WO2020034372A1 - 中微量元素混合剂及包裹中微量元素肥料的制备方法 - Google Patents

中微量元素混合剂及包裹中微量元素肥料的制备方法 Download PDF

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WO2020034372A1
WO2020034372A1 PCT/CN2018/109474 CN2018109474W WO2020034372A1 WO 2020034372 A1 WO2020034372 A1 WO 2020034372A1 CN 2018109474 W CN2018109474 W CN 2018109474W WO 2020034372 A1 WO2020034372 A1 WO 2020034372A1
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trace element
medium
fertilizer
sulfur
medium trace
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PCT/CN2018/109474
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English (en)
French (fr)
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王仁宗
王瑞
操素芬
吴初柱
孙金艳
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湖北富邦科技股份有限公司
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Priority to MA49181A priority Critical patent/MA49181B1/fr
Publication of WO2020034372A1 publication Critical patent/WO2020034372A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C9/00—Fertilisers containing urea or urea compounds
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D5/00—Fertilisers containing magnesium
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/20—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for preventing the fertilisers being reduced to powder; Anti-dusting additives
    • 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

Definitions

  • the invention relates to the technical field of novel fertilizer coatings, in particular to a method for preparing a mixture of medium and trace elements and a package of trace element fertilizers.
  • medium and trace element fertilizers In recent years, there has been more and more research and application of medium and trace element fertilizers at home and abroad, which has greatly promoted the progress of the fertilizer industry.
  • Common medium and trace elements are sulfur, calcium, magnesium, silicon, iron, manganese, copper, zinc, boron, and molybdenum. They are different from other elements such as nitrogen, phosphorus, and potassium.
  • medium and trace elements are essential nutrients for crops, their amount Generally, it is relatively small, and it is easily fixed by the soil and loses its fertilizer effect after application.
  • chelated trace element fertilizers In order to solve the problem that trace elements are fixed, chelated trace element fertilizers have appeared on the market, which can greatly improve the utilization rate of fertilizers, but due to its high cost, it greatly affects its promotion and use.
  • Patent WO03 / 071855A3 and patent WO2008 / 131535A1 disclose a method for preparing medium and trace element fertilizers: preparing trace element materials containing copper, zinc, manganese and other trace elements into fine powder, and then wrapping them on the surface of granular fertilizers or seeds to obtain medium and trace amounts. Elemental fertilizer or seed. In order to achieve a good wrapping effect, the fine powder is preferably 325 mesh. When the fine powder contains trace elements in the form of oxides, acidifiers such as organic acids need to be mixed at the same time to accelerate the release of trace elements. The disadvantage of this technology is that the amount of medium and trace element fine powder is limited, and it cannot meet the needs of fertilizer upgrade. At the same time, there is a phenomenon that the medium and trace element fine powder is wrapped and removed.
  • Patent WO01 / 87803A1 discloses a sulfur-containing fertilizer and a preparation method thereof.
  • the specific method is to disperse sulfur and trace elements one by one during the granulation process of the fertilizer. Fertilizer interior. This process is not only complicated, but the production process is not easy to control.
  • the main disadvantage is that sulfur is added internally. There is a risk of sulfur explosion due to the return of materials in the production process.
  • Patents US2014 / 0216120A1, US2014 / 0109639A1 and CN103771998A and other patents introduce a fertilizer containing medium element sulfur, trace elements, phosphate ore and other substances.
  • the specific method is to add trace element substances to liquid sulfur and use steel belts.
  • the granulator prepares sulfur fertilizer containing medium and trace elements.
  • This technology requires adding a water-absorbing material to the sulfur to accelerate the disintegration of the sulfur.
  • the problem is that the prepared granular fertilizer contains only sulfur and trace elements. Due to the small amount used in the process, it is difficult to achieve a uniform distribution of middle and trace elements. It will cause the local concentration in the soil to be too high, or the local concentration to be too low or not even, especially in field crops.
  • Patent US8679219B2 introduces a sulfur-containing fertilizer and a preparation method thereof, which is specifically manifested by grinding a sulfur powder and a liquid such as phosphoric acid with a dispersing grinder to finally obtain micron-sized sulfur particles, and then adding other fertilizer components to remove excess water After granulation, a granular fertilizer containing sulfur is prepared.
  • sulfur wet milling can reduce dust and reduce the risk of sulfur explosion, but there are problems in that the process is long, the operation is tedious, it is not easy to control, and the cost is too high.
  • Patent US4857098, patent WO2008 / 103728A1, patent WO2015 / 070496A1, patent CN100516003C, patent CN101805235B, patent CN103553849A, patent CN104496691A, patent CN104108977A, patent CN106316620A and other patents relate to sulfur-coated urea and sulfur-coated thiomagnesium fertilizer to improve the Utilization rate, and finally realize the slow release and loss control of urea. In order to better meet this requirement, it is generally necessary to wrap a layer of sealant substance outside the sulfur coating.
  • the outermost sealant is generally paraffin wax, hydrocarbon wax, modified polymer wax, natural beeswax, urea resin, polymer Polymers and other substances.
  • the main role of the sulfur element in the sulfur-coated urea is to block the coating and cooperate with the blocking agent to achieve the slow-release effect of urea.
