CN104446752A - Copper-based nutrition protective agent containing calcium amino acid chelate and production method of copper-based nutrition protective agent - Google Patents

Copper-based nutrition protective agent containing calcium amino acid chelate and production method of copper-based nutrition protective agent Download PDF

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CN104446752A
CN104446752A CN 201410624544 CN201410624544A CN104446752A CN 104446752 A CN104446752 A CN 104446752A CN 201410624544 CN201410624544 CN 201410624544 CN 201410624544 A CN201410624544 A CN 201410624544A CN 104446752 A CN104446752 A CN 104446752A
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calcium
copper
amino acid
protective agent
chelate
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CN 201410624544
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CN104446752B (en
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张民
路艳艳
杨越超
唐灵云
马金昭
马丽
田晓飞
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山东农业大学
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    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05CNITROGENOUS FERTILISERS
    • C05C11/00Other nitrogenous fertilisers
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05DINORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00Other inorganic fertilisers
    • C05D9/02Other inorganic fertilisers containing trace elements
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES 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
    • C05G3/00Mixtures of one or more fertilisers with materials not having a specially fertilising activity
    • C05G3/0005Further uses of fertiliser, also the form in which it is presented, e.g. by englobed granules
    • C05G3/0047Further uses of fertiliser, also the form in which it is presented, e.g. by englobed granules by incorporating into a matrix

Abstract

The invention relates to a copper-based nutrition protective agent containing calcium amino acid chelate and a production method of the copper-based nutrition protective agent. The calcium amino acid chelate is added based on the copper-based nutrition protective agent; after being sprayed with the copper-based nutrition protective agent, a plant is provided with required calcium element and nitrogen element; calcium is chelated or complexed, so the calcium stably exists in a suspension liquid; after being sprayed, the calcium is easy to absorb, so that the copper-based nutrition protective agent has a sterilization effect and a nutritional effect and can be used for correcting symptoms such as calcium deficiency of crops in order to improve the stress resistance, yield and quality of the crops. The copper-based nutrition protective agent containing the calcium amino acid chelate is high in content of effective components, good in suspension property, high in adhesive force to the surface of the plant, large in uniformity, resistant to rain wash, lasting in medicinal effect and capable of reducing spraying times and remarkably improving the economic, social and ecological benefits.

Description

一种含氨基酸螯合钙的铜基营养保护剂及其生产方法 Copper nutrition protective agent and a method of producing calcium-containing amino acid chelate

(—) (-)

技术领域 FIELD

[0001] 本发明涉及一种含氨基酸螯合钙的铜基营养保护剂及生产方法,属于植物营养与植物保护剂。 [0001] The present invention relates to a method for producing copper nutrition protective agent containing calcium amino acid chelate, belonging to plant nutrition and plant protection agents.

(二) (two)

背景技术 Background technique

[0002] 钙是植物体内重要的必需元素,是植物主要代谢和发育的调控者,它对植物细胞结构、生理功能和果实发育有着重要的作用,对提高果实品质、增加贮藏性等也具有重要的意义。 [0002] Calcium is an important essential element of plants, and plant metabolism is the main regulator of development, its plant cell structure, physiological functions and plays an important role in fruit development, to improve fruit quality, storability, also increasing important meaning. 在土壤中,尤其是石灰性土壤中磷和钙常形成磷酸钙盐沉淀而造成磷的固定,进而降低了磷肥的利用率和钙素的有效性,影响作物的产量、品质和抗性,特别是随着设施栽培的发展,磷肥的大量施用和作物产量的大幅度提高,有关一些作物缺钙的生理性病害或施钙增产的报道逐渐增多。 In the soil, especially in calcareous soils and calcium phosphate calcium phosphate precipitate formed often caused fixed phosphorus, thereby reducing the effectiveness and utilization of calcium phosphate, affecting the yield and quality of crops, and resistant, particularly with the development of cultivation, a substantial increase large number of application of phosphate fertilizer and crop yield, crop calcium deficiency related to a number of physiological diseases or applying calcium increase coverage gradually increased. 氨基酸螯合钙是由多种氨基酸与无机钙盐或氧化物、氢氧化物等通过化学合成反应而生产的一种有机钙类物质,从而大大提高了植物对钙的吸收,具有稳定的化学性能、高的生物效价、无毒等优点,可起到补充钙元素及氨基酸的双重作用。 Calcium amino acid chelate is a variety of amino acids with inorganic calcium salts or oxides, hydroxides produced by a chemical reaction of a synthesis of organic calcium-based material, thus greatly improving the absorption of calcium in plants, has stable chemical properties high biological potency, non-toxic, etc., can play a dual role of calcium and amino acid supplement. 氨基酸作为螯合剂,稳定常数适中,不受土壤pH及其它离子的干扰,其中钙元素由氨基酸螯合,不易被土壤固定,便于作物的吸收。 Amino acid as a chelating agent, moderate stability constants, soil pH, and without the interference of other ions, wherein the amino acid chelated calcium can not easily be fixed to the soil, crop easy to absorb.

