WO2019075971A1 - 一种水溶性肥料及其制备方法 - Google Patents

一种水溶性肥料及其制备方法 Download PDF

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WO2019075971A1
WO2019075971A1 PCT/CN2018/076370 CN2018076370W WO2019075971A1 WO 2019075971 A1 WO2019075971 A1 WO 2019075971A1 CN 2018076370 W CN2018076370 W CN 2018076370W WO 2019075971 A1 WO2019075971 A1 WO 2019075971A1
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Prior art keywords
water
titanium
soluble fertilizer
fertilizer according
gluconic acid
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PCT/CN2018/076370
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English (en)
French (fr)
Inventor
家新发
付荣伟
马玲
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日正九安科技（北京）有限公司
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Publication of WO2019075971A1 publication Critical patent/WO2019075971A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C11/00—Other nitrogenous fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
    • 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
    • C05G5/20—Liquid fertilisers

Definitions

  • the invention relates to the field of processing of fertilizers, in particular to a water-soluble fertilizer and a preparation method thereof.
  • Titanium-containing fertilizer has been proved to be a broad-spectrum, low-use functional fertilizer, which has a good promoting effect on plant physiological activities, can enhance the absorption of various nutrients by plants, and enhance plant disease resistance and stress resistance.
  • the ability to increase crop yields and improve crop quality is therefore a promising new fertilizer variety.
  • Due to the unstable nature of the inorganic titanium salt it is easy to decompose into water-insoluble titanium dioxide under natural conditions and cannot be absorbed and utilized by plants.
  • organic chelated complex titanium fertilizers have been developed and have been applied to agricultural production. In the technical measures.
  • the organic titanium functional fertilizers that have been used include VC (ascorbic acid) titanium, titanium citrate, complex organic acids (tartaric acid, citric acid, malic acid, mandelic acid, lactic acid, etc.) complexed titanium and amine carboxyl complexing agents. (EDTA, HEDTA, EDDHA, etc.) complexes titanium and has achieved good application results.
  • the object of the present invention is to provide a water-soluble fertilizer which firstly combines gluconic acid as a ligand to complex titanium ions to form a functional fertilizer of titanium gluconate complex.
  • This type of fertilizer is non-toxic and better. It is absorbed and utilized by crops, is environmentally friendly, and the ratio of each element is more reasonable. It can improve the yield and quality of crops, and it will not cause soil compaction. It has the advantages of soil control and environmental protection, and is very suitable for crop production.
  • a second object of the present invention is to provide a preparation method using the above water-soluble fertilizer, wherein the preparation method has the advantages of close connection, simple operation, no three wastes, safety and environmental protection, and the fertilizer efficiency of the variety is realized by rational design of the whole preparation method. Improvement is worthy of widespread application.
  • the present invention provides a water-soluble fertilizer mainly composed of a titanium gluconate complex and a basic substance, wherein the titanium gluconate complex is composed of a gluconic acid substance and a titanium compound according to a coordination molar ratio (2) -5): 1 made.
  • organic titanium functional fertilizers such as VC (ascorbic acid) titanium, titanium citrate, complex organic acids (tartaric acid, citric acid, malic acid, mandelic acid, lactic acid, etc.) complex titanium, amine carboxyl network
  • VC ascorbic acid
  • complex organic acids tartaric acid, citric acid, malic acid, mandelic acid, lactic acid, etc.
  • EDTA, HEDTA, EDDHA, etc. complexes titanium and has achieved good application results.
  • titanium functional fertilizers also have a series of problems, such as poor stability, high production cost, complicated manufacturing process, poor compatibility with other fertilizers, and effective absorption of crop growth.
  • the present invention provides a water-soluble fertilizer containing a titanium gluconate complex, which is not only highly efficient and environmentally friendly, but also can be well absorbed by crops and plants, and has a wide application range. Has a wide range of promotional value.
  • the titanium gluconate complex is prepared from a gluconic acid substance and a titanium compound according to a coordination molar ratio (2-5): 1, in fact, the ligand gluconic acid can be mass-produced industrially and has been widely used in foods.
  • Additives and feed additives are ordinary glucose, and the toxicity is very low.
  • the downstream products such as gluconolactone, calcium gluconate, sodium gluconate, zinc gluconate and ferrous gluconate are recognized as food nutrition regulating additives.
  • Gluconic acid itself is easily digested and absorbed by the organism, and is also very easily degraded by nature. It can be regarded as a non-toxic, non-polluting green substance.
  • gluconic acid has not been used as a ligand to complex titanium ions to prepare titanium gluconate complex.
  • the present invention firstly uses gluconic acid as a ligand to complex titanium ions to form a complex to obtain a water-soluble fertilizer, and has achieved good fertilizer efficiency.
  • the complex formed by the gluconic acid ligand and the titanium ion has high stability, and the complex can participate in nutrient metabolism in the plant, is fully absorbed and utilized by the plant, promotes vegetative growth and reproductive growth of the plant, and can be degraded in nature. Harmless substances will not adversely affect the environment.
  • the gluconic acid substance and Ti(IV) satisfy the following relationship: 2 ⁇ (number of moles of ligand): the number of moles of Ti (IV) ⁇ 5, preferably, the gluconic acid substance and the titanium compound are coordinated
  • the molar ratio can also be 3:1, 4:1, etc., through reasonable coordination of the number of moles, so that the two can form an effective complex.
  • the titanium compound includes a tetravalent titanium compound, preferably a soluble tetravalent titanium compound.
  • the tetravalent titanium ion formed after the tetravalent titanium compound is dissolved can be combined with a plurality of ligands to form a stable chelate compound.
  • the titanium compound includes at least one of titanium sulfate, titanium oxysulfate, titanium chloride, titanium bromide, titanium nitrate, and titanium oxychloride.
  • the gluconic acid substance includes at least one of gluconic acid, gluconate, and gluconate. Further, the gluconate includes at least one of calcium gluconate, sodium gluconate, zinc gluconate, and ferrous gluconate, and the gluconate includes gluconolactone.
