WO2013082879A1 - Solid coated slow-release selenium fertilizer and preparation method therefor - Google Patents

Solid coated slow-release selenium fertilizer and preparation method therefor Download PDF

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Publication number
WO2013082879A1
WO2013082879A1 PCT/CN2012/070473 CN2012070473W WO2013082879A1 WO 2013082879 A1 WO2013082879 A1 WO 2013082879A1 CN 2012070473 W CN2012070473 W CN 2012070473W WO 2013082879 A1 WO2013082879 A1 WO 2013082879A1
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Prior art keywords
selenium
fertilizer
core
release
selenium fertilizer
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PCT/CN2012/070473
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French (fr)
Chinese (zh)
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李飞
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苏州硒谷科技有限公司
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Publication of WO2013082879A1 publication Critical patent/WO2013082879A1/en

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C05D9/02—Other inorganic fertilisers containing trace elements
    • 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
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/30—Layered or coated, e.g. dust-preventing coatings
    • C05G5/38—Layered or coated, e.g. dust-preventing coatings layered or coated with wax or resins

Definitions

  • the present invention relates to the manufacture of fertilizers, and more particularly to a method for producing a slow-release fertilizer containing a stone-based solid coated film, which belongs to the field of fertilizer and fertilizer manufacturing. Background technique
  • Selenium is an essential trace element for humans and animals. It has many important biological functions such as anti-oxidation, immunity enhancement, and growth promotion. At the same time, selenium is also a beneficial element of higher plants, and proper selenium supplement can enhance plant resistance. Sexuality, increase the accumulation of organic matter, achieve the beneficial effects of plant selenium-enriched function and increase production and quality. China is a selenium-deficient country, with selenium-deficient areas accounting for about 72% of the country's land area, and there are nearly 1 billion people at risk of selenium deficiency. Diet is the main source of selenium in the human body. The lack of selenium in the soil caused by our country has led to the lack of litchi in the whole plant food-animal food-human body food chain.
  • Cipheral Patent Application No. 03 136148. X discloses a selenium-enriched fertilizer sprayed on leaves and a preparation method thereof, wherein the weight ratio is: nitrogen 39.7-42.77, phosphorus 16.1 - 16.8, potassium 16.8- 18.2, Selenium 1.0-1.9, zinc 0.9-0.98, iron 2.4-2.8, calcium 0.82-0.92, magnesium 0.9-0.96, manganese 1.4-1.58, copper 1.2-1.44, molybdenum 0.08-0.09, boron 1.48-1 .58, sodium 8.2-9.1, organic acid 0.88-0.96 selenium-enriched spray fertilizer to achieve the production of selenium-enriched agricultural products. At present, there are many kinds of selenium fertilizers sprayed on the foliar surface.
  • the selenite or selenite is sprayed several times after fermentation or complexing agent to achieve the production of selenium-enriched agricultural products (for example, the application number is 961 1533 1 .8, 200610078710. 1 , 201010100788.5 Chinese patent application, etc.).
  • the two weaknesses of foliar application limit its application: On the one hand, the organic conversion process of selenite is mainly concentrated in the roots, and the conversion rate of selenium produced by foliar spraying is limited, inorganic selenium. The residue is serious and has potential toxicity risks (Zhu, Y., E. Pilon-Smits, et al. 2009); on the other hand, the application process of foliar fertilizer is heavy, the labor cost is large and the plant itself has the risk of burning .
  • 200910044507.6 discloses a selenium-enriched bio-organic fertilizer and a production method thereof, which utilizes chicken manure or pig manure, dried cake, gluten, selenium ore powder, micro-fertilizer, selenium-enriched sweetener and biological preparation
  • selenium-enriched bio-organic fertilizer by processes such as preparation, activation, deodorization, mixing, mixing, inoculation, fermentation, drying, inspection and packaging; Chinese Patent Application No. 2008 100 17763.
  • a humic acid silicon selenium fertilizer is prepared by mixing humic acid, sodium selenite and silicon micropowder to prepare humic acid silicon selenium fertilizer.
  • Chinese Patent Application No. 200710084619.5 discloses a solid granular selenium fertilizer and a method for producing the same, the solid granular selenium fertilizer having 19 to 33 parts of pumice, 65 to 80 parts of bentonite, selenate or selenite 0.5 to 2 As a raw material, the pumice and bentonite are crushed, sieved and mixed, then the selenite or selenate is dissolved in 20-30 parts of water, prepared into a solution for spraying, and then dried, cooled, sieved and selected.
  • the present invention proposes a method for enhancing the utilization and sustained release performance of the selenium-containing fertilizer by using the coating technology.
  • a solid coated slow release selenium fertilizer comprising selenium fertilizer particles, characterized in that the selenium fertilizer particles have a core-shell structure, the selenium fertilizer The core of the particle is a selenium-containing fat core, and the shell of the selenium fertilizer particle is a coating wrapped on the outer side of the selenium-containing fat core.
  • the selenium-containing fertilizer core comprises any one or a combination of two or more of selenium ore fines, selenite, and selenate after activation treatment.
  • the selenium-containing core is any one of the activated selenium ore powder, selenite, and selenate, or any combination of two or more and the filler of the fat core is 1:
  • the fertilizer filler is an organic fertilizer or humic acid having a pH of 7.5 to 9.
  • the core filler is fulvic acid having a pH of 7.5 to 9.
  • the mass ratio of the coating film and the selenium-containing core in the selenium fertilizer granule is 0.05 to 0.4:1. 1 ⁇ 0.25 : 1 ⁇ The mass ratio of the film and the selenium-containing core is 0. 1 ⁇ 0.25: 1.
  • the coating material is selected from the group consisting of montmorillonite, kaolinite, vermiculite, sepiolite, palygorskite, diatomaceous earth, coal powder, activated carbon, natural rubber, gum arabic, gelatin, sodium alginate, fiber.
  • lignin starch, polyethylene, polyvinyl chloride, polypropylene, polyvinyl alcohol, polyacrylamide urea, aldehyde resin, sodium decyl cellulose, ethyl cellulose sodium, or any combination of two or more .
  • the selenium content of the selenium fertilizer particles ranges from 0.005 % to 40%.
  • Another object of the present invention is to provide a method for preparing the solid coated slow release selenium fertilizer, characterized in that the method comprises the following steps:
  • the pH of the coating material is adjusted to 7.5 to 9 with an alkaline substance, and then a coating operation is performed to form a coating on the surface of the core of the selenium fertilizer particles.
  • the technical problem to be solved by the present invention is that the utilization rate of various types of soil selenium fertilizer is low, and the effective selenium is easily reduced to an ineffective selenium in an environmental medium or adsorbed by iron-aluminum oxide or macromolecular organic matter in the soil. It affects the absorption of selenium by plants and increases the pressure of soil on the risk of selenium residues.
  • the present invention provides an efficient slow release selenium fertilizer composed of a film layer and a selenium-containing fertilizer core.
  • the selenium-containing fertilizer core can provide plant effective selenium for high-efficiency slow-release selenium fertilizer, and the source of selenium can be any one of activated selenium ore powder, selenite, and selenate, or The above three are mixed in any ratio.
  • the selenium-containing fertilizer core is produced by directly granulating the selenium source material or by mixing the selenium source material with the fat core filler in a ratio of 1:1 to 1000, followed by granulation.
  • the fat filler may be selected from a slightly alkaline substance capable of slowing down the effective selenium reduction, such as a slightly alkaline organic fertilizer, humic acid, etc.; preferably, the fertilizer filler is selected from fulvic acid extracted from humic acid.
  • the selenium-containing core is adjusted to a pH of 7.5 to 9, such as calcium hydroxide, sodium hydroxide, potassium hydroxide or the like by adding a hydroxide before granulation.
