【技术领域】【Technical field】
本发明属于化学肥料技术领域。更具体地，本发明涉及一种尿素包膜复合乳液，还涉及所述尿素包膜复合乳液的制备方法，还涉及所述尿素包膜复合乳液的用途。The invention belongs to the technical field of chemical fertilizers. More specifically, the present invention relates to a urea-coated composite emulsion, a method for preparing the urea-coated composite emulsion, and an application of the urea-coated composite emulsion.
【背景技术】【Background technique】
包膜控释化肥能有效控制养分的释放速率，满足植物吸收需求，提高养分利用率20%以上，是解决农业高效清洁利用化肥的重要技术手段。目前，包膜材料主要有聚烯烃、聚氨酯和聚合物乳液等。以聚合物乳液制备的包膜控释化肥，其释放曲线呈“S”型，与植物养分吸收规律匹配性好，而且乳液以水为分散介质，是一种清洁的控释肥包膜剂，因此，研究开发乳液包膜化肥具有重要的应用价值。Coated controlled-release chemical fertilizers can effectively control the release rate of nutrients, meet the needs of plants for absorption, and increase nutrient utilization by more than 20%. It is an important technical means to solve the problem of efficient and clean use of chemical fertilizers in agriculture. At present, the coating materials mainly include polyolefin, polyurethane and polymer emulsion. The coated controlled-release fertilizer prepared by polymer emulsion has an "S"-shaped release curve, which matches well with the absorption of plant nutrients, and the emulsion uses water as the dispersion medium, which is a clean controlled-release fertilizer coating agent. Therefore, the research and development of emulsion-coated fertilizers has important application value.
Thompson、Tsunehisa和Tzika等人（US，005089041；US，005186732；JP，03275583；Tzika M，2003）使用聚偏二氯乙烯等乳液为主要包膜材料，制备聚合物乳液包膜肥料，并受到广泛关注。1992年日本旭化成工业株式会社在其专利（Tsunehisa S，1992）中介绍了使用苯乙烯（St）、丁二烯（BD）、丙烯酸丁酯（BA）、N-羟甲基丙烯酰胺、丙烯酸等功能单体共聚合成乳液，作为包膜材料制得包膜肥料；Donida等人(Donida MW，2002）以丙烯酸酯乳液为包膜材料，聚乙二醇为增塑剂、滑石粉为助流剂、二氧化钛为着色剂制备包膜肥料；韩国高科技研究（Savant N，1983）使用聚丙烯酸系聚合物乳液制备包膜肥料。CN 101244966A公开了由纤维素、聚乙烯醇、聚氨酯预聚物、交联剂、乳化剂、引发剂、植物生长调节剂与去离子水制成的水溶性高分子聚合物乳液，以及使用该乳液制备自控缓释肥料。CN 102020510A公开了一种以苯丙乳液与凹凸棒石粉末形成内层包膜，在所述内层包膜的表面以石蜡形成的外层包膜的缓释氮肥。姚俊杰等人（姚俊杰，2005）进行了使用丙烯酸系聚合物乳液包膜肥料的研究。Thompson, Tsunehisa and Tzika et al. (US, 005089041; US, 005186732; JP, 03275583; Tzika M, 2003) used polyvinylidene chloride and other emulsions as the main coating materials to prepare polymer emulsion coating fertilizers, and have been widely accepted. focus on. In 1992, Japan Asahi Chemical Industry Co., Ltd. introduced the use of styrene (St), butadiene (BD), butyl acrylate (BA), N-methylol acrylamide, acrylic acid, etc. in its patent (Tsunehisa S, 1992). Functional monomers are copolymerized into an emulsion, which is used as a coating material to prepare a coated fertilizer; Donida et al. (Donida MW, 2002) used acrylate emulsion as a coating material, polyethylene glycol as a plasticizer, and talcum powder as a glidant , Titanium dioxide as a colorant to prepare coated fertilizers; Korean high-tech research (Savant N, 1983) used polyacrylic acid polymer emulsions to prepare coated fertilizers. CN 101244966A discloses a water-soluble high molecular polymer emulsion made of cellulose, polyvinyl alcohol, polyurethane prepolymer, crosslinking agent, emulsifier, initiator, plant growth regulator and deionized water, and the use of the emulsion Prepare self-controlled slow-release fertilizers. CN 102020510A discloses a slow-release nitrogen fertilizer that forms an inner coating with styrene-acrylic emulsion and attapulgite powder, and forms an outer coating with paraffin on the surface of the inner coating. Yao Junjie et al. (Yao Junjie, 2005) conducted research on the use of acrylic polymer emulsion to coat fertilizers.
但是，聚合物乳液合成单体自身的性质决定了一些常用聚合物乳液直接用作包膜剂后存在冷脆热粘、耐水性和结构稳定性不理想等问题，导致该类聚合物包膜控释肥料养分释放期不长。现有文献报道的乳液包膜控释肥料养分释放期一般在1个月以内。造成乳液包膜控释肥料养分释放性能较差的原因除了聚合物乳液本身的室温成膜性、耐水性和聚合物的强度以外，还与包膜工艺条件和控制措施密切相关。However, the nature of polymer emulsion synthesis monomer itself determines that some commonly used polymer emulsions have problems such as cold and brittle hot stickiness, water resistance and structural stability after being directly used as coating agents, which lead to the control of such polymer coatings. The nutrient release period of the release fertilizer is not long. The nutrient release period of the emulsion-coated controlled-release fertilizer reported in the existing literature is generally within one month. The reason for the poor nutrient release performance of the emulsion-coated controlled-release fertilizer is not only the room temperature film-forming property, water resistance and polymer strength of the polymer emulsion itself, but also closely related to the coating process conditions and control measures.
为了提高聚合物乳液的性能，采用具有不同性能的聚合物乳液进行共混改性是常用的方法，本发明利用采用水性聚氨酯与苯丙乳液共混的方法，制备包膜剂，并发明了使用该包膜剂制备包膜控释肥料的工艺方法。In order to improve the performance of polymer emulsions, it is a common method to use polymer emulsions with different properties to carry out blending and modification. The present invention utilizes the method of blending water-based polyurethane and styrene-acrylic emulsion to prepare a coating agent, and invents the use of The film-coating agent is a process for preparing film-coated controlled-release fertilizers.
【发明内容】【Content of invention】
[要解决的技术问题][Technical problem to be solved]
本发明的目的是提供一种尿素包膜复合乳液。The object of the present invention is to provide a kind of urea coated composite emulsion.
本发明的另一个目的是提供所述尿素包膜复合乳液的制备方法。Another object of the present invention is to provide a preparation method of the urea-coated composite emulsion.
本发明的另一个目的是提供所述尿素包膜复合乳液的用途。Another object of the present invention is to provide the application of the urea-coated composite emulsion.
[技术方案][Technical solutions]
本发明是通过下述技术方案实现的。The present invention is achieved through the following technical solutions.
本发明涉及一种尿素包膜复合乳液。The invention relates to a urea-coated composite emulsion.
