chloride, urea, calcium superphosphate, calcium magnesium phosphate, ground phosphate rock, ammonium phosphate, phosphorus nitrate, potassium nitrate or potassium dihydrogen phosphate.
Preferably, the inorganic fertilizer is urea.
In a second aspect, the invention provides a method for preparing the controlled release fertilizer according to the first aspect, wherein a polyurethane coating material is sprayed on the surface of an inorganic fertilizer to form a polymer film layer, so as to obtain the controlled release fertilizer.
The preparation method can specifically comprise the following steps:
a small test fluidized bed with a bed body diameter of 150mm, a cone bottom inlet diameter of 100mm and a cone bucket inclination angle of 65 degrees is used as coating equipment, and the fluidizing gas amount is about 120m3H, coating operation is carried out under the condition that the temperature is 80 ℃.
During coating, firstly weighing 1000 g of large-particle urea with the diameter of 2-4 mm, placing the large-particle urea in a fluidized bed in a working state, and fluidizing and preheating the large-particle urea; after 2 minutes, 40g of the coating agent (the total amount of isocyanate and polyol, R is 1.12, the ratio is adjusted according to the formula design) is slowly added into the fluidized bed by a peristaltic pump, and the adding time is controlled to be 15 minutes.
The polyurethane coating material is formed by quickly mixing an A phase and a B phase in a liquid phase cavity in a two-fluid nozzle. After being mixed, the mixture is atomized and sprayed on the surface of fertilizer particles, and the polyurethane coating material can rapidly generate chemical reaction on the surface of the fertilizer particles to form a high-molecular polymer film.
In a third aspect, the present invention provides the use of a controlled release fertilizer according to the first aspect for promoting crop growth.
Compared with the prior art, the invention has the following beneficial effects:
the controlled release fertilizer provided by the invention has excellent controlled release performance, the initial dissolution rate is generally below 2%, the differential dissolution rate can be as low as about 0.83%, the maximum release period can be more than 70 days, and the maximum release period can be about 99 days.
The polyurethane coating material provided by the invention takes modified castor oil and diisocyanate as main reaction raw materials, and the mechanical property and the processing property of the coating are improved by adding the chain extender, the auxiliary agent and the catalyst.
Drawings
FIG. 1 is a diagram of a process for preparing a controlled release fertilizer, wherein 1-a Roots blower, 2-a gas buffer tank, 3-a heater, 4-a fluidized bed, 5-an air compressor, 6-a nozzle, 7-A envelope liquid storage tank, 8-a peristaltic pump A, 9-B envelope liquid storage tank, and 10-a peristaltic pump B.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The diphenylmethane diisocyanate used in the invention is PM200 produced by Wanhua nicotineau, and the modified castor oil is polyoxyethylene hydrogenated castor oil with the trade name of cremophor CO 40.
The meaning of the R values in the following examples of the invention is: the molar ratio of isocyanate groups in the diisocyanate to the total hydroxyl group content (NCO/OH), the total hydroxyl group content being the sum of the amount of hydroxyl groups in the polyol and the amount of hydroxyl groups in the chain extender.
The meaning of CO in the examples is the molar percentage content of hydroxyl groups in the modified castor oil.
The meaning of the initial dissolution rate is as follows: under the condition of water soaking, the dissolved nutrients account for the mass percent of the total nutrients in the first day. Initial dissolution rate etat1，ηt1＝Mt1/M×100％
The differential dissolution rate has the following meaning: under water immersion conditions, the differential percent of nutrient dissolution per day over the test period was measured, except for the first day. Differential dissolution rate eta△t，η△t＝(ηtn－ηt1)/(tn－t1)×100％]
Wherein, tnOn the nth day, t1On day 1, ηntCumulative release rate, η, for the nth dayt1For initial dissolution rate, Mt1The nutrient amount dissolved out on the 1 st day, and M is the total nutrient amount in the coated fertilizer.