  • sulfur-coated urea when sulfur-coated urea is applied to the soil, with the dissolution of urea, sulfur will exist in the form of "coated shells", which decompose and release slowly, which is not conducive to the utilization of sulfur.
  • the added paraffin, hydrocarbon wax, modified polymer wax, natural beeswax, urea-formaldehyde resin, high-molecular polymer and other substances have defects and risks such as non-degradation and environmental pollution after use.
  • Patents CN102811979A and CN105367235A disclose a method for preparing a micronutrient fertilizer: coating an isolation layer on a phosphate fertilizer such as ammonium phosphate, calcium superphosphate, and heavy superphosphate, and then bonding one or more micronutrients Attached to the release coating.
  • the role of the barrier coating is to prevent chemical reactions between trace elements and phosphate.
  • the material of the barrier coating is required to not react with both phosphate and trace elements.
  • Polyethyleneimine polymers, urea, ammonium sulfate, and sulfuric acid are commonly used. Potassium, magnesium sulfate, calcium sulfate, elemental sulfur, silicate and other substances.
  • micronutrient elements wrapped by this technology have the risk of powdering.
  • the fertilizers wrapped with trace elements have the risk of aggravating the agglomeration.
  • the related research and application of the above-mentioned trace element fertilizers have largely promoted the progress of the fertilizer industry.
  • the medium and micronutrients have an irreplaceable important role in the growth and development of crops. Therefore, how to easily, quickly, efficiently and safely add the medium and microelements is of great significance.
  • the value and efficiency of medium and micronutrients are maximized to achieve the synergy and balance of medium and microelements and large amounts of elements.
  • the purpose of the present invention is to overcome the problems in the prior art mentioned above, and provide a method for preparing a medium and trace element mixture and a trace element fertilizer in a package.
  • This technology can quickly upgrade conventional fertilizers to one or more medium and trace elements.
  • New-type fertilizer, the double-effect medium and trace elements that can be added are sulfur, calcium, magnesium, silicon, iron, manganese, copper, zinc, boron, and molybdenum.
  • the invention quickly and flexibly adds medium and trace elements; solves the problem that it is difficult to uniformly disperse pure medium and trace element granules in the soil to cause crop poisoning; by adding a swelling material, the disintegration of the sulfur film layer into sulfur particles is accelerated, and the block shape is solved Sulfur particle size is too large to be absorbed by crops; the medium and trace element film formed in this way is firmly combined with fertilizer particles and is not easy to fall off; it can wrap the medium and trace element materials combining fast-acting and long-acting, which is beneficial to the entire growth cycle of the crop. Nutritional needs.
  • sulfur is used as a carrier to encapsulate medium and trace elements on the surface of the fertilizer, and the medium and trace element mixture includes both water-soluble and water-insoluble types, and water-soluble. Elements can be quickly released to quickly meet crop growth needs.
  • the swelling material is added to the coating layer, which can disintegrate the medium and trace elements into particles, which is easily absorbed by the crop root system.
  • sulfur will be converted into sulfuric acid by the action of soil sulfur bacteria, and the activated water is hardly soluble Type trace elements, so that the balance between quick and slow effects of medium and trace elements is achieved, and the nutrient requirements of the entire growth cycle of the crop are better satisfied.
  • the concentration of trace elements is too high, which can easily cause local poisoning of crops.
  • the medium and trace elements in the present invention are spray-coated on the surface of the granular fertilizer, and the content of the trace elements is controllable and the concentration is appropriate.
  • the medium and trace element coated fertilizer prepared by the present invention is applied to the soil, the medium and trace element film layer will be disintegrated into fine particles in the presence of water under the action of the swelling material, and evenly dispersed in the soil to avoid local crops. Poisoning.
  • the surface of the new fertilizer prepared by this solution is a layer of sulfur-supported trace element film.
  • the chemical inertness of sulfur makes the coated fertilizer difficult to absorb moisture and agglomerate. Therefore, it is possible to reduce or even eliminate the use of fertilizer anti-caking agent , Thereby reducing the cost of fertilizer production.
  • Medium and trace element mixture which consists of medium and trace elements and swelling material. Each component is calculated by mass percentage. It is characterized by: 50% -90% sulfur in the mixture, 5% -20% sulfur, The mass ratio of other medium and trace elements is 5% -45%.
  • the preparation method is: heating sulfur to liquid state, adding medium and trace elements and swelling material in liquid sulfur and mixing them to obtain a medium and trace element mixture.
  • the medium and trace elements are one or more of simple substances, oxides, or anhydrous compounds containing sulfur, calcium, magnesium, silicon, iron, manganese, copper, zinc, boron, and molybdenum.
  • the swelling material is one or more of chitosan, cellulose, sodium polyacrylate, polyacrylamide, and polyvinyl alcohol.
  • the molecular weight of the swelling material is 5000-100,000.
  • the medium and trace element mixture is characterized in that the medium and trace elements are divided into two types according to solubility: water-soluble type and water-insoluble type.
  • the medium and trace element mixture contains at least one water-soluble substance.