该尿素包膜复合乳液的组成如下，以重量份计：The composition of this urea-coated composite emulsion is as follows, in parts by weight:
所述的水性聚氨酯乳液的活化温度是40~60℃；The activation temperature of the water-based polyurethane emulsion is 40 to 60°C;
所述的苯丙乳液的玻璃化转化温度是20~25℃，最低成膜温度是16~21℃。The glass transition temperature of the styrene-acrylic emulsion is 20-25°C, and the minimum film-forming temperature is 16-21°C.
水性聚氨酯乳液是以水代替有机溶剂作为分散介质的新型聚氨酯乳液。水性聚氨酯乳液以水为溶剂，具有无污染、安全可靠、相容性好等优点。在本发明中，其活化温度为40~60℃的水性聚氨酯乳液都是可以使用的，它们都是目前市场上销售的产品，例如拜耳公司以商品名DispercollU54销售的水性聚氨酯，它的固体含量为50重量%，粘度40-400mPa.s，活化温度45-55℃。Water-based polyurethane emulsion is a new type of polyurethane emulsion that uses water instead of organic solvents as the dispersion medium. Water-based polyurethane emulsion uses water as a solvent, which has the advantages of no pollution, safety and reliability, and good compatibility. In the present invention, its activation temperature is that the aqueous polyurethane emulsion of 40～60 ℃ all can use, and they all are the products sold on the market at present, for example the aqueous polyurethane that Bayer Company sells with trade name DispercollU54, and its solid content is 50% by weight, viscosity 40-400mPa.s, activation temperature 45-55°C.
苯丙乳液，即苯乙烯-丙烯酸酯乳液，是由苯乙烯和丙烯酸酯单体经乳液共聚得到的。它是乳白色液体，其玻璃化温度14-25℃、固体含量40~50重量%，粘度80~2000mPa·s，单体残留量小于0.5重量%，pH值8~9。苯丙乳液附着力好，其胶膜具有透明，耐水、耐油、耐热、耐老化性能良好等特点。其玻璃化转化温度20~25℃与最低成膜温度16~21℃的苯丙乳液在本发明中都是可以使用的，它们都是目前市场上销售的产品，例如罗门哈斯公司以商品名AS-2010销售的苯丙乳液，其固体含量49重量%，玻璃化转化温度21℃，最低成膜温度20℃。Styrene-acrylic emulsion, that is, styrene-acrylate emulsion, is obtained by emulsion copolymerization of styrene and acrylate monomers. It is a milky white liquid with a glass transition temperature of 14-25°C, a solid content of 40-50% by weight, a viscosity of 80-2000mPa·s, a residual monomer content of less than 0.5% by weight, and a pH value of 8-9. Styrene-acrylic emulsion has good adhesion, and its film has the characteristics of transparency, water resistance, oil resistance, heat resistance and aging resistance. Its glass transition temperature 20～25 ℃ and the styrene-acrylic emulsion of minimum film-forming temperature 16～21 ℃ all can be used in the present invention, and they all are the product that sells on the market at present, for example Rohm and Haas Company sells as commodity The styrene-acrylic emulsion sold under the name AS-2010 has a solid content of 49% by weight, a glass transition temperature of 21°C, and a minimum film-forming temperature of 20°C.
去离子水是指除去了呈离子形式杂质后的纯水，主要是采用离子交换树脂处理方法或采用RO反渗透法获得的纯水，是目前市场上销售的产品。Deionized water refers to pure water after removing impurities in the form of ions. It is mainly pure water obtained by ion exchange resin treatment or RO reverse osmosis. It is a product currently on the market.
脂肪醇聚氧乙烯醚硫酸钠（AES）或烷基聚氧乙烯醚（平平加O）是非离子表面活性剂，是目前市场上销售的产品，例如国药集团销售的产品。Fatty alcohol polyoxyethylene ether sodium sulfate (AES) or alkyl polyoxyethylene ether (Pingping plus O) is a non-ionic surfactant, which is a product currently on the market, such as the product sold by Sinopharm Group.
在本发明中，水性聚氨酯乳液为15~25重量份时，如果苯丙乳液小于50重量份时，则会大大降低膜层的柔韧性；如果苯丙乳液大于70重量份时，则会大大提高膜层的亲水性；因此，水性聚氨酯乳液为15~25重量份时，苯丙乳液为50~70重量份是合适的。同样地，水性聚氨酯乳液为15~25重量份时，如果去离子水小于14重量份时，则会因固含率太高导致成膜过程中容易出现膜层龟裂；如果去离子水大于24重量份时，则会因共混乳液固含率太低而增加脱水负荷；因此，水性聚氨酯乳液为15~25重量份时，去离子水为14~24重量份是合适的。水性聚氨酯乳液为15~25重量份时，如果其非离子表面活性剂小于0.8重量份时，则会导致乳液共混不均匀；如果非离子表面活性剂大于1.2重量份时，则会因表面活性剂的存在而影响成膜过程；因此，水性聚氨酯乳液为15~25重量份时，非离子表面活性剂为0.8~1.2重量份是合适的。In the present invention, when the water-based polyurethane emulsion is 15 to 25 parts by weight, if the styrene-acrylic emulsion is less than 50 parts by weight, the flexibility of the film layer will be greatly reduced; if the styrene-acrylic emulsion is greater than 70 parts by weight, it will be greatly improved. The hydrophilicity of film layer; Therefore, when aqueous polyurethane emulsion is 15～25 weight parts, styrene-acrylic emulsion is 50～70 weight parts and is suitable. Similarly, when the water-based polyurethane emulsion is 15 to 25 parts by weight, if the deionized water is less than 14 parts by weight, film cracks will easily occur in the film-forming process because the solid content is too high; if the deionized water is greater than 24 parts by weight When the weight part is used, the dehydration load will be increased because the solid content of the blended emulsion is too low; therefore, when the water-based polyurethane emulsion is 15-25 parts by weight, 14-24 parts by weight of deionized water is suitable. When the water-based polyurethane emulsion is 15 to 25 parts by weight, if its nonionic surfactant is less than 0.8 parts by weight, it will cause uneven blending of the emulsion; The presence of the agent affects the film-forming process; therefore, when the water-based polyurethane emulsion is 15-25 parts by weight, the non-ionic surfactant is suitable for 0.8-1.2 parts by weight.
优选地，所述的尿素包膜复合乳液的组成如下，以重量份计：Preferably, the composition of the urea-coated composite emulsion is as follows, in parts by weight:
更优选地，所述的尿素包膜复合乳液的组成如下，以重量份计：More preferably, the composition of described urea-coated composite emulsion is as follows, in parts by weight:
本发明还涉及所述尿素包膜复合乳液的制备方法。The invention also relates to a preparation method of the urea-coated composite emulsion.
