技术领域technical field
本发明属于肥料控释技术领域。特别涉及用于肥料控释的新型的溶剂型可降解的一种聚合物控释肥料包膜及其制备方法。The invention belongs to the technical field of fertilizer controlled release. In particular, it relates to a novel solvent-based degradable polymer controlled-release fertilizer coating for controlled-release of fertilizers and a preparation method thereof.
背景技术Background technique
控释肥料是指通过各种调控机制预先设定肥料在作物生长季节的释放模式，使其养分释放与作物需肥规律相一致的肥料。因此研究开发控释肥制备技术，使其养分释放时间和释放量与作物的需肥规律相吻合，最大限度的减少肥料损失，提高肥料利用率，降低化肥施用总量，降低施肥成本，减少环境污染，是当前化学肥料的发展方向之一。Controlled-release fertilizers refer to fertilizers that pre-set the release mode of fertilizers during the growing season of crops through various regulatory mechanisms, so that the release of nutrients is consistent with the law of fertilizer requirements of crops. Therefore, research and development of controlled-release fertilizer preparation technology, make its nutrient release time and release amount consistent with the law of fertilizer demand of crops, reduce fertilizer loss to the greatest extent, improve fertilizer utilization rate, reduce the total amount of chemical fertilizer application, reduce fertilization costs, and reduce environmental pollution. Pollution is one of the development directions of current chemical fertilizers.
聚合物膜材是决定控释肥性质的关键因素，聚合物包膜控释肥料按膜材不同的发展状况大致如下：(1)回收旧塑料和聚烯烃类包膜肥料，其特点是包膜工艺简单，但是使用有的毒有机溶剂，且材料不能在土壤中降解。1993年北京化工学院申请专利(中国专利：93100227.3)，以聚苯乙烯、聚乙烯、聚丙烯或聚氯乙烯为主材料，以吸附性的无机或有机物质粉末如膨润土等、共混填充物有动植物有机废料和矿物物质为包膜液助剂的包膜液体系。2003年中国农业大学申请专利(中国专利：03155813.5)，以聚烯烃为主要包膜材料，以松节油苯、甲苯、二甲苯为溶剂，以石蜡、有机物料淀粉等、无机物料碳酸钙等为包膜液助剂的包膜液体系。2004年山东农业大学申请专利(中国专利：200410035783.3)，以回收废旧热塑性树脂(聚苯乙烯树脂和聚乙烯树脂)为主要材料，以四氯乙烯和二氯甲烷为主要溶剂，以矿物粉、谷物粉、橡胶粉为包膜液助剂的包膜液体系；2005年北京市农林科学院申请专利(中国专利：200510000039.4)，以回收高分子材料(聚丙烯)为主要包膜材料，以松节油为溶剂，以沸石粉为包膜液助剂的包膜材料体系；(2)热固性树脂类包膜肥料，这类肥料的特点是成本较低，但该包膜工艺比较复杂。2003年南京大学等申请专利(中国专利：03132085.6)，脲醛树脂为包膜材料，以酸性甲醛水溶液为溶剂，以表面处理剂桐油或以桐油改性的酚醛树脂为包膜液助剂的包膜液体系；2004年山东农业大学申请专利(中国专利：200410024050.X)，以热固性有机高分子聚合物(改型环氧树脂和胺类固化剂)为主要材料；(3)热塑性树脂类包膜肥，其特点是材料比较柔软，机械性能优良。2001年中国科学院沈阳应用生态研究所申请专利(中国专利：01133415.0)，丙烯酸树脂和纤维素、淀粉为主要材料、以乙醇、丙酮、二氯甲烷、环己烷和甲苯为溶剂的包膜液体系；2003年华南农业大学申请专利(中国专利：03140097.3)，以水溶性树脂为主要材料，以醋酸水溶液为主要溶剂，以膨润土为包膜液助剂的包膜液体系；2005年南京理工大学申请专利(中国专利：200510094536.5)，以水乳液型和水溶液性胶粘剂为包膜材料的包膜体系。(4)可降解型聚合物包膜肥，这类包膜材料的特点是在土壤中可以完全为微生物所降解。1987和1989年日本的窒素公司在中国申请了相关的三项专利(中国专利：87105398，87105467，89101193)，以具降解性聚烯烃和聚醚多元醇为主要材料的包膜材料配方。2002年南京大学等申请专利(中国专利：02137895.9)，以硝化纤维素为包膜材料，以乙醇、乙醚为混合溶剂，以干性油脂添加剂桐油为包膜液助剂的包膜液体系。但是，在实际应用中，我国乃至世界控释肥领域制约其发展的最主要问题是聚合物膜材价格比较高、种类比较单一，实际应用的膜材基本上还没有突破回收的旧塑料或聚烯烃类材料，这些材料在土壤中难以降解，长期使用必然会带来严重的环境后果。相配套的包膜工艺多使用毒性大的有机溶剂，如四氯乙烯、氯仿、甲苯、二氯乙烷等，生产过程中存在火灾、安全隐患。已报道的可降解聚合物包膜工艺实际应用过于复杂而难以真正推广、应用。本发明提供了一种专门针对包膜控释肥料的新型可降解聚合物材料的制备方法以及利用此专项材料制备包膜控释肥料的方法。本发明所涉及的包膜材料及其包膜肥料的制备工艺经济可行。本发明可降解聚合物包膜控释肥料在国内外未见报道，在国内未见使用。Polymer film material is the key factor determining the properties of controlled-release fertilizers. The development status of polymer-coated controlled-release fertilizers according to different film materials is roughly as follows: (1) Recycling old plastics and polyolefin-coated fertilizers, which are characterized by coating The process is simple, but some toxic organic solvents are used, and the materials cannot be degraded in soil. In 1993, Beijing Institute of Chemical Technology applied for a patent (Chinese patent: 93100227.3). It is made of polystyrene, polyethylene, polypropylene or polyvinyl chloride as the main material, and is filled with absorbent inorganic or organic powder such as bentonite. The coating fluid system in which animal and plant organic waste and mineral substances are used as coating fluid additives. In 2003, China Agricultural University applied for a patent (Chinese patent: 03155813.5), using polyolefin as the main coating material, using turpentine, benzene, toluene, and xylene as solvents, and using paraffin, organic material starch, etc., and inorganic materials such as calcium carbonate as the coating Coating liquid system of liquid additives. In 2004, Shandong Agricultural University applied for a patent (Chinese patent: 200410035783.3), using recycled waste thermoplastic resin (polystyrene resin and polyethylene resin) as the main material, tetrachloroethylene and methylene chloride as the main solvent, mineral powder, grain Powder and rubber powder are coating liquid additives; in 2005, the Beijing Academy of Agriculture and Forestry applied for a patent (Chinese patent: 200510000039.4), using recycled polymer materials (polypropylene) as the main coating material, and turpentine as the solvent , a coating material system that uses zeolite powder as a coating liquid additive; (2) thermosetting resin coated fertilizers. This type of fertilizer is characterized by low cost, but the coating process is relatively complicated. In 2003, Nanjing University and others applied for a patent (Chinese patent: 03132085.6), using urea-formaldehyde resin as the coating material, using acidic formaldehyde solution as the solvent, and using tung oil as the surface treatment agent or phenolic resin modified with tung oil as the coating liquid auxiliary agent Liquid system; Shandong Agricultural University applied for a patent in 2004 (Chinese patent: 200410024050.X), with thermosetting organic polymer (modified epoxy resin and amine curing agent) as the main material; (3) thermoplastic resin coating Fertilizer, which is characterized by relatively soft material and excellent mechanical properties. In 2001, the Shenyang Institute of Applied Ecology of the Chinese Academy of Sciences applied for a patent (Chinese patent: 01133415.0). The coating liquid system uses acrylic resin, cellulose, and starch as