  • the material of the coating may be selected from inorganic clay minerals or substances having strong adsorption, such as montmorillonite, kaolinite, vermiculite, sepiolite, palygorskite, diatomaceous earth, coal powder and activated carbon. , or use the above substances mixed in any ratio; the coating material can also be selected from organic materials such as natural rubber, gum arabic, gelatin, sodium alginate, cellulose, lignin, starch, polyethylene, polychlorinated Ethylene, polypropylene, polyvinyl alcohol, polyacrylamide urea, aldehyde resin, sodium decyl cellulose, ethyl fibril plug, and the like.
  • the coating material is treated with an alkaline substance before use, and the pH is adjusted to 7.5 to 9 by adding a basic substance, and a basic substance such as calcium hydroxide, sodium hydroxide, potassium hydroxide or the like can be used.
  • the manufacturing process of the high-efficiency slow-release selenium fertilizer is as follows: a process of coating a selenium source material such as selenium ore powder, sodium selenite, and a toner cartridge: the selenium-containing core particles are rolled in a turntable or a drum, and the package is coated with a high-pressure spray gun. The film material is sprayed onto the surface of the fertilizer granule, wherein the weight ratio of the envelope to the selenium-containing core is 0.05 to 0.4:1. 1 ⁇ 0.25 : 1 ⁇ The weight ratio of the coating and the selenium-containing core is 0. 1 ⁇ 0.25 : 1 .
  • the solid coated slow-release selenium fertilizer is composed of a selenium-containing fat core and an envelope.
  • Selenium-containing fertilizer The core comprises any one of activated selenium ore fines, selenite, and selenate, or may be obtained by dry granulation by mixing the above three in any ratio.
  • the selenium-containing core is prepared by any one of the activated selenium ore powder, selenite, and selenate, or the above three are mixed in an arbitrary ratio and the filler is as follows: Dry granulation is carried out after the ratio of 1-1000 is mixed.
  • the selenium-containing fertilizer core is adjusted to pH 7.5 to 9 with an alkaline substance before granulation.
  • the pH of the coating material was adjusted to 7.5 to 9 with an alkaline substance before the coating process.
  • the effective selenium is reduced or adsorbed by other minerals in the soil, and has obvious sustained release characteristics, which can be stably and fully supplied to the plant for absorption and utilization, and remains in the soil.
  • the reduction of bioavailable selenium can effectively reduce the risk of environmental selenium pollution.
  • Example 1 The above scheme will be further described below in conjunction with specific embodiments. It is to be understood that the examples are intended to illustrate the invention and not to limit the scope of the invention. The implementation conditions used in the examples can be further adjusted according to the conditions of the specific manufacturer, and the unspecified implementation conditions are usually the conditions in the routine experiment. Example 1
  • Sodium selenite is used as the selenium source material, and different proportions of filler and film materials are selected.
  • the selenium source material and the filler are thoroughly mixed and then subjected to dry granulation to form a pellet core, and then the drum coating method is used to convert different proportions.
  • the coating material is sprayed onto the surface of the granular fertilizer to obtain a solid slow release selenium fertilizer.
  • the biomass and average selenium content of growing crops were counted.
  • the amount of selenium in the solid slow release selenium fertilizer was evaluated. The specific experimental results are shown in Table 1:
  • Humic acid 0.001:1 0.05: 1 0.045% 12% Any ratio of palygorskite, diatomaceous earth or both
  • Humic acid 0.005:1 0.15:1 0.2% 18% gelatin or sodium alginate
  • the pH is adjusted to 7.5-9 and the pH is adjusted to 7.5-9.
  • Sodium selenate is used as the selenium source material, and different proportions of filler and film materials are selected.
  • the selenium source material and the filler are thoroughly mixed and then subjected to dry granulation to form a pellet core, and then the drum package is used to make different proportions of the package.
  • the membrane material is sprayed onto the surface of the granular fertilizer to obtain a solid slow release selenium fertilizer.
  • Table 2 Table 2 Experimental results using sodium selenate as a selenium source
  • Fulvic acid 0.002:1 Activated carbon or three of them are 0.1:1 0.07% 20%
  • the pH is adjusted to 7.5-9
  • Fulvic acid 2:1 activated carbon or three of them are mixed 0.1:1 0.02% 10%
  • the pH is adjusted to 7.5-9
  • the selenite, selenate, and activated ore powder are mixed at any ratio and used as a selenium source material. Different proportions of filler and film materials are selected, and the selenium source material and the filler are thoroughly mixed and then subjected to dry granulation to prepare a granular fertilizer. The core is then sprayed onto the surface of the granular core by a drum coating method to obtain a solid slow release selenium fertilizer. In the field experiment, after 4-6 months of growth cycle, the biomass and average selenium content of the growing crops were counted to evaluate the utilization of selenium in the solid slow-release selenium fertilizer. The specific experimental results are shown in Table 4: Table 4 Experimental results using sodium selenate as a selenium source
  • Fulvic acid 2:1 activated carbon or three of them are 0.1:1 0.08% 18%
  • the pH is adjusted to 7.5-9

Abstract

A solid coated slow-release selenium fertilizer comprising a selenium fertilizer particle. The selenium fertilizer particle has a core-shell structure. The core of the selenium fertilizer particle is a selenium fertilizer-containing core. The shell of the selenium fertilizer particle is a coating covering the exterior of the selenium fertilizer-containing core. The slow-release selenium fertilizer reduces coprecipitation-sedimentation or absorption of available selenium by other minerals in the soil, provides significant slow-release characteristics, allows for stable and adequate supply for absorption and utilization by plants, for reduced non-bioavailable selenium residues in the soil, and for effectively mitigated risks of environmental selenium pollution.

Description

固体包膜緩释硒肥及其制备方法  Solid coated slow release selenium fertilizer and preparation method thereof
技术领域 Technical field
本发明涉及肥料制造， 特别涉及一种含石西固体包膜緩释肥料的制造方 法， 属于肥料及肥料制造领域。 背景技术  The present invention relates to the manufacture of fertilizers, and more particularly to a method for producing a slow-release fertilizer containing a stone-based solid coated film, which belongs to the field of fertilizer and fertilizer manufacturing. Background technique
硒是人和动物所必需的微量元素， 具有抗氧化、 增强免疫力、 促进生 长等多种重要的生物学功能； 同时， 硒也是高等植物的有益元素， 适量的 硒补充能增强植物的抗逆性， 增加有机物的积累， 实现植物富硒功能化及 增产提质等有益效果。 我国是一个缺硒大国， 缺硒区域占国土面积的 72% 左右， 存在缺硒风险的人群高达近 10亿。 饮食是人体摄入硒的主要来源， 我国源于土壤的硒缺乏导致了整个"植物性食物——动物性食物——人体" 食物链中石西的缺乏。  Selenium is an essential trace element for humans and animals. It has many important biological functions such as anti-oxidation, immunity enhancement, and growth promotion. At the same time, selenium is also a beneficial element of higher plants, and proper selenium supplement can enhance plant resistance. Sexuality, increase the accumulation of organic matter, achieve the beneficial effects of plant selenium-enriched function and increase production and quality. China is a selenium-deficient country, with selenium-deficient areas accounting for about 72% of the country's land area, and there are nearly 1 billion people at risk of selenium deficiency. Diet is the main source of selenium in the human body. The lack of selenium in the soil caused by our country has led to the lack of litchi in the whole plant food-animal food-human body food chain.
