WO2018001366A1 - 有机-无机聚合保水肥料及其制备方法 - Google Patents

有机-无机聚合保水肥料及其制备方法 Download PDF

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WO2018001366A1
WO2018001366A1 PCT/CN2017/091230 CN2017091230W WO2018001366A1 WO 2018001366 A1 WO2018001366 A1 WO 2018001366A1 CN 2017091230 W CN2017091230 W CN 2017091230W WO 2018001366 A1 WO2018001366 A1 WO 2018001366A1
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organic
inorganic
water
parts
retaining
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PCT/CN2017/091230
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English (en)
French (fr)
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朱彦芳
杜志勇
朱弘智
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青岛鑫垚地农业科技股份有限公司
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Priority to BR112018001420-6A priority Critical patent/BR112018001420A2/pt
Priority to RU2018102162A priority patent/RU2697092C2/ru
Priority to EP17809165.8A priority patent/EP3305746A4/en
Priority to US15/746,962 priority patent/US10544065B2/en
Priority to AU2017279605A priority patent/AU2017279605B2/en
Priority to CA2989711A priority patent/CA2989711C/en
Publication of WO2018001366A1 publication Critical patent/WO2018001366A1/zh
Priority to ZA2018/00166A priority patent/ZA201800166B/en

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G1/00—Mixtures of fertilisers belonging individually to different subclasses of C05
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F11/00—Other organic fertilisers
    • C05F11/08—Organic fertilisers containing added bacterial cultures, mycelia or the like
    • 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
    • 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
    • C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
    • 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
    • C05G3/80—Soil conditioners
    • 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
    • C05G5/10—Solid or semi-solid fertilisers, e.g. powders
    • C05G5/12—Granules or flakes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C08K2003/287—Calcium, strontium or barium nitrates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse

Definitions

  • the invention relates to the field of fertilizers, in particular to an organic-inorganic polymeric water-retaining fertilizer and a preparation method thereof.
  • the invention relates to a preparation method of an organic-inorganic polymerization water-retaining fertilizer, which is a method for fusion copolymerization of a polymer water-absorbing resin and an inorganic nutrient factor, thereby having the function of water and fertilizer, water retention and fertilizer retention, and slow release synchronization-water and fertilizer control.
  • New materials for water retention and fertilizer such as release function, pest and disease resistance function, soil conditioning function, etc.
  • organic matter content ⁇ 20%; water absorption multiple 10g / g - 20g / g; nitrogen, phosphorus, potassium total nutrients 35% -40%; calcium, magnesium, silicon, sulfur, medium element total nutrient ⁇ 5%; initial The nutrient release rate is ⁇ 15%; (the implementation standard of the company "organic-inorganic polymerization water-retaining fertilizer": Q/370203XYD001-2016).
  • the key technology of the water-retaining agent coating slow-release technology is to uniformly wrap the water-retaining agent on the fertilizer core under special equipment, or to first coat a fertilizer core with a water-blocking slow-release coating to achieve nutrient sustained release. Function, and then the outermost layer of water-repellent coating, to achieve water retention.
  • a capsule type product has a low proportion of fertilizer due to the water retaining agent, limited water absorption ratio, nutrient slow release and moisture release are not synchronized, and the cost of the coating is too high, so it is difficult to apply to agricultural production;
  • Heterogeneous Fertilizer Technology It is an organic-inorganic fusion copolymerization technology. It is essentially a new structural material of organic-inorganic fusion copolymerization. It is a three-dimensional network structure hydrophilic group produced by ingenious fusion of organic water retention factor and inorganic nutrient factor. , with biodegradable, slow release effect. Double protection and double control, water and fertilizer, and slow release synchronization; disease resistance and deworming, soil conservation, optimization of micro-ecological environment; improvement of soil, fertility and fertility, and improvement of human nutrition and health. Fundamentally solve the national sustainable development strategy of water conservation, weight loss and drug reduction.
  • the above-mentioned compounding and coating technology of water-retaining controlled release fertilizer has its own advantages and disadvantages, and it does not achieve the desired effect in production practice.