the main materials, and ethanol, acetone, methylene chloride, cyclohexane, and toluene as solvents. ; In 2003, South China Agricultural University applied for a patent (Chinese patent: 03140097.3), which uses water-soluble resin as the main material, acetic acid aqueous solution as the main solvent, and bentonite as the coating liquid additive; in 2005, Nanjing University of Science and Technology applied Patent (Chinese patent: 200510094536.5), a coating system with water emulsion type and aqueous solution adhesive as the coating material. (4) Degradable polymer-coated fertilizer, which is characterized by the fact that it can be completely degraded by microorganisms in the soil. In 1987 and 1989, Japan's Susu Corporation applied for three related patents in China (Chinese patents: 87105398, 87105467, 89101193), a coating material formula with degradable polyolefin and polyether polyol as the main materials. In 2002, Nanjing University and others applied for a patent (Chinese patent: 02137895.9), using nitrocellulose as the coating material, ethanol and ether as the mixed solvent, and the coating fluid system with the dry oil additive tung oil as the coating fluid auxiliary agent. However, in practical applications, the main problem restricting its development in the field of controlled release fertilizers in my country and even in the world is that the price of polymer membranes is relatively high and the types are relatively single. Olefin materials are difficult to degrade in soil, and long-term use will inevitably bring serious environmental consequences. The matching coating process mostly uses highly toxic organic solvents, such as tetrachloroethylene, chloroform, toluene, dichloroethane, etc., and there are fire and safety hazards in the production process. The actual application of the reported degradable polymer coating technology is too complicated to be really popularized and applied. The invention provides a method for preparing a novel degradable polymer material specially for film-coated controlled-release fertilizers and a method for preparing film-coated controlled-release fertilizers using the special material. The preparation process of the coated material and the coated fertilizer involved in the present invention is economically feasible. The degradable polymer-coated controlled-release fertilizer of the present invention has not been reported at home and abroad, and has not been used in China.
发明内容Contents of the invention
本发明的目的是提供一种聚合物包膜控释肥料及其制备方法，其特征在于，所述聚合物包膜控释肥料是在颗粒肥料表面包覆一层占颗粒肥总重量的3％～15％的可降解型聚合物膜材。The object of the present invention is to provide a polymer-coated controlled-release fertilizer and a preparation method thereof, wherein the polymer-coated controlled-release fertilizer is coated with a layer on the surface of the granular fertilizer accounting for 3% of the total weight of the granular fertilizer ~15% degradable polymer film.
所述聚合物包膜控释肥料的制备工艺步骤：The preparation process steps of the polymer-coated controlled-release fertilizer:
1)所述聚合物膜材的制备如下：在反应器中，将按重量份数比为丙烯酸0～30、丙烯酸甲酯0～30、丙烯酸乙酯0～60、丙烯酸丁酯0～60、甲基丙烯酸甲酯0～70、甲基丙烯酸丁酯0～70、甲基丙烯酸0～20、丙烯酸-2-异辛酯0～50、苯乙烯0～60、醋酸乙烯酯0～30、丙烯酸-α-赖氨酸酯0～20、4-乙烯基吡啶0～25的一种或两种以上的单体混合后，通氮气，加热升温、待温度升高至70～90℃时，加入聚合物重量份数比为0.05～0.2份的引发剂，引发聚合反应，反应2～7小时后，得到聚合物膜材，冷却出料备用；其中，制得的聚合物膜材的玻璃化转变温度为-25～80℃，聚合物分子量为103～107；1) The preparation of the polymer film is as follows: in the reactor, the ratio of parts by weight of acrylic acid 0-30, methyl acrylate 0-30, ethyl acrylate 0-60, butyl acrylate 0-60, Methyl methacrylate 0-70, butyl methacrylate 0-70, methacrylic acid 0-20, acrylate-2-isooctyl 0-50, styrene 0-60, vinyl acetate 0-30, acrylic acid -After mixing one or two or more monomers of α-lysine ester 0~20 and 4-vinylpyridine 0~25, pass nitrogen gas, heat up, and when the temperature rises to 70~90°C, add An initiator with a polymer weight ratio of 0.05 to 0.2 parts initiates a polymerization reaction. After reacting for 2 to 7 hours, a polymer film is obtained, which is cooled and discharged for later use; wherein, the glass transition of the prepared polymer film The temperature is -25～80℃, and the molecular weight of the polymer is 103～107;
2)按聚合物膜材占颗粒肥总重量的3％~15％的比例称取聚合物膜材：加入聚合物膜材重量份数比为1～40倍的混合溶剂，搅拌混匀后，同时添加各种填料、助剂，使其全部溶解，制得聚合物包膜液；2) Weigh the polymer film according to the ratio of the polymer film to 3% to 15% of the total weight of the granular fertilizer: add a mixed solvent with a weight ratio of 1 to 40 times the weight of the polymer film, stir and mix, At the same time, various fillers and additives are added to dissolve them all to obtain a polymer coating solution;
3)选择粒级在2～4mm的圆粒状肥料，将粒状肥料置于沸腾式流化床包膜塔内，在55～75℃下进行10～15分钟预热，流化压力调整至使肥料颗粒充分沸腾状为准，雾化压力为3kpa；热风温度为50～70℃条件下，将包膜液均匀涂覆在颗粒肥料表面；3) Select a round granular fertilizer with a particle size of 2-4mm, place the granular fertilizer in a fluidized bed coating tower, preheat it at 55-75°C for 10-15 minutes, and adjust the fluidization pressure to make the fertilizer The particle is fully boiled, the atomization pressure is 3kpa; the coating liquid is evenly coated on the surface of the granular fertilizer under the condition of hot air temperature of 50-70°C;
4)一次包膜完成后在包膜塔内继续烘干5～30分钟，在颗粒表面形成一层塑料膜，混合溶剂通过冷凝器回收再利用；停机将包好的肥料放出，冷却即为成品聚合物包膜控释肥料。4) After the primary coating is completed, continue to dry in the coating tower for 5 to 30 minutes to form a layer of plastic film on the surface of the particles, and the mixed solvent is recycled and reused through the condenser; stop the machine and release the wrapped fertilizer, and the finished product is cooled Polymer coated controlled release fertilizer.