  • the preparation method of the trace element fertilizer in the package is characterized by the following steps: placing conventional granular fertilizer in a wrapping drum, a disc or a fluidized bed device with a heating function, and the medium and trace element mixture Sprayed on the surface of the granular fertilizer heated to a certain temperature, after cooling and solidification, a layer of medium and trace element film was formed on the surface of the fertilizer.
  • the conventional granular fertilizer is one of compound fertilizer, compound fertilizer, urea, potassium fertilizer, calcium superphosphate, heavy superphosphate, monoammonium phosphate, diammonium phosphate, ammonium nitrate and calcium ammonium nitrate.
  • compound fertilizer compound fertilizer, urea, potassium fertilizer, calcium superphosphate, heavy superphosphate, monoammonium phosphate, diammonium phosphate, ammonium nitrate and calcium ammonium nitrate.
  • urea potassium fertilizer
  • the certain temperature means that the granular fertilizer needs to be preheated to 40-60 ° C in the drum, disc or fluidized bed equipment.
  • the invention has the advantages of: 1. fast and flexible addition of medium and trace elements; 2. solving the problem of uniform dispersion of medium and trace elements in the soil to avoid local poisoning; 3, the film formed by the wrapped medium and trace element material is combined with fertilizer particles It is firm and not easy to fall off; 4. It can wrap the middle and trace element materials combining fast-acting and long-acting, which is beneficial to the nutritional demand of the whole growth cycle of the crop; 5. It greatly reduces the granular fertilizer upgraded to new-type fertilizers because it is wrapped with medium and trace elements. The agglomeration trend can reduce or even avoid the use of fertilizer anti-caking agents; 6. There is no return in the production process, and the fertilizer can be safely sulfurized. 7. The new type of granular fertilizer obtained by this method not only has the functions of preventing moisture, caking, and powdering, but also provides various medium and trace elements for the fertilizer to meet the balanced nutritional demand of the crop and promote the healthy growth of the crop.
  • composition of the mixture is as follows: 75% sulfur, 10% zinc oxide, 5% zinc sulfate (without water), and 10% sodium polyacrylate having a molecular weight of 5000.
  • the sulfur is heated to a liquid state, and medium zinc and zinc oxide, zinc sulfate and sodium polyacrylate are added to the liquid sulfur and mixed uniformly to prepare a medium and trace element mixture.
  • a new type of fertilizer for preparing trace elements in the package Add diammonium phosphate (DAP: 18-46-0) to the wrapping drum and preheat to 60 ° C. Addition ratio of medium and trace element mixture: 1 ton of diammonium phosphate is used to wrap 120kg of medium and trace element mixture. The wrapped granular fertilizer is cooled and then packed.
  • DAP diammonium phosphate
  • Zinc is one of the essential trace elements in plants. It is an activator of various enzymes during plant growth and development. Zinc deficiency in plants can cause slow plant growth, small leaves, and prone to disease, which affects crop quality and yield. Sugarcane, rapeseed, soybean, peanut, beet and other crops have a very high demand for sulfur. After this technology upgrades diammonium phosphate to medium and trace element fertilizers, the medium and trace elements are evenly distributed on the surface of the fertilizer. Water-soluble zinc and oxidation in the form of zinc sulfate Water-soluble zinc in the form of zinc combines with each other. The combination of fast-acting sulfur in the form of sulfate and long-acting sulfur in the form of elemental sulfur can greatly enhance the synergistic effect of phosphorus and double-effect sulfur, and phosphorus and double-effect zinc.
  • the coated fertilizer coated with the medium and trace element mixture does not need to add additional anti-caking agents, moisture-proof agents, and anti-whitening agents, and has the effect of preventing moisture and whitening, and the coating layer does not affect the nutrients of the coated fertilizers. Release normally.
  • composition of the mixture is as follows: 50% sulfur, 15% magnesium oxide, 10% zinc oxide, 10% anhydrous copper sulfate, 10% boric acid, and 5% chitosan with a molecular weight of 50,000.
  • the sulfur is heated to a liquid state, and medium magnesium, zinc oxide, anhydrous copper sulfate, boric acid, and chitosan are added to the liquid sulfur and mixed to prepare a medium and trace element mixture.
  • composition of the mixture is as follows: 90% sulfur, 5% boric acid, and 5% cellulose with a molecular weight of 60,000. Sulfur is heated to a liquid state, medium boric acid and cellulose are added to the liquid sulfur and mixed uniformly to prepare a medium and trace element mixture.
  • Urea is upgraded to sulfur-containing and boron urea through this technology. Boron can promote the absorption of nitrogen, which can improve the utilization rate of nitrogen. At the same time, sulfur and nitrogen are also synergistic. Both are protein components and are indispensable for chlorophyll formation.
  • composition of the mixture is as follows: 60% sulfur, 10% magnesium oxide, 5% zinc oxide, 5% manganese sulfate, 10% molecular weight of 100,000 chitosan and 10% polyvinyl alcohol of 60,000. Sulfur is heated to a liquid state, medium magnesium oxide, zinc oxide, manganese sulfate, chitosan and polyvinyl alcohol are added to the liquid sulfur and mixed to obtain a medium and trace element mixture.