  • the organic-inorganic fusion copolymerization technology has the following advantages: low production cost, good quality and low price; labor saving, time saving, energy saving and environmental protection; non-toxic and harmless, degradable, no residue; non-volatile, no loss; no burning, no explosion; Safe, long-term effective; quality is safe and reliable.
  • a first object of the present invention is to provide an organic-inorganic polymeric water-retaining fertilizer, wherein the organic-inorganic polymeric water-retaining fertilizer contains a biological enzyme, which can activate biological active components in the soil and enhance fertilizer efficiency;
  • a second object of the present invention is to provide a method for preparing the organic-inorganic polymeric water-retaining fertilizer, which is low in cost, energy-saving and environmentally friendly.
  • One aspect of the invention relates to an organic-inorganic polymeric water-retaining fertilizer, which is a copolymer obtained by fusion polymerization of an organic water-retaining monomer and inorganic nutrients under the action of a catalyst, a biological enzyme and a modifier.
  • the copolymer has a three-dimensional network hydrophilic group structure.
  • the water-absorbing polymer, the inorganic nutrient and the bio-enzyme chemical bond are integrated as a whole, and the three-dimensional network structure of the water-absorbing polymer realizes the water retention and slow release, and prolongs the action time of the fertilizer.
  • the biological enzyme added by the invention can activate the probiotic microorganisms in the soil, promote the growth of the crop, and play a role in assisting the enhancement of the fertilizer effect.
  • the biological enzyme added by the present invention proves that a chemical bond is formed with other components by infrared spectroscopy, thereby achieving a sustained release and long-acting effect.
  • the organic-inorganic polymeric water-retaining fertilizer is mainly composed of an organic monomer, a biological enzyme and an inorganic nutrient, and the monomer comprises acrylic acid and a derivative thereof.
  • the monomer is acrylic acid.
  • the inorganic nutrient comprises calcium magnesium nitrate, urea, monoammonium phosphate and potassium salt; preferably, the potassium salt comprises potassium sulfate and potassium chloride.
  • the biological enzyme is one or more of a protease, a cellulase, a lipase, a pectinase and an enzyme, and more preferably, the biological enzyme is a protease, a cellulase, a lipase, Two or more of pectinase and enzyme enzyme.
  • the combination of two or more biological enzymes can better activate microorganisms in the soil.
  • the modifier includes the modifier being two or more of protein powder, cellulose powder, pectin, fat, and starch.
  • the role of the modifier is mainly to load the enzyme, and in addition, the selection of suitable modifiers is also beneficial to the organism.
  • the enzyme is fully released in the actual application of the fertilizer.
  • the organic-inorganic polymeric water-retaining fertilizer comprises 400-600 parts by weight of organic monomers, 8900-9600 parts of inorganic nutrients, 50-100 parts of modifiers, and 5-15 parts of biological enzymes.
  • the invention significantly reduces the amount of organic monomers, so that during the preparation process, the reaction temperature is lowered and the reaction cost is strongly controlled.
  • the inorganic nutrient comprises the following components in parts by weight:
  • the fertilizer has a pH of 3-8, an organic matter mass fraction of more than 20%, a water absorption ratio of 10 g/g to 20 g/g, a total NPK content of 35% to 40%, calcium, magnesium, silicon and sulfur.
  • the total content is more than 5%, and the initial nutrient release rate is less than 15%.
  • Another aspect of the invention relates to a method for preparing the organic-inorganic polymeric water-retaining fertilizer, wherein an organic monomer is neutralized by a catalyst, and then an inorganic nutrient and a metasilicate are added, followed by an initiator and The crosslinking agent is stirred sufficiently to form a solution, catalyzed by adding a biological enzyme, and copolymerized to obtain a copolymer, which is granulated and dried.
  • the catalyst is an inorganic alkali solution.
  • the catalyst is selected from the group consisting of hydrogen peroxide. Sodium solution, potassium hydroxide solution, ammonia water and calcium hydroxide solution.
  • the organic-inorganic polymeric water-retaining fertilizer of the invention also adds metasilicate, mainly of metasilicate
  • the role is: 1. Supplementing silicon nutrients;
  • the method comprises the steps of:
  • step 2) stirring the mixture in step 2) to form a solution, adding the modifier and the biological enzyme to the solution, and stirring for 10-20 minutes to obtain a copolymer;
  • the copolymer is dried, pulverized, and sieved to form granules.