该尿素包膜复合乳液制备方法的步骤如下：The steps of the preparation method of the urea-coated composite emulsion are as follows:
首先将14~24重量份去离子水放到容器中，用浓氨水将其pH值调节至7.8~8.2；然后使用高剪切分散乳化机，在转速480~520rpm的条件下分别顺序地加入50~70重量份苯丙乳液、0.8~1.2重量份脂肪醇聚氧乙烯醚硫酸钠或烷基聚氧乙烯醚与15~25重量份水性聚氨酯乳液，然后在转速15000~20000rpm的条件下搅拌8~10min，于是得到所述的尿素包膜复合乳液。First, put 14~24 parts by weight of deionized water into the container, adjust its pH value to 7.8~8.2 with concentrated ammonia water; then use a high-shear dispersing emulsifier, add 50 ~70 parts by weight of styrene-acrylic emulsion, 0.8~1.2 parts by weight of fatty alcohol polyoxyethylene ether sodium sulfate or alkyl polyoxyethylene ether and 15~25 parts by weight of water-based polyurethane emulsion, and then stirred at a speed of 15000~20000rpm for 8~ 10min, thus obtaining the described urea-coated composite emulsion.
本发明使用的高剪切分散乳化机是目前市场上销售的产品，例如上海弗鲁克流体机械制造有限公司以商品名FM200销售的高剪切分散乳化机，其转速300~23000rpm，无级变速控制。The high-shear dispersing emulsifying machine used in the present invention is a product currently on the market, such as the high-shearing dispersing emulsifying machine sold by Shanghai Fluke Fluid Machinery Manufacturing Co., Ltd. under the trade name FM200, its rotating speed is 300 ~ 23000rpm, stepless speed change control.
本发明还涉及另一种用于尿素包膜的尿素包膜复合乳液。The invention also relates to another urea-coated composite emulsion used for urea coating.
该尿素包膜复合乳液的组成如下，以重量份计：The composition of this urea-coated composite emulsion is as follows, in parts by weight:
所述的水性聚氨酯乳液的活化温度是40~60℃；The activation temperature of the water-based polyurethane emulsion is 40 to 60°C;
所述的苯丙乳液的玻璃化转化温度是20~25℃，最低成膜温度是16~21℃；The glass transition temperature of the styrene-acrylic emulsion is 20-25°C, and the minimum film-forming temperature is 16-21°C;
所述的有机硅乳液水乳型涂料的拉伸强度≥0.5兆帕，断裂伸长率≥80%。The tensile strength of the silicone emulsion water-emulsion paint is ≥0.5 MPa, and the elongation at break is ≥80%.
所述的水性聚氨酯乳液、苯丙乳液、去离子水、脂肪醇聚氧乙烯醚硫酸钠或烷基聚氧乙烯醚如前面所述，在此不再赘述。The water-based polyurethane emulsion, styrene-acrylic emulsion, deionized water, fatty alcohol polyoxyethylene ether sodium sulfate or alkyl polyoxyethylene ether are as described above, and will not be repeated here.
硅油的油含量一般是20~30重量%，pH 6~8。它在3000r/min条件下离心稳定性达到15~30min。它的表面张力小，耐热，抗氧化。它是在如十二烷基磺酸钠之类的阴离子表面活性剂或在如十六烷基三甲基溴化铵之类阳离子表面活性剂和催化剂的存在下，由八甲基环四硅氧烷进行乳液聚合而得到的。它是目前市场上销售的产品，例如北京宝威乳胶有限公司以商品名POLYWELL PE-2199销售的有机硅乳液。The oil content of silicone oil is generally 20~30% by weight, pH 6~8. Its centrifugal stability reaches 15~30min under the condition of 3000r/min. It has low surface tension, heat resistance and oxidation resistance. It is synthesized from octamethylcyclotetrasilane in the presence of anionic surfactants such as sodium dodecylsulfonate or cationic surfactants such as cetyltrimethylammonium bromide and a catalyst Obtained by emulsion polymerization of oxane. It is a product currently on the market, such as the silicone emulsion sold by Beijing Baowei Latex Co., Ltd. under the trade name POLYWELL PE-2199.
水性聚氨酯乳液为15~25重量份时，如果有机硅乳液小于2重量份时，则会降低膜层的亲水性；如果有机硅乳液大于8重量份时，则会导致膜层脆硬从而降低膜层机械稳定性；因此，水性聚氨酯乳液为15~25重量份时，有机硅乳液为2~8重量份是合适的。水性聚氨酯乳液、苯丙乳液、去离子水与非离子表面活性剂如前面所述，在此不再赘述。When the water-based polyurethane emulsion is 15 to 25 parts by weight, if the silicone emulsion is less than 2 parts by weight, the hydrophilicity of the film layer will be reduced; if the silicone emulsion is greater than 8 parts by weight, it will cause the film layer to be brittle and hard to reduce The mechanical stability of the film layer; therefore, when the water-based polyurethane emulsion is 15-25 parts by weight, the silicone emulsion is suitable for 2-8 parts by weight. The water-based polyurethane emulsion, styrene-acrylic emulsion, deionized water and non-ionic surfactant are as described above, and will not be repeated here.
优选地，所述的尿素包膜复合乳液的组成如下，以重量份计：Preferably, the composition of the urea-coated composite emulsion is as follows, in parts by weight:
更优选地，所述的尿素包膜复合乳液的组成如下，以重量份计：More preferably, the composition of described urea-coated composite emulsion is as follows, in parts by weight:
本发明还涉及上述尿素包膜复合乳液的制备方法。The present invention also relates to a preparation method of the above-mentioned urea-coated composite emulsion.
该尿素包膜复合乳液制备方法的步骤如下：The steps of the preparation method of the urea-coated composite emulsion are as follows:
首先将14~24重量份去离子水放到容器中，用浓氨水将其pH值调节至7.8~8.2；然后使用高剪切分散乳化机，在转速480~520rpm的条件下分别顺序地加入50~70重量份苯丙乳液、0.8~1.2重量份脂肪醇聚氧乙烯醚硫酸钠或烷基聚氧乙烯醚、15~25重量份水性聚氨酯乳液与2~8重量份有机硅乳液，然后在转速15000~20000rpm的条件下搅拌8~10min，于是得到所述的尿素包膜复合乳液。First, put 14~24 parts by weight of deionized water into the container, adjust its pH value to 7.8~8.2 with concentrated ammonia water; then use a high-shear dispersing emulsifier, add 50 ~70 parts by weight of styrene-acrylic emulsion, 0.8~1.2 parts by weight of fatty alcohol polyoxyethylene ether sodium sulfate or alkyl polyoxyethylene ether, 15~25 parts by weight of water-based polyurethane emulsion and 2~8 parts by weight of silicone emulsion, and then Stirring for 8-10 minutes under the condition of 15000-20000 rpm, thus obtaining the urea-coated composite emulsion.
使用的高剪切分散乳化机如前面所述，在此不再赘述。The high-shear dispersing and emulsifying machine used is as described above and will not be repeated here.
本发明还涉及使用上述尿素包膜复合乳液制备包膜尿素肥料的方法。该包膜尿素肥料制备方法的步骤如下：The present invention also relates to a method for preparing coated urea fertilizer by using the above-mentioned urea-coated composite emulsion. The steps of the preparation method of the coated urea fertilizer are as follows:
具体工艺流程参见附图1，其中1-尿素预热转鼓，2-空气压缩机，3-罗茨鼓风机，4-气体缓冲罐，5-加热器，6-换热器，7-流化床，8-包膜液储槽，9-蠕动泵，10-热处理转鼓。See accompanying drawing 1 for the specific process flow, wherein 1-urea preheating drum, 2-air compressor, 3-Roots blower, 4-gas buffer tank, 5-heater, 6-heat exchanger, 7-fluidization Bed, 8-coating liquid storage tank, 9-peristaltic pump, 10-heat treatment drum.