  • the heavy superphosphate After being wrapped, the heavy superphosphate is upgraded to a medium and trace element fertilizer containing double-effect sulfur, calcium, magnesium, zinc, and manganese. It is especially suitable for crops with a high demand for sulfur and calcium, such as peanuts, peas, potatoes, citrus, Beets and other crops.
  • composition of the mixture is as follows: 55% sulfur, 25% sodium metasilicate, 8% zinc oxide, and 12% cellulose with a molecular weight of 80,000.
  • the sulfur is heated to a liquid state, and sodium metasilicate, zinc oxide and cellulose are added to the liquid sulfur and mixed uniformly to prepare a medium and trace element mixture.
  • a new type of fertilizer for preparing trace elements in the package Add high nitrogen-type potassium sulfate compound fertilizer (NPK: 20-10-10) to the wrapping drum and preheat to 60 ° C. Addition ratio of medium and trace element mixture: 1 ton of compound fertilizer is wrapped with 200kg of medium and trace element mixture, and the wrapped granular fertilizer is cooled and then packed.
  • NPK nitrogen-type potassium sulfate compound fertilizer
  • the high-nitrogen potassium sulfate compound fertilizer was upgraded to obtain a new fertilizer containing medium, trace elements containing sulfur, silicon, and zinc, which can be used as a high-efficiency special fertilizer for rice.
  • Silicon is an important nutrient element for plant bodies, and is ranked as the fourth largest element after nitrogen, phosphorus, and potassium by the international soil community. Silicon fertilizer can improve the resistance of crops to diseases and insect pests, and reduce the occurrence of various diseases and insect pests.
  • the crop absorbs silicon, it can form silicified cells in the plant body, thicken the cell wall of the surface layer of stems and leaves, increase the cuticle, and form a solid protective layer Insects are not easy to bite, germs are difficult to invade, and crop resistance can be improved.
  • silicon fertilizer rice, wheat, corn, peanut, soybean, watermelon, fruit tree, vegetable and other crops can generally increase yield by 10% to 25%. With the synergy of sulfur and zinc, the role of silicon is more significant.