所述混合溶剂由乙酸乙酯∶乙酸丁酯∶环己烷＝0～80∶0～80∶0～80的重量份数比混合配制而成。The mixed solvent is prepared by mixing ethyl acetate:butyl acetate:cyclohexane=0-80:0-80:0-80 in parts by weight.
所述填料为石蜡、滑石粉、沸石粉和膨润土中至少两种，其中石蜡占聚合物膜材的重量比为0～0.03，滑石粉占聚合物膜材的重量比为0～0.02，沸石粉占聚合物膜材的重量比为0～0.01，膨润土占聚合物膜材的重量比为0～0.02。The filler is at least two kinds of paraffin, talcum powder, zeolite powder and bentonite, wherein the weight ratio of paraffin wax to the polymer membrane material is 0-0.03, the weight ratio of talc powder to the polymer membrane material is 0-0.02, and the zeolite powder The weight ratio of the bentonite to the polymer membrane material is 0-0.01, and the weight ratio of the bentonite to the polymer membrane material is 0-0.02.
所述助溶剂为甲基异丁基酮、三甲基环己酮和二乙二醇单丁醚中至少一种，其中甲基异丁基酮占聚合物膜材的重量比为0～0.03，三甲基环己酮占聚合物膜材的重量比为0～0.02，二乙二醇单丁醚占聚合物膜材的重量比为0～0.02。The co-solvent is at least one of methyl isobutyl ketone, trimethylcyclohexanone and diethylene glycol monobutyl ether, wherein the weight ratio of methyl isobutyl ketone to the polymer film is 0-0.03 , the weight ratio of trimethylcyclohexanone to the polymer film material is 0-0.02, and the weight ratio of diethylene glycol monobutyl ether to the polymer film material is 0-0.02.
所述引发剂为过氧化苯甲酰、偶氮异丁腈中的一种，用量为聚合物重量份数的0.05～0.2。The initiator is one of benzoyl peroxide and azoisobutyronitrile, and the dosage is 0.05-0.2 parts by weight of the polymer.
所述粒状肥料可选尿素、碳酸铵、硝酸铵、硫酸铵，硫酸钾、氯化钾、硝酸钾、磷酸氢二铵、磷酸二氢铵或复合肥。The granular fertilizer can be selected from urea, ammonium carbonate, ammonium nitrate, ammonium sulfate, potassium sulfate, potassium chloride, potassium nitrate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate or compound fertilizer.
本发明的有益效果是与以往的包膜肥料相比，本发明实现了真正意义上的采用合成的可降解型聚合物制造包膜肥料的方法。具有以下的明显的优点：The beneficial effect of the present invention is that compared with the conventional film-coated fertilizers, the present invention realizes a real method of using synthetic degradable polymers to manufacture film-coated fertilizers. Has the following obvious advantages:
1.包膜材料进行了特殊的配方设计，专门针对肥料的包膜用途，材料应用的针对性大大的提高。本系列的包膜材料具有良好的成膜性能，具有良好的抗水性能，并且可以在自然界中自行降解，属于环保材料。1. The coating material has a special formula design, which is specially designed for the coating of fertilizers, and the pertinence of material application is greatly improved. This series of coating materials has good film-forming properties, good water resistance, and can be degraded in nature, which is an environmentally friendly material.
2.与常用的加热溶解聚合物工艺不同，采用不加热的方式溶解聚合物膜材，减少能耗及溶解过程中的溶剂的挥发。2. Different from the commonly used process of heating and dissolving polymers, the polymer film is dissolved without heating, which reduces energy consumption and volatilization of solvents during the dissolution process.
3.包膜工艺简单，采用普通的流化床包膜方法，投资成本低，简便可行。3. The coating process is simple, using the common fluidized bed coating method, low investment cost, simple and feasible.
4.通过改变膜材料中单体的组成及比例，调控膜材料的分子量大小及玻璃化转变温度，进而优化膜材的柔韧性、硬度和抗冲击性能。4. By changing the composition and ratio of the monomers in the membrane material, the molecular weight and glass transition temperature of the membrane material can be adjusted to optimize the flexibility, hardness and impact resistance of the membrane material.
5.通过改变膜材料中亲疏水单体的组成及比例，调控膜材料的亲疏水性、耐水性及通透性，从而更能实现良好的控释效果。5. By changing the composition and ratio of hydrophilic and hydrophobic monomers in the membrane material, the hydrophilic and hydrophobic properties, water resistance and permeability of the membrane material can be adjusted, so as to achieve a better controlled release effect.
6.通过优化膜材的结构及厚度，膜材价格只是常规膜材价格的70％，从而大大降低了肥料的生产成本，使控释肥料在大田作物上推广应用成为可能。6. By optimizing the structure and thickness of the membrane material, the price of the membrane material is only 70% of the price of conventional membrane materials, which greatly reduces the production cost of fertilizers and makes it possible to popularize and apply controlled-release fertilizers on field crops.
具体实施方式Detailed ways
本发明提供一种聚合物包膜控释肥料及其制备方法，所述聚合物包膜控释肥料是在颗粒肥料表面包覆一层占颗粒肥总重量的3％至15％的可降解型聚合膜材。The invention provides a polymer-coated controlled-release fertilizer and a preparation method thereof. The polymer-coated controlled-release fertilizer is a degradable fertilizer that is coated on the surface of the granular fertilizer and accounts for 3% to 15% of the total weight of the granular fertilizer. polymer film.