  • the titanium compound may include one or both of titanyl sulfate and titanium sulfate
  • the gluconic acid may include gluconic acid, gluconolactone, calcium gluconate, sodium gluconate, zinc gluconate, gluconic acid.
  • One or more of the ferrous irons are preferably one or both of gluconic acid and gluconolactone.
  • the water-soluble new fertilizer also contains a basic substance, neutralizing the acidity of the liquid with an alkaline substance, and neutralizing until the pH of the solution is weakly acidic or neutral.
  • the above basic substance may be an organic base or an inorganic base, and the organic base includes at least one of ethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, ethylenediamine, triethylamine, and isopropylamine.
  • the inorganic base includes at least one of ammonia water, potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, and barium hydroxide.
  • the alkaline substance may include ammonium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, ethylenediamine, triethylamine.
  • ammonium hydroxide potassium hydroxide
  • calcium hydroxide barium hydroxide
  • ethanolamine diethanolamine
  • triethanolamine diethylenetriamine
  • triethylenetetramine ethylenediamine
  • triethylamine triethylamine.
  • isopropylamine One or a mixture of isopropylamine.
  • the water-soluble fertilizer also includes a medium amount of elements, a combination of trace elements and water, and the mass ratio of water to titanium compound can be controlled between (4-30):1, in addition to being controlled at 5:1. , 6:1, 7:1, 8:1, 9:1, 10:1, etc.
  • the chelated trace elements include at least one of zinc, magnesium, iron, manganese, copper, cobalt, and molybdenum.
  • the present invention also provides a method for preparing the water-soluble fertilizer, which comprises: mixing gluconic acid substance with titanium compound according to a coordination molar ratio (2-5):1 to form glucose. Titanate complex.
  • the temperature at which the gluconic acid substance is mixed and coordinated with the titanium compound is 25-60 ° C, and the time is 1-3 h. Further, it further comprises: neutralizing the titanium gluconate complex with a basic substance, and sedimenting and filtering.
  • the water-soluble fertilizer preparation method of the embodiment of the invention is simple, the operation condition is mild, the mixing and the stirring are uniform, the content of each element in the obtained water-soluble fertilizer product is within the ideal index range, and there is no agglomerated small particles, because if there is agglomeration The appearance of particles is not easily absorbed by plants.
  • the gluconic acid substance is mixed with water at 25 to 60 ° C to form a mixed solution, and then the reaction is carried out to form an aqueous solution which is more advantageous for the subsequent reaction.
  • the stirring mode is high-speed shear stirring, and the stirring rate is controlled between 500-1500 rpm. .
  • the time of settling is controlled to substantially achieve the effect of sedimentation of the filtration residue between 24-48 hours.
  • the process of concentration can be concentrated by heating or concentrated by vacuum drying, and the finer the particle size control during the pulverization process, the better the subsequent addition of other elements is more conducive to the mutual compatibility of various substances.
  • the role works together.
  • the water-soluble fertilizer containing titanium gluconate complex of the present invention has high stability of a complex formed by a gluconic acid ligand and titanium ions. Under long-term normal storage conditions, no discoloration or precipitation. After freezing at -18 ° C for 1 day and storage at 50 ° C for 14 days, no hydrolysis, no precipitation, and no reduction in titanium (IV) ion content. Suitable for a wide range of applications.
  • the present invention provides a water-soluble fertilizer which firstly combines gluconic acid as a ligand to complex titanium ions to form a functional fertilizer of titanium gluconate complex, which is non-toxic and better.
  • the ground is absorbed and utilized by crops, is environmentally friendly, and the ratio of each element is more reasonable. It can improve the yield and quality of crops, and does not cause soil compaction. It has the advantages of soil control and environmental protection, and is very suitable for crop production applications;
  • the preparation method of the water-soluble fertilizer of the invention has the advantages of close connection, simple operation, no three wastes, safety and environmental protection, and the fertilizer efficiency improvement of the variety is realized by rational design of the whole preparation method, and is worthy of widespread application.
  • the specific preparation method of the water-soluble fertilizer includes the following steps:
  • the filtrate is diluted with water to a titanium ion concentration of 10.0 g / L (the determination of titanium ion concentration, according to the industry standard NYT 2879-2015 "water soluble fertilizer cobalt, titanium content determination” 5.2 titanium content determination plasma emission spectrometry specified method get on).
  • Example 2 2.0 ml of the water-soluble fertilizer of the above Example 1 was weighed as a sample, diluted with water to 1000 ml (i.e., a titanium ion concentration of 20 mg/L per sample), and then sealed and stored at room temperature to observe the time at which precipitation occurred. The sample remained clear and transparent after 7 days. After testing, the titanium ion concentration was still 20 mg/L.
  • the water-soluble fertilizer prepared in the above Example 1 was diluted with water as a sample to a titanium ion concentration of 20 mg/L, and then subjected to a field experiment.
  • the specific steps include:
  • Test crop cucumber, Jinyou 10, whose seeds were purchased from Liaoning Seed Company.
  • Test site From February to June 2016, it was carried out in the 300M2 greenhouse of Li Hongzhi, Dawangzhangzi Village, Brownpu Town, Lingyuan City, Liaoning province.
  • the test site was the local ordinary sandy bottom black soil field. Conventional water and fertilizer management.
  • Test design spraying the above samples in the three-quarter (three-zone) area of the greenhouse, planting cucumbers, spraying the first time on the 30th day after planting, and spraying the above samples to 20mg/L, the remaining four
  • the same area (contrast area) is sprayed with the same amount of water (blank control CK).
  • a second spray was applied on the 45th day after sowing, and then sprayed once every 10 days, in the same manner as above, and sprayed 5 times in total.
  • Fruit survey The top flower of cucumber fruit in the treatment area is not easy to fall off, the shape of the melon strip is straight, the diameter is enlarged by about 0.5cm, the length is increased by 3-5cm, the section of the melon heart is yellow-green, and the taste is refreshing.
  • the fruit section of the comparison area was yellowish white and the taste was poor.