The method for testing the controlled release performance of the controlled release fertilizer comprises the following steps:
the nutrient release performance of the coated fertilizer is measured by adopting a water immersion method, 10.00g of a controlled release fertilizer sample is weighed and put into a nylon mesh bag with the particle size of 150pm (100 meshes), the nylon mesh bag is put into a plastic bottle with the volume of 250mL after being sealed, 200mL of deionized water is added, and the nylon mesh bag is placed in a biochemical constant temperature incubator with the temperature of 25 ℃ for standing culture. The sampling time was 1,3, 5, 7, 10, 14, 28 days. During sampling, 100mL of aqueous solution is taken out to determine the urea content, the rest solution is poured out, a 250mL plastic bottle containing a nylon bag is washed for 3 times by deionized water, then 200mL of deionized water is added, the plastic bottle is covered and sealed, and then the plastic bottle is placed into a constant temperature incubator to be continuously cultured, and each fertilizer is repeatedly used for three times. The urea nitrogen is measured by p-dimethylaminobenzaldehyde spectrophotometry.
The preparation method of the controlled release fertilizer in the following examples of the invention is carried out according to the following steps:
the modified castor oil is preheated to 60 ℃, then the chain extender, the catalyst and the auxiliary agent are sequentially added, and are uniformly mixed by a high-speed stirrer, and finally the temperature is raised to 80 ℃ to obtain the component A, and the component A is kept at a constant temperature for later use.
The controlled release fertilizer is prepared by preheating diphenylmethane diisocyanate to 80 ℃, quickly mixing the component A and the component B in a liquid phase cavity in a two-fluid nozzle, immediately atomizing the mixed polyurethane coating material, spraying the atomized polyurethane coating material on the surface of urea particles, and quickly carrying out chemical reaction on the polyurethane coating material on the surface of the urea particles to form a high-molecular polymer film layer.
The process flow chart of the preparation of the controlled release fertilizer is shown in figure 1, wherein the inorganic fertilizer takes urea as an example, and the actual working flow is as follows:
the first step is to turn on the roots blower 1 to generate the fluidization gas; the fluidization gas passes through the gas buffer tank 2, so that weak pulses of the fluidization gas generated by the Roots machine are eliminated, and the gas flow becomes stable.
The second step is to turn on the electric heater 3 and the fluidizing gas is heated to 80 c before entering the fluidized bed 4.
And thirdly, adding the large-particle urea into the fluidized bed, and under the baking of the fluidized gas, keeping the large-particle urea in a state of waiting for coating.
The fourth step is to turn on the air compressor 5 to provide atomizing air to the nozzle 6.
And the fifth step is to open two peristaltic pumps A and B, namely 8 and 10 at the same time, respectively deliver the component A in the coating liquid storage tank A7 and the component B in the coating liquid storage tank B9 to the inner cavity of the nozzle 6 according to the metering relation, and after the components are rapidly mixed, the mixture is sprayed into the fluidized bed by compressed air and atomized.
And the sixth step is that the atomized polyurethane film material in the fluidized bed 4 is fully contacted with the large-particle urea, the polyurethane film material is coated on the surface of the large-particle urea, and a film layer is formed by polymerization reaction, so that the coated controlled-release fertilizer is prepared.
And seventhly, after finishing the spraying of the polyurethane film material, closing the two peristaltic pumps, continuing to react and cure for 10 minutes, taking out the controlled release fertilizer from the top of the fluidized bed by using a discharge cylinder, and then closing the electric heater 3, the air compressor 5 and the Roots blower 1 in sequence to finish the preparation process of the controlled release fertilizer once.
Example 1
And (2) component A: modified castor oil (CO is 100 percent), stannous octoate 0.05 percent, paraffin 1 percent and R value 1.12;
and (B) component: diphenylmethane diisocyanate.
Example 2
And (2) component A: modified castor oil (90% of CO), stannous octoate 0.05%, paraffin 1% and R value 1.12; 10% of BDO;
and (B) component: diphenylmethane diisocyanate.
Example 3
And (2) component A: modified castor oil (90% of CO), stannous octoate 0.05%, paraffin 1% and R value 1.12; 10% of PDO;
and (B) component: diphenylmethane diisocyanate.
Example 4
And (2) component A: modified castor oil (90% of CO), stannous octoate 0.05%, paraffin 1% and R value 1.12; TMP 10%;
and (B) component: diphenylmethane diisocyanate.
Example 5
And (2) component A: modified castor oil (with 95% of CO), stannous octoate 0.05%, paraffin 1% and R value 1.12; BDO 5 percent;
and (B) component: diphenylmethane diisocyanate.
Example 6
And (2) component A: modified castor oil (85% of CO), stannous octoate 0.05%, paraffin 1% and R value 1.12; 15% of BDO;
and (B) component: diphenylmethane diisocyanate.
