WO2006131056A1 - Fertilizing method for agricultural irrigation - Google Patents

Fertilizing method for agricultural irrigation Download PDF

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Publication number
WO2006131056A1
WO2006131056A1 PCT/CN2006/001167 CN2006001167W WO2006131056A1 WO 2006131056 A1 WO2006131056 A1 WO 2006131056A1 CN 2006001167 W CN2006001167 W CN 2006001167W WO 2006131056 A1 WO2006131056 A1 WO 2006131056A1
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WO
WIPO (PCT)
Prior art keywords
fertilizer
water
activator
phosphate
acid
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PCT/CN2006/001167
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French (fr)
Chinese (zh)
Inventor
Diping Li
Xiucheng Xu
Haobin Wang
Dongguang Li
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Higheffi Tech.Ltd.Corp.Beijing
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Application filed by Higheffi Tech.Ltd.Corp.Beijing filed Critical Higheffi Tech.Ltd.Corp.Beijing
Publication of WO2006131056A1 publication Critical patent/WO2006131056A1/en
Priority to IL187811A priority Critical patent/IL187811A/en

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01C—PLANTING; SOWING; FERTILISING
    • A01C23/00—Distributing devices specially adapted for liquid manure or other fertilising liquid, including ammonia, e.g. transport tanks or sprinkling wagons
    • A01C23/04—Distributing under pressure; Distributing mud; Adaptation of watering systems for fertilising-liquids
    • A01C23/042—Adding fertiliser to watering systems
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures

Definitions

  • the present invention relates to an agricultural production technique, and more particularly to an agricultural irrigation and fertilization method.
  • the fertigation methods used in various countries and regions of the world require the use of appropriate liquid or fully water-soluble solid fertilizers.
  • the nitrogen and potassium fertilizers currently used in agriculture are mainly water-soluble, and the fertilization method is applied. It should be simple and easy to implement, and there are no serious problems.
  • Phosphate fertilizers such as industrial grade, food grade ammonium phosphate, potassium dihydrogen phosphate, etc., are also fully water soluble, so it should be feasible to use fertigation methods.
  • most of the phosphate fertilizers currently used in agriculture are partially water-soluble or water-insoluble, and it is difficult to use fertigation methods to implement fertigation of crops.
  • Some fertilizers containing medium and trace elements are also water-insoluble.
  • the object of the present invention is to develop an agricultural fertigation method, which can not only continuously provide phosphorus for crops, but also fully defluorinate the fertilizer effect of the water-insoluble phosphate fertilizer, improve the utilization rate of the fertilizer, and provide various medium and trace elements. And enhance the ability of crops to resist viruses and lodging.
  • fertigation refers to an irrigation method that uses a fully water-soluble solid or liquid fertilizer to provide the required nutrients to crops through a micro-irrigation system, which can be used together with irrigation water. Enter the field to increase the yield of irrigated crops with the least amount of nutrients.
  • the above-mentioned irrigation and fertilization, using an irrigation system can achieve high precision in terms of fertilization amount, fertilization time and fertilization space, and is a combination of precise fertilization and precise irrigation.
  • the method of the present invention mainly uses water-insoluble phosphate fertilizer granules and water-insoluble fertilizers or mineral granules containing medium and micro-elements as raw materials.
  • the water-insoluble phosphate fertilizer refers to the solubility of the phosphate fertilizer in the water at room temperature and atmospheric pressure is less than or equal to
  • the water-insoluble medium and trace element fertilizer or mineral means that the solubility of the fertilizer or mineral containing the medium or trace element in water at room temperature and atmospheric pressure is less than or equal to 100 mg/kg, preferably less than or equal to 50 mg/kg, more preferably less than or equal to 20 mg/kg.
  • the water-insoluble phosphate fertilizer particles are selected from the group consisting of phosphate rock powder, acid phosphate fertilizer and hot phosphate fertilizer.
  • the phosphate rock powder is a phosphate fertilizer directly pulverized from phosphate rock.
  • the phosphorus-containing compound in phosphate rock is mainly composed of fluoroapatite.
  • Phosphate rock powder is a poorly soluble phosphate fertilizer containing 8% of total phosphorus. Under the ⁇ soluble phosphorus, the fertilizer is slow and long lasting.
  • the acid phosphate fertilizer is obtained by treating phosphate rock powder with an acid such as sulfuric acid, nitric acid or hydrochloric acid. Precipitated calcium phosphate is included in the acid phosphate fertilizer.
  • the precipitated calcium phosphate can be obtained by reacting phosphate rock with sulfuric acid, nitric acid, hydrochloric acid or the like to form phosphoric acid, and then precipitating with lime milk.
  • the hot phosphate fertilizer is a high-temperature decomposing phosphate ore produced by burning electric power or fuel
  • the prepared phosphate fertilizer mainly includes defluorinated phosphate fertilizer, sintered calcium nano-phosphorus fertilizer, calcium metaphosphate, steel slag phosphate fertilizer, calcium magnesium phosphate fertilizer.
  • Defluorinated phosphate fertilizer is made by reacting fluoroapatite with water vapor at high temperature (1500 ° C). The response is as follows:
  • the phosphorus content of defluorinated phosphate fertilizer (P 2 0 5 ) is about 19-38%, which belongs to the ⁇ soluble phosphate fertilizer.
  • Sintered calcium, sodium and phosphate fertilizers are formed by sintering phosphate rock with sodium carbonate and silica sand at high temperature (1250 ° C). The product contains P 2 0 5 28-30%.
  • Calcium metaphosphate is prepared by contacting phosphate rock powder with P 2 0 5 gas at 950 ° C. The reaction is as follows:
  • Metaphosphate glassy yellow crystals, phosphorus (? 205) of up to 60% -70%, may be soluble in neutral ammonium citrate solution.
  • Steel slag phosphate fertilizer is a by-product of the steelmaking industry. It is dark brown powder and strongly alkaline.
  • the form of phosphorus is tetracalcium phosphate (Ca 4 P 2 0 9 ) and double salt of calcium silicate and calcium silicate (Ca 4 P 2 0 9 -CaSi0 3 ), both are soluble in citric acid and ammonium citrate solutions.
  • Calcium, magnesium and phosphate fertilizers are based on phosphate rock, flux (serpentine, olivine, etc.) and fuel (anthracite, coke, etc.) and heated to 1450.
  • the product obtained by drying and grinding is usually dark gray, grayish green or dark green powder, and has good physical properties. Non-hygroscopic, non-caking, alkaline reaction, but not corrosive. It is a glass body composed mainly of phosphorus, silicon, calcium and magnesium. It has no clear molecular formula and molecular weight.
  • the product contains P 2 0 5 14-18% and is soluble in 2% citric acid.
  • Calcium magnesium phosphate fertilizer also contains MgO 8-20%, CaO 25-40%, Si0 2 22-32%, FeO 0.5-3% and the like.
  • the medium trace elements are calcium, magnesium, sulfur, boron, molybdenum, zinc, manganese, iron, copper and nickel, as well as beneficial element silicon and the like.
  • Calcium is a structural component of the cell wall, which has a certain effect on the synthesis of proteins, and is also a cofactor for some enzymatic reactions, and has a special effect on regulating the physiological balance of the medium. Therefore, when the crop is deficient in calcium, the plant is short and the root system is poorly developed. The cell wall is deficient in calcium, easily invaded by viruses, and will rot and die in severe cases;
  • Magnesium is a constituent element of chlorophyll, an activator of many enzymes, and promotes the synthesis of fat as well as the metabolism of nitrogen.
  • the reticular tissue of the leaves is yellow or white, and even becomes brown or even necrotic.
  • Magnesium-deficient pasture can cause convulsions in livestock.