  • Harvesting period survey The harvesting period is greatly extended, and the treatment area is delayed by 20-40 days than the comparison area, and more than 3-5 fruits are harvested. The yield increase can reach more than 50%.
  • the specific preparation method of the water-soluble fertilizer includes the following steps:
  • the filtrate was diluted with water to a titanium ion concentration of 10.0 g/L (the mass ratio of titanyl sulfate to water was controlled between (4-30):1). Then, the filtrate was added to a liquid EDTA cerium zinc, manganese, iron, magnesium ammonium salt solution (in which the element content is Mn + Zn + Fe + Mg ⁇ 100 g / L), and the ratio was 1:2, and the mixture was uniformly mixed.
  • the water-soluble fertilizer of the above Example 2 was diluted to a titanium ion of 10 mg/L for treating wheat. Demonstration test site: From March to May 2017, 2.1 mu of Liuyuannong block in Luying Village, Siying Township, Cheng'an County, Hebei province, and 0.7 mu of land. Wheat variety: "gas blast”. Water and fertilizer conditions: 50 kg of compound fertilizer (2-25-5). The treatment method of the treatment area is sprayed once in the jointing stage of wheat and sprayed once again in the heading stage. The fertilizer applied is: water-soluble fertilizer diluted to 10 mg/L in Example 2 and potassium dihydrogen phosphate 1 ⁇ , urea 1.5 % mixed spray. The treatment in the control zone was the same, and only the same concentration of potassium dihydrogen phosphate and urea were sprayed.
  • the specific preparation method of the water-soluble fertilizer includes the following steps:
  • the filtrate was heated and evaporated to a weight loss of about 40%, and then converted into a vacuum drying at 80 ° C, taken out as a paste, and cooled to a solid. Then, the solid is added to a mixture of solid powdered EDTA chelating zinc, manganese, iron, magnesium potassium salt and sodium octaborate (the element content of which is Mn+Zn+Fe+B+Mg ⁇ 20%), added The ratio is 1:4, and the mixture is pulverized evenly.
  • the water-soluble fertilizer prepared in the above Example 3 was diluted and dissolved in water, and diluted with water to a titanium ion of 10 mg/L and 15 mg/L for treating jujube trees.
  • the specific preparation method of the water-soluble fertilizer includes the following steps:
  • the filtrate was heated and evaporated to a weight loss of about 40%, and then converted into a vacuum drying at 80 ° C, taken out as a paste, and cooled to a solid. Then, the solid is added to a mixture of solid powdered EDTA chelating zinc, manganese, iron, magnesium potassium salt and sodium octaborate (the element content of which is Mn+Zn+Fe+B+Mg ⁇ 20%), added The ratio is 1:4, and the mixture is pulverized evenly.
  • the water-soluble fertilizer prepared in Example 4 of the present invention was also tested in the same manner as in the method of treating jujube of Example 3.
  • the water-soluble fertilizer of the invention has good fertilizer effect, is more easily absorbed by plants and crops, and has a wide range of use, and general crops, fruit trees and the like can be applied.
  • This embodiment provides a water-soluble fertilizer, and the specific preparation method comprises the following steps:
  • the filtrate is added to a liquid EDTA cerium zinc, manganese, iron, magnesium ammonium salt solution (in which the element content is Mn + Zn + Fe + Mg ⁇ 100 g / L), the ratio is 1:2, and the mixture is uniformly mixed.
  • This embodiment provides a water-soluble fertilizer, and the specific preparation method comprises the following steps:
  • titanium nitrate 200 mol was dissolved in 250 kg of water at 60 ° C, and 1000 mol of sodium gluconate was added thereto, and stirred at 60 ° C and a rotation speed of 1500 rpm for 3 hours to form a titanium gluconate complex. After aging for 1 d, 1500 mol of ammonia water was slowly added thereto, and the mixture was stirred at 60 ° C and a rotation speed of 1000 rpm for 1 hour. Settling at 60 ° C for 48 h. The precipitated insoluble matter was filtered off. The filtrate was diluted with water to a titanium ion concentration of 10.0 g/L (the mass ratio of titanium nitrate to water was controlled between (4-30):1).
  • the filtrate is added to a liquid EDTA cerium zinc, manganese, iron, magnesium, cobalt ammonium salt solution (in which the element content is Mn+Zn+Fe+Mg+Co ⁇ 100g/L), and the ratio is 1:2. ,well mixed.
  • This embodiment provides a water-soluble fertilizer, and the specific preparation method comprises the following steps:
  • the filtrate is added to the liquid EDTA ⁇ zinc, manganese, iron, magnesium, molybdenum ammonium salt solution (the element content of Mn + Zn + Fe + Mg + Mo ⁇ 100g / L), the ratio of 1:2 ,well mixed.
  • This embodiment provides a water-soluble fertilizer, and the specific preparation method comprises the following steps:
  • titanium bromide 250 mol was dissolved in 190 kg of water at 25 ° C, 700 mol of zinc gluconate was added, and the mixture was stirred at 25 ° C and 500 rpm for 1 hour to form a titanium gluconate complex. After aging for 3 days, 1000 mol of ethylenediamine was slowly added, and the mixture was stirred at 25 ° C and a rotation speed of 1000 rpm for 1 hour. Settling at 50 ° C for 24 h. The precipitated insoluble matter was filtered off. The filtrate was diluted with water to a titanium ion concentration of 10.0 g/L (the mass ratio of titanium bromide to water was controlled between (4-30):1).
  • the filtrate is added to a liquid EDTA cerium zinc, manganese, iron, magnesium ammonium salt solution (in which the element content is Mn + Zn + Fe + Mg ⁇ 100 g / L), the ratio is 1:2, and the mixture is uniformly mixed.
  • the water-soluble fertilizer prepared in Examples 5-8 was diluted and dissolved in water, and diluted with water to a titanium ion of 10 mg/L for treating jujube trees.