随着社会经济的发展和物质水平的提高， 人们对健康饮食的观念不断 增强， 富硒功能化食品在市场上越来越受到欢迎。 在我国缺硒地区， 施用 含石西肥料能有效提高农产品中的石西含量， 生产出富石西食品。 近年来， 已经 有多种含硒肥料问世。  With the development of social economy and the improvement of material level, people's concept of healthy eating has been continuously enhanced, and selenium-enriched functional food has become more and more popular in the market. In China's selenium-deficient areas, the application of Shixi fertilizer can effectively increase the content of the stone in the agricultural products and produce Fushixi food. In recent years, a variety of selenium-containing fertilizers have been introduced.
申请号为 03 136148. X的中国专利公开了一种喷施于叶子的富硒肥料 及其制备方法，其利用重量比例为：氮 39.7-42.77，磷 16. 1 - 16.8，钾 16.8- 18.2, 硒 1.0- 1 .9，锌 0.9-0.98，铁 2.4-2.8，钙 0.82-0.92，镁 0.9-0.96，锰 1.4- 1 .58，铜 1.2- 1 .44，钼 0.08-0.09，硼 1.48- 1 .58，钠 8.2-9.1，有机酸 0.88-0.96的富硒喷施 肥料， 以实现富硒农产品的生产。 目前叶面喷施的硒肥种类很多， 一般釆 用***盐或者***盐经发酵或络合剂以后进行多次叶面喷施， 以实现 富硒农产 品 的 生 产 （ 如 申 请号 为 961 1533 1 .8、 200610078710. 1 、 201010100788.5 的中国专利申请等）。 但是， 叶面喷施存在的两个弱点局 限了其应用： 一方面由于植株对***盐的有机转化过程主要集中在***， 通过叶面喷施生产的农产品硒的转换率有限， 无机硒的残留严重， 具 有潜在毒害风险 （ Zhu， Y.， E. Pilon-Smits, et al. 2009 ); 另一方面叶面肥的 施用过程工作量大， 人工成本大且对植株本身有烧苗风险。  Chinese Patent Application No. 03 136148. X discloses a selenium-enriched fertilizer sprayed on leaves and a preparation method thereof, wherein the weight ratio is: nitrogen 39.7-42.77, phosphorus 16.1 - 16.8, potassium 16.8- 18.2, Selenium 1.0-1.9, zinc 0.9-0.98, iron 2.4-2.8, calcium 0.82-0.92, magnesium 0.9-0.96, manganese 1.4-1.58, copper 1.2-1.44, molybdenum 0.08-0.09, boron 1.48-1 .58, sodium 8.2-9.1, organic acid 0.88-0.96 selenium-enriched spray fertilizer to achieve the production of selenium-enriched agricultural products. At present, there are many kinds of selenium fertilizers sprayed on the foliar surface. Generally, the selenite or selenite is sprayed several times after fermentation or complexing agent to achieve the production of selenium-enriched agricultural products (for example, the application number is 961 1533 1 .8, 200610078710. 1 , 201010100788.5 Chinese patent application, etc.). However, the two weaknesses of foliar application limit its application: On the one hand, the organic conversion process of selenite is mainly concentrated in the roots, and the conversion rate of selenium produced by foliar spraying is limited, inorganic selenium. The residue is serious and has potential toxicity risks (Zhu, Y., E. Pilon-Smits, et al. 2009); on the other hand, the application process of foliar fertilizer is heavy, the labor cost is large and the plant itself has the risk of burning .
除了叶面喷施硒肥， 目前另一种重要形式的硒肥为土施硒肥， 其只要 制造方法一般为利用高硒矿物或含硒盐 （***盐、 硒酸盐等） 与其他成 分进行搅拌、 混合等处理过程。 申请号为 02128368.0的中国专利申请公开 了一种利用硒矿生产硒肥的方法，该方法将硒矿粉碎、利用氨水活化处理. 再与氮、 磷、 钾等肥相混配制成硒肥。 申请号为 200910044507.6的中国专 利申请公开了一种富硒生物有机肥及其生产方法，利用鸡粪或猪粪、枯饼. 谷糠、 硒矿粉、 微肥、 富硒增甜素和生物制剂等材料， 经备料、 激活、 去 臭、 拌合、 拌料、 接种、 发酵、 干燥、 委检和包装等工艺生产富硒生物有 机肥；申请号为 2008 100 17763. 1 的中国专利申请公开了一种腐植酸硅硒肥 料， 将腐植酸、 ***钠、 硅微粉进行搅拌混合制备腐植酸硅硒肥料。 但 是， 这些施入到土壤中的含硒肥料， 其中能被植物吸收利用的主要为可溶 态和可交换态的硒酸盐和***盐形态 （魏显有， 刘云惠等， 1999. "土壤 中硒的形态分布及有效态研究." 河北农业大学学报）， 但是， 生物有效态 的硒在土壤中容易受到土壤 pH和 Eh的影响发生形态变化，我国大部分地 区土壤均为酸性土壤， 在偏酸和偏还原条件下， 硒酸盐和***盐很容易 发生还原反应， 变成不可被植物吸收利用的元素态的硒（李永华， 王五一， 2002. "硒的土壤环境化学研究进展." 土壤通报 33 (003 ) : 230-233. )。而且， 通过硒肥施入到土壤中的生物有效硒（***盐等）在土壤中还会受到土 壤中铁铝氧化物、 大生物有机分子的强烈吸附而不能被植物吸收利用， 从 而导致硒肥肥效的低下。 据报道， 直接向大田中施用***钠的利用率一 般低于 20%。 In addition to foliar application of selenium fertilizer, another important form of selenium fertilizer is applied to soil by selenium fertilizer, as long as The manufacturing method generally uses a high-selenium mineral or a selenium-containing salt (selenite, selenate, etc.) to be stirred and mixed with other components. Chinese Patent Application No. 02128368.0 discloses a method for producing selenium fertilizer by using selenium ore, which pulverizes selenium ore and activates it with ammonia water, and then mixes with nitrogen, phosphorus and potassium to prepare selenium fertilizer. Chinese Patent Application No. 200910044507.6 discloses a selenium-enriched bio-organic fertilizer and a production method thereof, which utilizes chicken manure or pig manure, dried cake, gluten, selenium ore powder, micro-fertilizer, selenium-enriched sweetener and biological preparation For the production of selenium-enriched bio-organic fertilizer by processes such as preparation, activation, deodorization, mixing, mixing, inoculation, fermentation, drying, inspection and packaging; Chinese Patent Application No. 2008 100 17763. A humic acid silicon selenium fertilizer is prepared by mixing humic acid, sodium selenite and silicon micropowder to prepare humic acid silicon selenium fertilizer. However, these selenium-containing fertilizers applied to the soil, which are mainly absorbed and utilized by plants, are soluble and exchangeable selenate and selenite forms (Wei Xianyou, Liu Yunhui et al., 1999. The morphological distribution and effective state of selenium in soil. "Journal of Hebei Agricultural University", however, bio-effective selenium is susceptible to morphological changes in soil by soil pH and Eh. Most of the soil in China is acidic soil. Under the conditions of partial acid and partial reduction, selenate and selenite are easily reduced to become elemental selenium that cannot be absorbed and utilized by plants (Li Yonghua, Wang Wuyi, 2002. Selenium Soil Environmental Chemistry) Research progress." Soil Bulletin 33 (003): 230-233.). Moreover, bio-effective selenium (selenite, etc.) applied to the soil by selenium fertilizer is strongly adsorbed by iron-aluminum oxides and large bioorganic molecules in the soil, and cannot be absorbed and utilized by plants, thereby causing selenium. Fertilizer effect is low. It has been reported that the utilization rate of sodium selenite directly to the field is generally less than 20%.