  • the composition of the mixture is as follows: 65% sulfur, 5% magnesium oxide, 10% zinc oxide, 8% zinc sulfate, and 12% polyacrylamide with a molecular weight of 100,000.
  • the sulfur is heated to a liquid state, and medium magnesium, zinc oxide, zinc sulfate, and polyacrylamide are added to the liquid sulfur and mixed uniformly to prepare a medium and trace element mixture.
  • Zinc is one of the essential trace elements in plants. It is an activator of various enzymes during plant growth and development. Zinc deficiency in plants can cause slow plant growth, small leaves, and prone to disease, which affects crop quality and yield. Magnesium is involved in the synthesis of chlorophyll and is an important element necessary for crops. This technology upgrades monoammonium phosphate to medium and trace element fertilizers. Water-soluble zinc in the form of zinc sulfate and water-insoluble zinc in the form of zinc oxide are combined with each other, and fast-acting sulfur in the form of sulfate and long-acting sulfur in the form of elemental sulfur are combined. It also adds magnesium, which can greatly enhance the synergistic effect of phosphorus and double-effect sulfur, and phosphorus and double-effect zinc.

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Abstract

中微量元素混合剂及包裹中微量元素肥料的制备方法。中微量元素混合剂中硫磺占50％-90％，溶胀材料占5％-20％，硫之外的中微量元素占5％-45％，制备方法：在液态硫磺中添加中微量元素和溶胀材料并混合均匀。包裹中微量元素肥料的制备方法：将常规颗粒肥料置于具有加热功能的包裹设备中，中微量元素混合剂加热到一定温度后，喷涂在颗粒肥料表面，经冷却固化，在肥料表面形成一层中微量元素膜。优点：快速、灵活添加中微量元素；解决中微量元素在土壤中均匀分散问题，避免局部中毒；包裹中微量元素材料形成的膜与肥料颗粒结合牢固，不易脱落；可包裹速效与长效相结合的中微量元素材料，利于作物全生长周期对营养的需求。

Description

中微量元素混合剂及包裹中微量元素肥料的制备方法 技术领域
本发明涉及新型肥料包膜技术领域，具体为中微量元素混合剂及包裹中微量元素肥料的制备方法。
背景技术
中国农业经历了连续多年的快速发展，取得了举世瞩目的成就。与此同时，粗放的增长模式带来诸多问题：资源快速消耗，环境污染严重，土地资源功能退化等。高养分速效肥料利用率极其低下，肥料流失造成的农业面源污染非常严重。随着我国现代农业技术和农业生产结构的改革与完善，适应我国农业生产需求、环境友好的肥料将会成为我国肥料的主体，肥料产业的发展也会向着肥料养分高效化、肥料施用简便化、肥料成本经济化、环境影响生态化、作物养分平衡化等方向发展。平衡施肥是实现农业高质量发展的关键，作物所需的养分除了氮、磷、钾等元素以外，还有中微量元素和有机肥等，中微量元素对作物的产品和品质都有极大的影响。
近年来，国内***绕中微量元素肥料有越来越多的研究和应用，极大推动了肥料行业的进步。常见的中微量元素有硫、钙、镁、硅、铁、锰、铜、锌、硼、钼等元素，不同于氮磷钾等元素，中微量元素虽然是作物必需的营养元素，但其用量一般比较少，且施用后极易被土壤固定从而失去肥效。为了解决微量元素被固定的问题，市场上出现了螯合态的微量元素肥料，可极大提升肥料利用率，但因其成本偏高，很大程度上影响其推广使用。国内曾经有将微量元素肥料制备成大颗粒状的做法，然而由于中微量元素用量少，必然存在施肥的不均匀问题，且大颗粒肥料会造成土壤局部浓度过高，使土壤和作物中毒。针对上述存在的诸多问题，国内外相关研究者开展了大量关于中微量元素肥料开发和应用的工作。
专利WO03/071855A3和专利WO2008/131535A1公开了一种中微量元素肥料的制备方法：将含有铜、锌、锰等微量元素物质制备成细粉，然后包裹到颗粒肥料或种子表面，得到含有中微量元素的肥料或种子。为了实现好的包裹效果，要求细粉最好是325目。当细粉中含有氧化物形态微量元素时，需要同时混入有机酸等酸化剂，以加速微量元素 的释放。该技术的缺点是中微量元素细粉的包裹量有限，不能满足肥料升级的需求，同时存在中微量元素细粉包裹后脱粉的现象。