A、预热处理A. Preheating
将粒径2~4mm尿素颗粒放于预热转鼓中，在温度48~52℃的条件下进行预热处理4~6min；Put the urea particles with a particle size of 2~4mm in the preheating drum, and perform preheating treatment at a temperature of 48~52°C for 4~6 minutes;
所述的预热转鼓1是一种在肥料工业技术领域中通常使用的设备。The preheating drum 1 is a device commonly used in the technical field of fertilizer industry.
B、流化B. Fluidization
开启流化床设备的风机与加热器，调节流化气量和温度，使流化床处于工作状态，然后加入步骤A的预热尿素颗粒，使其处于湍动流化状态。Turn on the fan and heater of the fluidized bed equipment, adjust the volume and temperature of the fluidized gas to keep the fluidized bed in a working state, and then add the preheated urea particles in step A to make it in a turbulent fluidized state.
所述的风机例如是罗茨鼓风机3。The fan is, for example, a Roots blower 3 .
具体地，开启控制系统电源，按下罗茨鼓风机3启动按钮和电加热器5按钮，并调节流化气量，使气体经缓冲罐4和电加热器5进入流化床7，使流化床7处于工作状态。Specifically, turn on the power supply of the control system, press the Roots blower 3 start button and the electric heater 5 button, and adjust the amount of fluidizing gas so that the gas enters the fluidized bed 7 through the buffer tank 4 and the electric heater 5, so that the fluidized bed 7 is in working condition.
所述的流化床7是一种在肥料工业技术领域中通常使用的设备，它通常包括流化气均布室、气体分布板、底部倒椎、圆柱形主体（直径通常为20~30cm）、扩大段和雾化喷嘴六个组成部分。The fluidized bed 7 is a kind of equipment commonly used in the technical field of fertilizer industry, which usually includes a fluidized gas uniform distribution chamber, a gas distribution plate, an inverted cone at the bottom, and a cylindrical body (usually 20 to 30 cm in diameter) , expansion section and atomizing nozzle six components.
C、喷涂C. Spraying
使用蠕动泵通过喷头，在压缩气压力为0.1~0.3MP、温度22~28℃与速率10~30ml/min的条件下将以尿素重量计20~30%所述的尿素包膜复合乳液喷涂在所述处于湍动流化状态的尿素颗粒表面上，形成一种包膜尿素。Use a peristaltic pump to spray the urea-coated composite emulsion described in 20-30% by weight of urea on the nozzle under the conditions of compressed air pressure of 0.1-0.3MP, temperature of 22-28°C and rate of 10-30ml/min. A kind of coated urea is formed on the surface of the urea particles in the turbulent fluidization state.
具体地，使用蠕动泵9将装在包膜液储槽8中的本发明尿素包膜复合乳液输送给喷头，同时控制空气压缩机2的气体压力和流量，压缩气体经换热器6恒温处理后，将喷头中的尿素包膜复合乳液雾化、喷涂、包覆在流化床7内处于湍动状态的大颗粒尿素表面上。Specifically, a peristaltic pump 9 is used to deliver the urea-coated composite emulsion of the present invention contained in the coating liquid storage tank 8 to the nozzle, while controlling the gas pressure and flow rate of the air compressor 2, and the compressed gas is treated at a constant temperature by the heat exchanger 6 Finally, the urea-coated composite emulsion in the nozzle is atomized, sprayed, and coated on the surface of the large-grained urea in a turbulent state in the fluidized bed 7 .
D、防粘结处理D. Anti-bonding treatment
往步骤C得到的包膜尿素中喷入以包膜尿素重量计0.5~1%的液体石蜡进行防粘结处理2.0-5.0分钟，然后放置于温度75~85℃的热处理转鼓中，添加以包膜尿素重量计0.5~1%的石蜡，再在温度75~85℃下热处理15~25min，然后冷却到温度50℃，得到所述的包膜尿素肥料。Spray 0.5-1% liquid paraffin based on the weight of the coated urea into the coated urea obtained in step C for anti-adhesive treatment for 2.0-5.0 minutes, then place it in a heat treatment drum at a temperature of 75-85°C, add 0.5-1% paraffin by weight of the coated urea, heat treatment at a temperature of 75-85° C. for 15-25 minutes, and then cooled to a temperature of 50° C. to obtain the coated urea fertilizer.
所述的热处理转鼓是一种在肥料工业技术领域中通常使用的设备。The heat treatment drum is a kind of equipment commonly used in the technical field of fertilizer industry.
根据本发明，所述的尿素用一种选自碳酸氢铵、碳酸铵、硫酸铵、氯化铵、硝酸铵、磷酸一氢铵、磷酸二氢铵、硫酸钾或氯化钾的水溶性肥料代替。According to the present invention, the urea is treated with a water-soluble fertilizer selected from ammonium bicarbonate, ammonium carbonate, ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, potassium sulfate or potassium chloride replace.
具体地，除了对尿素进行包膜外，采用本发明方法可以对上述水溶性肥料进行包膜，从而可以提高肥料利用率，减少肥料流失，保护了环境。Specifically, in addition to coating the urea, the method of the present invention can be used to coat the above-mentioned water-soluble fertilizer, so that the utilization rate of the fertilizer can be improved, the loss of the fertilizer can be reduced, and the environment can be protected.
本发明的特点在于利用采用水性聚氨酯、苯丙乳液与有机硅乳液共混制备一种水溶性肥料的包膜剂，并使用该包膜剂制备得到包膜控释肥料。水性聚氨酯与苯丙乳液二元共混乳液延缓了快速释放阶段的斜率，使包膜控释肥料的释放期得到明显的增长，是单纯使用苯丙乳液包膜的1.5倍。而使用有机硅乳液、水性聚氨酯与苯丙乳液三元共混乳液作为包膜剂制备的包膜肥料，明显延长了快速释放起始时间，使其在水浸泡15天的条件下释放10%左右，这与种子养分临近期（约20天）内养分吸收量很少相适宜，同时其快速释放阶段的斜率也得到有效控制，释放期延长。采用聚合物乳液共混改性，能够提高变包膜肥料的控释性能，尤其是采用三元共混能够很好的与植物养分吸收相匹配。The present invention is characterized in that a water-soluble fertilizer coating agent is prepared by blending water-based polyurethane, styrene-acrylic emulsion and organic silicon emulsion, and the coated controlled-release fertilizer is prepared by using the coating agent. The binary blend emulsion of water-based polyurethane and styrene-acrylic emulsion delayed the slope of the rapid release phase, and significantly increased the release period of the coated controlled-release fertilizer, which was 1.5 times that of the simple coating of styrene-acrylic emulsion. However, the coated fertilizer prepared by using silicone emulsion, water-based polyurethane and styrene-acrylic emulsion ternary blend emulsion as the coating agent significantly prolongs the initial time of rapid release, allowing it to release about 10% under the condition of 15 days of water soaking. , which is suitable for the little nutrient uptake in the near period of seed nutrient (about 20 days), and at the same time, the slope of the rapid release stage is also effectively controlled, and the release period is prolonged. The polymer emulsion blending modification can improve the controlled-release performance of the variable coating fertilizer, especially the ternary blending can well match the plant nutrient absorption.