[0003] 本发明的优势在于在铜基营养多功能保护剂的基础上,加入植物需要的氨基酸螯合钙,使本产品的有效成分含量更高,提供植物更多的营养。 [0003] The advantage of the present invention is based on a copper-based nutritional multifunctional protective agent, adding calcium amino acid chelate plants need to make the active ingredient content of the product is higher, providing a plant more nutrients. 与ZL201110441906.3(铜基营养多功能叶面肥及其制备方法)的主要区别是本发明加入了氨基酸螯合钙,更易被植物叶片吸收,提供植物所需要的氮元素和钙元素,减少和矫正植物的缺钙症状,提高产品的产量和品质。 And ZL201110441906.3 (copper multifunctional foliar nutrients and preparation method) of the present invention, the main difference is the addition of calcium amino acid chelate, plant leaves more easily absorbed, calcium and nitrogen to provide the desired plant, and reduced symptoms of calcium deficiency correction plant, improving yield and quality of products.

(三) (three)

发明内容 SUMMARY

[0004] 为解决上述问题,本发明提供了一种含氨基酸螯合钙的铜基营养保护剂及生产方法,是采用氢氧化铜胶体,添加氨基酸螯合钙及不同比例的分散剂、润湿剂、抗絮凝剂等,并经过砂磨机工艺制备含氨基酸的铜基营养保护剂悬浮剂产品,或经过闪蒸干燥机工艺制备含氨基酸螯合钙的铜基营养保护剂可湿性粉状产品,或经过喷雾干燥塔工艺制备含氨基酸螯合钙的铜基营养保护剂干悬浮剂产品。 [0004] In order to solve the above problems, the present invention provides a method for producing copper nutrition protective agent containing calcium amino acid chelate, is the use of colloidal hydroxide, calcium amino acid chelate and adding different proportions of dispersant, wetting agent, anti-flocculant and preparation process of a sand mill after amino acid-containing copper-based nutritional product protection agent, suspending agent, or after the process of flash dryer prepared containing calcium amino acid chelate copper-based nutritional product protection wettable powder , or can be prepared through the process of spray-drying tower containing calcium amino acid chelate copper-based protective agent nutritional dry flowable products. 这种产品具有营养和杀菌双重功能。 This product has a dual function of nutrition and sterilization.

[0005] 一种含氨基酸螯合钙的铜基营养保护剂,以粉状产品的干基计(重量比):含有氨基酸螯合钙40-46% ;其余成分的含量为:氢氧化铜胶体46-52%、助剂为分散剂D-425烷基萘磺酸缩聚物钠盐3%、分散剂SPR磺酸盐类和磷酸酯盐类阴离子表面活性剂的混合物2%、润湿剂EFW烷基萘磺酸盐和阴离子润湿剂的混合物2%和抗絮凝剂DC7磺酸盐类和磷酸酯盐类阴离子表面活性剂的混合物1% ;各组分含量百分比之和为100% ; [0005] The protecting agent containing copper-based nutritional amino acid chelated calcium, pulverulent product on a dry basis (weight ratio): calcium amino acid chelate comprising 40-46%; the content of the remaining ingredients of: cupric hydroxide colloid 46-52%, dispersant aids D-425 alkylnaphthalene sulfonic acid sodium salt 3% polycondensate, dispersant mixture SPR sulfonates and phosphate ester anionic surfactant 2%, wetting agent EFW alkyl naphthalene sulfonate, and a mixture of anionic wetting agent and 2% of a mixture of deflocculating DC7 sulfonates and phosphate ester anionic surfactant 1%; the percentage content of each component is 100%;

[0006] 所述的氨基酸螯合钙是复合氨基酸螯合钙、谷氨酸螯合钙或天冬氨酸螯合钙。 Calcium amino acid chelate [0006] The compound is calcium amino acid chelate, glutamic acid or aspartic acid chelated calcium chelate calcium.