  • Example 5 Example 6
  • Example 7 Fruit set rate (fruit / hanging) 0.30 0.35 0.37 0.35 0.36 Yield per plant, kg 7.2 9.5 9.8 9.6 9.6 Average single fruit weight, g 8.0 9.7 10.0 9.8 10.0
  • the invention provides a water-soluble fertilizer which is non-toxic, can be better absorbed by crops, is environmentally friendly, and has a more reasonable ratio of elements, can improve the yield and quality of crops, and does not cause soil compaction. It has the advantages of soil control, green environmental protection, etc. It is very suitable for the application of crop production. At the same time, the preparation method of the water-soluble fertilizer is closely connected before and after the steps, the operation is simple, no three wastes are produced, safe and environmentally friendly, and the whole preparation method is reasonable. The design achieves the fertilizer efficiency improvement of this variety of fertilizers, and is very suitable for large-scale industrial production, which is worthy of widespread application.

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Abstract

本发明提供了一种水溶性肥料及其制备方法，水溶性肥料主要由葡萄糖酸钛络合物和碱性物质组成，其中所述葡萄糖酸钛络合物由葡萄糖酸类物质与钛化合物按照配位摩尔比(2-5)：1制得。制备方法包括：(A)将葡萄糖酸类物质与钛化合物配位25-60℃反应1-3h形成葡萄糖酸钛络合物；(B)陈化1-3d后中和，沉降过滤，添加其他物质即可。本发明实施例的水溶性肥料首次将葡萄糖酸作为配位体络合钛离子，形成葡萄糖酸钛络合物功能性肥料，该类型肥料无毒、能更好地被农作物吸收利用、对环境友好，各元素配比更加合理，能够提高农作物的产量以及品质，而且不会使得土壤板结，具有治理土壤、绿色环保等优点。

Description

一种水溶性肥料及其制备方法
相关申请的交叉引用
本申请要求于2017年10月20日提交中国专利局的申请号为2017109810972、名称为“一种水溶性肥料及其制备方法”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
本发明涉及肥料的加工领域，具体而言，涉及一种水溶性肥料及其制备方法。
背景技术
关于元素钛在农业中的应用，目前已有很多关于元素钛在农业中的应用的研究报道。现已证明含钛肥料是一种广谱性、用量少的功能性肥料，其对植物的生理活动具有良好的促进作用，能够提高植物对各种营养元素的吸收，增强植物抗病抗逆能力，增加作物产量，改善作物品质，因此含钛肥料是一种很有前途的新型肥料品种。由于无机钛盐性质不稳定，极容易在自然条件下分解成不溶于水的二氧化钛，不能为植物吸收利用，目前已经开发了多种有机螯合络合钛的肥料品种，并且已经应用于农业生产的技术措施中。
现已使用的有机钛功能性肥料品种，有VC(抗坏血酸)钛、柠檬酸钛、复合有机酸(酒石酸、柠檬酸、苹果酸、苦杏仁酸和乳酸等)络合钛、胺羧络合剂(EDTA、HEDTA、EDDHA等)络合钛，并取得了良好的应用效果。
但是现有技术中应用的肥料还存在一系列的问题，比如稳定性欠佳，生产成本高、制造工艺比较复杂、与其他肥料的兼容性不佳，影响农作物生长的有效吸收等等。
有鉴于此，特提出本发明。
发明内容
本发明的目的在于提供一种水溶性肥料，该水溶性肥料首次将葡萄糖酸作为配位体络合钛离子，形成葡萄糖酸钛络合物功能性肥料，该类型肥料无毒、能更好地被农作物吸收利用、对环境友好，各元素配比更加合理，能够提高农作物的产量以及品质，而且不会使得土壤板结，具有治理土壤、绿色环保等优点，非常适于农作物生产方面的应用。
本发明的第二目的在于提供采用上述水溶性肥料的制备方法，该制备方法前后步骤衔接紧密，操作简单，无三废产生，安全环保，通过对整个制备方法的合理设计实现了该品 种肥料的肥效提升，值得广泛推广应用。
为了实现本发明的上述目的，特采用以下技术方案：