  • Sulfur is a constituent of proteins and enzymes and is also found in certain physiologically active substances and is an integral part of the nitrogenase system. When the crop is deficient in sulfur, the growth is severely impeded and the leaves are chlorotic or yellow.
  • silicon is not an essential nutrient for crops, the lack of silicon in crops is prone to lodging and viruses invade surface cells. Therefore, silicon is an important beneficial element for many crops, especially silicon-rich rice, sugar cane, and bamboo.
  • Trace elements are often part of enzymes or coenzymes in plants and have strong specificity. They are indispensable and irreplaceable for crop growth and development.
  • the fertilizer used in the present invention is accompanied by a medium or trace element, or is additionally formulated with water.
  • a soluble fertilizer or mineral containing trace elements is additionally formulated with water.
  • the water-insoluble medium or trace element-containing fertilizer or mineral is one or more fertilizers or minerals selected from the group consisting of water-insoluble calcium, magnesium, sulfur, boron, molybdenum, zinc, manganese, iron or copper.
  • the water-insoluble calcium fertilizer or mineral is, for example, calcium sulfate, phosphogypsum, industrial waste, such as steel industry slag.
  • the water-insoluble magnesium fertilizer or mineral is, for example, magnesite, dolomite.
  • the water-insoluble sulfur fertilizer or mineral is, for example, calcium sulfate, zinc sulfide ore, pyrite, phosphogypsum, sulfur.
  • the water-insoluble boron fertilizer or mineral is, for example, a boron magnesium ore, a boron mud.
  • the water-insoluble molybdenum fertilizer or mineral is, for example, molybdenum slag.
  • the water-insoluble zinc fertilizer or mineral is, for example, zinc oxide or zinc sulfide.
  • the water-insoluble manganese fertilizer or mineral is, for example, manganese oxide or manganese-containing slag.
  • the water-insoluble iron fertilizer or mineral is, for example, ferrous oxide or pyrite.
  • the water-insoluble copper fertilizer or mineral is, for example, copper oxide or copper slag.
  • the phosphate fertilizer and the fertilizer or mineral containing the medium and trace elements are dissolved in water very low.
  • the solubility and dissolution rate of the water-insoluble phosphate fertilizer and the fertilizer or mineral containing the medium and trace elements are appropriately increased, so that an activator is added during the fertigation process.
  • an activator is understood to be a compound which destroys the structure of a water-insoluble phosphate fertilizer and a non-water-soluble micronutrient fertilizer or mineral, thereby releasing nutrients in the water-insoluble fertilizer.
  • the activator is one or more compounds selected from the group consisting of inorganic acids, organic acids, inorganic salts and amide nitrogen fertilizers.
  • the action mechanism of the activator and the water-insoluble phosphate fertilizer and the water-insoluble medium-and-micro element fertilizer or mineral is that the ion exchange reaction between the hydrogen ion or the alkali metal element ion and the phosphate ion and the medium trace element ion is performed. Released into irrigation water.
  • the inorganic acid is one or more inorganic acids selected from the group consisting of hydrochloric acid, nitric acid and sulfuric acid.
  • the organic acid is one or more organic acids selected from the group consisting of oxalic acid, citric acid, formic acid and benzoic acid.
  • the inorganic salt is one or more inorganic salts selected from the group consisting of sodium hydrogen sulfate, potassium hydrogen sulfate, ammonium nitrate, magnesium sulfate, potassium sulfate, ammonium sulfate, ammonium chloride, potassium chloride and potassium nitrate.
  • the amide nitrogen fertilizer is urea.
  • the invention relates to a method for agricultural fertigation. This method is characterized in that it comprises the following steps:
  • the water-insoluble acid phosphate fertilizer is precipitated calcium phosphate.
  • the water-insoluble hot phosphate fertilizer is selected from the group consisting of defluorinated phosphate fertilizer, sintered calcium sodium phosphate fertilizer, calcium metaphosphate, steel slag phosphate fertilizer, calcium magnesium phosphate fertilizer.
  • the water-insoluble medium trace element fertilizer or mineral particles are one or more fertilizers or minerals selected from the group consisting of water-insoluble calcium, magnesium, sulfur, boron, molybdenum, zinc, manganese, iron or copper.
  • the calcium is, for example, calcium sulfate, phosphogypsum, industrial waste, such as steel industry slag;
  • the magnesium is, for example, magnesite, dolomite;
  • the sulfur is, for example, calcium sulfate, zinc sulfide ore, pyrite Phosphogypsum, sulfur;
  • the boron is, for example, boraxite or boron mud;
  • the molybdenum is, for example, molybdenum slag;
  • the zinc is, for example, zinc oxide or zinc sulfide;
  • the manganese is, for example, manganese oxide, The manganese slag;
  • the iron is, for example, ferrous oxide or pyrit
  • the particle size of the phosphate rock, phosphate fertilizer, medium or trace element fertilizer or mineral is 0.5-3 mils, preferably 0.7-1.5 mils; more preferably 0.8-1.0 mils. If the particle size is less than 0.5 mils, the bed resistance is too large and the power consumption is large; if the particle size is larger than 3 mils, a longer contact time is required, and the leaching efficiency is lower.
  • the mixing ratio of the water-insoluble phosphate fertilizer particles to the medium-trace element fertilizer or mineral particles is 100: 0-2; preferably 100: 0-1; more preferably 100: 0-0.3;
  • An activator aqueous solution is prepared by dissolving one or more activators selected from the group consisting of inorganic acids, organic acids, inorganic salts and amide nitrogen fertilizers in water.
  • the inorganic acid is one or more inorganic acids selected from the group consisting of hydrochloric acid, nitric acid and sulfuric acid.
  • the organic acid is one or more organic acids selected from the group consisting of oxalic acid, citric acid, formic acid or benzoic acid.
  • the inorganic salt is one or more inorganic salts selected from the group consisting of sodium hydrogen sulfate, potassium hydrogen sulfate, ammonium nitrate, magnesium sulfate, potassium sulfate, ammonium sulfate, ammonium chloride, potassium chloride or potassium nitrate.
  • the amide gas fertilizer is urea.
  • the aqueous solution of the activator has a mass concentration of 5 to 30%; preferably 5-15%; more preferably 8 to 12%.
  • the mass concentration of the aqueous solution of the activator is higher than 30%, some of the inorganic salts are incompletely dissolved, less than 5%, and the volume of the activator tank is too large.
  • the mixing ratio of the aqueous solution of the activator to water is from 1:1000 to 1:100, preferably from 1:500 to 1:100; more preferably 1:200.
  • the concentration of the activator is too dilute to reduce the solubility of the water-insoluble particles; less than 1:100, the activator is too concentrated, for the water-insoluble particles Dissolution is too fast, which may cause the irrigation water to repeat the precipitation and block the water pipeline.
  • the linear velocity of the diluted activator solution through the fixed bed of fertilizer granules is 0.1-5 cm/sec; preferably 0.5-2 cm/sec; more preferably 0.8-1.2 cm/sec.
  • the contact time is too short, and the fixed bed is required to be high and soluble.
  • the output is too small. If the line speed is less than 0.1 cm/sec, the fixed bed container is too large, the equipment investment is high, and the efficiency is low.
  • the mass concentration to the irrigation water is P 2 0 5 1 by selecting the water-insoluble fertilizer, the type of activator, controlling the mixing ratio of the aqueous solution of the activator and water, and the linear velocity of the diluted activator solution.
  • P 2 0 5 1 by selecting the water-insoluble fertilizer, the type of activator, controlling the mixing ratio of the aqueous solution of the activator and water, and the linear velocity of the diluted activator solution.
  • Such selection methods will be described in detail in the section of the description of the specification.