[0007] 所述的氨基酸螯合钙的制备方法为:在75±5°C的恒温水浴中将氨基酸和氢氧化钙溶于水中,调节pH为7.5±0.5,使其充分溶解,反应时间为60min-90min,所述氨基酸和氢氧化钙的摩尔比为2:1。 Preparation of calcium amino acid chelate [0007] according to: 75 ± 5 ° C in a constant temperature water bath of calcium hydroxide and amino acids dissolved in water, adjusted to pH 7.5 ± 0.5, sufficiently dissolved, the reaction time is 60min-90min, the amino acid and calcium hydroxide is a molar ratio of 2: 1.

[0008] 本发明制备的铜基营养保护剂产品可以是悬浮剂、干悬浮剂或可湿性粉剂产品。 [0008] The copper-based protective agent nutritional product of the present invention may be prepared in suspension, wettable powder or dry flowable products. 使用时,该保护剂产品与水按重量比1:500-1000混合,混合后悬液的pH值为7.0-8.0。 In use, the protective agent is a product with water in a weight ratio 1: 500-1000 mixing, after mixing the suspension pH value of 7.0-8.0.

[0009] 一种含氨基酸螯合钙的铜基营养保护剂,其制作方法如下: [0009] The protecting agent containing copper nutritional amino acid chelated calcium, its production method is as follows:

[0010] (I)将一定质量的硫酸铜缓慢加入到一定体积(硫酸铜与氨水的质量与体积比为1.2-1.3)的氨水中,不停搅拌使其完全溶解,形成铜的配位络合物溶液,反应时间为20-30min ;然后以喷入雾滴的形式加入一定体积(硫酸铜质量与氢氧化钠溶液体积比为1.6-1.7)浓度为5mol/L的氢氧化钠溶液,时间为70_90min,使生成的氢氧化铜胶体平均粒径小于5 μ m ;之后用自来水洗涤氢氧化铜胶体悬液3-4次,使其pH值达到7.5±0.5,经静置或离心除去上清液得到氢氧化铜胶体悬液;后经风干或在温度低于45°C的烘箱中烘干得到氢氧化铜胶体粉末。 [0010] (I) to a mass of copper sulfate was slowly added to a volume (of copper sulfate and ammonia mass to volume ratio of 1.2 to 1.3) aqueous ammonia, stirring constantly and completely dissolved to form a coordination complex of copper polymer solution, the reaction time is 20-30min; then added in the form of droplets sprayed into a volume (mass of copper sulfate and sodium hydroxide solution volume ratio of 1.6-1.7) at a concentration of 5mol / L sodium hydroxide solution, time is 70_90min, that the average particle diameter of the colloidal cupric hydroxide generated is less than 5 μ m; after the suspension washed with water 3-4 times hydroxide colloid, so that a pH of 7.5 ± 0.5, the supernatant was removed by centrifugation or standing hydroxide solution to obtain a colloidal suspension; after air drying or drying in an oven at a temperature below 45 ° C the obtained colloidal copper hydroxide powder.

[0011] (2)在75±5°C的恒温水浴中将氨基酸和氢氧化钙溶于水中,调节pH为7.5 + 0.5,使其充分溶解,反应时间为60min-90min,所述氨基酸和氢氧化钙的摩尔比为2:1,经离心、 [0011] (2) at 75 ± 5 ° C constant temperature water bath of calcium hydroxide and amino acids dissolved in water, adjusted to pH 7.5 + 0.5, sufficiently dissolved, the reaction time is 60min-90min, the amino acid and hydrogen the molar ratio of calcium oxide to 2: 1, by centrifugation,

纯化得到氨基酸螯合钙液体产品。 Calcium amino acid chelate to give a liquid product.

[0012] (3)在计算出精确配比的基础上,向上述(I)中制备的氢氧化铜胶体粉末中加入配方助剂分散剂、润湿剂、抗絮凝剂等。 [0012] (3) On the basis of the calculated exact proportions, adding the dispersant formulation aids, wetting agents, the cupric hydroxide colloid deflocculant powders prepared (I) in the above. 再加入上述⑵中制备的氨基酸螯合钙溶液。 Was added calcium amino acid chelate in the solution prepared above ⑵.