  • the organic-inorganic polymeric water-retaining fertilizer of the invention forms a three-dimensional network structure of the inorganic water-retaining factor and the organic nutrient factor, thereby functioning as a sustained release and water retention;
  • the organic-inorganic polymeric water-retaining fertilizer of the present invention contains a biological enzyme, which can activate biological active components in the soil and enhance fertilizer efficiency;
  • the organic-inorganic polymeric water-retaining fertilizer of the invention has a low content of acrylic acid, so that the preparation can be completed at a low temperature during the reaction;
  • the preparation method of the invention has low cost and environmental protection.
  • 1 is a schematic view showing the production process of the organic-inorganic polymerization water-retaining fertilizer of the present invention
  • Fig. 3 is a comparison of the amount of soil microorganisms after three years of application of the organic-inorganic polymeric water-retaining fertilizer and the common chemical fertilizer of the present invention.
  • the pH of the fertilizer prepared according to the formula is 6.5, the organic matter content is 20.5%, the water absorption ratio is 16.5g/g, the total nitrogen, phosphorus and potassium content is 37%, and the nitrogen content is 9.9%.
  • Phosphorus oxide 9.6%, potassium oxide 17.8%; calcium, magnesium, silicon, sulfur total content 17.9%, including calcium oxide 2.1%, magnesium oxide 1.5%, silica 0.02%, sulfur dioxide 14.3%, and initial nutrient release rate 8.3 %.
  • step 2) stirring the mixture in step 2) to form a solution, adding the modifier and the biological enzyme to the solution, and stirring for 20 minutes to obtain a copolymer;
  • the pH of the fertilizer prepared according to the formula is 6.9, the organic matter content is 24.1%, the water absorption ratio is 19.6 g/g, the total nitrogen, phosphorus and potassium content is 39.4%, and the nitrogen content is 10.9%.
  • step 2) stirring the mixture in step 2) to form a solution, adding the biological enzyme to the solution, and stirring for 15 minutes to obtain a copolymer;
  • the pH of the fertilizer prepared according to the formula is 6.8, the organic matter content is 22.3%, the water absorption ratio is 17.3g/g, the total nitrogen, phosphorus and potassium content is 35.9%, and the nitrogen content is 9.2%.
  • bio-enzyme 10 parts of bio-enzyme (5 parts of protease, 3 parts of cellulase, 2 parts of enzyme)
  • step 2) stirring the mixture in step 2) to form a solution, adding the biological enzyme to the solution, heating to 45 ° C, stirring for 10 minutes, to obtain a copolymer;
  • the pH of the fertilizer prepared according to the formula is 6.5, the organic matter content is 21%, the water absorption ratio is 17.5g/g, the total content of NPK is 40%, and the nitrogen content is 10.9%.
  • Phosphorus oxide 10.3%, potassium oxide 18.8%; calcium, magnesium, silicon, sulfur total content 20.8%, including 2.6% calcium oxide, 1.9% magnesium oxide, 0.04% silica, 16.3% sulfur dioxide, and initial nutrient release rate 7.8 %.
  • the nutrient slow release period of the organic-inorganic polymeric water-retaining fertilizer prepared by the method of Example 4 was 80 days, and the characteristic curve of the total nutrient slow release property of the zygote fertilizer was "S" type (see figure 2).
  • the release characteristics of the fertilizer in the soil showed a sustained release property, which indicates that the application of the fertilizer in the soil is beneficial to the stability and sustained release of nutrients.
  • the fertilizer can be known to have a water absorption ratio of 10.21g/g- 19.33 g / g, an average of 17.5 g / g, its absorption of 0.9% NaCl solution ranged from 14.06 g / g to 18.32 g / g, with an average of 16.56 g / g.
  • the water absorption capacity can have a water retention capacity of 5 g/g or more, which has practical application value.
  • Example 4 The soil was applied as in Example 4 to prepare an organic-inorganic polymeric water-retaining fertilizer and a common fertilizer (without biological enzymes), and the number of microorganisms in the soil was statistically compared three years later. The results are shown in Fig. 3.
  • the number of soil bacteria increased to 17.69 times, the number of actinomycetes increased to 2.16 times, and the fungi decreased by 1/3.