本发明的尿素包膜复合乳液可以用于任何水溶性肥料进行包膜。The urea-coated composite emulsion of the present invention can be used for coating any water-soluble fertilizer.
本发明的包膜肥料可作为基肥、追肥使用。The coated fertilizer of the present invention can be used as base fertilizer and topdressing fertilizer.
本发明的包膜肥料使用量需根据土壤状况、作物品种、作物生育期、作物营养状况等因素进行确定。The usage amount of the coated fertilizer of the present invention needs to be determined according to factors such as soil condition, crop variety, crop growth period, and crop nutritional status.
除非另有说明，本发明所涉及的“％”均为重量百分比。Unless otherwise specified, the "%" involved in the present invention are all percentages by weight.
[有益效果][beneficial effect]
本发明的尿素包膜复合乳液延缓了肥料快速释放阶段的斜率，使包膜控释肥料的释放期得到明显的增长，是单纯使用苯丙乳液包膜的1.5倍。而使用有机硅乳液、水性聚氨酯与苯丙乳液三元共混乳液作为包膜剂制备的包膜肥料，明显延长了快速释放起始时间，使其在水浸泡15天的条件下释放10%左右，这与种子养分临近期（约20天）内养分吸收量很少相适宜，同时其快速释放阶段的斜率也得到有效控制，释放期延长。采用聚合物乳液共混改性，能够提高变包膜肥料的控释性能，尤其是采用三元共混能够很好的与植物养分吸收相匹配。本发明的包膜复合乳液可以用于任何水溶性肥料进行包膜，具有非常广泛的应用前景。The urea-coated composite emulsion of the present invention delays the slope of the quick-release phase of the fertilizer, and significantly prolongs the release period of the coated controlled-release fertilizer, which is 1.5 times that of the simple styrene-acrylic emulsion coating. However, the coated fertilizer prepared by using silicone emulsion, water-based polyurethane and styrene-acrylic emulsion ternary blend emulsion as the coating agent significantly prolongs the initial time of rapid release, allowing it to release about 10% under the condition of 15 days of water soaking. , which is suitable for the little nutrient uptake in the near period of seed nutrient (about 20 days), and at the same time, the slope of the rapid release stage is also effectively controlled, and the release period is prolonged. The polymer emulsion blending modification can improve the controlled-release performance of the variable coating fertilizer, especially the ternary blending can well match the plant nutrient absorption. The coating composite emulsion of the invention can be used for coating any water-soluble fertilizer, and has very wide application prospects.
【附图说明】【Description of drawings】
图1是流化床喷雾制备复合乳液包膜尿素的工艺流程图Fig. 1 is the process flow diagram of preparing compound emulsion coated urea by fluidized bed spraying
1-尿素预热转鼓，2-空气压缩机，3-罗茨鼓风机，4-气体缓冲罐，5-加热器，6-换热器，7-流化床，8-包膜液储槽，9-蠕动泵，10-热处理转鼓。1-Urea preheating drum, 2-Air compressor, 3-Roots blower, 4-Gas buffer tank, 5-Heater, 6-Heat exchanger, 7-Fluidized bed, 8-Coating liquid storage tank , 9-peristaltic pump, 10-heat treatment drum.
图2不同包膜剂制备包膜肥料的养分释放累积曲线。Fig. 2 Cumulative curves of nutrient release of coated fertilizers prepared with different coating agents.
【具体实施方式】【Detailed ways】
通过下述实施例将能够更好地理解本发明。The present invention will be better understood by the following examples.
实施例1：本发明尿素包膜复合乳液的制备Embodiment 1: Preparation of urea-coated composite emulsion of the present invention
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
首先将14重量份去离子水放到容器中，用浓氨水将其pH值调节至7.8；然后使用上海弗鲁克流体机械制造有限公司以商品名FM200销售的高剪切分散乳化机，在转速480rpm的条件下分别顺序地加入50重量份由罗门哈斯公司以商品名AS-2010销售的苯丙乳液，其固体含量49重量%、玻璃化转化温度21℃；0.8重量份国药集团销售的脂肪醇聚氧乙烯醚硫酸钠；15重量份由拜耳公司以商品名Dispercoll U54销售的水性聚氨酯乳液，其固体含量50重量%、粘度40-400mPa.s、活化温度45-55℃；然后在转速15000rpm的条件下搅拌8min，于是得到所述的尿素包膜复合乳液。First put 14 parts by weight of deionized water into the container, and adjust its pH value to 7.8 with concentrated ammonia water; Under the condition of 480rpm, 50 parts by weight of styrene-acrylic emulsion sold by Rohm and Haas under the trade name AS-2010 were sequentially added, with a solid content of 49% by weight and a glass transition temperature of 21°C; Fatty alcohol polyoxyethylene ether sodium sulfate; 15 parts by weight of the aqueous polyurethane emulsion sold by Bayer under the trade name Dispercoll U54, its solid content 50% by weight, viscosity 40-400mPa.s, activation temperature 45-55 ℃; Stirring for 8 minutes under the condition of 15000 rpm, thus obtaining the urea-coated composite emulsion.
实施例2：本发明尿素包膜复合乳液的制备Embodiment 2: Preparation of urea-coated composite emulsion of the present invention
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
按照与实施例1相同的实施方式进行，只是首先将24重量份去离子水放到容器中，用浓氨水将其pH值调节至8.2；然后使用所述的高剪切分散乳化机，在转速520rpm的条件下分别顺序地加入70重量份所述的苯丙乳液；1.2重量份所述的烷基聚氧乙烯醚；25重量份所述的水性聚氨酯乳液；然后在转速20000rpm的条件下搅拌10min，于是得到所述的尿素包膜复合乳液。Carry out according to the same embodiment as Example 1, just put 24 parts by weight deionized water in the container at first, adjust its pH value to 8.2 with concentrated ammonia water; Under the condition of 520rpm, add 70 parts by weight of the described styrene-acrylic emulsion sequentially respectively; 1.2 parts by weight of the described alkyl polyoxyethylene ether; 25 parts by weight of the described water-based polyurethane emulsion; then stir for 10min under the condition of rotating speed 20000rpm , so as to obtain the described urea-coated composite emulsion.
实施例3：本发明尿素包膜复合乳液的制备Embodiment 3: Preparation of urea-coated composite emulsion of the present invention
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
按照与实施例1相同的实施方式进行，只是首先将18重量份去离子水放到容器中，用浓氨水将其pH值调节至8.0；然后使用所述的高剪切分散乳化机，在转速500rpm的条件下分别顺序地加入56重量份所述的苯丙乳液；0.9重量份所述的脂肪醇聚氧乙烯醚硫酸钠；18重量份所述的水性聚氨酯乳液；然后在转速15000~2000018001600rpm的条件下搅拌8~10910min，于是得到所述的尿素包膜复合乳液。Carry out according to the same embodiment as Example 1, just put 18 parts by weight of deionized water into the container at first, adjust its pH value to 8.0 with concentrated ammonia water; Under the condition of 500rpm, add the styrene-acrylic emulsion described in 56 parts by weight sequentially respectively; The fatty alcohol polyoxyethylene ether sodium sulfate described in 0.9 parts by weight; The water-based polyurethane emulsion described in 18 parts by weight; Under the condition of stirring for 8-10910min, the urea-coated composite emulsion is obtained.