  • the container used in the practice of the present invention may be any apparatus capable of filling the phosphate fertilizer and containing medium or micro-element fertilizer or mineral particles to form a fixed bed.
  • a device may for example be a container selected from the group consisting of tanks, tanks, columns and columns.
  • the sections of the troughs, tanks, columns and columns may be of any shape, such as round, square, rectangular, polygonal, elliptical.
  • the invention may be practiced using pulsating beds, fluidized beds, and the like, which are known to those skilled in the art.
  • the invention is practiced with a fixed bed and a pulsating bed, more preferably a fixed bed.
  • This example first selects a water-insoluble phosphate rock.
  • the phosphate rock powder is sieved to obtain phosphorus having a diameter of about 2 mm and containing P 2 0 5 20%, CaO 28%, MgO 6%, SiO 2 20%, Fe0 1%, MnO 0.2% by mass of the phosphate rock particles.
  • the ore particles weigh 500kg of this phosphate rock particles and 0.25kg of zinc oxide, 0.25kg of boron-magnesium ore, and mix them evenly into a cylindrical reactor with an effective volume of 0.5m 3 to form a fixed bed of fertilizer. Fixed bed.
  • an activator solution was prepared. Weigh 20kg ammonium sulfate, 5kg 36% hydrochloric acid, 3.5kg potassium sulfate, 5kg magnesium sulfate in 300kg of water under stirring at room temperature, thus obtaining an aqueous solution of activator, and filling the prepared activator solution into the storage tank. use.
  • the diluted activator solution is passed through the fertilizer fixed bed to obtain an irrigation water containing P 2 0 5 20 mg/kg, CaO 26 mg/kg, MgO 13 mg/kg, Si0 2 by mass. 3 mg/kg, Fe0 2 mg/kg, B 2 0 3 lmg/kg, Zn 3 mg/kg, Mn 1 mg/kg, N 70 mg/kg, S 90 mg/kg and K 2 0 29 mg/kg.
  • the raw materials were weighed in the following proportions to prepare an activator solution: 5 kg of magnesium sulfate, 20 kg of potassium nitrate, 5 kg of urea, and 100 kg of water. This activator was charged into a storage tank having an effective volume of 0.3 m 3 .
  • the irrigation water introduced from the irrigation system at a flow rate of 10 m 3 /h is added to the activator solution in a ratio of 1000:1 to obtain a diluted activator solution, and the diluted activator solution is passed through the fixed bed. Obtained an irrigation water containing P 2 0 5 50 mg/kg, N 50 mg/kg, K 2 0 90 mg/kg, CaO 100 mg/kg, MgO 36 mg/kg, Si0 2 by mass 60 mg/kg, FeO 5 mg/kg, B 2 0 3 5 mg/kg.
  • Select steel slag phosphate with a particle diameter of about 1.5 mm which contains P 2 0 5 18 %, CaO 40%, MgO 3%, Si0 2 5%, FeO 10%, MnO 3%, and weigh 100 Kg.
  • the steel slag phosphate fertilizer is added to a reactor having an effective volume of 0.2 m 3 to form a fixed bed.
  • the raw materials were weighed in the following proportions to prepare an activator solution: 5 kg of potassium nitrate, 5 kg of 98% sulfuric acid, 25 kg of ammonium chloride, and 200 kg of water.
  • the activator is loaded into an effective volume of 0.3 m 3 In the tank.
  • the irrigation water with a flow rate of 10 m 3 /h is added to the activator solution in a ratio of 300:1 to obtain a diluted activator solution, and the diluted activator solution is passed through the above fixed bed.
  • the nutrient content of the irrigation water produced by the fertigation method of the present invention can be varied within a large range to accommodate this change.
  • the fertigation method of the invention can save the fertilizer amount by 30-60% compared with the traditional fertilization method, and the fertilizer utilization rate can reach 70-90%, which is a modern agricultural method for water and fertilizer utilization. In addition, it is also conducive to the realization of agricultural industrialization.

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  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Soil Sciences (AREA)
  • Environmental Sciences (AREA)
  • Fertilizers (AREA)

Abstract

A fertilizing method for agricultural irrigation includes a step of passing aqueous solution of activation agents through a fertilizer fixed bed composed of nonaqueous granular phosphatic fertilizer and fertilizer or mineral containing medium or trace element to achieve irritation water for irritating plants. With the method of present invention, the consumption of fertilizer can less 30-60% than that of conventionally fertilizing method, and thus the utilization ratio of fertilizer is up to 70-90%.

Description

一种农业灌溉施肥方法  Agricultural fertigation method
【技术领域] [Technical Field]
本发明涉及一种农业生产技术， 更具体地， 本发明涉及一种农业灌 溉施肥方法。  The present invention relates to an agricultural production technique, and more particularly to an agricultural irrigation and fertilization method.
[背景技术]  [Background technique]
随着世界人口的急剧增长和世界经济的高速发展，世界水资源消耗 飞速增加， 同时对水资源的破坏日趋严重， 根据***粮农组织统计和 预测， 在 1950-2000年间， 世界人均水资源拥有量减少了 25%。 中国的 水资源状况更为严峻，人均占有河川径流量仅为世界人均占有量的 1/4, 而且分布不均， 其中辽河、 海河、 黄河、 淮河四个流域片， 耕地占全国 总量的 45.2%, 人口占全国总人口的 38.4%, 而水资源的占有量仅为全 国的 9.6%。 于是， 这些地区的农业灌溉用水和肥料的利用率是制约粮 食增产的主要因素， 因此， 釆用新的灌溉技术， 提高水和肥料的利用率 对于农业持续发展将具有十分重要的意义。  With the rapid growth of the world population and the rapid development of the world economy, the world's water consumption has increased rapidly, and the damage to water resources has become increasingly serious. According to the statistics and forecasts of the UN Food and Agriculture Organization, the world's per capita water resources during the period 1950-2000 Reduced by 25%. China's water resources are even more severe. The per capita river runoff is only one-fourth of the world's per capita possession, and it is unevenly distributed. Among them, the Liaohe, Haihe, Yellow River and Huaihe Rivers have four river basins, and the cultivated land accounts for 45.2% of the national total. %, the population accounts for 38.4% of the country's total population, while water resources are only 9.6% of the country. As a result, the utilization of agricultural irrigation water and fertilizer in these areas is the main factor that restricts food production. Therefore, using new irrigation techniques to improve the utilization of water and fertilizer will be of great significance for the sustainable development of agriculture.