  • the beneficial bacteria in the soil are mainly bacteria and actinomycetes, and the pathogenic bacteria in the soil are mainly fungi.

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Pest Control & Pesticides (AREA)
  • Soil Sciences (AREA)
  • Biochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Fertilizers (AREA)
  • Environmental & Geological Engineering (AREA)

Abstract

一种有机-无机聚合保水肥料，所述有机-无机聚合保水肥料是有机保水单体与无机养分在催化剂、生物酶和改性剂的作用下融合聚合而成的共聚物，所述共聚物具有三维网状亲水性基团结构。制备方法为有机单体在催化剂作用下得到中和预聚体后，添加引发剂和交联剂，同时添加无机养分，充分搅拌使其形成溶液，添加生物酶进行催化，融合聚合后得到共聚体，造粒烘干。催化剂是无机碱溶液，所述催化剂选自氢氧化钠溶液、氢氧化钾溶液、氨水、氢氧化钙溶液。

Description

一种有机-无机聚合保水肥料及其制备方法
相关申请的交叉引用
本申请要求于2016年07月01日提交中国专利局的申请号为201610512162.2、名称为“一种有机-无机聚合保水肥料及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及肥料领域，具体而言，涉及一种有机-无机聚合保水肥料及其制备方法。
背景技术
本发明涉及一种有机-无机聚合保水肥料的制备方法，是通过高分子吸水树脂和无机养分因子融合共聚反应的方法，从而使其具有水肥同体-保水保肥功能、缓释同步-水肥双控释功能、抗病虫害功能、土壤调理功能等的保水肥新材料。
其技术指标：有机质含量≥20％；吸水倍数10g/g-20g/g；氮、磷、钾总养分35％-40％；钙、镁、硅、硫中量元素总养分≥5％；初期养分释放率≤15％；(本企业《有机-无机聚合保水肥料》执行标准：Q/370203XYD001-2016)。
全球化学肥料是农业生产中最大的物质投入，据联合国粮农组织的统计资料表明，在提高单产中，化肥对增产所起的作用占40％～60％。但是生产实践表明，由于化学肥料本身性质和土壤环境条件及农业措施等综合影响，化学肥料利用率很低。中国因肥料养分利用率低所造成的养分资源浪费是十分惊人的。最新权威数据显示，我国农民每年由于盲目过量施肥造成的直接经济损失平均每公顷达650元，付出环境代价大约为730亿元，肥料每年流失 1100多亿元。如何提高化学肥料的利用率，减小因施肥不当造成的环境污染问题，可持续发展高效农业已成为世界各国共同关注的问题。
自21世纪初以来，保水肥料的研制和应用为解决这个问题提出了新的思路。保水剂与肥料一体化的研制已经成为世界肥料研究的前沿技术热点，有机-无机混合包膜技术得到发展。保水缓控释肥料研制以来，保水剂与无机养分复混缓释技术和保水剂包膜缓释技术得到了应用和发展。现代树脂包膜技术按发展进程有以下代表类型：保水剂与无机养分复混缓释技术。其关键技术是保水剂与无机养分的复配比例，该技术因保水因子与无机养分因子为物理掺和，所以其养分缓释性能有限，因保水剂成本太高，无法大面积应用于生产实际；
保水剂包膜缓释技术，其关键技术是在特殊设备下，将保水剂均匀包裹于肥料核芯上，或者先在肥料核芯上包裹一层阻水缓释涂层，先实现养分缓释功能，再最外层包裹保水剂涂层，实现保水功能。但是此类包膜型产品，因保水剂所占肥料比例偏低，吸水倍率有限，养分缓释与水分缓释不同步，且包膜成本过高，故很难应用于农业生产实际；