所述聚合物膜材的制备如下：在反应器中，将按重量份数比为丙烯酸0～30、丙烯酸甲酯0～30、丙烯酸乙酯0～60、丙烯酸丁酯0～60、甲基丙烯酸甲酯0～70、甲基丙烯酸丁酯0～70、甲基丙烯酸0～20、丙烯酸-2-异辛酯0～50、苯乙烯0～60、醋酸乙烯酯0～30、丙烯酸-α-赖氨酸酯0～~20、4-乙烯基吡啶0～25的一种或两种以上的单体混合，通氮气、加热升温、待温度升高至70～90℃时，加入过氧化苯甲酰0～0.2或偶氮异丁腈0～0.2，引发聚合反应，反应2～7小时后，得到聚合物膜材。再加入混合溶剂搅拌混匀、同时添加各种填料、助剂，使其全部溶解，制得聚合物包膜液。其中，制得的聚合物膜材的玻璃化转变温度为-25～80℃，聚合物分子量为103～107。The preparation of the polymer film is as follows: in the reactor, the ratio of acrylic acid 0-30, methyl acrylate 0-30, ethyl acrylate 0-60, butyl acrylate 0-60, methyl Methyl acrylate 0-70, butyl methacrylate 0-70, methacrylic acid 0-20, acrylate-2-isooctyl 0-50, styrene 0-60, vinyl acetate 0-30, acrylic acid-α -Lysine ester 0~~20, 4-vinylpyridine 0~25, one or two or more monomers are mixed, nitrogen gas is passed, the temperature is raised, and when the temperature rises to 70~90°C, add peroxide Benzoyl 0-0.2 or azoisobutyronitrile 0-0.2 initiates a polymerization reaction, and after 2-7 hours of reaction, a polymer film material is obtained. Then add a mixed solvent, stir and mix evenly, and add various fillers and additives at the same time to make them all dissolve, so as to obtain a polymer coating liquid. Wherein, the glass transition temperature of the prepared polymer film is -25-80°C, and the molecular weight of the polymer is 103 -107 .
溶剂的选择：针对上述专利中的溶剂毒性问题，本发明根据“相似相溶”的原理，选择结构相近、低毒、性能优越的溶剂进行实验，筛选溶解性能优良、挥发速度适中、低毒的溶剂，寻找既能很好地溶解该聚合物，又能符合喷雾沉淀相转化法成膜工艺要求的溶剂。溶剂的选择步骤如下：用100ml量筒量取按乙酸乙酯∶乙酸丁酯∶环己烷＝0～80∶0～80∶0～80的重量份数比配制的混合溶剂加入到500ml反应瓶中，安放于铁架台上，加入4g该聚合物干物质，分别放入机械搅拌的搅拌浆、温度计、回流装置。打开搅拌电源，在20～28℃或室温下搅拌约五分钟，观察发现，该聚合物溶解，成为真溶液。该真溶液为透明低粘性，用玻璃棒蘸取溶液后，在空气中，溶剂挥发迅速，在玻璃棒上形成一层完整的薄膜。聚合物真溶液放置到室温，溶液保持透明状态。Solvent selection: Aiming at the problem of solvent toxicity in the above-mentioned patents, the present invention selects solvents with similar structures, low toxicity and superior performance for experiments based on the principle of "like dissolves like", and screens solvents with excellent solubility, moderate volatilization speed and low toxicity. Solvent, look for a solvent that can dissolve the polymer well and meet the requirements of the spray precipitation phase inversion film forming process. The selection steps of the solvent are as follows: use a 100ml graduated cylinder to measure the mixed solvent prepared in the ratio of parts by weight of ethyl acetate: butyl acetate: cyclohexane=0～80:0～80:0～80 and add it to the 500ml reaction flask , put it on an iron stand, add 4g of the polymer dry matter, and put it into a mechanically stirred stirring paddle, a thermometer, and a reflux device. Turn on the stirring power, stir at 20-28°C or room temperature for about five minutes, and observe that the polymer dissolves and becomes a true solution. The true solution is transparent and low-viscosity. After dipping the solution with a glass rod, the solvent evaporates rapidly in the air and forms a complete film on the glass rod. The true polymer solution was placed at room temperature, and the solution remained transparent.
聚合物包膜控释肥料的包膜工艺按以下步骤进行：在反应器中，将合成的聚合物膜材100份，加入100～4000份混合溶剂，同时按上述比例添加各种填料、助剂，加热升温、搅拌后制成聚合物包膜液，冷却转移备用；称取3kg的包膜液(其中聚合物膜材占颗粒肥总重量的12％)，5kg粒级在2～4mm的圆粒状肥料(如尿素)，将粒状肥料置于沸腾式包膜塔内，在55～75℃下进行10～15分钟预热，流化压力调整至使肥料颗粒充分沸腾状为准，雾化压力为3kpa；热风温度为50～70℃条件下，将包膜液均匀涂覆在颗粒肥料表面，一次包膜完成后在包膜塔内继续烘干5～30分钟，在颗粒表面形成一层塑料膜，溶剂通过冷凝器回收再利用；停机将包好的肥料放出，冷却即为成品控释包衣尿素肥料。The coating process of polymer-coated controlled-release fertilizers is carried out in the following steps: In the reactor, add 100-4000 parts of mixed solvent to 100 parts of the synthesized polymer film, and add various fillers and additives according to the above ratio , heat up and stir to make polymer coating solution, cool and transfer for subsequent use; take 3kg of coating solution (wherein the polymer film material accounts for 12% of the total weight of the granular fertilizer), and 5kg of round particles with a particle size of 2 to 4mm Granular fertilizer (such as urea), put the granular fertilizer in a boiling coating tower, preheat it at 55-75°C for 10-15 minutes, adjust the fluidization pressure to make the fertilizer particles fully boiled, and the atomization pressure 3kpa; the hot air temperature is 50-70°C, evenly coat the coating liquid on the surface of the granular fertilizer, after the first coating is completed, continue to dry in the coating tower for 5-30 minutes, and form a layer of plastic on the surface of the granular fertilizer The membrane and solvent are recovered and reused through the condenser; the machine is shut down to release the wrapped fertilizer, and after cooling, the finished controlled-release coated urea fertilizer is produced.
针对上述专利中的包膜液助剂问题，本发明的根据将低包膜液粘性、提高单位面涂覆率、有效调节控释性能、降低包膜厚度原则，筛选性能优良包膜液的、助剂。加入填料石蜡、滑石粉、沸石粉或膨润土、助剂甲基异丁基酮、三甲基环己酮或二乙二醇单丁醚以调节肥料表面性质。Aiming at the problem of coating fluid additives in the above-mentioned patents, the present invention is based on the principles of low coating fluid viscosity, increased coating rate per unit surface, effective regulation of controlled release performance, and reduced coating thickness, and screening of coating fluids with excellent performance, Auxiliary. Add filler paraffin, talcum powder, zeolite powder or bentonite, additives methyl isobutyl ketone, trimethylcyclohexanone or diethylene glycol monobutyl ether to adjust the surface properties of the fertilizer.