为了提高硒肥的利用率及实现硒肥长期緩释吸收的效果， 现有含硒肥 料已经有向緩释方向发展的趋势。申请号为 200710084619.5 的中国专利申 请公开了一种固体颗粒硒肥及其制造方法，该固体颗粒硒肥以浮石 19 ~ 33 份、 膨润土 65 ~ 80份、 硒酸盐或***盐 0.5 ~ 2份为原料， 将浮石、 膨 润土粉碎过筛后混合， 然后将***盐或硒酸盐溶解于 20 ~ 30份水中， 配制成溶液进行喷淋， 再经烘干、 冷却、 分筛后选取 2mm ~ 4mm的颗粒 状硒肥。 该方法虽然在一定程度上解决了固体硒肥养分流失的问题， 但由 于其中***盐或硒酸盐吸附在浮石内核上还是会受到土壤外界条件的 直接影响， 受到还原作用而失去生物有效性； 同时， 吸附到浮石内核上的 有效态硒在土壤中能否顺利的解吸附顺利被植物吸收利用尚不明确。 申请 号 2007 10150882.X的中国专利申请公开了一种复合包膜緩释肥料， 釆用 无机有机结合多层包膜方式制作复合包膜緩释肥料， 但其主要针对对象为 氮磷钾肥或复合肥， 且其包膜材料未考虑硒肥的实效和释放特性。 本发明 因此而来。 发明内容 In order to improve the utilization rate of selenium fertilizer and realize the long-term slow release absorption of selenium fertilizer, the existing selenium-containing fertilizer has a tendency to develop in a slow release direction. Chinese Patent Application No. 200710084619.5 discloses a solid granular selenium fertilizer and a method for producing the same, the solid granular selenium fertilizer having 19 to 33 parts of pumice, 65 to 80 parts of bentonite, selenate or selenite 0.5 to 2 As a raw material, the pumice and bentonite are crushed, sieved and mixed, then the selenite or selenate is dissolved in 20-30 parts of water, prepared into a solution for spraying, and then dried, cooled, sieved and selected. 2mm ~ 4mm granular selenium fertilizer. Although this method solves the problem of nutrient loss of solid selenium fertilizer to some extent, it is affected by the external conditions of the soil due to the adsorption of selenite or selenate on the core of pumice. At the same time, it is not clear whether the effective selenium adsorbed onto the pumice core can be smoothly absorbed by the plant in the soil. Application The Chinese patent application No. 2007 10150882.X discloses a composite coated slow-release fertilizer, which is prepared by using an inorganic-organic combined multi-layer coating method to produce a composite coated slow-release fertilizer, but the main target is NPK fertilizer or compound fertilizer. , and its coating material does not consider the effectiveness and release characteristics of selenium fertilizer. The present invention thus comes. Summary of the invention
为了解决现有土施含硒肥料存在的失效率高、 有效緩释特征不明显等 缺陷， 本发明提出了一种利用包膜技术增强含硒肥料利用率和緩释性能的 方法。  In order to solve the defects of high failure rate and ineffective sustained release characteristics of the existing soil-containing selenium-containing fertilizer, the present invention proposes a method for enhancing the utilization and sustained release performance of the selenium-containing fertilizer by using the coating technology.
为了解决现有技术中的上述问题， 本发明提供的技术方案是： 一种固体包膜緩释硒肥， 包括硒肥颗粒， 其特征在于所述硒肥颗粒具 有核壳结构， 所述硒肥颗粒的核为含硒肥芯， 所述硒肥颗粒的壳为包裹在 含硒肥芯外侧的包膜。  In order to solve the above problems in the prior art, the technical solution provided by the present invention is: a solid coated slow release selenium fertilizer, comprising selenium fertilizer particles, characterized in that the selenium fertilizer particles have a core-shell structure, the selenium fertilizer The core of the particle is a selenium-containing fat core, and the shell of the selenium fertilizer particle is a coating wrapped on the outer side of the selenium-containing fat core.
优选的， 所述含硒肥芯包含经活化处理后的硒矿粉、 ***盐、 硒酸 盐中的任意一种或者两种以上的任意组合。  Preferably, the selenium-containing fertilizer core comprises any one or a combination of two or more of selenium ore fines, selenite, and selenate after activation treatment.
优选的， 所述含硒肥芯为活化处理后的硒矿粉、 ***盐、 硒酸盐中 的任意一种或者两种以上的任意组合与肥芯填充料按照重量比为 1： Preferably, the selenium-containing core is any one of the activated selenium ore powder, selenite, and selenate, or any combination of two or more and the filler of the fat core is 1:
1〜 1000的比例混合的混合物。 Mix the mixture in a ratio of 1 to 1000.
优选的， 所述肥芯填充料为 pH值为 7.5〜9的有机肥或腐植酸。  Preferably, the fertilizer filler is an organic fertilizer or humic acid having a pH of 7.5 to 9.
优选的， 所述肥芯填充料为 pH值为 7.5〜9的富里酸。  Preferably, the core filler is fulvic acid having a pH of 7.5 to 9.
优选的， 所述硒肥颗粒中包膜和含硒肥芯的质量比为 0.05〜0.4 : 1。 优选的， 所述硒肥颗粒中包膜和含硒肥芯的质量比为 0. 1〜0.25 : 1。 优选的， 所述包膜材料选用蒙脱石、 高岭石、 蛭石、 海泡石、 坡缕石、 硅藻土、 煤粉、 活性炭、 天然橡胶、 ***胶、 明胶、 海藻酸钠、 纤维素， 木质素、 淀粉、 聚乙烯、 聚氯乙烯、 聚丙烯、 聚乙烯醇、 聚丙烯酰胺脲、 醛树脂、 曱基纤维素钠、 乙基纤维素钠的一种或者两种以上的任意组合。  Preferably, the mass ratio of the coating film and the selenium-containing core in the selenium fertilizer granule is 0.05 to 0.4:1. 1〜0.25 : 1。 The mass ratio of the film and the selenium-containing core is 0. 1~0.25: 1. Preferably, the coating material is selected from the group consisting of montmorillonite, kaolinite, vermiculite, sepiolite, palygorskite, diatomaceous earth, coal powder, activated carbon, natural rubber, gum arabic, gelatin, sodium alginate, fiber. , lignin, starch, polyethylene, polyvinyl chloride, polypropylene, polyvinyl alcohol, polyacrylamide urea, aldehyde resin, sodium decyl cellulose, ethyl cellulose sodium, or any combination of two or more .
优选的， 所述硒肥颗粒的硒含量范围在 0.005 %〜40%。  Preferably, the selenium content of the selenium fertilizer particles ranges from 0.005 % to 40%.
本发明的另一目的在于提供一种所述固体包膜緩释硒肥的制备方法， 其特征在于所述方法包括以下步骤：  Another object of the present invention is to provide a method for preparing the solid coated slow release selenium fertilizer, characterized in that the method comprises the following steps:
( 1 ) 将所述含硒肥芯用碱性物质将 pH调节至 7.5〜9后进行造粒， 形 成硒肥颗粒的核； (1) granulating the selenium-containing core with an alkaline substance to adjust the pH to 7.5 to 9 The core of selenium fertilizer particles;
( 2 ) 用碱性物质将包膜材料的 pH调节至 7.5〜9后进行包膜作业， 在 所述硒肥颗粒的核表面形成包膜。  (2) The pH of the coating material is adjusted to 7.5 to 9 with an alkaline substance, and then a coating operation is performed to form a coating on the surface of the core of the selenium fertilizer particles.