本发明实施例提供了一种水溶性肥料，主要由葡萄糖酸钛络合物和碱性物质组成，其中所述葡萄糖酸钛络合物由葡萄糖酸类物质与钛化合物按照配位摩尔比(2-5)：1制得。
现有技术中，有机钛功能性肥料品种很多，比如VC(抗坏血酸)钛、柠檬酸钛、复合有机酸(酒石酸、柠檬酸、苹果酸、苦杏仁酸和乳酸等)络合钛、胺羧络合剂(EDTA、HEDTA、EDDHA等)络合钛，并取得了良好的应用效果。
但是上述钛功能性肥料还存在一系列的问题，比如稳定性欠佳，生产成本高、制造工艺比较复杂、与其他肥料的兼容性不佳，影响农作物生长的有效吸收等等。
本发明为了切实解决现有技术中存在的技术问题，提供了一种含有葡萄糖酸钛络合物的水溶性肥料，不仅高效环保，而且能够很好的为农作物、植物所吸收，应用范围广，具有广泛的推广价值。
其中，葡萄糖酸钛络合物由葡萄糖酸类物质与钛化合物按照配位摩尔比(2-5)：1制得的，其实配位体葡萄糖酸在工业上可以大量生产，已广泛用于食品添加剂和饲料添加剂。上游原料来源是普通的葡萄糖，毒性很低，下游产物葡萄糖酸内酯、葡萄糖酸钙、葡萄糖酸钠、葡萄糖酸锌、葡萄糖酸亚铁等已是公认的食品营养调节添加剂。葡萄糖酸本身容易被生物消化吸收利用，也非常容易被大自然降解，可视为一种无毒、不污染环境的绿色物质。它可以和锌离子、钙离子、铁离子、锂离子等生成稳定的络合物，试验证明，将葡萄糖酸和钛(IV)离子配位能形成稳定性比较好的络合物，可以做为一种新型含钛的功能性肥料应用，成为一种农业生产的有效增产的新技术措施，而现有技术中还没有将萄糖酸作为配位体络合钛离子，制备葡萄糖酸钛络合物功能性肥料的报道，本发明首次将萄糖酸作为配位体来络合钛离子形成络合物制得水溶性肥料，并取得了良好的肥效。
该葡萄糖酸配位体和钛离子形成的络合物稳定性高，该络合物能参与植物体内的营养代谢，充分被植物吸收利用，促进植物的营养生长和生殖生长，能在自然界降解成无害物质，不会给环境带来不利影响。
葡萄糖酸类物质和Ti(IV)满足下列关系式：2≤(配位体摩尔数)∶Ti(IV)的摩尔数≤5之间，优选地，萄糖酸类物质与钛化合物按照配位摩尔比还可以为3：1、4：1等，通过合理的配位摩尔数控制，才可以使得两者能够形成有效的络合物。
其中，钛化合物包括四价钛化合物，优选为可溶性的四价钛化合物。四价钛化合物溶解后形成的四价钛离子，能够与多种配体配合形成稳定的螯合物。可选地，钛化合物包括硫酸钛、硫酸氧钛、氯化钛、溴化钛、硝酸钛和氯化氧钛中的至少一种。
葡萄糖酸类物质包括葡萄糖酸、葡萄糖酸盐和葡萄糖酸酯中的至少一种。进一步地， 葡萄糖酸盐包括葡萄糖酸钙、葡萄糖酸钠、葡萄糖酸锌、葡萄糖酸亚铁中的至少一种，葡萄糖酸酯包括葡萄糖酸内酯。
可选地，钛化合物可包括硫酸氧钛、硫酸钛中的一种或两种，葡萄糖酸类物质可包括葡萄糖酸、葡萄糖酸内酯、葡萄糖酸钙、葡萄糖酸钠、葡萄糖酸锌、葡萄糖酸亚铁中的一种或多种，优选为葡萄糖酸、葡萄糖酸内酯中的一种或两种。
除了上述两种物质，水溶新肥料中还包含碱性物质，用碱性物质中和料液的酸性，中和至溶液酸碱度为弱酸性或中性。上述碱性物质可以是有机碱或无机碱，有机碱包括乙醇胺、二乙醇胺、三乙醇胺、二乙烯三胺、三乙烯四胺、乙二胺、三乙胺、异丙胺中的至少一种。无机碱包括氨水、氢氧化钾、氢氧化钠、氢氧化锂、氢氧化钙、氢氧化镁和氢氧化钡中的至少一种。可选地，碱性物质可包括氢氧化铵、氢氧化钾、氢氧化钙、氢氧化钡、乙醇胺、二乙醇胺、三乙醇胺、二乙烯三胺、三乙烯四胺、乙二胺、三乙胺、异丙胺中的一种或几种混合。
此外，水溶性肥料中还包括中量元素、鳌合微量元素和水，水与钛化合物的质量比可控制在(4-30):1之间，除此之外还可以控制在5：1、6：1、7：1、8：1、9：1、10：1等。可选地，螯合微量元素包括锌、镁、铁、锰、铜、钴和钼中的至少一种。
本发明实施例除了提供了一种水溶性肥料，还提供了该水溶性肥料的制备方法，其包括：将葡萄糖酸类物质与钛化合物按照配位摩尔比(2-5)：1混合形成葡萄糖酸钛络合物。其中葡萄糖酸类物质与所述钛化合物混合配位的温度为25-60℃，时间为1-3h。进一步地，其还包括：将所述葡萄糖酸钛络合物用碱性物质进行中和，并沉降过滤。
在实际应用中，具体包括如下步骤：
(A)将葡萄糖酸类物质与钛化合物配位25-60℃反应1-3h形成葡萄糖酸钛络合物；
(B)陈化1-3d后中和，沉降过滤，添加其他物质即可。
本发明实施例的水溶性肥料制备方法简单，操作条件温和，混合搅拌均匀，得到的水溶性肥料产品中各元素的含量在理想指标范围内，而且不会出现团聚的小颗粒，因为如果有团聚的颗粒出现植物不容易吸收。
优选地，步骤(A)中，将葡萄糖酸类物质25-60℃与水混合形成混合溶液，再进行反应，形成水溶液更有利于后续反应的有效进行。
此外，尤其是在反应络合过程中以及陈化、中和过程中最好进行不断的搅拌，以促进反应过程的高效进行，搅拌方式是高速剪切搅拌，搅拌速率控制在500-1500rpm之间。
优选地，沉降的时间控制在24-48h之间基本可以达到沉降过滤残渣的效果。
优选地，沉降过滤后浓缩脱水成膏体，粉碎，再加入其他鳌合态微量元素水溶性固体肥料，粉碎分散混合均匀。
其中，浓缩的过程中可采用加热蒸发浓缩或采用真空干燥浓缩的方式，粉碎过程中的粒度控制的越细越好，这样后续添加其他元素后，也更利于各种物质的相互伍配，互相作用共同发挥效果。
本发明的含有葡萄糖酸钛络合物水溶性肥料，葡萄糖酸配位体和钛离子形成的络合物稳定性高。在长期正常储存条件下，不变色、不沉淀。-18℃冷冻1天和50℃储存14天后，不水解，无沉淀析出，钛(Ⅳ)离子含量不减少。适于广泛推广应用。