实施例4：本发明尿素包膜复合乳液的制备Embodiment 4: Preparation of urea-coated composite emulsion of the present invention
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
按照与实施例1相同的实施方式进行，只是首先将20重量份去离子水放到容器中，用浓氨水将其pH值调节至8.0；然后使用所述的高剪切分散乳化机，在转速510rpm的条件下分别顺序地加入62重量份所述的苯丙乳液；1.0重量份所述的烷基聚氧乙烯醚；22重量份所述的水性聚氨酯乳液；然后在转速1600rpm的条件下搅拌10min，于是得到所述的尿素包膜复合乳液。Carry out according to the same embodiment as Example 1, just at first put 20 parts by weight of deionized water into the container, adjust its pH value to 8.0 with concentrated ammonia water; Under the condition of 510rpm, respectively sequentially add 62 parts by weight of the described styrene-acrylic emulsion; 1.0 parts by weight of the described alkyl polyoxyethylene ether; 22 parts by weight of the described water-based polyurethane emulsion; then stir for 10min under the condition of rotating speed 1600rpm , so as to obtain the described urea-coated composite emulsion.
实施例5：本发明尿素包膜复合乳液的制备Embodiment 5: Preparation of urea-coated composite emulsion of the present invention
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
首先将14重量份去离子水放到容器中，用浓氨水将其pH值调节至7.8；然后使用上海弗鲁克流体机械制造有限公司以商品名FM200销售的高剪切分散乳化机，在转速480rpm的条件下分别顺序地加入50重量份由罗门哈斯公司以商品名AS-2010销售的苯丙乳液，其固体含量49重量%、玻璃化转化温度21℃；0.8重量份国药集团销售的脂肪醇聚氧乙烯醚硫酸钠；15重量份由拜耳公司以商品名Dispercoll U54销售的水性聚氨酯乳液，其固体含量50重量%、粘度40-400mPa.s、活化温度45-55℃；2重量份由北京宝威乳胶有限公司以商品名POLYWELL PE-2199销售的有机硅乳液，然后在转速15000rpm的条件下搅拌8min，于是得到所述的尿素包膜复合乳液。First put 14 parts by weight of deionized water into the container, and adjust its pH value to 7.8 with concentrated ammonia water; Under the condition of 480rpm, 50 parts by weight of styrene-acrylic emulsion sold by Rohm and Haas under the trade name AS-2010 were sequentially added, with a solid content of 49% by weight and a glass transition temperature of 21°C; Fatty alcohol polyoxyethylene ether sodium sulfate; 15 parts by weight of water-based polyurethane emulsion sold by Bayer under the trade name Dispercoll U54, with a solid content of 50% by weight, a viscosity of 40-400mPa.s, and an activation temperature of 45-55°C; 2 parts by weight The silicone emulsion sold by Beijing Baowei Latex Co., Ltd. under the trade name POLYWELL PE-2199 was then stirred for 8 minutes at a rotational speed of 15000 rpm, thus obtaining the urea-coated composite emulsion.
实施例6：本发明尿素包膜复合乳液的制备Embodiment 6: Preparation of urea-coated composite emulsion of the present invention
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
按照与实施例5相同的实施方式进行，只是首先将24重量份去离子水放到容器中，用浓氨水将其pH值调节至8.2；然后使用所述的高剪切分散乳化机，在转速520rpm的条件下分别顺序地加入70重量份所述的苯丙乳液；1.2重量份所述的烷基聚氧乙烯醚；25重量份所述的水性聚氨酯乳液；8重量份所述的有机硅乳液，然后在转速20000rpm的条件下搅拌10min，于是得到所述的尿素包膜复合乳液。Carry out according to the same embodiment as Example 5, just at first put 24 parts by weight deionized water in the container, adjust its pH value to 8.2 with concentrated ammonia water; Under the condition of 520rpm, respectively sequentially add 70 parts by weight of the described styrene-acrylic emulsion; 1.2 parts by weight of the described alkyl polyoxyethylene ether; 25 parts by weight of the described water-based polyurethane emulsion; 8 parts by weight of the described silicone emulsion , and then stirred for 10 min under the condition of a rotating speed of 20000 rpm, so as to obtain the urea-coated composite emulsion.
实施例7：本发明尿素包膜复合乳液的制备Embodiment 7: Preparation of urea-coated composite emulsion of the present invention
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
按照与实施例5相同的实施方式进行，只是首先将16重量份去离子水放到容器中，用浓氨水将其pH值调节至8.0；然后使用所述的高剪切分散乳化机，在转速500rpm的条件下分别顺序地加入54重量份所述的苯丙乳液；0.9重量份所述的脂肪醇聚氧乙烯醚硫酸钠；17重量份所述的水性聚氨酯乳液；4重量份所述的有机硅乳液，然后在转速1800rpm的条件下搅拌9min，于是得到所述的尿素包膜复合乳液。Carry out according to the same embodiment as Example 5, just first put 16 parts by weight of deionized water into the container, adjust its pH value to 8.0 with concentrated ammonia water; then use the described high-shear dispersing emulsifier, Under the condition of 500rpm, add the styrene-acrylic emulsion described in 54 parts by weight sequentially respectively; The fatty alcohol polyoxyethylene ether sodium sulfate described in 0.9 parts by weight; The water-based polyurethane emulsion described in 17 parts by weight; The silicon emulsion was then stirred for 9 minutes at a rotational speed of 1800 rpm, thus obtaining the urea-coated composite emulsion.
实施例8：本发明尿素包膜复合乳液的制备Embodiment 8: Preparation of urea-coated composite emulsion of the present invention
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
按照与实施例5相同的实施方式进行，只是首先将22重量份去离子水放到容器中，用浓氨水将其pH值调节至8.0；然后使用所述的高剪切分散乳化机，在转速510rpm的条件下分别顺序地加入65重量份所述的苯丙乳液；1.0重量份所述的烷基聚氧乙烯醚；24重量份所述的水性聚氨酯乳液；6重量份所述的有机硅乳液，然后在转速1600rpm的条件下搅拌10min，于是得到所述的尿素包膜复合乳液。Carry out according to the same embodiment as Example 5, just put 22 parts by weight of deionized water into the container at first, adjust its pH value to 8.0 with concentrated ammonia water; Under the condition of 510rpm, respectively sequentially add 65 parts by weight of the described styrene-acrylic emulsion; 1.0 parts by weight of the described alkyl polyoxyethylene ether; 24 parts by weight of the described water-based polyurethane emulsion; 6 parts by weight of the described silicone emulsion , and then stirred for 10 min at a rotating speed of 1600 rpm, thus obtaining the urea-coated composite emulsion.