专利WO01/87803A1、专利EP2248790A1、专利CN100434399C、专利CN1380879A和专利CN1990434A公开了一种含硫肥料及其制备方法，具体做法是在肥料造粒过程中，将硫和微量元素一层一层分散在颗粒肥料内部。该工艺不仅复杂，而且生产过程不容易控制，最主要的缺点是硫为内部添加方式，生产过程中因有返料产生，存在硫磺***的风险。
专利US2014/0216120A1、专利US2014/0109639A1和专利CN103771998A等专利介绍了一种含有中量元素硫、微量元素、磷矿石等物质的肥料，具体做法是将微量元素物质加入液体硫磺中，利用钢带造粒机制备含有中微量元素的硫肥。该技术需要在硫磺中加入吸水材料以加速硫磺的崩解，存在的问题是所制备的颗粒肥料仅含有硫和微量元素，使用过程中由于用量很少，很难实现中微量元素的均匀分布，会造成土壤中局部浓度过高，局部浓度过低甚至没有，尤其在大田作物中使用效果不佳。
专利US8679219B2介绍了一种含硫肥料及其制备方法，具体表现为用分散研磨机将硫磺粉与磷酸等液体研磨，最终得到微米级粒径的硫磺颗粒，然后加入其它肥料组分，除去多余水分后造粒，制备成含有硫磺的颗粒肥料。该技术中硫磺湿磨可以减少粉尘，降低硫磺***风险，但存在问题是该工艺流程较长，操作繁琐，不易控制，成本过高。
专利US4857098、专利WO2008/103728A1、专利WO2015/070496A1、专利CN100516003C、专利CN101805235B、专利CN103553849A、专利CN104496691A、专利CN104108977A和专利CN106316620A等专利涉及到硫包衣尿素和硫包衣硫镁肥，以提高尿素的利用率，最终实现尿素的缓释和控失。为了更好的达到这个要求，一般需要在硫包衣外面再包裹一层封闭剂物质，最外层的封闭剂一般是石蜡、烃类蜡、改性聚合蜡、天然蜂蜡、脲醛树脂、高分子聚合物等物质。硫包衣尿素中的硫元素主要作用是包衣阻隔，与封闭剂协同以达到尿素缓释效果。然而，当硫包衣尿素施于土壤后，随着尿素的溶出，硫会以“包衣壳”形式存在，其分解释放较慢，不利于硫的利用。且添加的石蜡、烃类蜡、改性聚合蜡、天然蜂蜡、脲醛树脂、高分子聚合物等物质及其使用后存在不降解、环境污染等缺陷及风险。
专利CN102811979A和专利CN105367235A公开了一种微量营养元素肥料的制备方 法：在磷铵、过磷酸钙、重过磷酸钙等磷酸盐肥料上涂覆隔离层，然后将一种或多种微量营养元素粘附于隔离涂层外面。隔离涂层的作用是避免微量元素与磷酸盐发生化学反应，隔离涂层的材料要求与磷酸盐和微量元素均不发生反应，常用的有聚乙烯亚胺类聚合物、尿素、硫酸铵、硫酸钾、硫酸镁、硫酸钙、元素硫、硅酸盐等物质。该技术包裹的微量营养元素存在脱粉风险，同时，包裹了微量元素后的肥料具有加剧结块的风险。为了使肥料可以自由流动，使用前还需要在肥料中添加1％左右的滑石。
上述中微量元素肥料的相关研究和应用，很大程度上推动了肥料行业的进步。中微量营养元素对作物的生长发育具有不可替代的重要作用，因此，如何简单、快捷、高效率、安全地实现中微量元素的添加具有十分重要的意义。在常规肥料的基础上，最大化中微量营养元素的价值和使用效率，以达到中微量元素和大量元素的协同和平衡。
发明内容
本发明目的为了克服上述现有技术存在的问题，提供一种中微量元素混合剂及包裹中微量元素肥料的制备方法，本技术可以快速将常规肥料升级为含一种或多种中微量元素的新型肥料，可以添加的双效态的中微量元素有硫、钙、镁、硅、铁、锰、铜、锌、硼、钼等元素。本发明快速、灵活添加中微量元素；解决纯中微量元素颗粒剂在土壤中难以均匀分散造成作物中毒的问题；以添加溶胀材料的方式，加快硫磺膜层的崩解成硫磺微粒，解决块状硫磺粒径太大，难以被作物吸收的问题；此方式形成的中微量元素膜与肥料颗粒结合牢固，不易脱落；可包裹速效与长效相结合的中微量元素材料，利于作物全生长周期对营养的需求。
不同于常规的在肥料中添加单质硫的方法，其多采用在造粒时内添加硫，此种方式会在生产过程中产生返料，硫粉尘极易在***中累积，存在***的风险，而本发明只需要利用外部包膜的方式，包膜后即得成品，安全性更高。
不同于硫包衣缓释尿素，本发明中利用硫为载体，将中微量元素包裹在肥料表面，且中微量元素混合剂同时包含水易溶型和水难溶型两种，水易溶型元素可以快速释放，快速满足作物生长需求。与此同时，在包膜层中加入溶胀材料，能将中微量元素崩解成微粒，极易被作物根系吸收，另一方面硫磺会在土壤硫细菌的作用下转化成硫酸，活化水难溶型微量元素，如此实现中微量元素速效和缓效的平衡，更好的满足作物整个生长 周期的养分需求。
不同于纯中微量元素颗粒剂，其微量元素浓度过高，极易造成作物局部中毒。本发明中的中微量元素是以包膜形式喷涂在颗粒肥料表面，微量元素的含量可控，浓度合适。与此同时，本发明制备的中微量元素包膜肥料施在土壤中后，中微量元素膜层在溶胀材料的作用下，遇水会崩解成微粒，均匀分散在土壤中，避免作物了局部中毒。
采用本方案制备的新型肥料表面是一层硫为载体的微量元素膜层，硫的化学惰性，使得包膜后的肥料不易吸潮，不易结块，因此可以减少甚至不使用肥料防结块剂，从而降低肥料生产成本。
本发明的具体实现方式如下：