[0013] (4)经砂磨机充分研磨分散后得到含氨基酸螯合钙的铜基营养保护剂悬浮剂产品O [0013] (4) by a sand mill to obtain sufficient grinding calcium amino acid chelate-containing copper-based nutritional product O-protecting agent suspension after the dispersion

[0014] (5)或在上述(3)的基础上,将原料经闪蒸干燥机干燥后得到含氨基酸螯合钙的铜基营养保护剂可湿性粉剂产品。 [0014] (5) or on the basis of the above (3), the material was flash dryer and dried to give a copper-based wettable powder nutritional products containing protective agent calcium amino acid chelate.

[0015] (6)或在上述(3)的基础上,将原料经过喷雾干燥塔得到含氨基酸螯合钙的铜基营养保护剂干悬浮剂产品。 [0015] (6) or on the basis of the above (3), the material obtained after spray-drying tower dry flowable copper-based nutritional product containing protective agent calcium amino acid chelate.

[0016] 本发明的要点是: [0016] The gist of the invention are:

[0017] 要点之一是:改变波尔多液制剂传统配方,使用氢氧化铵和氢氧化钠取代传统的氢氧化钙,避免了钙与硫酸根离子反应生成硫酸钙沉淀的问题。 One [0017] The point is: Bordeaux mixture formulation changes traditional recipes, sodium hydroxide, ammonium hydroxide and calcium hydroxide to replace the traditional, avoids the problems roots calcium sulfate ions precipitate calcium sulfate reaction. 这样可以减少分散剂、润湿剂等助剂的用量,大幅度降低生产成本。 This reduces dispersants, wetting agents amounts of processing aids, significantly reduce production costs.

[0018] 要点之二是:将一定质量的硫酸铜缓慢加入一定体积的氨水中,不停地搅拌使其完全溶解形成铜的配位络合物,反应时间控制在20-30分钟。 [0018] The two points are: a certain quality of copper sulfate was slowly added to a volume of aqueous ammonia, stirred constantly to complete dissolution of the copper coordination complex is formed, the reaction time is controlled at 20-30 minutes. 氢氧化钠溶液以雾滴形式喷入,通过控制氢氧化钠溶液的浓度和喷雾速度,来控制氢氧化铜胶体悬液的粒度,使其平均粒径小于5 μ m。 Sodium hydroxide solution was injected in the form of droplets, by controlling the concentration of sodium hydroxide solution and the spray rate to control the particle size of copper hydroxide colloidal suspension, so that the mean particle size of less than 5 μ m. 在配制氢氧化铜胶体悬液过程结束后,用自来水洗涤反应产物3-4次,使其pH值达到7.5±0.5。 After the end of the preparation hydroxide colloid suspension process, the reaction product was washed 3-4 times with tap water, so that a pH of 7.5 ± 0.5. 该工艺流程所需的生产设备简单,反应用时短,可控制在1.5-2小时。 The required process equipment is simple, short reaction time, can be controlled in 1.5-2 hours.

[0019] 要点之三是:在计算出精确配比的基础上,向上述氢氧化铜胶体粉末中加入一定量的氨基酸螯合钙及各种助剂,不仅可以为植物生长提供易于吸收的钙素营养,而且在水中易分散悬浮性好,喷在植物表面后粘着性强,耐雨水冲刷,不仅使用方便,操作简单易行,而且可以减少喷药次数和用量。 [0019] The third point is: the calculated ratio on the basis of precise, adding an amount of amino acid chelated calcium and various additives to the colloid of copper hydroxide powder, calcium may be provided not only easy to absorb for plant growth nutrition, easily dispersible in water and good suspension, spraying plant surfaces after adhesion, resistance to rain erosion, is not only easy to use, simple operation, and can reduce the amount and frequency of spraying.

[0020] 本发明的效果: [0020] The effect of the invention:

[0021] 本发明在现有的铜基营养保护剂的基础上,采用优化的制备技术和生产设备,生产出价格低、效果好的含氨基酸螯合钙的铜基营养保护剂产品。 [0021] The present invention is based on the existing copper-based protective agent on Nutrition, optimized preparation techniques and production equipment to produce low cost, good effect protecting agent containing copper-based nutritional calcium amino acid chelate product. 这种铜基营养保护剂产品不仅具有杀菌和拟菌作用,而且能够为植物的生长提供氮和钙元素,使用方便,省时省工,减少了资源的浪费和污染,具有良好的经济和社会效益。 This copper-based nutritional products are not only protecting agent with bactericidal and bacteriostatic proposed, but also to provide nitrogen and calcium for the growth of plants, easy to use, saving labor, reducing waste and pollution of resources, with good economic and social benefit.