实施例9：使用本发明的包膜复合乳液制备包膜尿素肥料Embodiment 9: Prepare coated urea fertilizer using the coated composite emulsion of the present invention
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
A、预热处理A. Preheating
将由山东瑞星化工有限公司生产的粒径2~4mm尿素颗粒放于预热转鼓1中，在温度52℃的条件下进行预热处理4min；Put urea granules with a particle size of 2~4mm produced by Shandong Rising Chemical Co., Ltd. in the preheating drum 1, and perform preheating treatment at a temperature of 52°C for 4 minutes;
B、流化B. Fluidization
开启流化床7设备的风机与加热器，调节流化气量和温度，使流化床处于工作状态，然后加入步骤A的预热尿素颗粒，使其处于湍动流化状态；Turn on the fan and heater of the fluidized bed 7 equipment, adjust the fluidization gas volume and temperature, make the fluidized bed in working condition, and then add the preheated urea particles of step A to make it in a turbulent fluidized state;
C、喷涂C. Spraying
使用蠕动泵9通过喷头，在压缩气压力为0.1MP、温度28℃与速率30ml/min的条件下将以尿素重量计20%实施例1制备的尿素包膜复合乳液喷涂在所述处于湍动流化状态的尿素颗粒表面上，形成一种包膜尿素；Use a peristaltic pump 9 to spray the urea-coated composite emulsion prepared in Example 1 by 20% by weight of urea on the turbulent under the conditions that the compressed air pressure is 0.1MP, the temperature is 28°C, and the rate is 30ml/min. On the surface of the urea particles in the fluidized state, a kind of coated urea is formed;
D、防粘结处理D. Anti-bonding treatment
往步骤C得到的包膜尿素中喷入以包膜尿素重量计0.5%的液体石蜡进行防粘结处理2.0分钟，然后放置于温度85℃的烘干机转鼓中，添加以包膜尿素重量计1.0%的石蜡，再在温度85℃下热处理15min，然后冷却到温度50℃，得到所述的包膜尿素肥料。Spray 0.5% liquid paraffin based on the weight of coated urea into the coated urea obtained in step C for anti-adhesive treatment for 2.0 minutes, then place it in a drum of a dryer at a temperature of 85°C, add the weight of coated urea 1.0% paraffin, heat treatment at a temperature of 85° C. for 15 minutes, and then cooled to a temperature of 50° C. to obtain the coated urea fertilizer.
实施例10：使用本发明的包膜复合乳液制备包膜尿素肥料Example 10: Prepare coated urea fertilizer using the coated composite emulsion of the present invention
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
A、预热处理A. Preheating
将由山东瑞星化工有限公司生产的粒径2~4mm尿素颗粒放于预热转鼓1中，在温度48℃的条件下进行预热处理6min；Put urea granules with a particle size of 2~4mm produced by Shandong Rising Chemical Co., Ltd. in the preheating drum 1, and perform preheating treatment at a temperature of 48°C for 6 minutes;
B、流化B. Fluidization
开启流化床设备7的风机与加热器，调节流化气量和温度，使流化床处于工作状态，然后加入步骤A的预热尿素颗粒，使其处于湍动流化状态；Turn on the fan and heater of the fluidized bed equipment 7, adjust the fluidization gas volume and temperature, make the fluidized bed in working condition, then add the preheated urea particles of step A to make it in a turbulent fluidized state;
C、喷涂C. Spraying
使用蠕动泵9通过喷头，在压缩气压力为0.3MP、温度22℃与速率10ml/min的条件下将以尿素重量计30%实施例5制备的尿素包膜复合乳液喷涂在所述处于湍动流化状态的尿素颗粒表面上，形成一种包膜尿素；Use the peristaltic pump 9 to pass through the nozzle, and the urea-coated composite emulsion prepared in the urea weight 30% embodiment 5 will be sprayed on the turbulent under the condition that the compressed air pressure is 0.3MP, the temperature is 22 ℃ and the speed is 10ml/min. On the surface of the urea particles in the fluidized state, a kind of coated urea is formed;
D、防粘结处理D. Anti-bonding treatment
往步骤C得到的包膜尿素中喷入以包膜尿素重量计1.0%的液体石蜡进行防粘结处理5.0分钟，然后放置于温度75℃的烘干机转鼓中，添加以包膜尿素重量计0.5%的石蜡，再在温度75℃下热处理25min，然后冷却到温度50℃，得到所述的包膜尿素肥料。Spray 1.0% liquid paraffin in the weight of coated urea into the coated urea obtained in step C for anti-adhesive treatment for 5.0 minutes, then place it in a dryer drum at a temperature of 75°C, add the weight of coated urea 0.5% paraffin, heat treatment at a temperature of 75° C. for 25 minutes, and then cooled to a temperature of 50° C. to obtain the coated urea fertilizer.
试验实施例：复合包膜控释肥料养分释放性能的测定Test Example: Determination of Nutrient Release Performance of Composite Coated Controlled Release Fertilizer
采用水浸泡法对不同包膜剂处理的包膜控释肥料的养分释放性能进行测定，三种不同包膜剂所制备的包膜肥料养分释放累积率见表1。The nutrient release performance of the coated controlled-release fertilizer treated with different coating agents was measured by water immersion method. The nutrient release accumulation rate of the coated fertilizer prepared by three different coating agents is shown in Table 1.
表1：不同包膜剂制备包膜肥料的养分释放累积释放率Table 1: Cumulative release rate of nutrient release of coated fertilizer prepared by different coating agents
由表1的结果可知，单独使用苯丙乳液制备的包膜控释肥料在水浸泡条件下，存在10天后开始有一个快速释放阶段，其释放曲线（见附图2）表现为典型的“S”型。As can be seen from the results in Table 1, the coated controlled-release fertilizer prepared using styrene-acrylic emulsion alone begins to have a rapid release phase after 10 days of existence under water soaking conditions, and its release curve (see accompanying drawing 2) shows a typical "S "type.