本发明适用的肥料可以是各种水溶性的颗粒肥料，包括尿素、碳酸铵、硝酸铵、硫酸铵，硫酸钾、氯化钾、硝酸钾、磷酸氢二铵、磷酸二氢铵等，可以是单质肥料，也可以是复合肥；要求颗粒肥料的粒径为：最为适宜粒径在2~4mm。采用小颗粒尿素，也可以用于加工生产高尔夫草坪果岭专用控释肥。在本发明中，采用的是大颗粒尿素和复合肥，大颗粒尿素先过筛，控制粒径在2~4mm范围内。The applicable fertilizer of the present invention can be various water-soluble granular fertilizers, including urea, ammonium carbonate, ammonium nitrate, ammonium sulfate, potassium sulfate, potassium chloride, potassium nitrate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, etc., can be Elemental fertilizers can also be compound fertilizers; the particle size of granular fertilizers is required: the most suitable particle size is 2~4mm. Small granules of urea can also be used to process and produce special controlled-release fertilizers for golf lawns and greens. In the present invention, large-grain urea and compound fertilizer are used, and the large-grain urea is sieved first to control the particle size within the range of 2 to 4 mm.
生物降解性评价：将不同的聚合物膜材，准确称量后埋入土壤中，每隔1个月取样，清洗掉表面的泥土后干燥，再次称量，计算出试样重量损失率。Biodegradability evaluation: Accurately weigh different polymer membranes and bury them in the soil, take samples every month, wash off the soil on the surface, dry them, weigh them again, and calculate the weight loss rate of the samples.
释放特性检验：取研制出的肥料样品，放入尼龙网袋中，然后浸入200ml蒸馏水中，密封，置于25℃恒温培养箱中，分别于累积释放速率达80％时，取出25ml浸泡液进行分析，将剩余浸泡液倒掉，重新加入200ml蒸馏水，保持总体积不变。同时，另取相同的包膜肥料，经磨细至100目，测定试样中所含各该养分含量。测定项目和方法：尿素中N用分光光度法；复合肥中N、P、K用常规分析方法。Release characteristic test: Take the developed fertilizer sample, put it into a nylon mesh bag, then immerse it in 200ml of distilled water, seal it, place it in a constant temperature incubator at 25°C, and take out 25ml of the soaking solution when the cumulative release rate reaches 80%. For analysis, pour out the remaining soaking liquid, and add 200ml of distilled water again to keep the total volume constant. At the same time, take the same coated fertilizer, grind it to 100 mesh, and measure the nutrient content contained in the sample. Determination items and methods: Spectrophotometry is used for N in urea; conventional analysis methods are used for N, P and K in compound fertilizer.
该高分子不同于其他材料之处在于，可以控制高分子材料的分子量大小及分布进而达到控制膜材释放的作用。如分子量过低则膜材强度降低，若分子量过高则塑化成性困难，该聚合物的玻璃化转变温度为-25～80℃，聚合物分子量的范围是103～107。The polymer is different from other materials in that it can control the molecular weight and distribution of the polymer material to achieve the effect of controlling the release of the membrane material. If the molecular weight is too low, the strength of the film material will decrease. If the molecular weight is too high, the plasticization will be difficult. The glass transition temperature of the polymer is -25-80°C, and the polymer molecular weight ranges from 103 to 107 .
下面列举具体例子对本发明予以进一步说明。The following specific examples are given to further illustrate the present invention.
实施例1Example 1
将丙烯酸乙酯∶甲基丙烯酸甲酯∶甲基丙烯酸按重量份数比56∶38∶6的比例混合，搅拌、通氮气，加热升温至75℃时，加入聚合物重量份数比为0.05份的过氧化苯甲酰，引发聚合反应，反应2~7小时后，得到聚合物膜材。将合成的聚合物膜材100g混溶于2500g按重量份数比的乙酸乙酯∶环己烷为2∶3的混合溶剂中，加入分别占聚合物膜材重量比为0.05的膨润土、0.05的滑石粉、0.02的石蜡和0.01的甲基异丁基酮的混合物，搅拌溶解制得包膜液。将1500g直径为2～4mm的颗粒状尿素装入沸腾流化床中，加热至60～80℃。在热风温度为70℃下，用双流体喷嘴在空气雾化压力为3kpa，以每分钟2g的进度喷涂，将溶液全部喷涂到颗粒状尿素上。所得的控释尿素，高分子膜约占肥料总重量的6％左右，此肥料在25℃的水中，养分控制释放时间约为5个月。Mix ethyl acrylate: methyl methacrylate: methacrylic acid in a ratio of 56:38:6 by weight, stir, blow nitrogen, and when the temperature rises to 75°C, add 0.05 parts by weight of polymer The benzoyl peroxide triggers a polymerization reaction, and after 2-7 hours of reaction, a polymer film is obtained. 100g of the synthesized polymer film material is miscible in 2500g of ethyl acetate in the ratio of parts by weight: cyclohexane is a mixed solvent of 2:3, adding bentonite, 0.05 bentonite and 0.05 A mixture of talcum powder, 0.02 of paraffin and 0.01 of methyl isobutyl ketone was stirred and dissolved to obtain a coating solution. Put 1500g of granular urea with a diameter of 2-4mm into the fluidized fluidized bed and heat it to 60-80°C. At a hot air temperature of 70°C, use a two-fluid nozzle at an air atomization pressure of 3kpa, spray at a rate of 2g per minute, and spray all the solution onto the granular urea. The obtained controlled-release urea, the polymer film accounts for about 6% of the total weight of the fertilizer, and the controlled release time of the nutrient is about 5 months for the fertilizer in water at 25°C.