[0022] 本发明生产的产品与以往的铜基营养多功能叶面肥产品相比,由于加入了氨基酸螯合钙,这种螯合态的钙素更易于被植物吸收,更有效的矫正作物的缺钙症状,同时还可为作物提供直接吸收利用的氨基酸有机态氮,促进受病害或逆境胁迫的叶片正常生理功能的恢复,提高作物抗逆性、产量和品质。 [0022] The products of the present invention as compared to conventional copper-based fertilizer nutrients multifunction product, since the addition of the calcium amino acid chelate, this state of calcium chelate is more readily absorbed by plants, more efficient crop correction calcium deficiency symptoms, while also providing for the amino acid directly absorbed by plant organic nitrogen, or disease by promoting the recovery blade Stress normal physiological function, improve the crop resistance, yield and quality. 在苹果、葡萄、番茄、辣椒等作物上喷施本产品的试验结果表明,不仅显著减少了病害的发生和增加了产量,而且显著提高了果实中的钙含量、糖酸比、维生素C含量等,增加了耐储性和外观品质。 On apples, grapes, tomatoes, peppers and other crops sprayed with the test results of this product it shows that not only significantly reduced the incidence and increased production of disease, but also significantly increased the calcium content in the fruit, sugar acid ratio, vitamin C content, etc. , increasing the appearance quality and storability. 因此,本发明产品具有以往铜基营养保护剂显著不同的优势和特点。 Accordingly, the present invention is significantly different from the conventional product has advantages and characteristics of the copper-based nutrition protective agent.

(四) (four)

附图说明 BRIEF DESCRIPTION

[0023] 图1含氨基酸螯合钙的铜基营养保护剂产品生产工艺流程图。 [0023] FIG 1 copper production process nutrition protective agent containing calcium amino acid chelate of FIG.

[0024] 图中:1、称取一定质量的硫酸铜;2、将其缓慢加入到一定体积的氨水中,在不断搅拌的条件下,使其充分反应;3、将一定浓度和一定体积的氢氧化钠溶液以雾滴的形式喷入到反应物2中;4、洗涤氢氧化铜胶体三至四次,使其pH值达到7.5±0.5为止,经静置或离心除去上清液,得到氢氧化铜胶体悬液;5、逐渐向上述氢氧化铜胶体悬液中加入适量的氨基酸螯合钙液体;6、逐渐向5中加入适量的分散剂、润湿剂、抗絮凝剂等助剂,并充分搅拌;7、将混合物经研磨、或经喷雾干燥、或经闪蒸干燥得到含氨基酸螯合钙的铜基营养保护剂产品;8、经检验合格后即包装为成品。 [0024] FIG: 1. Weigh a certain quality of copper sulfate; 2, which was slowly added to a volume of ammonia, under conditions of continuous stirring, the reaction sufficiently; 3, a certain concentration and volume of sodium hydroxide solution in the form of droplets sprayed into the reaction 2; 4, hydroxide colloid was washed three to four times, so that the pH value reached 7.5 ± 0.5, the supernatant was removed by centrifugation or standing, to give hydroxide colloidal suspension; 5, was gradually added to the appropriate amount of copper hydroxide colloid suspension liquid calcium amino acid chelate; 6, was gradually added an appropriate amount of 5 to dispersants, wetting agents, adjuvants deflocculant and stir; 7, and the mixture was milled, spray drying, or, dried or flashed-protecting agent to obtain copper-based nutritional product containing calcium amino acid chelate; 8 passed the test after packaging for the finished product.

(五) (Fives)

具体实施方式 Detailed ways

[0025] 下面结合具体实施例对本发明作进一步阐述,但本发明并不限于以下实施例。 [0025] The following embodiments in conjunction with specific embodiments of the present invention is further illustrated, but the present invention is not limited to the following embodiments. 所述方法如无特别说明均为常规方法。 The method according to a conventional method are not particularly described. 所述材料如无特别说明均能从公开商业途径而得。 As the material is not particularly described can obtained from commercial sources disclosed.