中微量元素混合剂，由中微量元素和溶胀材料组成，各组分按质量百分比计，其特征在于：混合剂中硫磺占比50％-90％，溶胀材料占比5％-20％，硫之外的中微量元素质量占比5％-45％，制备方法为：将硫磺加热至液态，在液态硫磺中添加中微量元素和溶胀材料并混合均匀制得中微量元素混合剂。
所述中微量元素为含有硫、钙、镁、硅、铁、锰、铜、锌、硼、钼等元素的单质、氧化物或无水化合物中的一种或几种。
所述的溶胀材料为壳聚糖、纤维素、聚丙烯酸钠、聚丙烯酰胺、聚乙烯醇中的一种或几种。
所述的溶胀材料的分子量为5000-100000。
所述的中微量元素混合剂，其特征在于：所述中微量元素根据溶解性分为两种：水易溶型和水难溶型。
所述中微量元素混合剂中至少包含一种水易溶性物质。
所述的包裹中微量元素肥料的制备方法，其特征在于按以下步骤进行:将常规颗粒肥料置于具有加热功能的包裹滚筒、圆盘或流化床设备中，所述的中微量元素混合剂喷涂在加热到一定温度的颗粒肥料表面，经冷却固化，在肥料表面形成一层中微量元素膜。
所述常规颗粒肥料为复合肥、复混肥、尿素、钾肥、过磷酸钙、重过磷酸钙、磷酸一铵、磷酸二铵、硝酸铵、硝酸铵钙一切能做成颗粒状肥料中的一种或二种以上的混合物。
所述的一定温度是指颗粒肥料在滚筒、圆盘或流化床设备中需预热至40-60℃。
本发明的优点在于：1、快速、灵活添加中微量元素；2、解决了中微量元素在土壤中的均匀分散问题，避免局部中毒；3、包裹的中微量元素材料形成的膜与肥料颗粒结合牢固，不易脱落；4、可包裹速效与长效相结合的中微量元素材料，利于作物全生长周期对营养的需求；5、大幅降低了因包裹了中微量元素而升级为新型肥料的颗粒肥料结块趋势，可以减少甚至不使用肥料防结块剂；6、生产过程没有返料，肥料可实现安全加硫。7、利用该方法得到的新型颗粒肥料，不仅具备防潮防结防粉化功能，同时为肥料提供各种中微量元素，满足作物对营养的均衡需求，促进作物健康生长。
具体实施方式
下面结合具体实施例对本发明作进一步说明，包括但不仅限于以下案例，以下实施例各物质按重量份计。
实施案例1
(1)制备中微量元素混合剂。混合剂组成如下：75％硫、10％氧化锌、5％硫酸锌(不含水)和10％分子量为5000的聚丙烯酸钠。将硫磺加热至液态，在液态硫磺中添加中氧化锌、硫酸锌和聚丙烯酸钠并混合均匀制得中微量元素混合剂。
(2)制备包裹中微量元素的新型肥料。在包裹滚筒中加入磷酸二铵(DAP：18-46-0)，预热至60℃。中微量元素混合剂添加比例：1吨磷酸二铵包裹120kg中微量元素混合剂，包裹后的颗粒肥料冷却后进行包装。
(3)最终制备得到的新型中微量元素肥料养分如下：
  N P 2O 5 单质S SO 4 2- 水易溶Zn 水难溶Zn
养分组成 16％ 41％ 8％ 0.32％ 0.22％ 0.84％
锌是植物必需的微量元素之一，是植物生长发育过程中多种酶的活化剂，植物缺锌会导致植株生长缓慢，叶片小，且容易发生病害，从而影响作物品质和产量。甘蔗、油菜、大豆、花生、甜菜等作物对硫的需求量非常大，本技术将磷酸二铵升级为中微量元素肥料后，中微量元素均匀分布在肥料表面，硫酸锌形态的水溶锌和氧化锌形态的水难溶锌相互结合，硫酸根形态的速效硫和单质硫形态的长效硫相结合，可以极大提升磷和双效硫、磷和双效锌的协同增效作用。
包膜了中微量元素混合剂后的包膜肥料不需要额外添加防结块剂、防潮剂、防泛白 剂即具有防结防潮防泛白效果，且包膜层不影响包膜肥料养分的正常释放。
实施案例2
(1)制备中微量元素混合剂。混合剂组成如下：50％硫、15％氧化镁、10％氧化锌、10％无水硫酸铜、10％硼酸和5％分子量为50000的壳聚糖。将硫磺加热至液态，在液态硫磺中添加中氧化镁、氧化锌、无水硫酸铜、硼酸和壳聚糖并混合均匀制得中微量元素混合剂。
(2)制备包裹中微量元素的新型肥料。在具有加热功能的圆盘中中加入复合肥(NPK：15-15-15)，预热至40℃。中微量元素混合剂添加比例：1吨复合肥包裹150kg中微量元素混合剂，包裹后的颗粒肥料冷却后进行包装。
(3)最终制备得到的新型中微量元素肥料养分如下：
  N P 2O 5 K 2O 单质S SO 4 2- 水难溶Mg 水难溶Zn 水易溶Cu 水易溶B
养分组成 13％ 13％ 13％ 6.5％ 0.78％ 1.2％ 1.0％ 0.5％ 0.23％
常规复合肥(15-15-15)升级后，得到含有中微量元素双效硫、镁、锌、铜和硼的中微量元素复合肥，各元素之间相互协同，实现极好的植物营养功能。
实施案例3
(1)制备中微量元素混合剂。混合剂组成如下：90％硫、5％硼酸和5％分子量为60000的纤维素。将硫磺加热至液态，在液态硫磺中添加中硼酸和纤维素并混合均匀制得中微量元素混合剂。
(2)制备包裹中微量元素的新型肥料。在底喷流化床设备中加入尿素(46-0-0)，预热至55℃。中微量元素混合剂添加比例：1吨尿素包裹200kg中微量元素混合剂，包裹后的颗粒肥料冷却后进行包装。
(3)最终制备得到的新型中微量元素肥料养分如下：
  N 单质S 水易溶B
养分组成 38％ 15％ 0.14％
尿素经过本技术升级为含硫、硼尿素，硼对氮的吸收具有促进作用，可以提高氮素的利用率。同时，硫和氮之间也是协同作用，两者都是蛋白质成分，也是叶绿素形成不可或缺的。
实施案例4
(1)制备中微量元素混合剂。混合剂组成如下：60％硫、10％氧化镁、5％氧化锌、5％硫酸锰、10％分子量为100000壳聚糖和10％分子量为60000的聚乙烯醇。将硫磺加热至液态，在液态硫磺中添加中氧化镁、氧化锌、硫酸锰、壳聚糖和聚乙烯醇并混合均匀制得中微量元素混合剂。