直到现在世界各国、各地区釆用的灌溉施肥方法都需要釆用适当的 液体或全水溶性的固体肥料， 例如， 目前农业上通常使用的氮肥和钾肥 主要是水溶性的， 釆用灌溉施肥方法应是简单易行的， 不存在严重的问 题； 磷肥中， 例如工业级、 食品级磷酸铵、 磷酸二氢钾等少数品种也是 全水溶性的， 因此采用灌溉施肥方法应也是可行的。 然而， 目前农业上 通常使用的大多数磷肥品种是部分水溶性或非水溶性的，难以釆用灌溉 施肥方法实施农作物的灌溉施肥。含中微量元素的一些肥料也是非水溶 性的。 因此， 也难以采用灌溉施肥方法实施农作物的灌溉施肥。 现在， 在大多数情况下这些非水溶性肥料都作为基肥施用，这时作物对磷等资 源的利用率一直很低， 只有 8-20%, 碱性土壤尤其如此。 这种基肥施用 方法的缺陷是显而易见的。 因此， 为了克服这种缺陷， 本发明人经过多 年研究， 成功地研制出非水溶性肥料的灌溉施肥， 这种方法能够充分发 挥灌溉与施肥相结合的优越性，为农作物连续提供磷及其它中微量元素 源， 是一种解决灌溉施肥中磷源问题的全新思路， 到目前为止尚未检索 到任何相关的文献资料。 Until now, the fertigation methods used in various countries and regions of the world require the use of appropriate liquid or fully water-soluble solid fertilizers. For example, the nitrogen and potassium fertilizers currently used in agriculture are mainly water-soluble, and the fertilization method is applied. It should be simple and easy to implement, and there are no serious problems. Phosphate fertilizers, such as industrial grade, food grade ammonium phosphate, potassium dihydrogen phosphate, etc., are also fully water soluble, so it should be feasible to use fertigation methods. However, most of the phosphate fertilizers currently used in agriculture are partially water-soluble or water-insoluble, and it is difficult to use fertigation methods to implement fertigation of crops. Some fertilizers containing medium and trace elements are also water-insoluble. Therefore, it is also difficult to implement fertigation of crops by fertigation. Now, in most cases, these water-insoluble fertilizers are applied as base fertilizers. At this time, the utilization rate of resources such as phosphorus by crops has been very low, only 8-20%, especially in alkaline soils. The drawbacks of this base fertilizer application method are obvious. Therefore, in order to overcome such defects, the inventors have succeeded in developing irrigation and fertilization of water-insoluble fertilizers after many years of research, and this method can fully develop The combination of irrigation and fertilization provides a continuous supply of phosphorus and other medium and trace element sources for crops. It is a new way to solve the problem of phosphorus source in fertigation and fertilization. So far, no relevant literature has been retrieved.
[发明内容】  [Contents of the Invention]
【要解决的技术问题】  [Technical problems to be solved]
本发明的目的在于开发一种农业灌溉施肥方法，这种方法不仅可以 为农作物连续提供磷， 使非水溶性磷肥充分挥发其肥料效果， 提高肥料 利用率， 还可以提供多种中、 微量元素， 并增强作物抗病毒、 抗倒伏的 能力。  The object of the present invention is to develop an agricultural fertigation method, which can not only continuously provide phosphorus for crops, but also fully defluorinate the fertilizer effect of the water-insoluble phosphate fertilizer, improve the utilization rate of the fertilizer, and provide various medium and trace elements. And enhance the ability of crops to resist viruses and lodging.
【技术方案】  【Technical solutions】
本技术领域的技术人员知道，灌溉施肥是指使用全水溶性固体或液 体肥料，通过微灌***为农作物提供所需要营养元素而实施的一种灌溉 方法， 这种方法可以达到肥料随同灌溉用水一起进入田间， 达到以最少 量的营养元素使灌溉的作物增产。 所述的灌溉施肥， 利用一种灌溉*** 可以在施肥量、 施肥时间和施肥空间等方面达到很高的精度， 是精确施 肥与精确灌溉相结合的产物。  It is known to those skilled in the art that fertigation refers to an irrigation method that uses a fully water-soluble solid or liquid fertilizer to provide the required nutrients to crops through a micro-irrigation system, which can be used together with irrigation water. Enter the field to increase the yield of irrigated crops with the least amount of nutrients. The above-mentioned irrigation and fertilization, using an irrigation system, can achieve high precision in terms of fertilization amount, fertilization time and fertilization space, and is a combination of precise fertilization and precise irrigation.
本发明的方法主要使用非水溶性的磷肥颗粒和非水溶性的含中微 量元素的肥料或矿物颗粒作为原料。所述非水溶性磷肥系指这种或这些 磷肥在室温与大气压力的条件下在水中的溶解度小于或等于 The method of the present invention mainly uses water-insoluble phosphate fertilizer granules and water-insoluble fertilizers or mineral granules containing medium and micro-elements as raw materials. The water-insoluble phosphate fertilizer refers to the solubility of the phosphate fertilizer in the water at room temperature and atmospheric pressure is less than or equal to
1000mg/kg , 优选地小于或等于 500mg/kg , 更优选地小于或等于 300mg/kg。所述非水溶性含中微量元素肥料或矿物系指这种或这些含中 微量元素的肥料或矿物在室温与大气压力的条件下在水中的溶解度小 于或等于 100mg/kg，优选地小于或等于 50mg/kg, 更优选地小于或等于 20mg/kg。 1000 mg/kg, preferably less than or equal to 500 mg/kg, more preferably less than or equal to 300 mg/kg. The water-insoluble medium and trace element fertilizer or mineral means that the solubility of the fertilizer or mineral containing the medium or trace element in water at room temperature and atmospheric pressure is less than or equal to 100 mg/kg, preferably less than or equal to 50 mg/kg, more preferably less than or equal to 20 mg/kg.
所述的非水溶性磷肥颗粒选自磷矿粉、 酸制磷肥和热制磷肥。 所述的磷矿粉是直接由磷矿石粉碎而成的磷肥。磷矿石中含磷化合 物是以氟磷灰石为主的。 磷矿粉是一种难溶性磷肥， 含有占总磷 8%以 下的枸溶性磷， 肥效缓慢而持久。 The water-insoluble phosphate fertilizer particles are selected from the group consisting of phosphate rock powder, acid phosphate fertilizer and hot phosphate fertilizer. The phosphate rock powder is a phosphate fertilizer directly pulverized from phosphate rock. The phosphorus-containing compound in phosphate rock is mainly composed of fluoroapatite. Phosphate rock powder is a poorly soluble phosphate fertilizer containing 8% of total phosphorus. Under the 枸 soluble phosphorus, the fertilizer is slow and long lasting.
所述的酸制磷肥是用硫酸、 硝酸、 盐酸等酸类处理磷矿粉而成的。 在酸制磷肥中包括沉淀磷酸钙。沉淀磷酸钙可以由磷矿石与硫酸、硝酸、 盐酸等反应生成磷酸， 再用石灰乳沉淀制得。  The acid phosphate fertilizer is obtained by treating phosphate rock powder with an acid such as sulfuric acid, nitric acid or hydrochloric acid. Precipitated calcium phosphate is included in the acid phosphate fertilizer. The precipitated calcium phosphate can be obtained by reacting phosphate rock with sulfuric acid, nitric acid, hydrochloric acid or the like to form phosphoric acid, and then precipitating with lime milk.
以硝酸制造为例， 其反应如下：  Taking nitric acid production as an example, the reaction is as follows:
Ca5(P04)3-F + 10HNO3 3H3P04 + 5Ca(N03)2 +HF Ca 5 (P0 4 ) 3 -F + 10HNO 3 3H 3 P0 4 + 5Ca(N0 3 ) 2 +HF
3 H3PO4 +5 Ca(N03)2 +3Ca(OH)2→ 3CaHP04- 2H20 + 5 Ca(N03)2 由此可见， 沉淀磷酸钙的主要成分是磷酸二钙， 不溶于水， 但溶于 2%柠檬酸溶液中， 属于枸溶性磷肥， 含磷量 (P205)高， 一般为 30-40%。 3 H3PO4 +5 Ca(N0 3 ) 2 +3Ca(OH) 2 → 3CaHP0 4 - 2H 2 0 + 5 Ca(N0 3 ) 2 It can be seen that the main component of precipitated calcium phosphate is dicalcium phosphate, which is insoluble in water. However, it is soluble in 2% citric acid solution and belongs to bismuth soluble phosphate fertilizer. The phosphorus content (P 2 0 5 ) is high, generally 30-40%.
所述的热制磷肥是通过电力或燃料燃烧而产生的高温分解磷矿石， 制成的磷肥， 其中主要包括脱氟磷肥、 烧结钙纳磷肥、 偏磷酸钙、 钢渣 磷肥、 钙镁磷肥。  The hot phosphate fertilizer is a high-temperature decomposing phosphate ore produced by burning electric power or fuel, and the prepared phosphate fertilizer mainly includes defluorinated phosphate fertilizer, sintered calcium nano-phosphorus fertilizer, calcium metaphosphate, steel slag phosphate fertilizer, calcium magnesium phosphate fertilizer.