[0026] 实施例1: [0026] Example 1:

[0027] 称取5kg五水硫酸铜⑴,将其缓慢加入到6.5L浓度为25%的氨水中,不停搅拌使其完全溶解,形成铜的配位络合物溶液,反应时间为20-30min(2);然后以喷入雾滴的形式加入5mol/L氢氧化钠溶液10L,时间为70_90min,使生成的氢氧化铜胶体平均粒径小于5ym(3);之后用自来水洗涤氢氧化铜胶体悬液3-4次,使其pH值达到7.5±0.5,经静置或离心除去上清液得到氢氧化铜胶体悬液(4);经自然风干或在温度低于45°C的烘箱中烘干得到氢氧化铜胶体粉末;在75±51:恒温水浴中,将140g谷氨酸和35g氢氧化钙溶于350mL水中,调节pH为7.5±0.5,使其充分溶解,反应时间为60min-90min,经离心、纯化得到谷氨酸螯合钙液体产品;称取氢氧化铜胶体粉末300g,向其中加入上述谷氨酸螯合钙溶液(5);加入分散剂D-425 (烷基萘磺酸缩聚物钠盐)15g、分散剂SPR(磺酸盐类和磷酸酯盐类阴离子表面活性剂的混合物 [0027] Weigh 5kg sulfate pentahydrate ⑴, which was slowly added to 6.5L of a 25% aqueous ammonia, stirring constantly and completely dissolved to form a solution of copper coordination complex, the reaction time is 20 30min (2); then added in the form of droplets sprayed into 5mol / L sodium hydroxide solution 10L, time 70_90min, that the average particle diameter of the colloidal hydroxide of less than 5ym generated (3); copper hydroxide then washed with tap water 3-4 times a colloidal suspension, so that a pH of 7.5 ± 0.5, the supernatant was removed to give a colloidal suspension of copper hydroxide (4) by standing or centrifugation; oven at a temperature below 45 ° C by dry naturally or drying the obtained colloidal copper hydroxide powder; at 75 ± 51: constant temperature water bath, a 140g glutamate and 35g of calcium hydroxide was dissolved in 350mL of water, adjusted to pH 7.5 ± 0.5, sufficiently dissolved, the reaction time was 60min -90min, by centrifugation, to give a liquid product chelate calcium glutamate; colloid of copper hydroxide powder was weighed 300g, was added to the above solution chelate calcium glutamate (5); dispersant D-425 (alkyl 15g, a mixture of the sodium salt of naphthalenesulfonic acid polycondensate) the SPR dispersant (anionic sulfonates and phosphate ester surfactant )10g、润湿剂EFW(烷基萘磺酸盐和阴离子润湿剂的混合物)1g和抗絮凝剂DC7 (磺酸盐类和磷酸酯盐类阴离子表面活性剂的混合物)5g(6);将混合物经砂磨机研磨分散;用500mL水洗涤得到含氨基酸的铜基营养保护剂悬浮剂产品(7) (8)。 ) 10g, EFW wetting agent (a mixture of alkyl naphthalene sulfonate and anionic wetting agents) 1g and deflocculating DC7 (a mixture of anionic surfactants and phosphate ester sulfonates) 5g (6); the mixture was dispersed by a sand mill; obtained amino acid-containing nutritional copper washed with 500mL water suspension protecting agent (7) (8). 其中,氢氧化铜含量占产品干基重60%。 Wherein the hydroxide content of 60% dry weight of the product.

[0028] 所得悬浮剂中:按产品干基含Cu%= 39.18% ;含Ca%= 3.78% ;此悬浮剂产品在加水后喷施浓度为1:500-1000时的悬液pH为7.0-8.0。 [0028] The resulting suspension: Press dry product containing Cu% = 39.18%; containing Ca% = 3.78%; this product in suspension After adding water spraying concentration of 1: when the suspension is 7.0 to pH 500-1000 8.0.

[0029] 实施例2: [0029] Example 2:

[0030] 称取5kg五水硫酸铜⑴,将其缓慢加入到6.5L浓度为25%的氨水中,不停搅拌使其完全溶解,形成铜的配位络合物溶液,反应时间为20-30min(2);然后以喷入雾滴的形式加入5mol/L氢氧化钠溶液10L,时间为70_90min,使生成的氢氧化铜胶体平均粒径小于5μηι(3);之后用自来水洗涤氢氧化铜胶体悬液3-4次,使其pH值达到7.5±0.5,经静置或离心除去上清液得到氢氧化铜胶体悬液(4);经自然风干或在温度低于45°C的烘箱中烘干得到氢氧化铜胶体粉末;在75±5°C恒温水浴中,将140g谷氨酸和35g氢氧化钙溶于350mL水中,调节pH为7.5±0.5,使其充分溶解,反应时间为60min_90min,经离心、纯化、干燥得到谷氨酸螯合钙粉状产品;称取氢氧化铜胶体粉末300g,向其中加入上述谷氨酸螯合钙(5);加入分散剂D-425(烷基萘磺酸缩聚物钠盐)15g、分散剂SPR (磺酸盐类和磷酸酯盐类阴离子表面活性剂的 [0030] Weigh 5kg sulfate pentahydrate ⑴, which was slowly added to 6.5L of a 25% aqueous ammonia, stirring constantly and completely dissolved to form a solution of copper coordination complex, the reaction time is 20 30min (2); then added in the form of droplets sprayed into 5mol / L sodium hydroxide solution 10L, time 70_90min, copper hydroxide colloid so generated is less than the average particle diameter 5μηι (3); copper hydroxide then washed with tap water 3-4 times a colloidal suspension, so that a pH of 7.5 ± 0.5, the supernatant was removed to give a colloidal suspension of copper hydroxide (4) by standing or centrifugation; oven at a temperature below 45 ° C by dry naturally or drying the obtained colloidal copper hydroxide powder; at 75 ± 5 ° C water bath, the glutamic acid and 140g of calcium hydroxide was dissolved in 350mL 35g water, adjusted to pH 7.5 ± 0.5, sufficiently dissolved, the reaction time is 60min_90min, centrifugation, purified, and dried to obtain a powdery product chelated calcium glutamate; colloid of copper hydroxide powder was weighed 300g, was added to the above-described chelate calcium glutamate (5); dispersant D-425 (alkyl polycondensates of naphthalene sulfonic acid sodium salt) 15g, the SPR dispersant (anionic sulfonates and phosphate ester surfactant 合物)10g、润湿剂EFW(烷基萘磺酸盐和阴离子润湿剂的混合物)1g和抗絮凝剂DC7 (磺酸盐类和磷酸酯盐类阴离子表面活性剂的混合物)5g (6);将混合物经闪蒸干燥机闪蒸搅拌20min得到含谷氨酸螯合钙的铜基营养保护剂可湿性粉剂产品(7) (8)。 Compound) 10g, EFW wetting agent (a mixture of alkyl naphthalene sulfonate and anionic wetting agents) 1g and deflocculating DC7 (a mixture of anionic sulfonates and phosphate ester surfactant) 5g (6 ); the mixture was stirred for 20min to give flash dryer, flash glutamic acid-containing calcium chelating agent is a copper-based protective nutrients wettable powder product (7) (8). 其中,氢氧化铜含量占产品干基重60%。 Wherein the hydroxide content of 60% dry weight of the product.

[0031] 所得可湿性粉剂中:含Cu%= 39.18% ;含Ca%= 3.78% ;此可湿性粉剂产品在加水后喷施浓度为1:500-1000时的悬液pH为7.0-8.0。 [0031] Wettable powders are obtained: containing Cu% = 39.18%; containing Ca% = 3.78%; This wettable powder product after spraying with water at a concentration of 1: when the suspension is 7.0-8.0 pH 500-1000.

[0032] 实施例3: [0032] Example 3:

[0033] 加入过程如实施例1,但是在加入的添加物上有所区别。 [0033] The procedure as in Example 1 was added, but differ in the additive added. 如:利用天冬氨酸和氢氧化钙制备天冬氨酸螯合钙液体产品350mL,其他过程同实例I。 Such as: the use of calcium hydroxide was prepared and aspartic acid chelated calcium aspartate liquid product 350mL, with examples of other processes I.

[0034] 所得悬浮剂中:按产品干基含Cu%= 39.18% ;含Ca%= 3.78% ;此悬浮剂产品在加水后喷施浓度为1:500-1000时的悬液pH为7.0-8.0。 [0034] The resulting suspension: Press dry product containing Cu% = 39.18%; containing Ca% = 3.78%; this product in suspension After adding water spraying concentration of 1: when the suspension is 7.0 to pH 500-1000 8.0.

[0035] 实施例4: [0035] Example 4:

[0036] 加入过程如实施例2,但在加入的添加物上有所区别。 [0036] Add procedure as in Example 2, but differ in the additive added. 如:利用天冬氨酸和氢氧化钙制备天冬氨酸螯合钙160g,其它过程同实例2。 Such as: the use of aspartic acid and calcium hydroxide prepared aspartate chelated calcium 160g, other procedures as in Example 2.