本发明所要解决的技术问题在于目前各类土施硒肥利用率低下， 其中 的有效态硒容易在环境介质中被还原成无效态的硒或者被土壤中的铁铝 氧化物或大分子有机物吸附而影响植物对硒的吸收效果并增加土壤在硒 残留风险方面的压力。 为了解决这些技术问题， 本发明提供了一种由薄膜 层和含硒肥芯组成的高效緩释硒肥。  The technical problem to be solved by the present invention is that the utilization rate of various types of soil selenium fertilizer is low, and the effective selenium is easily reduced to an ineffective selenium in an environmental medium or adsorbed by iron-aluminum oxide or macromolecular organic matter in the soil. It affects the absorption of selenium by plants and increases the pressure of soil on the risk of selenium residues. In order to solve these technical problems, the present invention provides an efficient slow release selenium fertilizer composed of a film layer and a selenium-containing fertilizer core.
其中， 含硒肥芯可以为高效緩释硒肥提供植物有效硒， 其硒的来源可 以是经活化处理后的硒矿粉、 ***盐、 硒酸盐中的任意一种， 也可以是 由以上三者以任意比例混合所得。 含硒肥芯的制造方法为将硒源物质直接 进行造粒或者将硒源物质与肥芯填充料按照 1 : 1〜1000的比例混勾后再进 行造粒。 肥芯填充料可以选择能减緩有效硒还原作用的微碱性物质， 如调 节至微碱性的有机肥、 腐植酸等； 作为优选， 该肥料填充料选择为腐植酸 中提取的富里酸。作为优选，该含硒肥芯在造粒前通过添加氢氧化物将 pH 调节至 7.5〜9 , 如氢氧化钙、 氢氧化钠、 氢氧化钾等。  Among them, the selenium-containing fertilizer core can provide plant effective selenium for high-efficiency slow-release selenium fertilizer, and the source of selenium can be any one of activated selenium ore powder, selenite, and selenate, or The above three are mixed in any ratio. The selenium-containing fertilizer core is produced by directly granulating the selenium source material or by mixing the selenium source material with the fat core filler in a ratio of 1:1 to 1000, followed by granulation. The fat filler may be selected from a slightly alkaline substance capable of slowing down the effective selenium reduction, such as a slightly alkaline organic fertilizer, humic acid, etc.; preferably, the fertilizer filler is selected from fulvic acid extracted from humic acid. Preferably, the selenium-containing core is adjusted to a pH of 7.5 to 9, such as calcium hydroxide, sodium hydroxide, potassium hydroxide or the like by adding a hydroxide before granulation.
本发明中， 包膜的材料可以选用吸附性较强的无机粘土矿物或物质， 如蒙脱石、 高岭石、 蛭石、 海泡石、 坡缕石、 硅藻土、 煤粉以及活性炭等， 或者选用以任意比例混合的上述物质； 包膜材料还可以选取高分子类的有 机材料， 如天然橡胶、 ***胶、 明胶、 海藻酸钠、 纤维素、 木质素、 淀 粉、 聚乙烯、 聚氯乙烯、 聚丙烯、 聚乙烯醇、 聚丙烯酰胺脲、 醛树脂、 曱 基纤维素钠、 乙基纤丝塞等。 作为优选， 该包膜材料在使用前用碱性物质 处理， 通过添加碱性物质将 pH调节至 7.5〜9 , 碱性物质可以选用如氢氧化 钙、 氢氧化钠、 氢氧化钾等。  In the present invention, the material of the coating may be selected from inorganic clay minerals or substances having strong adsorption, such as montmorillonite, kaolinite, vermiculite, sepiolite, palygorskite, diatomaceous earth, coal powder and activated carbon. , or use the above substances mixed in any ratio; the coating material can also be selected from organic materials such as natural rubber, gum arabic, gelatin, sodium alginate, cellulose, lignin, starch, polyethylene, polychlorinated Ethylene, polypropylene, polyvinyl alcohol, polyacrylamide urea, aldehyde resin, sodium decyl cellulose, ethyl fibril plug, and the like. Preferably, the coating material is treated with an alkaline substance before use, and the pH is adjusted to 7.5 to 9 by adding a basic substance, and a basic substance such as calcium hydroxide, sodium hydroxide, potassium hydroxide or the like can be used.
该高效緩释硒肥的制造工艺为： 将硒源物质如硒矿粉、 ***钠、 硒 鼓包覆法工艺： 即含硒肥芯颗粒在转盘或转鼓中滚动， 用高压喷枪将包膜 材料喷到肥料颗粒表面， 其中包膜与含硒肥芯的重量比为 0.05〜0.4 : 1。 作 为优选， 包膜与含硒肥芯的重量比为 0. 1〜0.25 : 1 。  The manufacturing process of the high-efficiency slow-release selenium fertilizer is as follows: a process of coating a selenium source material such as selenium ore powder, sodium selenite, and a toner cartridge: the selenium-containing core particles are rolled in a turntable or a drum, and the package is coated with a high-pressure spray gun. The film material is sprayed onto the surface of the fertilizer granule, wherein the weight ratio of the envelope to the selenium-containing core is 0.05 to 0.4:1. 1〜0.25 : 1。 The weight ratio of the coating and the selenium-containing core is 0. 1~0.25 : 1 .
优选的， 该固体包膜緩释硒肥由含硒肥芯和包膜两部分组成。 含硒肥 芯包含经活化处理后的硒矿粉、 ***盐、 硒酸盐中的任意一种， 或者由 以上三者以任意比例混合后干法制粒所得。 作为优选的， 含硒肥芯由经活 化处理后的硒矿粉、 ***盐、 硒酸盐中的任意一种、 或者将以上三者以 任意比例混合后与肥芯填充料按照 1 : 1- 1000的比例混勾后再进行干法造 粒。 Preferably, the solid coated slow-release selenium fertilizer is composed of a selenium-containing fat core and an envelope. Selenium-containing fertilizer The core comprises any one of activated selenium ore fines, selenite, and selenate, or may be obtained by dry granulation by mixing the above three in any ratio. Preferably, the selenium-containing core is prepared by any one of the activated selenium ore powder, selenite, and selenate, or the above three are mixed in an arbitrary ratio and the filler is as follows: Dry granulation is carried out after the ratio of 1-1000 is mixed.
进行固体包膜緩释硒肥制备时， 含硒肥芯在造粒之前用碱性物质将 pH调节至 7.5〜9。 进行包膜工艺之前， 用碱性物质将包膜剂材料的 pH调 节至 7.5〜9。  When the solid coated slow-release selenium fertilizer is prepared, the selenium-containing fertilizer core is adjusted to pH 7.5 to 9 with an alkaline substance before granulation. The pH of the coating material was adjusted to 7.5 to 9 with an alkaline substance before the coating process.
本发明提供的高效緩释硒肥相对于现有的叶面喷施或根施硒肥产品 具备以下的有益效果：  The high-efficiency sustained-release selenium fertilizer provided by the invention has the following beneficial effects as compared with the existing foliar spray or root selenium fertilizer products:
1、 通过包膜， 减少了有效态硒在土壤中被其他矿物吸附或共沉淀固 定的情形，具备了明显的緩释特征，可较稳定和充分的供应植物吸收利用， 残留在土壤中的非生物有效态硒减少， 能有效减轻环境硒污染风险.  1. Through the capsule, the effective selenium is reduced or adsorbed by other minerals in the soil, and has obvious sustained release characteristics, which can be stably and fully supplied to the plant for absorption and utilization, and remains in the soil. The reduction of bioavailable selenium can effectively reduce the risk of environmental selenium pollution.
2、 通过调节含硒肥芯和包膜材料的 pH值， 构建独特的碱性微环境， 有利于硒有效形态的维持， 从而将硒肥的利用率从 5%以下提高到 25%左 右， 减少因还原作用造成的肥效丧失。  2. By adjusting the pH value of the selenium-containing fertilizer core and the coating material, a unique alkaline micro-environment is constructed, which is beneficial to the maintenance of the effective form of selenium, thereby increasing the utilization rate of selenium fertilizer from below 5% to about 25%, reducing Loss of fertilizer due to reduction.