脱氟磷肥是氟磷灰石在高温 (1500°C)下与水蒸汽作用制成的。 其反 应如下：  Defluorinated phosphate fertilizer is made by reacting fluoroapatite with water vapor at high temperature (1500 ° C). The response is as follows:
Ca5(P04)3'F + H20 Ca5(OH)(P04)3 + HF Ca 5 (P0 4 ) 3 'F + H 2 0 Ca 5 (OH)(P0 4 ) 3 + HF
2Ca5(OH)(P04)3→ 2Ca3(P04)2 + Ca4P209 + H20 2Ca 5 (OH)(P0 4 ) 3 → 2Ca 3 (P0 4 ) 2 + Ca 4 P 2 0 9 + H 2 0
脱氟磷肥含磷量 (P205)—般约 19-38%， 属于枸溶性磷肥。 The phosphorus content of defluorinated phosphate fertilizer (P 2 0 5 ) is about 19-38%, which belongs to the 枸 soluble phosphate fertilizer.
烧结钙钠磷肥是磷矿石与碳酸钠和硅砂在高温 (1250°C)下烧结而成 的。 产品含 P205 28-30%。 Sintered calcium, sodium and phosphate fertilizers are formed by sintering phosphate rock with sodium carbonate and silica sand at high temperature (1250 ° C). The product contains P 2 0 5 28-30%.
偏磷酸钙是磷矿粉在 950°C下与 P205气体接触制成的， 其反应如 下： Calcium metaphosphate is prepared by contacting phosphate rock powder with P 2 0 5 gas at 950 ° C. The reaction is as follows:
2Ca5(P04)3-F + 7 P205 + ¾0→ 10 Ca(P03)2 +2HF 2Ca 5 (P0 4 ) 3 -F + 7 P 2 0 5 + 3⁄40→ 10 Ca(P0 3 ) 2 +2HF
偏磷酸钙呈玻璃状微黄色晶体，含磷量(?205)可达60 % -70 % , 可溶 于中性柠檬酸铵溶液。 Metaphosphate glassy yellow crystals, phosphorus (? 205) of up to 60% -70%, may be soluble in neutral ammonium citrate solution.
钢渣磷肥是炼钢工业的副产品， 呈深棕色粉末状， 强碱性， 其中磷 的形态为磷酸四钙（Ca4P209)和磷酸西钙与硅酸钙 的复盐 (Ca4P209-CaSi03), 两者都溶于柠檬酸和柠檬酸铵溶液中。 钙镁磷肥是以磷矿、 助熔剂 (蛇紋石、 橄榄石等)和燃料 (无烟煤、 焦 炭等)为原料， 加热到 1450。C以上高温熔融， 出料时用高压水流喷射， 使骤冷并破碎成细小的玻璃状物， 经干燥、 磨细得到的产品， 通常呈深 灰、 灰绿或墨绿色粉末， 物理性状良好， 不吸湿， 不结块， 碱性反应， 但没有腐蚀性。 它是由磷、 硅、 钙和镁为主要成分构成的玻璃体， 无明 确的分子式和分子量， 产品含 P205 14-18%, 可溶于 2%的柠檬酸中。 钙 镁磷肥还含有 MgO 8-20%、 CaO 25-40%、 Si02 22-32%, FeO 0.5-3%等。 Steel slag phosphate fertilizer is a by-product of the steelmaking industry. It is dark brown powder and strongly alkaline. The form of phosphorus is tetracalcium phosphate (Ca 4 P 2 0 9 ) and double salt of calcium silicate and calcium silicate (Ca 4 P 2 0 9 -CaSi0 3 ), both are soluble in citric acid and ammonium citrate solutions. Calcium, magnesium and phosphate fertilizers are based on phosphate rock, flux (serpentine, olivine, etc.) and fuel (anthracite, coke, etc.) and heated to 1450. C is melted at a high temperature, and is sprayed with a high-pressure water stream during discharge to be quenched and broken into fine glass. The product obtained by drying and grinding is usually dark gray, grayish green or dark green powder, and has good physical properties. Non-hygroscopic, non-caking, alkaline reaction, but not corrosive. It is a glass body composed mainly of phosphorus, silicon, calcium and magnesium. It has no clear molecular formula and molecular weight. The product contains P 2 0 5 14-18% and is soluble in 2% citric acid. Calcium magnesium phosphate fertilizer also contains MgO 8-20%, CaO 25-40%, Si0 2 22-32%, FeO 0.5-3% and the like.
人们由植物营养学可以知道， 所有作物生长发育需要氣、 磷、 钾营 养元素外， 还需要许多种中微量营养元素。  It is known from plant nutrition that all crops require a variety of micronutrients in addition to gas, phosphorus and potassium nutrients.
所述的中微量元素是钙、 镁、 硫、 硼、 钼、 锌、 锰、 铁、 铜和镍， 以及有益元素硅等。  The medium trace elements are calcium, magnesium, sulfur, boron, molybdenum, zinc, manganese, iron, copper and nickel, as well as beneficial element silicon and the like.
钙是细胞壁的结构成分， 对蛋白质的合成有一定的作用， 也是某些 酶促反应的辅助因素， 并且对调节介质的生理平衡具有特殊的功效， 因 此， 作物缺钙时植株矮小，根系发育不良， 细胞壁缺钙， 易被病毒侵入, 严重时会腐烂死亡；  Calcium is a structural component of the cell wall, which has a certain effect on the synthesis of proteins, and is also a cofactor for some enzymatic reactions, and has a special effect on regulating the physiological balance of the medium. Therefore, when the crop is deficient in calcium, the plant is short and the root system is poorly developed. The cell wall is deficient in calcium, easily invaded by viruses, and will rot and die in severe cases;
镁是叶绿素构成元素， 是很多酶的活化剂， 还能促进脂肪的合成， 也参与氮的代谢。 作物缺镁时叶片网状组织呈黄色或白色， 乃至变成褐 色甚至坏死。 缺镁的牧草会引起牲畜抽搐病。  Magnesium is a constituent element of chlorophyll, an activator of many enzymes, and promotes the synthesis of fat as well as the metabolism of nitrogen. When the crop is deficient in magnesium, the reticular tissue of the leaves is yellow or white, and even becomes brown or even necrotic. Magnesium-deficient pasture can cause convulsions in livestock.
硫是蛋白质和酶的组成元素， 还存在于某些生理活性物质中， 也是 固氮酶***的一个组成部分。 作物缺硫时， 生长受到严重障碍， 叶片褪 绿或黄化。  Sulfur is a constituent of proteins and enzymes and is also found in certain physiologically active substances and is an integral part of the nitrogenase system. When the crop is deficient in sulfur, the growth is severely impeded and the leaves are chlorotic or yellow.
硅虽然不是作物的必需营养元素，但作物缺硅易发生倒伏及病毒侵 入表面细胞。 因此， 硅对许多作物， 特别是喜硅的水稻、 甘蔗、 竹子等 是重要的有益元素。  Although silicon is not an essential nutrient for crops, the lack of silicon in crops is prone to lodging and viruses invade surface cells. Therefore, silicon is an important beneficial element for many crops, especially silicon-rich rice, sugar cane, and bamboo.
微量元素在植物体内往往是酶或辅酶的组成部分，具有很强的专一 性， 是作物生长发育不可缺少和不可相互代替的。  Trace elements are often part of enzymes or coenzymes in plants and have strong specificity. They are indispensable and irreplaceable for crop growth and development.