合子肥料技术：就是有机-无机融合共聚技术，本质是一种有机-无机融合共聚的新结构体物质，是将有机保水因子与无机养分因子巧妙融合共聚产生的三维网状结构亲水性基团，具有可生物降解、缓控释作用。双保双控，水肥同体，缓释同步；抗病驱虫，保育土壤，优化微生态环境；改良土壤，培肥地力，完善人体营养健康。从根本上解决国家提出的节水、减肥、减药“一节两减”农业可持续发展战略问题。
上述保水缓控释肥料的复混和包膜技术各有利弊，在生产实践中达不到理想效果。有机-无机融合共聚技术具有以下优点：生产成本低，物美价廉；省工省时，节能环保；无毒无害，可降解，无残留；不挥发，不流失；不燃烧，不爆炸；贮存安全，长期有效；质量安全可靠。
有鉴于此，特提出本发明。
发明内容
本发明的第一目的在于提供一种有机-无机聚合保水肥料，所述的有机-无机聚合保水肥料含有生物酶，可以活化土壤中的生物活性成分，增强肥效；
本发明的第二目的在于提供一种所述有机-无机聚合保水肥料的制备方法，该方法成本低廉，节能环保。
为了实现本发明的上述目的，特采用以下技术方案：
本发明的一个方面涉及一种有机-无机聚合保水肥料，所述有机-无机聚合保水肥料是有机保水单体与无机养分在催化剂、生物酶和改性剂的作用下融合共聚而成的共聚物，所述共聚物具有三维网状亲水性基团结构。
本发明的有机-无机聚合保水肥料中，吸水性聚合物、无机养分和生物酶化学键合成整体，通过吸水性聚合物的三维网状结构实现保水缓释，延长肥料作用时间。
另一方面，本发明添加的生物酶能够活化土壤中的益生微生物，促进作物生长，起到辅助增强肥效的作用。此外，本发明添加的生物酶经红外光谱证明，与其他组份之间形成化学键，从而达到缓释、长效的作用。
优选地，所述有机-无机聚合保水肥料主要由有机单体、生物酶和无机养分融合共聚而成；所述单体包括丙烯酸及其衍生物，优选的，所述单体是丙烯酸。
优选地，所述无机养分包括硝酸钙镁、尿素、磷酸一铵和钾盐；优选的，所述钾盐包括硫酸钾和氯化钾。
优选地，所述生物酶是蛋白酶、纤维素酶、脂肪酶、果胶酶和酵素菌酶中的一种或多种，更优选地，所述生物酶是蛋白酶、纤维素酶、脂肪酶、果胶酶和酵素菌酶中的两种以上。
本发明的优选实施方式中，采用两种以上的生物酶配合使用可以对土壤中的微生物起到更好的活化作用。
优选地，改性剂包括所述改性剂是蛋白粉、纤维素粉、果胶、脂肪和淀粉中的两种以上。
改性剂的作用主要在于负载生物酶，另外，选取合适的改性剂也利于生物 酶在肥料实际应用中充分释放。
优选地，所述有机-无机聚合保水肥料包括按重量份计的有机物单体400-600份，无机养分8900-9600份，改性剂50-100份，生物酶5-15份。
本发明相较于其他现有技术，显著地减小了有机物单体的用量，因此在制备过程中，反应温度降低，反应成本得到有力控制。
优选地，所述无机养分包括按重量份计的以下组分：
Figure PCTCN2017091230-appb-000001
优选地，所述肥料的pH值为3-8，有机质的质量分数大于20％，吸水倍率10g/g-20g/g，氮磷钾总含量35％-40％，钙、镁、硅和硫总含量大于5％，初期养分释放率小于15％。
本发明的另一方面涉及所述有机-无机聚合保水肥料的制备方法，有机单体在催化剂的作用下得到中和预聚体后，同时添加无机养分和偏硅酸盐，后添加引发剂和交联剂，充分搅拌使其形成溶液，添加生物酶进行催化，融合共聚后得到共聚体，造粒烘干，优选地，所述催化剂是无机碱溶液，优选地，所述催化剂选自氢氧化钠溶液、氢氧化钾溶液、氨水和氢氧化钙溶液。
本发明的有机-无机聚合保水肥料中还添加了偏硅酸盐，偏硅酸盐的主要
作用在于：1.补充硅营养元素；
2.在反应中可以做一种助剂，对预聚体的反应起到一定催化作用。
优选地，所述方法包括以下步骤：