Example 7
And (2) component A: modified castor oil (with 95% of CO), stannous octoate 0.05%, paraffin 1% and R value 1.12; PDO 5%;
and (B) component: diphenylmethane diisocyanate.
Example 8
And (2) component A: modified castor oil (85% of CO), stannous octoate 0.05%, paraffin 1% and R value 1.12; 15% of PDO;
and (B) component: diphenylmethane diisocyanate.
Example 9
And (2) component A: modified castor oil (CO is 100 percent), stannous octoate is 0.05 percent, and R value is 1.12;
and (B) component: diphenylmethane diisocyanate.
Example 10
And (2) component A: modified castor oil (CO is 100 percent), stannous octoate 0.05 percent, fumed silica 1 percent and R value 1.12;
and (B) component: diphenylmethane diisocyanate.
Example 11
And (2) component A: modified castor oil (CO is 100 percent), stannous octoate 0.05 percent, fumed silica 1 percent, paraffin 1 percent and R value 1.12;
and (B) component: diphenylmethane diisocyanate.
Example 12
And (2) component A: modified castor oil (90% of CO), stannous octoate 0.05%, fumed silica 1%, paraffin 1% and R value 1.12; 10% of BDO;
and (B) component: diphenylmethane diisocyanate.
Example 13
And (2) component A: modified castor oil (CO is 100 percent), stannous octoate 0.1 percent, paraffin 1 percent and R value 1.12;
and (B) component: toluene diisocyanate.
Example 14
And (2) component A: modified castor oil (CO is 100 percent), stannous octoate 0.4 percent, paraffin 1 percent and R value 1.12;
and (B) component: dicyclohexylmethane diisocyanate.
The controlled release fertilizers obtained in examples 1 to 14 were subjected to release property tests, and the results are shown in table 1:
TABLE 1
| Examples | Initial dissolution Rate (%) | Differential dissolution rate (%) | Release period (Tian) |
| 1 | 1.30 | 1.80 | 45 |
| 2 | 1.76 | 1.11 | 72 |
| 3 | 1.98 | 1.30 | 61 |
| 4 | 1.13 | 3.45 | 24 |
| 5 | 1.90 | 1.90 | 42 |
| 6 | 1.86 | 1.13 | 70 |
| 7 | 2.27 | 1.68 | 47 |
| 8 | 0.22 | 1.34 | 60 |
| 9 | 3.30 | 4.80 | 17 |
| 10 | 1.62 | 1.65 | 48 |
| 11 | 1.86 | 1.39 | 57 |
| 12 | 0.62 | 0.83 | 99 |
| 13 | 1.43 | 1.94 | 48 |
| 14 | 1.51 | 1.98 | 50 |
The data in table 1 show that the addition of the chain extender has certain influence on the controlled release performance, different chain extenders have different influence degrees, the controlled release effect of the PDO or BDO is better, the release period can reach more than 60 days, and the longest period can reach more than 70 days.
The dosage of the chain extender can also influence the controlled release effect, the optimal effect of the comprehensive controlled release performance can be achieved when the molar percentage of the chain extender to the hydroxyl of the polyhydric alcohol is 10 percent to 90 percent, and the maximum release days can be more than 70 days. Therefore, the best effect is obtained when the molar ratio of hydroxyl groups in the polyol to hydroxyl groups in the chain extender is 9: 1.
The addition of the auxiliary agent is beneficial to improving the controlled release effect, and as can be seen from examples 1, 9, 10 and 11, the addition of the paraffin and the fumed silica is beneficial to further improving the controlled release effect. By comprehensively utilizing the optimized formula scheme 12, the controlled release fertilizer with the release period of 99 days can be obtained.
The applicant states that the present invention is illustrated by the above examples to the controlled release fertilizer of the present invention and the preparation method and application thereof, but the present invention is not limited to the above detailed method, i.e. it does not mean that the present invention must be implemented by the above detailed method. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (21)
1. The controlled release fertilizer is characterized by comprising a polyurethane coating material and an inorganic fertilizer, wherein the mass ratio of the polyurethane coating material to the inorganic fertilizer is (1-6): 1000;
the polyurethane coating material comprises the following components:
the component A comprises polyalcohol, a catalyst, a chain extender and an auxiliary agent; the component B comprises diisocyanate;
the polyol is modified castor oil;
the modified castor oil is polyoxyethylene hydrogenated castor oil;
the auxiliary agent is paraffin and/or fumed silica.