与现有技术相比，本发明的有益效果例如包括：
(1)本发明提供了一种水溶性肥料，该水溶性肥料首次将葡萄糖酸作为配位体络合钛离子，形成葡萄糖酸钛络合物功能性肥料，该类型肥料无毒、能更好地被农作物吸收利用、对环境友好，各元素配比更加合理，能够提高农作物的产量以及品质，而且不会使得土壤板结，具有治理土壤、绿色环保等优点，非常适于农作物生产方面的应用；
(2)本发明的水溶性肥料的制备方法前后步骤衔接紧密，操作简单，无三废产生，安全环保，通过对整个制备方法的合理设计实现了该品种肥料的肥效提升，值得广泛推广应用。
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
水溶性肥料的具体制备方法包括如下步骤：
在60℃下将40公斤硫酸钛溶解于300公斤水中，加入葡萄糖酸80公斤，在60℃、转速为500rpm的条件下搅拌1h形成葡萄糖酸钛络合物。陈化1-3d然后缓慢加入氢氧化铵120公斤，在60℃、转速为1000rpm的条件下搅拌1h。在50℃下沉降48h。(葡萄糖酸的总摩尔数)∶Ti(IV)的摩尔数为2.44。过滤出沉淀不溶物。将滤液用水稀释至钛离子浓度为10.0g/L(钛离子浓度的测定，可以按照行业标准NYT 2879－2015《水溶肥料钴、钛含量测定》5.2钛含量的测定等离子体发射光谱法规定的方法进行)。
量取上述实施例1的水溶性肥料2.0ml作为样品，用水稀释至1000ml(即每份样品中的钛离子浓度为20mg/L)，然后在室温环境下密封保存，观察出现沉淀的时间。该样品在7天后仍然保持澄清透明的状态。经检测，其中钛离子浓度仍为20mg/L。
然后将该样品50ml装在玻璃瓶中密封，在冰箱-18℃冷冻室环境下，保存12h，取出来后让其恢复室温，该样品仍然保持澄清透明的状态。
将上述样品50ml装于玻璃瓶密封，然后在恒温干燥箱50±2℃环境下，保存7天，取出后让其自然恢复室温，试样保持澄清透明的状态。经检测，其中钛离子浓度仍为20mg/L。
经过上述试验，可以发现使用葡萄糖酸作为配位体，络合得到的葡萄糖酸钛络合物，无论是在使用条件下还是在正常储存条件下均是相当稳定的。
将上述实施例1制备出的水溶性肥料作为样品用水稀释至钛离子浓度为20mg/L，然后进行大田实验，具体步骤包括：
供试作物：黄瓜，津优10号，其种子购自辽宁种子公司。
供试地点：2016年2-6月在辽宁省凌源市八里铺镇大王杖子村***的300M2大棚进行，试验地为当地普通沙底黑土田。常规水肥管理。
试验设计：大棚内四份之三区(处理区)域喷施上述样品，种植黄瓜，在定植后第30天进行第一次喷施，叶面喷施上述样品稀释至20mg/L，余四分之一区(对比区)域喷施等量清水(空白对照CK)。在播种后第45天进行第二次喷施，其后每隔10天喷施处理一次，方式同上，共喷施处理5次。
试验结果：观察叶片，茎秆的生长情况，处理区的叶片浓绿厚实，韧性好，黄叶、老叶很少，茎秆壮实，对比区的叶片和茎秆明显不如处理区，特别是叶片柔韧性较差。
果实调查：处理区的黄瓜果实顶花不易脱落，瓜条形状顺直，直径扩大0.5cm左右，长度增长3-5cm，瓜心断面呈黄绿色，口感爽口。对比区的果实断面呈黄白色，口感较差。采收期调查：采收期大大延长，处理区比对比区推迟拉秧20-40天，多采收3-5茬果实。增产率可达50％以上。
同一时期，在辽宁省凌源镇八里铺大王杖子村常宏宇、辽宁省凌源市八里铺镇大王杖子村李红波、吉林省榆树市五棵树镇永吉村刘国的黄瓜大棚内，应用效果基本情况，和上述应用效果一致，反应非常良好。
实施例2
水溶性肥料的具体制备方法包括如下步骤：
在25℃下将40公斤硫酸氧钛溶解于300公斤水中，加入葡萄糖酸内酯120公斤，在25℃、转速为500rpm的条件下搅拌1h形成葡萄糖酸钛络合物。陈化1-3d然后缓慢加入氢氧化钾36公斤，在25℃、转速为1000rpm的条件下搅拌1h。在50℃下沉降24h。(葡萄糖酸内酯的总摩尔数)∶Ti(IV)的摩尔数为3.67。过滤出沉淀不溶物。将滤液用水稀释至钛离子浓度为10.0g/L(硫酸氧钛与水的质量比控制在(4-30):1之间)。然后把此滤液添加 到液态的EDTA鳌合锌、锰、铁、镁的铵盐溶液(其中的元素含量Mn+Zn+Fe+Mg≥100g/L)中，添加比例1：2，混合均匀。
将上述实施例2的水溶性肥料稀释至钛离子10mg/L，用于处理小麦。示范试验地点：2017年3-5月，河北邯郸市成安县寺营乡吕彪村刘元农地块2.1亩，对比地块0.7亩。小麦品种：《气死风》。水肥条件：亩施复合肥(2-25-5)50kg。处理区的处理方法，在小麦拔节期喷施一次，在抽穗期再喷施一次，喷施的肥料为：实施例2稀释至10mg/L的水溶性肥料和磷酸二氢钾1‰、尿素1.5％混喷。对比区的处理方式相同，只喷施同等浓度的磷酸二氢钾和尿素。
对比效果：示范试验地块小麦长势明显优于对比地块小麦，茎秆粗壮，抗风灾不倒伏，根系发达，分蘖多，籽粒饱满，千粒重：试验田51.65g，对比田42.96g，千粒重增加20.2％。特别是试验田在麦粒成熟时茎秆仍能保持活杆。粗测增产幅度大于10％。
实施例3
水溶性肥料的具体制备方法包括如下步骤：