实施例2Example 2
在反应器中将丙烯酸丁酯∶甲基丙烯酸甲酯∶丙烯酸乙酯∶甲基丙烯酸按重量份数比40∶40∶15∶5的比例混合，搅拌、通氮气，加热升温至84℃，加入聚合物重量份数比为0.08份的过氧化苯甲酰，引发聚合反应，反应6小时后，得到聚合物膜材。将合成的聚合物膜材60g混溶于2000g按重量份数比的乙酸乙酯、乙酸丁酯、环己烷比例为2∶2∶1的混合溶剂中，加入分别占聚合物膜材重量比为0.05的膨润土、0.02的滑石粉、0.05的石蜡，0.01的甲基异丁基酮的混合物，搅拌下制得包膜液。将1500g直径为2～4mm颗粒状尿素装入沸腾流化床中，加热60～90℃。用双流体喷嘴在雾化压力为4kpa，以每分钟2g的速度喷涂于颗粒状尿素上，所得控释肥膜占全部控释肥总重的4％左右。此肥料在25℃水中，养分控制释放时间约为3个月。In the reactor, mix butyl acrylate: methyl methacrylate: ethyl acrylate: methacrylic acid in a ratio of 40:40:15:5 by weight, stir, blow nitrogen, heat up to 84°C, add The benzoyl peroxide with a polymer weight ratio of 0.08 parts initiates a polymerization reaction, and after 6 hours of reaction, a polymer film material is obtained. 60g of the synthesized polymer film is miscible in 2000g of ethyl acetate, butyl acetate, and cyclohexane in a mixed solvent with a ratio of 2:2:1 in parts by weight, adding 0.05 of bentonite, 0.02 of talc, 0.05 of paraffin, and 0.01 of methyl isobutyl ketone, and stir to prepare the coating solution. Put 1500g of granular urea with a diameter of 2-4mm into the fluidized fluidized bed and heat at 60-90°C. Spray on granular urea at a rate of 2g per minute at an atomization pressure of 4kpa with a dual-fluid nozzle, and the resulting controlled-release fertilizer film accounts for about 4% of the total weight of all controlled-release fertilizers. This fertilizer is in 25 ℃ water, and the nutrient release time is about 3 months.
实施例3Example 3
在反应器中将甲基丙烯酸丁酯∶甲基丙烯酸甲酯∶醋酸乙烯酯∶甲基丙烯酸按重量比57∶34∶8∶1的比例混合，搅拌、通氮气，加热升温至80℃，加入聚合物重量份数比为0.06份的过氧化苯甲酰，引发聚合反应，反应5小时后，得到聚合物膜材。将合成的聚合物膜材50g混溶于2000g按重量份数比的乙酸乙酯∶乙酸丁酯∶环己烷比例为2∶1∶2的混合溶剂中，加入分别占聚合物膜材重量比为0.05的膨润土，0.05的沸石粉，0.03石蜡，0.02的二乙二醇单丁醚的混合物，搅拌下制得包膜液。将1000g直径为2～5mm的颗粒状尿素装入沸腾流化床中，加热到70～80℃，热风温度为70℃，用双流体喷嘴在雾化压力为4kpa，以每分钟2g的速度喷涂于肥料颗粒上，所得控释钾肥，膜占全部肥料总重的5％左右，在25℃的水中，养分控制释放时间约为3个月。In the reactor, mix butyl methacrylate: methyl methacrylate: vinyl acetate: methacrylic acid in a ratio of 57:34:8:1 by weight, stir, blow nitrogen, heat up to 80°C, add The benzoyl peroxide with a polymer weight ratio of 0.06 parts initiates a polymerization reaction, and after 5 hours of reaction, a polymer film material is obtained. 50 g of the synthesized polymer film material is miscible in 2000 g of ethyl acetate in parts by weight: butyl acetate: cyclohexane ratio is 2: 1: 2 in the mixed solvent, adding 0.05 of bentonite, 0.05 of zeolite powder, 0.03 of paraffin, and 0.02 of diethylene glycol monobutyl ether are mixed, and the coating solution is prepared under stirring. Put 1000g of granular urea with a diameter of 2-5mm into the fluidized fluidized bed, heat it to 70-80°C, the temperature of the hot air is 70°C, use a two-fluid nozzle at an atomization pressure of 4kpa, and spray at a speed of 2g per minute On the fertilizer granules, the resulting controlled-release potassium fertilizer accounts for about 5% of the total weight of the total fertilizer. In water at 25°C, the controlled release time of nutrients is about 3 months.
实施例4Example 4
在反应器中将甲基丙烯酸丁酯∶甲基丙烯酸甲酯∶醋酸乙烯酯∶丙烯酸按重量比57∶34∶8∶1的比例混合，搅拌、通氮气，加热升温至87℃，加入聚合物重量份数比为0.1份的过氧化苯甲酰，引发聚合反应，反应5小时后，得到聚合物膜材。将合成的聚合物膜材100g混溶于3000g按重量份数比，乙酸乙酯∶乙酸丁酯∶环己烷比例为2∶2∶1的混合溶剂中，加入分别占聚合物膜材重量比为0.05的膨润土，0.5的滑石粉，0.02的石蜡，0.02的甲基异丁基酮，0.01的三甲基环己酮的混合物，搅拌下制得包膜液。将1000g直径为2～5mm的颗粒复合肥装入沸腾流化床中，加热至70～80℃用双流体喷嘴在雾化压力为4kpa，以每分钟2.5g的流量喷涂于复合肥颗粒表面上，所得控释肥膜所占全部控释肥重量的10％左右，此肥料在25℃的水或土壤中，养分控制释放时间约为8个月。In the reactor, mix butyl methacrylate: methyl methacrylate: vinyl acetate: acrylic acid in a ratio of 57:34:8:1 by weight, stir, blow nitrogen, heat up to 87°C, and add the polymer The benzoyl peroxide with a ratio of parts by weight of 0.1 part initiates a polymerization reaction, and after 5 hours of reaction, a polymer film material is obtained. 100g of the synthesized polymer film is miscible in 3000g by weight, ethyl acetate: butyl acetate: cyclohexane ratio is 2: 2: 1 mixed solvent, adding 0.05 of bentonite, 0.5 of talc, 0.02 of paraffin, 0.02 of methyl isobutyl ketone, and 0.01 of trimethylcyclohexanone, and stir to prepare the coating solution. Put 1000g of granular compound fertilizer with a diameter of 2-5mm into the fluidized fluidized bed, heat it to 70-80°C, spray it on the surface of the compound fertilizer particles at a flow rate of 2.5g per minute with a two-fluid nozzle at an atomization pressure of 4kpa , the obtained controlled-release fertilizer film accounts for about 10% of the weight of all controlled-release fertilizers, and the controlled-release time of nutrients for this fertilizer is about 8 months in water or soil at 25°C.