(2)制备包裹中微量元素的新型肥料。在包裹滚筒中加入重过磷酸钙(TSP:0-46-0)，预热至50℃。中微量元素混合剂添加比例：1吨重过磷酸钙包裹180kg中微量元素混合剂，包裹后的颗粒肥料冷却后进行包装。
(3)最终制备得到的新型中微量元素肥料养分如下：
  P 2O 5 单质S SO 4 2- Ca 水难溶Mg 水难溶Zn 水易溶Mn
养分组成 39％ 10％ 0.54％ 10％ 1.0％ 0.67％ 0.30％
经过包裹，重过磷酸钙升级成为含双效硫、钙、镁、锌和锰的中微量元素肥料，尤其适用于对硫和钙需求量比较大的作物，如花生、豌豆、马铃薯、柑橘、甜菜等作物。
实施案例5
(1)制备中微量元素混合剂。混合剂组成如下：55％硫、25％偏硅酸钠、8％氧化锌和12％分子量为80000的纤维素。将硫磺加热至液态，在液态硫磺中添加中偏硅酸钠、氧化锌和纤维素并混合均匀制得中微量元素混合剂。
(2)制备包裹中微量元素的新型肥料。在包裹滚筒中加入高氮型硫酸钾复合肥(NPK：20-10-10)，预热至60℃。中微量元素混合剂添加比例：1吨复合肥包裹200kg中微量元素混合剂，包裹后的颗粒肥料冷却后进行包装。
(3)最终制备得到的新型中微量元素肥料养分如下：
  N P 2O 5 K 2O 单质S 水难溶Zn 水易溶Si
养分组成 17％ 8％ 8％ 9％ 1.0％ 1.0％
本案例中高氮型硫酸钾复合肥经过升级，得到含有硫、硅和锌的中微量元素新型肥料，可以作为高效水稻专用肥使用。硅是植物体组成的重要营养元素，被国际土壤界列为继氮、磷、钾之后的第四大元素。硅肥能提高作物对病虫害的抵抗力，减少各种病虫害的发生，作物吸收硅后，可在植物体内形成硅化细胞，使茎叶表层细胞壁加厚，角质层增加，形成一个坚固的保护层，使昆虫不易咬动，病菌难以入侵，也可以提高作物抗倒伏能力。水稻、小麦、玉米、花生、大豆、西瓜、果树、蔬菜等作物，施用硅肥后， 一般可增产10％～25％。在硫和锌的协同之下，硅的作用更加显著。
实施案例6
(1)制备中微量元素混合剂。混合剂组成如下：65％硫、5％氧化镁、10％氧化锌、8％硫酸锌和12％分子量为100000的聚丙烯酰胺。将硫磺加热至液态，在液态硫磺中添加中氧化镁、氧化锌、硫酸锌和聚丙烯酰胺并混合均匀制得中微量元素混合剂。
(2)制备包裹中微量元素的新型肥料。在包裹滚筒中加入磷酸一铵(MAP：10-50-0)，预热至60℃。中微量元素混合剂添加比例：1吨磷酸一铵包裹100kg中微量元素混合剂，包裹后的颗粒肥料冷却后进行包装。
(3)最终制备得到的新型中微量元素肥料养分如下：
  N P 2O 5 水易溶Zn 水难溶Zn 水难溶Mg 单质S SO 4 2-
养分组成 9.1％ 45.4％ 0.29％ 0.73％ 0.28％ 5.9％ 0.43％
锌是植物必需的微量元素之一，是植物生长发育过程中多种酶的活化剂，植物缺锌会导致植株生长缓慢，叶片小，且容易发生病害，从而影响作物品质和产量。镁参与叶绿素的合成，是作物必需的重要元素。本技术将磷酸一铵升级为中微量元素肥料后，硫酸锌形态的水溶锌和氧化锌形态的水难溶锌相互结合，硫酸根形态的速效硫和单质硫形态的长效硫相结合，同时又补充了镁元素，可以极大提升磷和双效硫、磷和双效锌的协同增效作用。

Claims (9)

  1. 中微量元素混合剂，由中微量元素和溶胀材料组成，各组分按质量百分比计，其特征在于：混合剂中硫磺占比50％-90％，溶胀材料占比5％-20％，硫之外的中微量元素质量占比5％-45％，制备方法为：将硫磺加热至液态，在液态硫磺中添加中微量元素和溶胀材料并混合均匀，即得中微量元素混合剂。
  2. 如权利要求1所述的中微量元素混合剂，其特征在于：所述中微量元素为含有硫、钙、镁、硅、铁、锰、铜、锌、硼、钼元素的单质、氧化物或无水化合物中的一种或几种。
  3. 如权利要求1所述的中微量元素混合剂，其特征在于：所述的溶胀材料为壳聚糖、纤维素、聚丙烯酸钠、聚丙烯酰胺、聚乙烯醇中的一种或几种。
  4. 如权利要求3所述的中微量元素混合剂，其特征在于：所述溶胀材料的分子量为5000-100000。
  5. 如权利要求1所述的中微量元素混合剂，其特征在于：所述中微量元素根据溶解性分为两种：水易溶型和水难溶型。
  6. 如权利要求5所述的中微量元素混合剂，其特征在于：所述中微量元素混合剂中至少包含一种水易溶性物质。
  7. 包裹中微量元素肥料的制备方法，其特征在于按以下步骤进行:
    将常规颗粒肥料置于具有加热功能的包裹滚筒、圆盘或流化床设备中，权利要求1－6之一所述的中微量元素混合剂喷涂在加热到一定温度的颗粒肥料表面，经冷却固化，在肥料表面形成一层中微量元素膜。
  8. 如权利要求7所述的包裹中微量元素肥料的制备方法，其特征在于：所述常规颗粒肥料为复合肥、复混肥、尿素、钾肥、过磷酸钙、重过磷酸钙、磷酸一铵、磷酸二铵、硝酸铵、硝酸铵钙一切能做成颗粒状肥料中的一种或二种以上的混合物。
  9. 如权利要求7所述的包裹中微量元素肥料的制备方法，其特征在于：所述的一定温度是指颗粒肥料在滚筒、圆盘或流化床设备中需预热至40-60℃。
PCT/CN2018/109474 2018-08-17 2018-10-09 中微量元素混合剂及包裹中微量元素肥料的制备方法 WO2020034372A1 (zh)

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