在40℃下将40公斤硫酸氧钛、硫酸钛共同溶解于300公斤水中，加入葡萄糖酸内酯160公斤，在40℃、转速为700rpm的条件下搅拌3h形成葡萄糖酸钛络合物。陈化1-3d然后缓慢加入三乙醇胺36公斤，在50℃、转速为1500rpm的条件下搅拌1h。在50℃下沉降30h。(葡萄糖酸内酯的总摩尔数)∶Ti(IV)的摩尔数为4.88。过滤出沉淀不溶物，除去大部分硫酸根离子。将滤液加热蒸发浓缩至重量减少40％左右时，转换成80℃真空干燥，干燥成膏状物时取出，冷却成固体。然后把此固体添加到固态粉状的EDTA鳌合锌、锰、铁、镁的钾盐和八硼酸钠的混合物中(其中的元素含量Mn+Zn+Fe+B+Mg≥20％)，添加比例1：4，混合粉碎均匀。
将上述实施例3制备得到的水溶性肥料稀释溶解于水中，加水比例稀释为钛离子10mg/L、15mg/L，用于处理枣树。
处理枣树试验安排。示范试验地点：4-7月，山西运城市临猗县七级乡钦兵的枣树果园。枣树品种：当地脆枣。砂质土。树龄：5～10年。处理方法，在枣树初花期、幼果期和膨果期各喷施一次，全树喷施。实施例3稀释至10mg/L、15mg/L喷施。对比枣树处理方式相同，只喷施清水。各处理18株枣树。
对比效果：处理后的枣树长势明显优于对比枣树，叶色浓绿，坐果率提高，果实直径增大，裂果很少，果实增重，增产幅度37.5％。果实口感脆甜，具体效果见下表1数据
表1试验效果汇总
项目 对照(清水) 处理(10mg/L) 处理(15mg/L) 平均增加±％
坐果率(果/吊) 0.30 0.36 0.45 +35.0
单株产量，kg 7.2 9.5 10.3 +37.5
平均单果重，g 8.0 9.7 10.5 +26.2
实施例4
水溶性肥料的具体制备方法包括如下步骤：
在45℃下将40公斤硫酸氧钛、硫酸钛共同溶解于300公斤水中，加入葡萄糖酸内酯165公斤，在40℃、转速为800rpm的条件下搅拌2h形成葡萄糖酸钛络合物。陈化2d然后缓慢加入乙二胺、异丙胺36公斤，在55℃、转速为1200rpm的条件下搅拌1h。在35℃下沉降30h。(葡萄糖酸内酯的总摩尔数)∶Ti(IV)的摩尔数为5。过滤出沉淀不溶物，除去大部分硫酸根离子。将滤液加热蒸发浓缩至重量减少40％左右时，转换成80℃真空干燥，干燥成膏状物时取出，冷却成固体。然后把此固体添加到固态粉状的EDTA鳌合锌、锰、铁、镁的钾盐和八硼酸钠的混合物中(其中的元素含量Mn+Zn+Fe+B+Mg≥20％)，添加比例1：4，混合粉碎均匀。
将本发明实施例4制备得到的水溶性肥料参照实施例3的处理枣树的方法试验后也得到相同的结果。说明本发明的水溶性肥料肥效好，更易为植物、农作物所吸收，使用范围比较广，一般的农作物、果树等植物都可以适用。
实施例5
本实施例提供一种水溶性肥料，其具体制备方法包括如下步骤：
在25℃下将250mol的氯化钛溶解于190公斤水中，加入葡萄糖酸500mol，在25℃、转速为500rpm的条件下搅拌1h形成葡萄糖酸钛络合物。陈化3d然后缓慢加入氢氧化钠900mol，在25℃、转速为1000rpm的条件下搅拌1h。在50℃下沉降24h。过滤出沉淀不溶物。将滤液用水稀释至钛离子浓度为10.0g/L(氯化钛与水的质量比控制在(4-30):1之间)。然后把此滤液添加到液态的EDTA鳌合锌、锰、铁、镁的铵盐溶液(其中的元素含量Mn+Zn+Fe+Mg≥100g/L)中，添加比例1：2，混合均匀。
实施例6
本实施例提供一种水溶性肥料，其具体制备方法包括如下步骤：
在60℃下将200mol的硝酸钛溶解于250公斤水中，加入葡萄糖酸钠1000mol，在60℃、转速为1500rpm的条件下搅拌3h形成葡萄糖酸钛络合物。陈化1d然后缓慢加入氨水1500mol，在60℃、转速为1000rpm的条件下搅拌1h。在60℃下沉降48h。过滤出沉淀不溶物。将滤液用水稀释至钛离子浓度为10.0g/L(硝酸钛与水的质量比控制在(4-30):1之间)。然后把此滤液添加到液态的EDTA鳌合锌、锰、铁、镁、钴的铵盐溶液(其中的元素含量Mn+Zn+Fe+Mg+Co≥100g/L)中，添加比例1：2，混合均匀。
实施例7
本实施例提供一种水溶性肥料，其具体制备方法包括如下步骤：
在40℃下将200mol的氯化氧钛溶解于190公斤水中，加入葡萄糖酸内脂800mol，在25℃、转速为1000rpm的条件下搅拌1h形成葡萄糖酸钛络合物。陈化2d然后缓慢加入氢氧化镁1200mol，在40℃、转速为1000rpm的条件下搅拌2h。在40℃下沉降24h。过滤出沉淀不溶物。将滤液用水稀释至钛离子浓度为10.0g/L(氯化氧钛与水的质量比控制在(4-30):1之间)。然后把此滤液添加到液态的EDTA鳌合锌、锰、铁、镁、钼的铵盐溶液(其中的元素含量Mn+Zn+Fe+Mg+Mo≥100g/L)中，添加比例1：2，混合均匀。
实施例8
本实施例提供一种水溶性肥料，其具体制备方法包括如下步骤：
在25℃下将250mol的溴化钛溶解于190公斤水中，加入葡萄糖酸锌700mol，在25℃、转速为500rpm的条件下搅拌1h形成葡萄糖酸钛络合物。陈化3d然后缓慢加入乙二胺1000mol，在25℃、转速为1000rpm的条件下搅拌1h。在50℃下沉降24h。过滤出沉淀不溶物。将滤液用水稀释至钛离子浓度为10.0g/L(溴化钛与水的质量比控制在(4-30):1之间)。然后把此滤液添加到液态的EDTA鳌合锌、锰、铁、镁的铵盐溶液(其中的元素含量Mn+Zn+Fe+Mg≥100g/L)中，添加比例1：2，混合均匀。
试验例