[0037] 所得可湿性粉剂中:含Cu%= 39.18% ;含Ca%= 3.78% ;此粉状产品在加水后喷施浓度为1:500-1000时的悬液pH为7.0-8.0。 [0037] Wettable powders are obtained: containing Cu% = 39.18%; containing Ca% = 3.78%; this powdery product after spraying with water at a concentration of 1: when the suspension is 7.0-8.0 pH 500-1000.

[0038] 实施例5: [0038] Example 5:

[0039] 加入过程如实施例1,但是在加入的添加物上有所区别。 [0039] The procedure as in Example 1 was added, but differ in the additive added. 如:利用复合氨基酸和氢氧化钙制备复合氨基酸螯合钙液体产品350mL,其它过程同实例I。 Such as: the amino acid compound and the use of calcium hydroxide, calcium amino acid chelate complex prepared liquid product 350mL, with examples of other processes I.

[0040] 所得悬浮剂中:按产品干基含Cu%= 39.18% ;含Ca%= 3.78% ;此悬浮剂产品在加水后喷施浓度为1:500-1000时的悬液pH为7.0-8.0。 [0040] The resulting suspension: Press dry product containing Cu% = 39.18%; containing Ca% = 3.78%; this product in suspension After adding water spraying concentration of 1: when the suspension is 7.0 to pH 500-1000 8.0.

[0041] 实施例6: [0041] Example 6:

[0042] 加入过程如实施例2,但在加入的添加物上有所区别。 [0042] Add procedure as in Example 2, but differ in the additive added. 如:利用复合氨基酸和氢氧化钙制备复合氨基酸螯合钙160g,其它过程同实例2。 Such as: the amino acid compound and the use of calcium hydroxide, calcium amino acid chelate preparation of compound 160g, other procedures as in Example 2.

[0043] 所得可湿性粉剂中:含Cu% = 39.18% ;含Ca% = 3.78% ;此粉状产品在加水后喷施浓度为1:500-1000时的悬液pH为7.0-8.0。 [0043] Wettable powders are obtained: containing Cu% = 39.18%; containing Ca% = 3.78%; this powdery product after spraying with water at a concentration of 1: when the suspension is 7.0-8.0 pH 500-1000.

Claims (2)

1.一种含氨基酸螯合钙的铜基营养保护剂,其特征在于,以其粉状产品的干基计:含有重量比40-46%的氨基酸螯合钙; 所述的氨基酸螯合钙的制备方法为:在75±5°C的恒温水浴中将氨基酸和氢氧化钙溶于水中,调节pH为7.5±0.5,使其充分溶解,反应60min-90min,所述氨基酸和氢氧化钙的摩尔比为2:1 ;所述的氨基酸螯合钙是复合氨基酸螯合钙、谷氨酸螯合钙或天冬氨酸螯合钙。 A protective agent containing copper-based nutritional calcium amino acid chelate, characterized in that, in its powdered product a dry basis: containing ratio of 40-46% by weight of calcium amino acid chelate; the calcium amino acid chelate methods of preparation: at a constant temperature 75 ± 5 ° C in the water bath amino acid and calcium hydroxide dissolved in water, adjusted to pH 7.5 ± 0.5, sufficiently dissolved, the reaction 60min-90min, the amino acid and calcium hydroxide a molar ratio of 2: 1; the amino acid chelated calcium compound is calcium amino acid chelate, glutamic acid or aspartic acid chelated calcium chelate calcium.
2.如权利要求1所述的一种含氨基酸螯合钙的铜基营养保护剂,其特征在于,以其粉状产品的干基以重量比计:其余组分为氢氧化铜胶体46-52%、助剂为分散剂D-425烷基萘磺酸缩聚物钠盐3%、分散剂SPR磺酸盐类和磷酸酯盐类阴离子表面活性剂的混合物2%、润湿剂EFW烷基萘磺酸盐和阴离子润湿剂的混合物2%和抗絮凝剂DC7磺酸盐类和磷酸酯盐类阴离子表面活性剂的混合物I%。 2. The acid of claim 1 containing copper chelate calcium nutrition protective agent as claimed in claim, characterized in that its dry powdered products weight ratio: copper hydroxide colloid component remaining 46- 52%, dispersant aids D-425 alkylnaphthalene sulfonic acid sodium salt 3% polycondensate, dispersant mixture SPR sulfonates and phosphate ester anionic surfactant 2% wetting agent EFW alkyl anionic naphthalene sulphonate wetting agent and 2% I, and a mixture of deflocculating DC7 sulfonates and phosphate ester anionic surfactant%.
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