使用水性聚氨酯乳液与苯丙乳液的二元共混乳液延缓了快速释放阶段的斜率，使包膜控释肥料的释放期得到明显的增长，约是单纯使用苯丙乳液处理的1.5倍。而使用有机硅乳液、水性聚氨酯乳液与苯丙乳液的三元共混乳液作为包膜剂制备的包膜肥料，明显延长了快速释放起始时间，使其在水浸泡15天的条件下释放10%左右，这与种子养分临近期（约20天）内养分吸收量很少相适宜，同时其快速释放阶段的斜率也得到有效控制，释放期延长。采用聚合物乳液共混改性，能够提高变包膜肥料的控释性能，尤其是采用三元共混能够很好的与植物养分吸收相匹配。The use of the binary blend emulsion of water-based polyurethane emulsion and styrene-acrylic emulsion delayed the slope of the rapid release phase, and significantly increased the release period of the coated controlled-release fertilizer, which was about 1.5 times that of the simple use of styrene-acrylic emulsion. However, the coated fertilizer prepared by using the ternary blend emulsion of silicone emulsion, water-based polyurethane emulsion and styrene-acrylic emulsion as the coating agent significantly prolongs the initial time of rapid release, allowing it to release 100% fertilizer after soaking in water for 15 days. %, which is suitable for the nutrient uptake of seeds in the immediate period (about 20 days), and the slope of the rapid release stage is also effectively controlled, and the release period is prolonged. The polymer emulsion blending modification can improve the controlled-release performance of the variable coating fertilizer, especially the ternary blending can well match the plant nutrient absorption.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210447434.7ACN102964186B (en) | 2012-11-09 | 2012-11-09 | Urea-coated composite emulsion and preparation method and application thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210447434.7ACN102964186B (en) | 2012-11-09 | 2012-11-09 | Urea-coated composite emulsion and preparation method and application thereof |
| Publication Number | Publication Date |
|---|---|
| CN102964186A CN102964186A (en) | 2013-03-13 |
| CN102964186Btrue CN102964186B (en) | 2014-11-26 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210447434.7AExpired - Fee RelatedCN102964186B (en) | 2012-11-09 | 2012-11-09 | Urea-coated composite emulsion and preparation method and application thereof |
| Country | Link |
|---|---|
| CN (1) | CN102964186B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9416064B2 (en)* | 2013-08-07 | 2016-08-16 | Chinese Academy of Agricultural Sciences Institute of Agricultural Resources and Regional Planning | Method for producing controlled-release fertilizer coated with polyurethane |
| CN104058820B (en)* | 2014-05-24 | 2016-04-13 | 蚌埠味多多学生营养餐有限公司 | A kind of slow-release compound fertilizer promoting soil fertility |
| CN104108991A (en)* | 2014-06-23 | 2014-10-22 | 合肥长润农业科技有限公司 | Catechol-containing polyurethane coated slow release compound fertilizer |
| CN105481559B (en)* | 2015-12-22 | 2018-12-21 | 河北百禾丰化肥有限公司 | It is a kind of using organosilicon oligomer as coating sustained release Eco-fertilizer preparation method |
| CN105646097A (en)* | 2016-03-10 | 2016-06-08 | 河南力浮科技有限公司 | Sustained-released nano humic acid chelated zinc fertilizer production method |
| CN106673830A (en)* | 2016-12-27 | 2017-05-17 | 盐城工学院 | Three-layer enveloping type high-water-absorption slow release fertilizer and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948241A (en)* | 2005-10-13 | 2007-04-18 | 南京理工大学 | Polymer composite coated slow release fertilizer |
| CN101037368A (en)* | 2007-02-12 | 2007-09-19 | 山东省农业科学院土壤肥料研究所 | Biological biodegradable self-control slow-releasing fertilizer and preparation method thereof |
| CN101244966A (en)* | 2008-03-24 | 2008-08-20 | 山东省农业科学院土壤肥料研究所 | A kind of biodegradable multifunctional self-controlled slow-release fertilizer and preparation method thereof |
| CN101348397A (en)* | 2007-08-15 | 2009-01-21 | 山东金正大生态工程股份有限公司 | Aqueous polymer coated controlled release fertilizer and preparation thereof |
| CN101798253A (en)* | 2010-04-26 | 2010-08-11 | 张夫道 | Method for preparing water-soluble phenolic aldehyde and hydrocinnamic mixture urea coated slow release formulation |
| US20120227451A1 (en)* | 2008-07-16 | 2012-09-13 | Agrium Inc. | Controlled release fertilizer composition |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948241A (en)* | 2005-10-13 | 2007-04-18 | 南京理工大学 | Polymer composite coated slow release fertilizer |
| CN101037368A (en)* | 2007-02-12 | 2007-09-19 | 山东省农业科学院土壤肥料研究所 | Biological biodegradable self-control slow-releasing fertilizer and preparation method thereof |
| CN101348397A (en)* | 2007-08-15 | 2009-01-21 | 山东金正大生态工程股份有限公司 | Aqueous polymer coated controlled release fertilizer and preparation thereof |
| CN101244966A (en)* | 2008-03-24 | 2008-08-20 | 山东省农业科学院土壤肥料研究所 | A kind of biodegradable multifunctional self-controlled slow-release fertilizer and preparation method thereof |
| US20120227451A1 (en)* | 2008-07-16 | 2012-09-13 | Agrium Inc. | Controlled release fertilizer composition |
| CN101798253A (en)* | 2010-04-26 | 2010-08-11 | 张夫道 | Method for preparing water-soluble phenolic aldehyde and hydrocinnamic mixture urea coated slow release formulation |
| Publication number | Publication date |
|---|---|
| CN102964186A (en) | 2013-03-13 |
| Publication | Publication Date | Title |
|---|---|---|
| CN102964186B (en) | Urea-coated composite emulsion and preparation method and application thereof | |
| CN101973808B (en) | Starch coating material and application thereof in coated sustained/controlled release fertilizers | |
| CN100457694C (en) | Biological biodegradable self-control slow-releasing fertilizer and preparation method thereof | |
| CN103421161B (en) | A kind of polyurethane coated fertilizer and coated fertilizer thereof | |
| CN105315096B (en) | Preparation method of composite coated water-retaining slow-release urea | |
| CN105367230A (en) | Modified starch-g-PVA / wood residue composite superabsorbent coated slow-release fertilizer | |
| US3979535A (en) | Process for the spray application of aqueous paints by controlling the temperature of the air in the paint spray zone | |
| CN1666972A (en) | A kind of effect control urea and preparation method thereof | |
| CN106927951B (en) | Based on water dispersion nano SiO2Modified water-based polyacrylate coated controlled release fertilizer and preparation method thereof | |
| CN101353283A (en) | Preparation method of acrylate mixed polymer urea slow-release coating agent | |
| CN101244966B (en) | A kind of biodegradable multifunctional self-controlled slow-release fertilizer and preparation method thereof | |
| CN105294289A (en) | Dual-channel coated material regulated stress-resistant efficient slow-release fertilizer for paddy rice and preparation method thereof | |
| CN106431069A (en) | Slowly released type anti-rust microcapsules applied to steel reinforced concrete and preparation method thereof | |
| CN105272602B (en) | Coated fertilizer and its preparation method and application is blended with lotus leaf powder in a kind of starch | |
| CN102126890B (en) | Preparation method of environmentally friendly fertilizer envelope material | |
| CN110983755A (en) | Antibacterial nano after-finishing reagent for knitted fabric and preparation method thereof | |
| CN111517873B (en) | A kind of controlled-release fertilizer coating agent and preparation method thereof, controlled-release fertilizer and application thereof | |
| CN106365795A (en) | Compound coated slow-release fertilizer for garden planting and method for preparing compound coated slow-release fertilizer | |
| CN104059672B (en) | A kind of environmentally friendly salt alkali resistance water preserving agent | |
| CN104592439B (en) | A kind of interpenetrating networks emulsion and its synthetic method to metal base with high adhesion force | |
| CN108101628A (en) | The preparation process of three red sweet shaddock plantation soil amendment fertilizers | |
| CN101805235B (en) | Sulfur-coated urea fertilizer and preparation method thereof | |
| JP2010077569A (en) | Coating agent for thread and thread coated with the same | |
| CN103788311A (en) | Novel epoxy-polyacrylate core-shell emulsion and preparation method thereof | |
| CN103304740B (en) | Degradable polymer fertilizer envelope material as well as preparation method and application thereof |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | Granted publication date:20141126 Termination date:20191109 | |
| CF01 | Termination of patent right due to non-payment of annual fee |