1)将丙烯酸与催化剂混合，反应15-20分钟后得到中和预聚体；
2)向所述中和预聚体中依次添加所述无机养分，交联剂和引发剂，将温 度控制在65℃-70℃，反应15分钟，降温至35℃-55℃；
3)搅拌步骤2)中的混合物形成溶液，向所述溶液内添加所述改性剂和生物酶，搅拌10-20分钟后，得到共聚体；
4)所述共聚体经干燥、粉碎、筛分制成颗粒。
与现有技术相比，本发明的有益效果为：
1)本发明的有机-无机聚合保水肥料使无机保水因子和有机养分因子形成三维网状结构，从而起到缓释、保水的作用；
2)本发明的有机-无机聚合保水肥料含有生物酶，可以活化土壤中的生物活性成分，增强肥效；
3)本发明的有机-无机聚合保水肥料中丙烯酸含量低，因此在反应过程中可以在低温下完成制备；
4)本发明的制备方法，成本低廉，节约环保。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，以下将对实施例或现有技术描述中所需要使用的附图作简单地介绍。
图1为本发明的有机-无机聚合保水肥料的生产流程示意图；
图2是本发明的有机-无机聚合保水肥料在土柱中的淋溶特征；
图3是本发明的有机-无机聚合保水肥料和普通化肥施用三年后土壤微生物数量的对比。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
实施例1
准备按重量份计的以下原料：
丙烯酸 400份
催化剂 氢氧化钠水溶液，pH＝8.5
引发剂 过硫酸钾 10份
交联剂 乙二醇 20份
无机养分 尿素 1700份磷酸一铵 1500份 硫酸钾 3500份 硝酸钙 1000份 硫酸镁 1000份 硅酸钠 150份 硫酸锌 30份 硼酸钠 30份
生物酶 5份 (蛋白酶2份，纤维素酶3份)
蛋白粉 25份 纤维素粉 25份。
按照以下步骤制备肥料：
1)将丙烯酸与催化剂混合，反应15分钟后得到中和预聚体，随后向反应体系内添加所述无机养分；
2)向所述中和预聚体中依次添加无机养分、交联剂和引发剂，将反应体系控制在65℃-68℃，搅拌转速设定为70转，反应15分钟；降温至35℃；
3)搅拌步骤2)中的混合物形成溶液，向所述溶液内添加所述改性剂和生物酶，搅拌10分钟后，得到共聚体；
4)将所述共聚体引入造粒烘干机，得到颗粒肥料成品。
按照所述企业标准经实验室检测，按照该配方制备的肥料的pH值为6.5，有机质含量20.5％，吸水倍率16.5g/g，氮磷钾总含量37％，其中氮含量为9.9％，五氧化二磷9.6％，氧化钾17.8％；钙、镁、硅、硫总含量17.9％，其中氧化钙2.1％，氧化镁1.5％，二氧化硅0.02％，二氧化硫14.3％，以及初期养分释放率8.3％。
实施例2
准备按重量份计的以下原料：
丙烯酸 600份
催化剂 氢氧化钠水溶液，pH＝11.7
引发剂 过硫酸钾 20份
交联剂 乙二醇 30份
无机养分 尿素 1800份磷酸一铵 1600份 硫酸钾 3600份 硝酸钙 1100份 硫酸镁 1100份 硅酸钠 250份 硫酸锌 80份 硼酸钠80份
生物酶 15份(脂肪酶5份、果胶酶5份、酵素菌酶5份)
脂肪 25份 果胶 25份 淀粉 30份。
按照以下步骤制备肥料：
1)将丙烯酸与催化剂混合，反应20分钟后得到中和预聚体，随后向反应体系内添加所述无机养分；
2)向所述中和预聚体中依次添加无机养分、交联剂和引发剂，将反应体系控制温度在66℃-70℃，搅拌转速设定为80转，反应25分钟，降温至55℃；
3)搅拌步骤2)中的混合物形成溶液，向所述溶液内添加所述改性剂和生物酶，搅拌20分钟后，得到共聚体；
4)将所述共聚体引入造粒烘干机，得到颗粒肥料成品。