2. The controlled release fertilizer of claim 1, wherein the diisocyanate is any one of or a combination of at least two of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, or hexamethylene diisocyanate.
3. The controlled release fertilizer of claim 2, wherein the diisocyanate is diphenylmethane diisocyanate.
4. The controlled release fertilizer according to claim 1, wherein the molar ratio of the isocyanate group in the diisocyanate to the hydroxyl group in the polyol is (1.05-2): 1.
5. The controlled release fertilizer of claim 1, wherein the catalyst is stannous octoate.
6. The controlled release fertilizer of claim 1, wherein the amount of the catalyst is 0.01 to 0.5% based on 100% by mass of the polyurethane coating material.
7. The controlled release fertilizer of claim 1, wherein the chain extender comprises any one of 1, 3-propanediol, 1, 4-butanediol, or trimethylolpropane, or a combination of at least two thereof.
8. The controlled release fertilizer of claim 1, wherein the molar ratio of hydroxyl groups in the polyol to hydroxyl groups in the chain extender is (0.1-10): 1.
9. The controlled release fertilizer of claim 8, wherein the molar ratio of hydroxyl groups in the polyol to hydroxyl groups in the chain extender is (5-9): 1.
10. The controlled release fertilizer of claim 9, wherein the molar ratio of hydroxyl groups in the polyol to hydroxyl groups in the chain extender is 9: 1.
11. The controlled release fertilizer of claim 1, wherein the adjuvant is a combination of paraffin and fumed silica.
12. The controlled release fertilizer of claim 11, wherein the mass ratio of paraffin wax to fumed silica is 1: 1.
13. The controlled release fertilizer of claim 1, wherein the amount of the auxiliary agent is 1-2% based on 100% by mass of the polyurethane coating material.
14. The controlled release fertilizer of claim 1, wherein the polyurethane coating material is prepared by the following method:
preheating polyol, and mixing the preheated polyol with a chain extender, a catalyst and an auxiliary agent to obtain a component A; then, after the diisocyanate is preheated, the diisocyanate is mixed with the component A to obtain the polyurethane coating material.
15. The controlled release fertilizer of claim 14, wherein the polyol is preheated to a temperature of 50 ℃ to 70 ℃.
16. The controlled release fertilizer of claim 14, wherein after mixing to obtain component a, component a is warmed to 75-90 ℃.
17. The controlled release fertilizer of claim 14, wherein the diisocyanate is preheated to 75-90 ℃.
18. The controlled-release fertilizer according to claim 1, wherein the inorganic fertilizer comprises any one of ammonia water, ammonium bicarbonate, ammonium sulfate, ammonium chloride, urea, calcium superphosphate, calcium magnesium phosphate, powdered rock phosphate, ammonium phosphate, phosphorus nitrate, potassium nitrate, or potassium dihydrogen phosphate.
19. The controlled release fertilizer defined in claim 18, wherein the inorganic fertilizer is urea.
20. The method of preparing a controlled-release fertilizer according to any one of claims 1 to 19, wherein the controlled-release fertilizer is obtained by spraying a polyurethane coating material on the surface of an inorganic fertilizer to form a polymer film layer.
21. Use of the controlled release fertilizer of any one of claims 1-19 to promote crop growth.
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| CN111527851B (en) * | 2020-05-13 | 2021-04-06 | 浙江大学 | Photocatalytic foliar fertilization method |
| CN112159269B (en) * | 2020-09-23 | 2022-06-14 | 华南农业大学 | Vegetable oil-based polyurethane coated fertilizer and preparation method thereof |
| CN112142517A (en) * | 2020-09-28 | 2020-12-29 | 西安唯拓尔农业科技有限公司 | Large-particle slow and controlled release fertilizer |
| CN113264805A (en) * | 2021-06-23 | 2021-08-17 | 中国农业科学院农业资源与农业区划研究所 | Cellulose modified polyurethane coated fertilizer and preparation method and application thereof |
| CN115677418A (en) * | 2022-11-08 | 2023-02-03 | 山东省花生研究所 | Large-particle slow-release fertilizer and preparation method and application thereof |
| CN116375531A (en) * | 2023-03-30 | 2023-07-04 | 中国农业科学院农业资源与农业区划研究所 | Temperature-sensitive polyurethane coated controlled-release fertilizer and preparation method thereof |
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