3、 通过不同的包膜材料与含硒肥芯的重量比值， 可实现对不同生长 周期的作物的肥效供应。 具体实施方式  3. Through the weight ratio of different coating materials to selenium-containing fertilizer cores, fertilizer supply to crops with different growth cycles can be achieved. detailed description
以下结合具体实施例对上述方案做进一步说明。 应理解， 这些实施例 是用于说明本发明而不限于限制本发明的范围。 实施例中釆用的实施条件 可以根据具体厂家的条件做进一步调整， 未注明的实施条件通常为常规实 验中的条件。 实施例 1  The above scheme will be further described below in conjunction with specific embodiments. It is to be understood that the examples are intended to illustrate the invention and not to limit the scope of the invention. The implementation conditions used in the examples can be further adjusted according to the conditions of the specific manufacturer, and the unspecified implementation conditions are usually the conditions in the routine experiment. Example 1
以***钠作为硒源物质， 选择不同比例的填充料及薄膜材料， 将硒 源物质和填充料充分混合后进行干法制粒制成颗粒肥芯， 然后用转鼓包覆 法将不同比例的包膜材料喷涂到颗粒肥芯表面， 得到固体緩释硒肥。 在大 田试验中， 经过 4-6个月的生长周期， 统计生长作物的生物量及平均硒含 量评估该固体緩释硒肥中硒的利用率。 具体实验结果如表 1: Sodium selenite is used as the selenium source material, and different proportions of filler and film materials are selected. The selenium source material and the filler are thoroughly mixed and then subjected to dry granulation to form a pellet core, and then the drum coating method is used to convert different proportions. The coating material is sprayed onto the surface of the granular fertilizer to obtain a solid slow release selenium fertilizer. In the field trial, after 4-6 months of growth cycle, the biomass and average selenium content of growing crops were counted. The amount of selenium in the solid slow release selenium fertilizer was evaluated. The specific experimental results are shown in Table 1:
以***钠作为硒源实验结果  Experimental results using sodium selenite as a selenium source
硒肥含 硒肥利用 肥芯 包膜  Selenium fertilizer, selenium fertilizer, fertilizer core, coating
石西比例 率 包膜  Shixi proportional rate envelope
硒源与  Selenium source and
与肥  With fertilizer
填充料 填充料 材料  Filler filler material
芯重  Core weight
重量比  weight ratio
量比  Volume ratio
蒙脱石、 高岭石或两者  Montmorillonite, kaolinite or both
无 0 0.13:1 40% 10% 以任意比例混合  None 0 0.13:1 40% 10% Mixed in any ratio
蛭石、 海泡石或两者以  Vermiculite, sepiolite or both
腐植酸 0.001:1 0.05: 1 0.045% 12% 任意比例混合 坡缕石、 硅藻土或两者  Humic acid 0.001:1 0.05: 1 0.045% 12% Any ratio of palygorskite, diatomaceous earth or both
富里酸 0.002:1 0.1:1 0.08% 15% 以任意比例混合 天然橡胶、 ***胶、  Fulvic acid 0.002:1 0.1:1 0.08% 15% Mixed in any proportion Natural rubber, gum arabic,
腐植酸 0.005:1 0.15:1 0.2% 18% 明胶或海藻酸钠  Humic acid 0.005:1 0.15:1 0.2% 18% gelatin or sodium alginate
富里酸 0.01:1 纤维素、 木质素或淀粉 0.3:1 0.35% 23% 聚乙烯、 聚氯乙烯、 聚  Fulvic acid 0.01:1 Cellulose, lignin or starch 0.3:1 0.35% 23% polyethylene, polyvinyl chloride, poly
腐植酸 0.1:1 丙烯、 聚乙烯醇或聚丙 0.35:1 3.3% 26% 烯酰胺脲  Humic acid 0.1:1 Propylene, polyvinyl alcohol or polypropylene 0.35:1 3.3% 26% Enamide urea
搭树脂、 曱基纤维素钠  Resin, sodium thioglycolate
富里酸 1:1 0.4:1 32% 28% 或乙基纤丝塞  Fulvic acid 1:1 0.4:1 32% 28% or ethyl filament plug
pH调至 7.5-9的腐 pH调至 7.5-9的蒙脱 The pH is adjusted to 7.5-9 and the pH is adjusted to 7.5-9.
0.004:1 0.2:1 0.15% 33% 植酸 石、 高冷石或坡缕石  0.004:1 0.2:1 0.15% 33% phytic acid stone, high cold stone or palygorskite
纤维素、 木质素、 淀粉  Cellulose, lignin, starch
pH调至 7.5-9的富 Rich in pH to 7.5-9
0.008:1 或聚乙烯、 聚氯乙烯、 0.2:1 0.3% 35% 里酸  0.008:1 or polyethylene, polyvinyl chloride, 0.2:1 0.3% 35% linonic acid
聚丙烯 实施例 2  Polypropylene Example 2
以硒酸钠作为硒源物质， 选择不同比例的填充料及薄膜材料， 将硒源 物质和填充料充分混合后进行干法制粒制成颗粒肥芯， 然后用转鼓包覆法 将不同比例的包膜材料喷涂到颗粒肥芯表面， 得到固体緩释硒肥。 在大田 试验中， 经过 4-6个月的生长周期， 统计生长作物的生物量及平均硒含量 评估该固体緩释硒肥中硒的利用率。 具体实验结果如表 2: 表 2 以硒酸钠作为硒源实验结果 Sodium selenate is used as the selenium source material, and different proportions of filler and film materials are selected. The selenium source material and the filler are thoroughly mixed and then subjected to dry granulation to form a pellet core, and then the drum package is used to make different proportions of the package. The membrane material is sprayed onto the surface of the granular fertilizer to obtain a solid slow release selenium fertilizer. In the field experiment, after 4-6 months of growth cycle, the biomass and average selenium content of the growing crops were counted to evaluate the utilization of selenium in the solid slow-release selenium fertilizer. The specific experimental results are shown in Table 2: Table 2 Experimental results using sodium selenate as a selenium source
硒肥含 石西月巴矛 ij 肥芯 包膜  Selenium fertilizer containing Shixi Yueba spear ij fat core envelope
石西比例 用率 包膜  Percy Proportion
硒源与  Selenium source and
与肥  With fertilizer
填充料 填充料 材料  Filler filler material
芯重  Core weight
重量比  weight ratio
量比  Volume ratio
蒙脱石、 高冷石、  Montmorillonite, high cold stone,
无 0 蛭石或三者以任意 0.13:1 36% 15% 比混合  None 0 meteorite or three mixed in any 0.13:1 36% 15% ratio
海泡石、 煤粉或两  Sepiolite, pulverized coal or two
腐植酸 0.001:1 0.05: 1 0.04% 18% 者以任意比例混合  Humic acid 0.001:1 0.05: 1 0.04% 18% mixed in any ratio
坡缕石、 硅藻土、  Palygorskite, diatomaceous earth,
富里酸 0.002:1 活性炭或三者以任 0.1:1 0.07% 20% 意比混合  Fulvic acid 0.002:1 Activated carbon or three of them are 0.1:1 0.07% 20%
天然橡胶、 ***  Natural rubber, arabic
腐植酸 0.005:1 胶、 明胶或海藻酸 0.15:1 0.18% 23% 钠  Humic acid 0.005:1 Gum, gelatin or alginic acid 0.15:1 0.18% 23% sodium
纤维素、 木质素或  Cellulose, lignin or