实施例5Example 5
在反应器中将丙烯酸乙酯∶丙烯酸甲酯∶苯乙烯∶丙烯酸按重量比50∶39∶9∶2的比例配制成混合溶液，搅拌、通氮气，加热升温至78℃，加入聚合物重量份数比为0.12份的过氧化苯甲酰，引发聚合反应，反应3小时后，得到聚合物膜材。将合成的聚合物膜材100g混溶于2000g按重量份数比，乙酸乙酯、乙酸丁酯、环己烷比例为2∶2∶1的混合溶剂中，加入分别占聚合物重量比为0.03的膨润土，0.04的滑石粉，0.03的石蜡，0.01的甲基异丁基酮的混合物，搅拌下制得包膜液。将1500g直径为2～4mm颗粒状尿素装入沸腾流化床中，加热60～90℃。用双流体喷嘴在雾化压力为3kpa，以每分钟2g的速度喷涂于颗粒状尿素上，所得控释肥膜占全部控释肥总重的6％左右。此肥料在25℃水中，养分控制释放时间约为5个月。In the reactor, ethyl acrylate: methyl acrylate: styrene: acrylic acid is formulated into a mixed solution in a ratio of 50:39:9:2 by weight, stirred, blown with nitrogen, heated to 78°C, and added in parts by weight of polymer The benzoyl peroxide with a number ratio of 0.12 parts initiates a polymerization reaction, and after 3 hours of reaction, a polymer film is obtained. 100g of the synthesized polymer film is miscible in 2000g of a mixed solvent in which the ratio of ethyl acetate, butyl acetate, and cyclohexane is 2:2:1 by weight, and 0.03% by weight of the polymer is added. A mixture of bentonite, 0.04 talcum powder, 0.03 paraffin, and 0.01 methyl isobutyl ketone was stirred to prepare a coating solution. Put 1500g of granular urea with a diameter of 2-4mm into the fluidized fluidized bed and heat at 60-90°C. Spray on granular urea at a rate of 2g per minute at an atomization pressure of 3kpa with a dual-fluid nozzle, and the resulting controlled-release fertilizer film accounts for about 6% of the total weight of all controlled-release fertilizers. This fertilizer is in 25 ℃ water, and the nutrient release time is about 5 months.
实施例6Example 6
在反应器中将甲基丙烯酸甲酯∶丙烯酸乙酯∶丙烯酸∶4-乙烯基吡啶按重量比45∶46∶7∶2的比例配制成混合溶液，搅拌、通氮气，加热升温至90℃，加入聚合物重量份数比为0.15份的偶氮异丁腈，引发聚合反应，反应4小时后，得到聚合物膜材。将合成的聚合物膜材90g混溶于2000g按重量份数比，乙酸乙酯、乙酸丁酯、环己烷比例为2∶1∶2的混合溶剂中，加入分别占聚合物膜材重量比为0.03的膨润土，0.04滑石粉，0.03的石蜡，0.01的甲基异丁基酮的混合物，搅拌下制得包膜液。将1500g直径为2～4mm颗粒状尿素装入沸腾流化床中，加热60～90℃。用双流体喷嘴在雾化压力为4kpa，以每分钟2g的速度喷涂于颗粒状尿素上，所得控释肥膜占全部控释肥总重的6％左右。此肥料在25℃水中，养分控制释放时间约为3个月，高分子膜材12个月降解15％。In the reactor, methyl methacrylate: ethyl acrylate: acrylic acid: 4-vinylpyridine was formulated into a mixed solution in a ratio of 45:46:7:2 by weight, stirred, nitrogen was blown, and the temperature was raised to 90°C. Azoisobutyronitrile with a ratio of 0.15 parts by weight of the polymer was added to initiate a polymerization reaction, and after 4 hours of reaction, a polymer film material was obtained. 90g of the synthesized polymer film is miscible in 2000g of a mixed solvent of ethyl acetate, butyl acetate, and cyclohexane in a ratio of 2:1:2 by weight, and the weight ratio of the polymer film is added. 0.03 of bentonite, 0.04 of talc, 0.03 of paraffin, and 0.01 of methyl isobutyl ketone, and stir to prepare the coating solution. Put 1500g of granular urea with a diameter of 2-4mm into the fluidized fluidized bed and heat at 60-90°C. Spray on granular urea at a rate of 2g per minute at an atomization pressure of 4kpa with a dual-fluid nozzle, and the resulting controlled-release fertilizer film accounts for about 6% of the total weight of all controlled-release fertilizers. This fertilizer is in 25 ℃ water, and the nutrient release time is about 3 months, and the polymer membrane material degrades 15% in 12 months.
实施例7Example 7
在反应器中将丙烯酸乙酯∶甲基丙烯酸甲酯∶丙烯酸∶丙烯酸-2-异辛酯按重量比48∶41∶9∶2的比例配制成混合溶液，搅拌、通氮气，加热升温至80℃，加入聚合物重量份数比为0.06份的过氧化苯甲酰，引发聚合反应，反应7小时后，得到聚合物膜材。将合成的聚合物膜材90g混溶于2000g按重量份数比，乙酸乙酯、乙酸丁酯、环己烷比例为3∶1∶1的混合溶剂中，加入分别占聚合物膜材重量比为0.05的膨润土，0.05的滑石粉，0.03的石蜡，0.01甲基异丁基酮的混合物，搅拌下制得包膜液。将1500g直径为2~4mm颗粒状磷酸二氢铵装入沸腾流化床中，加热60~90℃。用双流体喷嘴在雾化压力为4kpa，以每分钟2g的速度喷涂于颗粒状磷酸二氢铵上，所得控释肥膜占全部控释肥总重的6％左右。此肥料在25℃水中，养分控制释放时间约为3个月。In the reactor, ethyl acrylate: methyl methacrylate: acrylic acid: 2-isooctyl acrylate is formulated into a mixed solution in a ratio of 48:41:9:2 by weight, stirred, nitrogen blown, and heated to 80 ℃, adding benzoyl peroxide with a ratio of 0.06 parts by weight of the polymer to initiate a polymerization reaction, and after 7 hours of reaction, a polymer film material was obtained. 90 g of the synthesized polymer film is miscible in 2000 g of a mixed solvent in which the ratio of ethyl acetate, butyl acetate and cyclohexane is 3:1:1 by weight, and the weight ratio of the polymer film is added. 0.05 of bentonite, 0.05 of talc, 0.03 of paraffin, and 0.01 of methyl isobutyl ketone, and stir to prepare the coating solution. Put 1500g of granular ammonium dihydrogen phosphate with a diameter of 2~4mm into the fluidized bed and heat at 60~90°C. Spray on granular ammonium dihydrogen phosphate at a rate of 2g per minute at an atomization pressure of 4kpa with a two-fluid nozzle, and the resulting controlled-release fertilizer film accounts for about 6% of the total weight of all controlled-release fertilizers. This fertilizer is in 25 ℃ water, and the nutrient release time is about 3 months.