按照所述企业标准经实验室检测，按照该配方制备的肥料的pH值为6.9，有机质含量24.1％，吸水倍率19.6g/g，氮磷钾总含量39.4％，其中氮含量为10.9％，五氧化二磷9.8％，氧化钾18.7％；钙、镁、硅、硫总含量20.5％，其中氧化钙2.1％，氧化镁1.9％，二氧化硅0.05％，二氧化硫16.4％，以及初期养分释放率5.1％。
实施例3
准备按重量份计的以下原料：
丙烯酸 500份
催化剂 氢氧化钠水溶液，pH＝9.5
引发剂 过硫酸钾 15份
交联剂 乙二醇 25份
无机养分 尿素 1750份磷酸一铵 1550份 硫酸钾 3550份 硝酸钙 1050份 硫酸镁 1050份 硅酸钠 200份 硫酸锌 50份 硼酸钠 50份
生物酶 10份 蛋白酶 10份
蛋白粉 75份。
按照以下步骤制备肥料：
1)将丙烯酸与催化剂混合，反应20分钟后得到中和预聚体，随后向反应体系内添加所述无机养分；
2)向所述中和预聚体中依次添加无机养分、交联剂和引发剂，将反应体系控制温度在66℃-70℃，搅拌转速设定为80转，反应20分钟，降温至50℃；
3)搅拌步骤2)中的混合物形成溶液，向所述溶液内添加所述生物酶，搅拌15分钟后，得到共聚体；
4)将所述共聚体引入造粒烘干机，得到颗粒肥料成品。
按照所述企业标准经实验室检测，按照该配方制备的肥料的pH值为6.8，有机质含量22.3％，吸水倍率17.3g/g，氮磷钾总含量35.9％，其中氮含量为9.2％，五氧化二磷9.4％，氧化钾17.3％；钙、镁、硅、硫总含量17.9％，其中氧化钙1.9％，氧化镁1.4％，二氧化硅0.04％，二氧化硫15.2％，以及初期养分释放率7.2％。
实施例4
准备按重量份计的以下原料：
丙烯酸 400份
催化剂 氢氧化钠水溶液，pH＝8.5
引发剂 过硫酸钾 10份
交联剂 乙二醇 20份
无机养分 尿素 1780份 肥磷酸一铵 1580份 硫酸钾 3580份 硝酸钙 1088份 硫酸镁 1088份 硅酸钠 200份 硫酸锌 50份 硼酸钠 50份
生物酶 10份(蛋白酶5份、纤维素酶3份、酵素菌酶2份)
大豆水解蛋白粉 30份 鱼粉 20份 骨粉 10份。
按照以下步骤制备肥料：
1)将丙烯酸与催化剂混合，反应15分钟后得到中和预聚体，随后向反应体系内添加所述无机养分；
2)向所述中和预聚体中依次添加无机养分、交联剂和引发剂，将反应体 系控制温度在66℃-68℃，搅拌转速设定为70转，反应15分钟，降温至50℃；
3)搅拌步骤2)中的混合物形成溶液，向所述溶液内添加所述生物酶，加热至45℃，搅拌10分钟后，得到共聚体；
4)将所述共聚体引入造粒烘干机，得到颗粒肥料成品。
按照所述企业标准经实验室检测，按照该配方制备的肥料的pH值为6.5，有机质含量21％，吸水倍率17.5g/g，氮磷钾总含量40％，其中氮含量为10.9％，五氧化二磷10.3％，氧化钾18.8％；钙、镁、硅、硫总含量20.8％，其中氧化钙2.6％，氧化镁1.9％，二氧化硅0.04％，二氧化硫16.3％，以及初期养分释放率7.8％。
实验例1
在土柱淋溶培养条件下，使用按实施例4中的方法制备有机-无机聚合保水肥料的养分缓释期为80天，合子肥料的总养分缓释性能特征曲线呈”S“型(见图2)。肥料在土壤中的释放特征呈现出持久的缓释性能，这说明该肥料施用在土壤中有利于养分的稳定和缓释。
根据企业标准Q/370203XYD 001-2016和《农林保水剂》NY 886-2010行业标准中对有机-无机聚合保水肥的吸水倍数测定方法，测定该肥料可知，其吸水倍数范围为10.21g/g-19.33g/g，平均为17.5g/g，其吸0.9％NaCl溶液倍数范围为14.06g/g-18.32g/g，平均为16.56g/g。这在生产实践中吸水倍数能具有5g/g以上的保水能力就具有实际应用价值。
对土壤施用按实施例4中的方法制备有机-无机聚合保水肥料以及普通肥料(不含生物酶)，三年后对土壤中的微生物数量进行统计对比，结果见图3。