富里酸 0.01:1 0.3:1 0.31% 25% 淀粉  Fulvic acid 0.01:1 0.3:1 0.31% 25% starch
聚乙烯、 聚氯乙烯、  Polyethylene, polyvinyl chloride,
腐植酸 0.1:1 聚丙烯、 聚乙烯醇 0.35:1 2.9% 28% 或聚丙烯酰胺脲  Humic acid 0.1:1 Polypropylene, polyvinyl alcohol 0.35:1 2.9% 28% or polyacrylamide urea
搭树脂、 曱基纤维  Resin, bismuth-based fiber
富里酸 1:1 0.4:1 28.5% 32% 素钠或乙基纤丝塞  Fulvic acid 1:1 0.4:1 28.5% 32% sodium or ethyl fibrils
pH调至 7.5-9的蒙  The pH is adjusted to 7.5-9
pH调至 7.5-9的腐植酸 0.004:1 脱石、 高冷石或坡 0.2:1 0.13% 35% 缕石  Humic acid adjusted to pH 7.5-9 0.004:1 Desulphurized, high cold stone or slope 0.2:1 0.13% 35% vermiculite
纤维素、 木质素、  Cellulose, lignin,
pH调至 7.5-9的富里酸 0.008:1 淀粉或聚乙烯、 聚 0.2:1 0.27% 40% 氯乙婦、 聚丙婦 实施例 3  Fulvic acid adjusted to pH 7.5-9 0.008:1 starch or polyethylene, poly 0.2:1 0.27% 40% chloroethene, polypropylene woman Example 3
选择硒含量在 1000 克 /千克以上的含硒矿粉， 经粉碎后用氨水经过 活化处理作为硒源物质， 选择不同比例的填充料及薄膜材料， 将硒源物质 和填充料充分混合后进行干法制粒制成颗粒肥芯， 然后用转鼓包覆法将不 同比例的包膜材料喷涂到颗粒肥芯表面， 得到固体緩释硒肥。 在大田试验 中， 经过 4-6个月的生长周期， 统计生长作物的生物量及平均硒含量评估 该固体緩释硒肥中硒的利用率。 具体实验结果如表 3: 以硒酸钠作为硒源实验结果 Selenium-containing ore fines with a selenium content of 1000 g/kg or more are selected, and after pulverization, ammonia water is used for activation treatment as a selenium source material, and different proportions of filler and film materials are selected, and the selenium source material and the filler are thoroughly mixed and then dried. The granules are made into granules, and then different proportions of the coating material are sprayed onto the surface of the granules by a drum coating method to obtain a solid slow release selenium fertilizer. In the field experiment, after 4-6 months of growth cycle, the biomass and average selenium content of the growing crops were counted to evaluate the utilization of selenium in the solid slow-release selenium fertilizer. The specific experimental results are shown in Table 3: Experimental results using sodium selenate as a selenium source
硒肥含 石西月巴矛 ij 肥芯 包膜  Selenium fertilizer containing Shixi Yueba spear ij fat core envelope
石西比例 用率 包膜  Percy Proportion
硒源与  Selenium source and
与肥  With fertilizer
填充料 填充料 材料  Filler filler material
芯重  Core weight
重量比  weight ratio
量比  Volume ratio
蒙脱石、 高冷石、  Montmorillonite, high cold stone,
无 0 蛭石或三者以任意 0.13:1 8.89% 5% 比混合  None 0 meteorite or three mixed in any 0.13:1 8.89% 5% ratio
海泡石、 煤粉或两  Sepiolite, pulverized coal or two
腐植酸 1:1 0.05: 1 0.01% 8% 者以任意比例混合  Humic acid 1:1 0.05: 1 0.01% 8% mixed in any ratio
坡缕石、 硅藻土、  Palygorskite, diatomaceous earth,
富里酸 2:1 活性炭或三者以任 0.1:1 0.02% 10% 意比混合  Fulvic acid 2:1 activated carbon or three of them are mixed 0.1:1 0.02% 10%
天然橡胶、 ***  Natural rubber, arabic
腐植酸 5:1 胶、 明胶或海藻酸 0.15:1 0.04% 12% 钠  Humic acid 5:1 Gum, gelatin or alginic acid 0.15:1 0.04% 12% sodium
纤维素、 木质素或  Cellulose, lignin or
富里酸 10:1 0.3:1 0.08% 14% 淀粉  Fulvic acid 10:1 0.3:1 0.08% 14% starch
聚乙烯、 聚氯乙烯、  Polyethylene, polyvinyl chloride,
腐植酸 100:1 聚丙烯、 聚乙烯醇 0.35:1 0.72% 12% 或聚丙烯酰胺脲  Humic acid 100:1 Polypropylene, polyvinyl alcohol 0.35:1 0.72% 12% or polyacrylamide urea
搭树脂、 曱基纤维  Resin, bismuth-based fiber
富里酸 1000:1 0.4:1 7.03% 14% 素钠或乙基纤丝塞  Fulvic acid 1000:1 0.4:1 7.03% 14% sodium or ethyl fibrils
pH调至 7.5-9的蒙  The pH is adjusted to 7.5-9
pH调至 7.5-9的腐植酸 4:1 脱石、 高冷石或坡 0.2:1 0.03% 16% 缕石  Humic acid adjusted to pH 7.5-9 4:1 decalcified, high cold stone or slope 0.2:1 0.03% 16% vermiculite
纤维素、 木质素、  Cellulose, lignin,
pH调至 7.5-9的富里酸 8:1 淀粉或聚乙烯、 聚 0.2:1 0.07% 18% 氯乙婦、 聚丙婦 实施例 4  Fulvic acid adjusted to pH 7.5-9 8:1 starch or polyethylene, poly 0.2:1 0.07% 18% chloroethene, polypropylene woman Example 4
将***盐、 硒酸盐、 活化矿粉以任意比例混合后作为硒源物质， 选 择不同比例的填充料及薄膜材料， 将硒源物质和填充料充分混合后进行干 法制粒制成颗粒肥芯， 然后用转鼓包覆法将不同比例的包膜材料喷涂到颗 粒肥芯表面， 得到固体緩释硒肥。 在大田试验中， 经过 4-6个月的生长周 期， 统计生长作物的生物量及平均硒含量评估该固体緩释硒肥中硒的利用 率。 具体实验结果如表 4: 表 4 以硒酸钠作为硒源实验结果 The selenite, selenate, and activated ore powder are mixed at any ratio and used as a selenium source material. Different proportions of filler and film materials are selected, and the selenium source material and the filler are thoroughly mixed and then subjected to dry granulation to prepare a granular fertilizer. The core is then sprayed onto the surface of the granular core by a drum coating method to obtain a solid slow release selenium fertilizer. In the field experiment, after 4-6 months of growth cycle, the biomass and average selenium content of the growing crops were counted to evaluate the utilization of selenium in the solid slow-release selenium fertilizer. The specific experimental results are shown in Table 4: Table 4 Experimental results using sodium selenate as a selenium source
硒肥含 石西月巴矛 ij 肥芯 包膜  Selenium fertilizer containing Shixi Yueba spear ij fat core envelope
石西比例 用率 踊源与填  Shixi proportion utilization rate source and fill
包膜与肥  Envelope and fertilizer
填充料 充料重量 材料  Filling material, filling weight, material
芯重量比  Core weight ratio
比  Than
蒙脱石、 高冷石、  Montmorillonite, high cold stone,
无 0 蛭石或三者以任意 0.13:1 28% 14% 比混合  None 0 meteorite or three mixed in any 0.13:1 28% 14% ratio
海泡石、 煤粉或两  Sepiolite, pulverized coal or two
腐植酸 1:1 0.05: 1 0.05% 15% 者以任意比例混合  Humic acid 1:1 0.05: 1 0.05% 15% mixed in any ratio
坡缕石、 硅藻土、  Palygorskite, diatomaceous earth,
富里酸 2:1 活性炭或三者以任 0.1:1 0.08% 18% 意比混合  Fulvic acid 2:1 activated carbon or three of them are 0.1:1 0.08% 18%
天然橡胶、 ***  Natural rubber, arabic