实施例8Example 8
在反应器中将丙烯酸乙酯∶丙烯酸甲酯∶甲基丙烯酸丁酯∶丙烯酸-α-赖氨酸酯按重量比52∶37∶9∶2的比例配制成混合溶液，搅拌、通氮气，加热升温至85℃，加入聚合物重量份数比为0.09份的偶氮异丁腈，引发聚合反应，反应6小时后，得到聚合物膜材。将合成的聚合物膜材60g混溶于2400g按重量份数比，乙酸乙酯、乙酸丁酯、环己烷比例为2∶1∶2的混合溶剂中，加入分别占聚合物膜材重量比为0.05的膨润土，0.03的石蜡，0.015的甲基异丁基酮的混合物，搅拌下制得包膜液。将1000g直径为2～4mm颗粒状15-15-15复合肥装入沸腾流化床中，加热60～90℃。用双流体喷嘴在雾化压力为4kpa，以每分钟2g的速度喷涂于颗粒状复合肥上，所得控释肥膜占全部控释肥总重的6％左右。此肥料在25℃水中，养分控制释放时间约为3个月，高分子膜材12个月降解12％。In the reactor, ethyl acrylate: methyl acrylate: butyl methacrylate: acrylic acid-α-lysine ester is formulated into a mixed solution in a ratio of 52:37:9:2 by weight, stirred, nitrogen, and heated The temperature was raised to 85° C., and azoisobutyronitrile with a ratio of 0.09 parts by weight of the polymer was added to initiate a polymerization reaction. After 6 hours of reaction, a polymer film material was obtained. 60 g of the synthesized polymer film is miscible in 2400 g of a mixed solvent in which the ratio of ethyl acetate, butyl acetate and cyclohexane is 2:1:2 by weight, and the weight ratio of the polymer film is respectively added. 0.05 of bentonite, 0.03 of paraffin, 0.015 of methyl isobutyl ketone mixture, under stirring to prepare the coating solution. Put 1000g of granular 15-15-15 compound fertilizer with a diameter of 2-4mm into the fluidized bed and heat at 60-90°C. Spray on the granular compound fertilizer at a rate of 2g per minute at an atomization pressure of 4kpa with a dual-fluid nozzle, and the resulting controlled-release fertilizer film accounts for about 6% of the total weight of all controlled-release fertilizers. This fertilizer is in 25 ℃ water, and the nutrient release time is about 3 months, and the polymer membrane material degrades 12% in 12 months.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710176037XACN101172913A (en) | 2007-10-18 | 2007-10-18 | A polymer-coated controlled-release fertilizer and its preparation method |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710176037XACN101172913A (en) | 2007-10-18 | 2007-10-18 | A polymer-coated controlled-release fertilizer and its preparation method |
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| CN101172913Atrue CN101172913A (en) | 2008-05-07 |
| Application Number | Title | Priority Date | Filing Date |
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| CNA200710176037XAPendingCN101172913A (en) | 2007-10-18 | 2007-10-18 | A polymer-coated controlled-release fertilizer and its preparation method |
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| CN102093133A (en)* | 2010-12-17 | 2011-06-15 | 滨州市鑫龙油田化工有限公司 | Preparation method of coated controlled-release fertilizer and coating equipment thereof |
| CN102134173A (en)* | 2011-04-26 | 2011-07-27 | 中国科学院南京土壤研究所 | Method for manufacturing slow control release fertilizer on the basis of a coating machine of a closed type fluidized bed and equipment thereof |
| CN102295491A (en)* | 2011-07-21 | 2011-12-28 | 中国农业大学 | Natural polymer modified coated controlled release fertilizer and preparation method thereof |
| CN102863275A (en)* | 2011-07-06 | 2013-01-09 | 乔保军 | Sustained or controlled-release potash fertilizer and preparation method thereof |
| CN108812159A (en)* | 2018-06-28 | 2018-11-16 | 大新县科学技术情报研究所 | A kind of sugarcane high-yield implantation methods |
| CN108893095A (en)* | 2018-09-11 | 2018-11-27 | 重庆交通大学 | A kind of polymer shell cladding material, polymer wrapped delay-released inorganic salt and preparation method |
| CN109206212A (en)* | 2018-09-14 | 2019-01-15 | 仲恺农业工程学院 | Preparation method of modified tung oil coated urea |
| CN109748759A (en)* | 2019-02-11 | 2019-05-14 | 权冉(银川)科技有限公司 | Water treatment material and soil purifying, repairing and fertilizing material and preparation and use method thereof |
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| CN102093133A (en)* | 2010-12-17 | 2011-06-15 | 滨州市鑫龙油田化工有限公司 | Preparation method of coated controlled-release fertilizer and coating equipment thereof |
| CN102093133B (en)* | 2010-12-17 | 2013-04-03 | 滨州市鑫龙油田化工有限公司 | Preparation method of coated controlled-release fertilizer and coating equipment thereof |
| CN102134173A (en)* | 2011-04-26 | 2011-07-27 | 中国科学院南京土壤研究所 | Method for manufacturing slow control release fertilizer on the basis of a coating machine of a closed type fluidized bed and equipment thereof |
| CN102863275A (en)* | 2011-07-06 | 2013-01-09 | 乔保军 | Sustained or controlled-release potash fertilizer and preparation method thereof |
| CN102295491A (en)* | 2011-07-21 | 2011-12-28 | 中国农业大学 | Natural polymer modified coated controlled release fertilizer and preparation method thereof |
| CN102295491B (en)* | 2011-07-21 | 2014-02-19 | 中国农业大学 | Coated controlled-release fertilizer modified by natural polymer and preparation method thereof |
| CN108812159A (en)* | 2018-06-28 | 2018-11-16 | 大新县科学技术情报研究所 | A kind of sugarcane high-yield implantation methods |
| CN108893095A (en)* | 2018-09-11 | 2018-11-27 | 重庆交通大学 | A kind of polymer shell cladding material, polymer wrapped delay-released inorganic salt and preparation method |
| CN108893095B (en)* | 2018-09-11 | 2021-02-05 | 重庆交通大学 | Polymer shell coating material, polymer-coated slow-release inorganic salt and preparation method |
| CN109206212A (en)* | 2018-09-14 | 2019-01-15 | 仲恺农业工程学院 | Preparation method of modified tung oil coated urea |
| CN109748759A (en)* | 2019-02-11 | 2019-05-14 | 权冉(银川)科技有限公司 | Water treatment material and soil purifying, repairing and fertilizing material and preparation and use method thereof |
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