因此， 在本发明使用的肥料中伴随有中微量元素， 或另外配入水不 溶性的含中微量元素的肥料或矿物。 Therefore, the fertilizer used in the present invention is accompanied by a medium or trace element, or is additionally formulated with water. A soluble fertilizer or mineral containing trace elements.
所述水不溶性的含中微量元素的肥料或矿物是一种或多种选自水 不溶性的含钙、 镁、 硫、 硼、 钼、 锌、 锰、 铁或铜的肥料或矿物。  The water-insoluble medium or trace element-containing fertilizer or mineral is one or more fertilizers or minerals selected from the group consisting of water-insoluble calcium, magnesium, sulfur, boron, molybdenum, zinc, manganese, iron or copper.
所述的含非水溶性钙肥或矿物例如是硫酸钙、 磷石膏、 工业废渣， 像钢铁工业炉渣。  The water-insoluble calcium fertilizer or mineral is, for example, calcium sulfate, phosphogypsum, industrial waste, such as steel industry slag.
所述的含非水溶性镁肥或矿物例如是菱镁矿、 白云石。  The water-insoluble magnesium fertilizer or mineral is, for example, magnesite, dolomite.
所述的含非水溶性硫肥或矿物例如是硫酸钙、 硫化锌矿、 硫铁矿、 磷石膏、 硫黄。  The water-insoluble sulfur fertilizer or mineral is, for example, calcium sulfate, zinc sulfide ore, pyrite, phosphogypsum, sulfur.
所述的含非水溶性硼肥或矿物例如是硼镁矿、 硼泥。  The water-insoluble boron fertilizer or mineral is, for example, a boron magnesium ore, a boron mud.
所述的含非水溶性钼肥或矿物例如是钼渣。  The water-insoluble molybdenum fertilizer or mineral is, for example, molybdenum slag.
所述的含非水溶性锌肥或矿物例如是氧化锌、 硫化锌。  The water-insoluble zinc fertilizer or mineral is, for example, zinc oxide or zinc sulfide.
所述的含非水溶性锰肥或矿物例如是氧化锰、 含锰矿渣。  The water-insoluble manganese fertilizer or mineral is, for example, manganese oxide or manganese-containing slag.
所述的含非水溶性铁肥或矿物例如是氧化亚铁、 硫铁矿砂。  The water-insoluble iron fertilizer or mineral is, for example, ferrous oxide or pyrite.
所述的含非水溶性铜肥或矿物例如是氧化铜、 炼铜矿渣。  The water-insoluble copper fertilizer or mineral is, for example, copper oxide or copper slag.
由上述内容可知，所述的磷肥和含中微量元素的肥料或矿物在水中 溶解很低。 为了实现灌溉施肥的目的， 使非水溶性磷肥和含中微量元素 的肥料或矿物的溶解度和溶解速度获得适当的提高， 因此在灌溉施肥过 程加入了一种活化剂。  It can be seen from the above that the phosphate fertilizer and the fertilizer or mineral containing the medium and trace elements are dissolved in water very low. In order to achieve the purpose of fertigation, the solubility and dissolution rate of the water-insoluble phosphate fertilizer and the fertilizer or mineral containing the medium and trace elements are appropriately increased, so that an activator is added during the fertigation process.
在本发明的意义上，活化剂应当理解是一种使非水溶性磷肥和含非 水溶性中微量元素肥料或矿物的结构受到破坏，从而释放出非水溶性肥 料中营养元素的化合物。  In the sense of the present invention, an activator is understood to be a compound which destroys the structure of a water-insoluble phosphate fertilizer and a non-water-soluble micronutrient fertilizer or mineral, thereby releasing nutrients in the water-insoluble fertilizer.
所述的活化剂是一种或多种选自无机酸、 有机酸、 无机盐和酰胺态 氮肥的化合物。  The activator is one or more compounds selected from the group consisting of inorganic acids, organic acids, inorganic salts and amide nitrogen fertilizers.
所述的活化剂与非水溶性磷肥和非水溶性含中微量元素肥料或矿 物的作用机制是， 以氢离子或碱金属元素离子与磷酸根离子、 中微量元 素离子发生离子置换反应而使后者释放到灌溉水中。  The action mechanism of the activator and the water-insoluble phosphate fertilizer and the water-insoluble medium-and-micro element fertilizer or mineral is that the ion exchange reaction between the hydrogen ion or the alkali metal element ion and the phosphate ion and the medium trace element ion is performed. Released into irrigation water.
所述的无机酸是一种或多种选自盐酸、 硝酸和硫酸的无机酸。 所述的有机酸是一种或多种选自草酸、柠檬酸、 甲酸和苯甲酸的有 机酸。 The inorganic acid is one or more inorganic acids selected from the group consisting of hydrochloric acid, nitric acid and sulfuric acid. The organic acid is one or more organic acids selected from the group consisting of oxalic acid, citric acid, formic acid and benzoic acid.
所述的无机盐是一种或多种选自硫酸氢钠、 硫酸氢钾、 硝酸铵、 硫 酸镁、 硫酸钾、 硫酸铵、 氯化铵、 氯化钾和硝酸钾的无机盐。  The inorganic salt is one or more inorganic salts selected from the group consisting of sodium hydrogen sulfate, potassium hydrogen sulfate, ammonium nitrate, magnesium sulfate, potassium sulfate, ammonium sulfate, ammonium chloride, potassium chloride and potassium nitrate.
所述的酰胺态氮肥是尿素。  The amide nitrogen fertilizer is urea.
基于对非水溶性磷肥和非水溶性含中微量元素肥料或矿物的认识 和发现， 本发明人作出了如下的发明。  Based on the knowledge and discovery of the water-insoluble phosphate fertilizer and the water-insoluble medium- and trace element fertilizer or mineral, the inventors made the following invention.
本发明涉及一种农业灌溉施肥的方法。这种方法的特征在于它包括 下述步骤：  The invention relates to a method for agricultural fertigation. This method is characterized in that it comprises the following steps:
(i)把一种或多种选自磷矿粉、酸制磷肥和热制磷肥的非水溶性磷肥 颗粒， 与非水溶性的中微量元素肥料或矿物颗粒混合后装入容器中， 制 备一种肥料颗粒固定床。  (i) mixing one or more water-insoluble phosphate fertilizer particles selected from the group consisting of phosphate rock, acid phosphate fertilizer and hot phosphate fertilizer, with water-insoluble medium and trace element fertilizer or mineral particles, and then filling into a container to prepare a A fixed bed of fertilizer particles.
所述非水溶性的酸制磷肥是沉淀磷酸钙。  The water-insoluble acid phosphate fertilizer is precipitated calcium phosphate.
所述非水溶性的热制磷肥选自脱氟磷肥、烧结钙钠磷肥、偏磷酸钙、 钢渣磷肥、 钙镁磷肥。  The water-insoluble hot phosphate fertilizer is selected from the group consisting of defluorinated phosphate fertilizer, sintered calcium sodium phosphate fertilizer, calcium metaphosphate, steel slag phosphate fertilizer, calcium magnesium phosphate fertilizer.