腐植酸 5:1 胶、 明胶或海藻酸 0.15:1 0.16% 22% 钠 纤维素、 木质素或  Humic acid 5:1 Gum, gelatin or alginic acid 0.15:1 0.16% 22% Sodium Cellulose, lignin or
富里酸 10:1 0.3:1 0.34% 26% 淀粉 聚乙烯、 聚氯乙烯、  Fulvic acid 10:1 0.3:1 0.34% 26% starch polyethylene, polyvinyl chloride,
腐植酸 100:1 聚丙烯、 聚乙烯醇 0.35:1 2.8% 28% 或聚丙烯酰胺脲 搭树脂、 曱基纤维  Humic acid 100:1 Polypropylene, polyvinyl alcohol 0.35:1 2.8% 28% or polyacrylamide urea Resin, fluorenyl fiber
富里酸 1000:1 0.4:1 24.2% 30% 素钠或乙基纤丝塞  Fulvic acid 1000:1 0.4:1 24.2% 30% sodium or ethyl fibrils
pH调至 7.5-9的蒙  The pH is adjusted to 7.5-9
pH调至 7.5-9的腐 Corrosion adjusted to pH 7.5-9
4:1 脱石、 高冷石或坡 0.2:1 0.15% 32% 植酸  4:1 decalcification, high cold stone or slope 0.2:1 0.15% 32% phytic acid
缕石  Meteorite
纤维素、 木质素、  Cellulose, lignin,
pH调至 7.5-9的富 Rich in pH to 7.5-9
8:1 淀粉或聚乙烯、 聚 0.2:1 0.29% 34% 里酸  8:1 starch or polyethylene, poly 0.2:1 0.29% 34% linoleic acid
氯乙婦、 聚丙婦 上述实例只为说明本发明的技术构思及特点， 其目的在于让熟悉此项 技术的人是能够了解本发明的内容并据以实施， 并不能以此限制本发明的 保护范围。 凡根据本发明精神实质所做的等效变换或修饰， 都应涵盖在本 发明的保护范围之内。  The above examples of the present invention are merely illustrative of the technical idea and the features of the present invention. The purpose of the present invention is to enable those skilled in the art to understand the contents of the present invention and to implement the present invention. range. Equivalent transformations or modifications made in accordance with the spirit of the invention are intended to be included within the scope of the invention.

Claims

权利要求 Rights request
1. 一种固体包膜緩释硒肥， 包括硒肥颗粒， 其特征在于所述硒肥颗粒具有核壳结构， 所述硒肥颗粒的核为含硒肥芯， 所述硒肥颗粒的壳为包裹在所述含硒肥芯外侧的包膜。  A solid coated slow-release selenium fertilizer, comprising selenium fertilizer particles, characterized in that the selenium fertilizer particles have a core-shell structure, the core of the selenium fertilizer particles is a selenium-containing fertilizer core, and the shell of the selenium fertilizer particles It is a coating wrapped on the outside of the selenium-containing core.
2. 根据权利要求 1所述的固体包膜緩释硒肥，其特征在于所述含硒肥芯包含经活化处 理后的硒矿粉、 ***盐、 硒酸盐中的任意一种或者两种以上的任意组合。  2. The solid coated slow release selenium fertilizer according to claim 1, wherein the selenium-containing fertilizer core comprises any one of activated selenium ore powder, selenite, and selenate. Any combination of two or more.
3. 根据权利要求 1所述的固体包膜緩释硒肥，其特征在于所述含硒肥芯为活化处理后 的硒矿粉、 ***盐、 硒酸盐中的任意一种或者两种以上的任意组合与肥芯填充料按照重 量比为 1 : 1〜1000的比例混合的混合物。  The solid coated slow-release selenium fertilizer according to claim 1, wherein the selenium-containing fertilizer core is any one or two of selenium ore powder, selenite, and selenate after activation treatment. Any combination of the above and the core filler are mixed in a ratio of 1:1 to 1000 by weight.
4. 根据权利要求 3所述的固体包膜緩释硒肥， 其特征在于所述肥芯填充料为 pH值为 7.5〜9的有机肥或腐植酸。  The solid coated slow-release selenium fertilizer according to claim 3, wherein the fertilizer filler is an organic fertilizer or humic acid having a pH of 7.5 to 9.
5. 根据权利要求 3所述的固体包膜緩释石西肥， 其特征在于所述肥芯填充料为 pH值为 7.5-9的富里酸。  The solid coated slow-release stone fertilizer according to claim 3, wherein the fertilizer filler is fulvic acid having a pH of 7.5-9.
6. 根据权利要求 1所述的固体包膜緩释硒肥，其特征在于所述硒肥颗粒中包膜和含硒 芯的质量比为 0.05〜0.4: 1。  The solid coated slow-release selenium fertilizer according to claim 1, wherein the mass ratio of the coating film and the selenium-containing core in the selenium fertilizer particles is 0.05 to 0.4:1.
7. 根据权利要求 1所述的固体包膜緩释石西肥，其特征在于所述石西肥颗粒中包膜和含石西 肥芯的质量比为 0.1〜0.25: 1。  The solid coated slow-release stone western fertilizer according to claim 1, wherein the mass ratio of the coating material and the stone-containing core core in the Shixi fertilizer granule is 0.1 to 0.25:1.
8. 根据权利要求 1所述的固体包膜緩释石西肥， 其特征在于所述包膜材料选用蒙脱石、 高岭石、 蛭石、 海泡石、 坡缕石、 硅藻土、 煤粉、 活性炭、 天然橡胶、 ***胶、 明胶、 海藻酸钠、 纤维素、 木质素、 淀粉、 聚乙烯、 聚氯乙烯、 聚丙烯、 聚乙烯醇、 聚丙烯酰胺 脲、 搭树脂、 曱基纤维素钠、 乙基纤维素钠的一种或者两种以上的任意组合。  The solid coated slow-release stone western fertilizer according to claim 1, wherein the coating material is montmorillonite, kaolinite, vermiculite, sepiolite, palygorskite, diatomaceous earth, Pulverized coal, activated carbon, natural rubber, gum arabic, gelatin, sodium alginate, cellulose, lignin, starch, polyethylene, polyvinyl chloride, polypropylene, polyvinyl alcohol, polyacrylamide urea, resin, ruthenium-based fiber One or a combination of two or more of sodium sodium or ethyl cellulose.
9. 根据权利要求 1所述的固体包膜緩释硒肥，其特征在于所述硒肥颗粒的硒含量范围 在 0.005%〜40%。  9. The solid coated slow release selenium fertilizer according to claim 1, wherein the selenium fertilizer particles have a selenium content ranging from 0.005% to 40%.
10. 一种权利要求 1 ~ 9中任意一项所述固体包膜緩释硒肥的制备方法，其特征在于所 述方法包括以下步骤：  10. A method of preparing a solid coated slow release selenium fertilizer according to any one of claims 1 to 9, wherein the method comprises the steps of:
( 1 )将所述含硒肥芯用碱性物质将 pH调节至 7.5〜9后进行造粒，形成硒肥颗粒的核； ( 2 )用碱性物质将包膜材料的 pH调节至 7.5〜9后进行包膜作业， 在所述硒肥颗粒的 核表面形成包膜。  (1) The selenium-containing core is adjusted to a pH of 7.5 to 9 with an alkaline substance, and then granulated to form a core of the selenium fertilizer particles; (2) adjusting the pH of the coating material to 7.5 with an alkaline substance. After 9, a coating operation was performed to form a coating on the surface of the core of the selenium fertilizer particles.
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