与常规化肥相比，在连续施用3年上述有机-无机聚合保水肥后，土壤细菌数量增加到17.69倍，放线菌数量增加到2.16倍，真菌降低了1/3。土壤中的有益菌主要是细菌和放线菌，土壤中的致病菌主要是真菌。
尽管已用具体实施例来说明和描述了本发明，然而应意识到，在不背离本 发明的精神和范围的情况下可以作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。尽管已用具体实施例来说明和描述了本发明，然而应意识到，在不背离本发明的精神和范围的情况下可以作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。

Claims (10)

  1. 一种有机-无机聚合保水肥料，其特征在于，所述有机-无机聚合保水肥料是共聚物，所述共聚物主要由有机保水单体与无机养分在催化剂、生物酶和改性剂的作用下融合共聚而成，所述共聚物具有三维网状亲水性基团结构。
  2. 根据权利要求1所述的有机-无机聚合保水肥料，其特征在于，所述有机-无机聚合保水肥料主要由有机单体、生物酶和无机养分融合共聚而成；所述单体包括丙烯酸及其衍生物；优选的，所述单体是丙烯酸。
  3. 根据权利要求1所述的有机-无机聚合保水肥料，其特征在于，所述无机养分包括硝酸钙镁、尿素、磷酸一铵、钾盐、硝酸钙、硫酸镁、硫酸锌、硅酸钠和硼酸钠中的一种或多种；优选的，所述钾盐包括硫酸钾和氯化钾。
  4. 根据权利要求1所述的有机-无机聚合保水肥料，其特征在于，所述生物酶是蛋白酶、纤维素酶、脂肪酶、果胶酶和酵素菌酶中的一种或多种，优选地所述生物酶是蛋白酶、纤维素酶、脂肪酶、果胶酶和酵素菌酶中的两种以上。
  5. 根据权利要求1所述的有机-无机聚合保水肥料，其特征在于，所述改性剂是蛋白粉、纤维素粉、果胶、脂肪、淀粉、鱼粉和骨粉中的两种以上；优选的，所述蛋白粉为大豆水解蛋白、鱼粉和骨粉中的两种以上。
  6. 根据权利要求1所述的有机-无机聚合保水肥料，其特征在于，所述有机-无机聚合保水肥料包括按重量份计的丙烯酸400-600份，无机养分8900-9600份，改性剂50-100份，生物酶5-15份。
  7. 根据权利要求1所述的有机-无机聚合保水肥料，其特征在于，所述无机养分包括按重量份计的以下组分：
    Figure PCTCN2017091230-appb-100001
    Figure PCTCN2017091230-appb-100002
  8. 根据权利要求1所述的有机-无机聚合保水肥料，其特征在于，所述肥料的pH值为3-8，有机质的质量分数大于20％，吸水倍率为10g/g-20g/g，氮磷钾总含量35％-40％，钙、镁、硅和硫总含量大于5％，初期养分释放率小于15％。
  9. 权利要求1-8任一项所述的有机-无机聚合保水肥料的制备方法，其特征在于，有机单体在催化剂的作用下得到中和预聚体后，同时添加无机养分和偏硅酸盐，后添加引发剂和交联剂，充分搅拌使其形成溶液，添加改性剂和生物酶进行催化，融合共聚后得到共聚体，造粒烘干，优选地，所述催化剂是无机碱溶液，优选地，所述催化剂选自氢氧化钠溶液、氢氧化钾溶液、氨水和氢氧化钙溶液。
  10. 根据权利要求9所述的方法，其特征在于，所述方法包括以下步骤：
    1)将丙烯酸与催化剂混合，反应15-20分钟后得到中和预聚体；
    2)向所述中和预聚体中依次添加所述无机养分、交联剂和引发剂，将温度控制在65℃-70℃，反应15-25分钟，降温至35℃-55℃；
    3)搅拌步骤2)中的混合物形成溶液，向所述溶液内添加所述改性剂和生物酶，搅拌10-20分钟后，得到共聚体；
    4)所述共聚体经干燥、粉碎和筛分制成颗粒。
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