所述非水溶性的中微量元素肥料或矿物颗粒是一种或多种选自非 水溶性的含钙、 镁、 硫、 硼、 钼、 锌、 锰、 铁或铜的肥料或矿物。 其中 所述的钙例如是硫酸钙、 磷石膏、 工业废渣， 像钢铁工业炉渣； 所述的 镁例如是菱镁矿、 白云石； 所述的硫例如是硫酸钙、硫化锌矿、硫铁矿、 磷石膏、 硫黄； 所述的硼例如是硼镁矿、 硼泥； 所述的钼例如是钼渣； 所述的锌例如是氧化锌、 硫化锌； 所述的锰例如是氧化锰、 含锰矿渣； 所述的铁例如是氧化亚铁、 硫铁矿砂； 所述的铜例如是氧化铜、 炼铜矿 渣。  The water-insoluble medium trace element fertilizer or mineral particles are one or more fertilizers or minerals selected from the group consisting of water-insoluble calcium, magnesium, sulfur, boron, molybdenum, zinc, manganese, iron or copper. The calcium is, for example, calcium sulfate, phosphogypsum, industrial waste, such as steel industry slag; the magnesium is, for example, magnesite, dolomite; the sulfur is, for example, calcium sulfate, zinc sulfide ore, pyrite Phosphogypsum, sulfur; the boron is, for example, boraxite or boron mud; the molybdenum is, for example, molybdenum slag; the zinc is, for example, zinc oxide or zinc sulfide; the manganese is, for example, manganese oxide, The manganese slag; the iron is, for example, ferrous oxide or pyrite; the copper is, for example, copper oxide or copper slag.
所述的磷矿粉、 磷肥、 含中微量元素肥料或矿物的粒度是 0.5-3亳 米， 优选地 0.7-1.5亳米； 更优选地 0.8-1.0亳米。 如果粒度小于 0.5亳 米则床层阻力太大， 动力消耗也大； 如果粒度大于 3亳米， 则需要更长 的接触时间， 浸出效率比较低。 所述非水溶性磷肥颗粒与所述中微量元素肥料或矿物颗粒的混合 比是 100: 0-2; 优选地 100: 0-1; 更优选地 100: 0-0.3; The particle size of the phosphate rock, phosphate fertilizer, medium or trace element fertilizer or mineral is 0.5-3 mils, preferably 0.7-1.5 mils; more preferably 0.8-1.0 mils. If the particle size is less than 0.5 mils, the bed resistance is too large and the power consumption is large; if the particle size is larger than 3 mils, a longer contact time is required, and the leaching efficiency is lower. The mixing ratio of the water-insoluble phosphate fertilizer particles to the medium-trace element fertilizer or mineral particles is 100: 0-2; preferably 100: 0-1; more preferably 100: 0-0.3;
(ii)将一种或多种选自无机酸、有机酸、无机盐和酰胺态氮肥的活化 剂溶于水中制备一种活化剂水溶液。  (ii) An activator aqueous solution is prepared by dissolving one or more activators selected from the group consisting of inorganic acids, organic acids, inorganic salts and amide nitrogen fertilizers in water.
其中，所述的无机酸是一种或多种选自盐酸、硝酸和硫酸的无机酸。 所述的有机酸是一种或多种选自草酸、柠檬酸、 甲酸或苯甲酸的有 机酸。  Wherein the inorganic acid is one or more inorganic acids selected from the group consisting of hydrochloric acid, nitric acid and sulfuric acid. The organic acid is one or more organic acids selected from the group consisting of oxalic acid, citric acid, formic acid or benzoic acid.
所述的无机盐是一种或多种选自硫酸氢钠、 硫酸氢钾、 硝酸铵、 硫 酸镁、 硫酸钾、 硫酸铵、 氯化銨、 氯化钾或硝酸钾的无机盐。  The inorganic salt is one or more inorganic salts selected from the group consisting of sodium hydrogen sulfate, potassium hydrogen sulfate, ammonium nitrate, magnesium sulfate, potassium sulfate, ammonium sulfate, ammonium chloride, potassium chloride or potassium nitrate.
所述的酰胺态氣肥是尿素。  The amide gas fertilizer is urea.
所述活化剂水溶液的质量浓度是 5-30%; 优选地 5-15%; 更优选地 8-12%。  The aqueous solution of the activator has a mass concentration of 5 to 30%; preferably 5-15%; more preferably 8 to 12%.
如果所述的活化剂水溶液的质量浓度高于 30%,某些无机盐溶解不 完全， 低于 5%, 活化剂槽容积过大。  If the mass concentration of the aqueous solution of the activator is higher than 30%, some of the inorganic salts are incompletely dissolved, less than 5%, and the volume of the activator tank is too large.
(iii)让在步骤 (ii)制备的所述活化剂水溶液与水混合得到一种稀释的 活化剂溶液， 然后让所述稀释的活化剂溶液通过在步骤 (i)制备的所述肥 料颗粒固定床得到一种灌溉水，所述的灌溉水含有磷以及各种中微量元 素， 这种灌溉水可直接灌溉作物，  (iii) mixing the aqueous solution of the activator prepared in the step (ii) with water to obtain a diluted activator solution, and then allowing the diluted activator solution to be fixed by the fertilizer granule prepared in the step (i) The bed is given an irrigation water containing phosphorus and various medium and trace elements, which can directly irrigate the crop.
其中所述活化剂水溶液与水的混合比以体积计是 1:1000至 1:100, 优选地 1:500至 1:100; 更优选地 1:200。  Wherein the mixing ratio of the aqueous solution of the activator to water is from 1:1000 to 1:100, preferably from 1:500 to 1:100; more preferably 1:200.
如果所述活化剂水溶液与水的混合比以体积计大于 1: 1000, 活化 剂浓度太稀， 降低对非水溶性颗粒的溶解能力； 小于 1: 100, 活化剂太 浓， 对非水溶性颗粒溶出太快， 可能引起灌溉水中继发式沉淀， 堵塞输 水管道。  If the mixing ratio of the aqueous solution of the activator to water is greater than 1:1000 by volume, the concentration of the activator is too dilute to reduce the solubility of the water-insoluble particles; less than 1:100, the activator is too concentrated, for the water-insoluble particles Dissolution is too fast, which may cause the irrigation water to repeat the precipitation and block the water pipeline.
所述稀释的活化剂溶液通过所述肥料颗粒固定床的线速度是 0.1-5 厘米 /秒； 优选地 0.5-2厘米 /秒； 更优选地 0.8-1.2厘米 /秒。  The linear velocity of the diluted activator solution through the fixed bed of fertilizer granules is 0.1-5 cm/sec; preferably 0.5-2 cm/sec; more preferably 0.8-1.2 cm/sec.
如果线速度高于 5厘米 /秒， 则接触时间太短， 需固定床层高且溶 出量太少，如果线速度低于 0.1厘米 /秒，固定床容器太大，设备投资高， 效率低。 If the line speed is higher than 5 cm/sec, the contact time is too short, and the fixed bed is required to be high and soluble. The output is too small. If the line speed is less than 0.1 cm/sec, the fixed bed container is too large, the equipment investment is high, and the efficiency is low.
通过选择所述的非水溶性肥料、 活化剂类型、 控制所述活化剂水溶 液与水的混合比与所述稀释的活化剂溶液的线速度，使得到灌溉水的质 量浓度是 P205 1-200 mg/kg, CaO 2-300 mg/kg, MgO 1-300 mg/kg, Si02 1-300 mg/kg Fe 1-100 mg/kg、 Cu 0-5 mg/kg、 Zn 0-5 mg/kg, Mn 0-5 mg/kg, B203 0-5 mg/kg, N 0-400 mg/kg、 S 0-300 mg/kg和 K20 0-200 mg/kg。 本说明书实施例部分将详细具体地说明这样一些选择方法。 The mass concentration to the irrigation water is P 2 0 5 1 by selecting the water-insoluble fertilizer, the type of activator, controlling the mixing ratio of the aqueous solution of the activator and water, and the linear velocity of the diluted activator solution. -200 mg/kg, CaO 2-300 mg/kg, MgO 1-300 mg/kg, Si0 2 1-300 mg/kg Fe 1-100 mg/kg, Cu 0-5 mg/kg, Zn 0-5 Mg/kg, Mn 0-5 mg/kg, B 2 0 3 0-5 mg/kg, N 0-400 mg/kg, S 0-300 mg/kg and K 2 0 0-200 mg/kg. Such selection methods will be described in detail in the section of the description of the specification.