将实施例5-8制备得到的水溶性肥料稀释溶解于水中，加水比例稀释为钛离子10mg/L，用于处理枣树。
处理枣树试验安排。示范试验地点：4-7月，山西运城市临猗县七级乡钦兵的枣树果园。枣树品种：当地脆枣。砂质土。树龄：5～10年。处理方法，在枣树初花期、幼果期和膨果期各喷施一次，全树喷施。实施例5-8稀释至钛离子浓度为10mg/L，进行喷施。对比例枣树处理方式相同，只喷施清水。各处理18株枣树，具体效果见下表2数据
表2试验效果汇总
项目 对比例 实施例5 实施例6 实施例7 实施例8
坐果率(果/吊) 0.30 0.35 0.37 0.35 0.36
单株产量，kg 7.2 9.5 9.8 9.6 9.6
平均单果重，g 8.0 9.7 10.0 9.8 10.0
由表2可以看出，采用实施例5-8所提供的水溶性肥料后，枣树的坐果率提高了17％-23％，单株产量提高了32％-36％，平均单果重提高了21％-25％，增产效果明显。且收获的果实口感脆甜，裂果率小，品质较高。
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。
工业实用性
本发明提供了一种水溶性肥料，该类型肥料无毒、能更好地被农作物吸收利用、对环境友好，各元素配比更加合理，能够提高农作物的产量以及品质，而且不会使得土壤板结，具有治理土壤、绿色环保等优点，非常适于农作物生产方面的应用；同时，该水溶性肥料的制备方法前后步骤衔接紧密，操作简单，无三废产生，安全环保，通过对整个制备方法的合理设计实现了该品种肥料的肥效提升，十分适合大规模的工业化生产，值得广泛推广应用。

Claims (20)

  1. 一种水溶性肥料，其特征在于，主要由葡萄糖酸钛络合物和碱性物质组成，其中所述葡萄糖酸钛络合物由葡萄糖酸类物质与钛化合物按照配位摩尔比(2-5)：1制得。
  2. 根据权利要求1所述的水溶性肥料，其特征在于，所述钛化合物包括四价钛化合物。
  3. 根据权利要求2所述的水溶性肥料，其特征在于，硫酸钛、硫酸氧钛、氯化钛、溴化钛、硝酸钛和氯化氧钛中的至少一种。
  4. 根据权利要求1所述的水溶性肥料，其特征在于，所述钛化合物包括硫酸氧钛、硫酸钛中的一种或两种。
  5. 根据权利要求1所述的水溶性肥料，其特征在于，所述葡萄糖酸类物质包括葡萄糖酸、葡萄糖酸盐和葡萄糖酸酯中的至少一种。
  6. 根据权利要求1所述的水溶性肥料，其特征在于，所述葡萄糖酸类物质包括葡萄糖酸、葡萄糖酸内酯、葡萄糖酸钙、葡萄糖酸钠、葡萄糖酸锌、葡萄糖酸亚铁中的一种或多种，优选为葡萄糖酸、葡萄糖酸内酯中的一种或两种。
  7. 根据权利要求1所述的水溶性肥料，其特征在于，所述碱性物质包括有机碱和无机碱中的至少一种。
  8. 根据权利要求7所述的水溶性肥料，其特征在于，所述有机碱包括乙醇胺、二乙醇胺、三乙醇胺、二乙烯三胺、三乙烯四胺、乙二胺、三乙胺、异丙胺中的至少一种。
  9. 根据权利要求7所述的水溶性肥料，其特征在于，所述无机碱包括氨水、氢氧化钾、氢氧化钠、氢氧化锂、氢氧化钙、氢氧化镁和氢氧化钡中的至少一种。
  10. 根据权利要求1所述的水溶性肥料，其特征在于，所述碱性物质包括氢氧化铵、氢氧化钾、氢氧化钙、氢氧化钡、乙醇胺、二乙醇胺、三乙醇胺、二乙烯三胺、三乙烯四胺、乙二胺、三乙胺、异丙胺中的一种或几种混合。
  11. 根据权利要求1-10任一项所述的水溶性肥料，其特征在于，所述水溶性肥料中还包括中量元素、鳌合微量元素和水；
    优选地，水与所述钛化合物的质量比控制在(4-30):1。
  12. 根据权利要求11所述的水溶性肥料，其特征在于，所述螯合微量元素包括锌、镁、铁、锰、铜、钴和钼中的至少一种。
  13. 一种水溶性肥料的制备方法，其特征在于，包括：
    将葡萄糖酸类物质与钛化合物按照配位摩尔比(2-5)：1混合形成葡萄糖酸钛络合物。
  14. 根据权利要求13所述的水溶性肥料的制备方法，其特征在于，还包括：
    将所述葡萄糖酸钛络合物用碱性物质进行中和，并沉降过滤。
  15. 根据权利要求13所述的水溶性肥料的制备方法，其特征在于，所述葡萄糖酸类物质与所述钛化合物混合配位的温度为25-60℃，时间为1-3h
  16. 权利要求1-12任一项所述的水溶性肥料的制备方法，其特征在于，主要包括如下步骤：
    (A)将葡萄糖酸类物质与钛化合物配位25-60℃反应1-3h形成葡萄糖酸钛络合物；
    (B)陈化1-3d后添加碱性物质中和，沉降过滤，添加其他物质即可。
  17. 根据权利要求16所述的水溶性肥料的制备方法，其特征在于，所述步骤(A)中，反应过程中进行搅拌，搅拌速率控制在500-1500rpm之间；
    优选地，将葡萄糖酸类物质25-60℃与水混合形成混合溶液，再进行反应。
  18. 根据权利要求16所述的水溶性肥料的制备方法，其特征在于，所述步骤(B)中，陈化过程中进行搅拌，搅拌速率控制在500-1500rpm之间。
  19. 根据权利要求16所述的水溶性肥料的制备方法，其特征在于，所述步骤(B)中，沉降的时间为24-48h。
  20. 根据权利要求16所述的水溶性肥料的制备方法，其特征在于，所述步骤(B)中，沉降过滤后热浓缩成膏体，粉碎后再添加中量元素、鳌合微量元素。
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