实施本发明时使用的容器可以是任何能够装填所述磷肥和含中微 量元素肥料或矿物颗粒， 构成固定床的设备。 这种设备可以例如是一种 选自槽、 罐、 塔和柱的容器。 所述槽、 罐、 塔和柱的截面可以任何形状 的， 例如圆的、 方的、 长方的、 多角形、 椭圆的。  The container used in the practice of the present invention may be any apparatus capable of filling the phosphate fertilizer and containing medium or micro-element fertilizer or mineral particles to form a fixed bed. Such a device may for example be a container selected from the group consisting of tanks, tanks, columns and columns. The sections of the troughs, tanks, columns and columns may be of any shape, such as round, square, rectangular, polygonal, elliptical.
除了固定床外， 还可以釆用本技术领域的技术人员已知的脉动床、 流化床等实施本发明。 优选地， 釆用固定床和脉动床， 更优选地采用固 定床实施本发明。  In addition to the fixed bed, the invention may be practiced using pulsating beds, fluidized beds, and the like, which are known to those skilled in the art. Preferably, the invention is practiced with a fixed bed and a pulsating bed, more preferably a fixed bed.
【具体实施方式】  【detailed description】
实施例一  Embodiment 1
这个实施例首先选择一种非水溶性的磷矿粉。这种磷矿粉经筛分得 到其直径约 2mm、 以磷矿颗粒质量计含有 P205 20%、 CaO 28%、 MgO 6%、 SiO2 20%、 Fe0 1%、 MnO 0.2%的磷矿颗粒， 称取 500kg的这种磷 矿颗粒以及 0.25kg氧化锌、 0.25kg硼镁矿，混合均匀后加到有效容积为 0.5m3的圆柱形反应器中， 构成一种称之肥料固定床的固定床。 This example first selects a water-insoluble phosphate rock. The phosphate rock powder is sieved to obtain phosphorus having a diameter of about 2 mm and containing P 2 0 5 20%, CaO 28%, MgO 6%, SiO 2 20%, Fe0 1%, MnO 0.2% by mass of the phosphate rock particles. The ore particles, weigh 500kg of this phosphate rock particles and 0.25kg of zinc oxide, 0.25kg of boron-magnesium ore, and mix them evenly into a cylindrical reactor with an effective volume of 0.5m 3 to form a fixed bed of fertilizer. Fixed bed.
其次， 制备活化剂溶液。 称取 20kg硫酸铵、 5kg 36%盐酸、 3.5kg 硫酸钾、 5kg硫酸镁在常温搅拌下溶于水 300kg中， 这样得到一种活化 剂水溶液， 将所配制的活化剂溶液装入储罐中待用。  Next, an activator solution was prepared. Weigh 20kg ammonium sulfate, 5kg 36% hydrochloric acid, 3.5kg potassium sulfate, 5kg magnesium sulfate in 300kg of water under stirring at room temperature, thus obtaining an aqueous solution of activator, and filling the prepared activator solution into the storage tank. use.
然后， 用水泵从灌溉***中以流量 10 m3/h引出灌溉用水， 再用计 量泵将上述储罐中的活化剂溶液以 50 升 /小时的速度加入到灌溉用水 中， 得到一种稀释的活化剂溶液， 其活化剂溶液与灌溉用水的比例是Then, use a water pump to draw irrigation water from the irrigation system at a flow rate of 10 m 3 /h, and then use a metering pump to add the activator solution in the tank to the irrigation water at a rate of 50 liters per hour. In the middle, a diluted activator solution is obtained, and the ratio of the activator solution to the irrigation water is
1:200。 让这种稀释的活化剂溶液通过所述的肥料固定床得到一种灌溉 水， 这种灌溉水含有以质量计 P205 20 mg/kg、 CaO 26mg/kg、 MgO 13mg/kg、 Si02 3mg/kg、 Fe0 2 mg/kg、 B203 lmg/kg、 Zn 3 mg/kg、 Mn 1 mg/kg、 N 70 mg/kg、 S 90 mg/kg和 K20 29 mg/kg。 1:200. The diluted activator solution is passed through the fertilizer fixed bed to obtain an irrigation water containing P 2 0 5 20 mg/kg, CaO 26 mg/kg, MgO 13 mg/kg, Si0 2 by mass. 3 mg/kg, Fe0 2 mg/kg, B 2 0 3 lmg/kg, Zn 3 mg/kg, Mn 1 mg/kg, N 70 mg/kg, S 90 mg/kg and K 2 0 29 mg/kg.
使用上述灌溉水进行了棉花的田间试验。 经 66.7公顷的棉田试验 表明， 在获得棉花产量相同的情况下， 比传统施肥量节省 60%。  A field trial of cotton was carried out using the above-mentioned irrigation water. A 66.7-hectare cotton field test showed a 60% savings over conventional fertilization with the same cotton yield.
实施例二  Embodiment 2
选择颗粒直径约 1mm的钙镁磷肥， 它以钙镁磷肥质量计含有 P205 14 %、 CaO 36%、 MgO 8%、 Si02 31%、 FeO 1.5%, 称取 200 kg这种钙 镁磷肥以及 3kg硼泥加到有效容积为 0.3m3的反应器中， 构成一种固定 床。 Select calcium-magnesium-phosphorus fertilizer with a particle diameter of about 1 mm, which contains P 2 0 5 14 %, CaO 36%, MgO 8%, Si0 2 31%, FeO 1.5% by mass of calcium magnesium phosphate, and weigh 200 kg of this calcium and magnesium. Phosphate fertilizer and 3 kg of boron sludge were added to a reactor having an effective volume of 0.3 m 3 to form a fixed bed.
按下述比例称取原料，配制活化剂溶液： 5kg硫酸镁， 20kg硝酸钾， 5kg尿素，水 100公斤。将这种活化剂装入有效容积为 0.3 m3的储罐中。 The raw materials were weighed in the following proportions to prepare an activator solution: 5 kg of magnesium sulfate, 20 kg of potassium nitrate, 5 kg of urea, and 100 kg of water. This activator was charged into a storage tank having an effective volume of 0.3 m 3 .
从灌溉***中以流量 10 m3/h引入的灌溉用水， 按照 1000: 1的比 例加到活化剂溶液中得到一种稀释的活化剂溶液，让这种稀释的活化剂 溶液通过上述固定床后得到一种灌溉水，这种灌溉水含有以质量计 P205 50 mg/kg, N 50 mg/kg, K20 90 mg/kg, CaO 100mg/kg、 MgO 36 mg/kg、 Si02 60 mg/kg、 FeO 5 mg/kg, B2035 mg/kg。 The irrigation water introduced from the irrigation system at a flow rate of 10 m 3 /h is added to the activator solution in a ratio of 1000:1 to obtain a diluted activator solution, and the diluted activator solution is passed through the fixed bed. Obtained an irrigation water containing P 2 0 5 50 mg/kg, N 50 mg/kg, K 2 0 90 mg/kg, CaO 100 mg/kg, MgO 36 mg/kg, Si0 2 by mass 60 mg/kg, FeO 5 mg/kg, B 2 0 3 5 mg/kg.
使用得到的灌溉水进行了葡萄的田间试验。 经 10公顷的葡萄试验 表明， 在获得葡萄产量相同的情况下， 比传统施肥量节省 30%。  Field trials of the grapes were carried out using the obtained irrigation water. Tests on 10 hectares of grapes showed a 30% savings over conventional fertilization with the same yield.
实施例三  Embodiment 3
选择颗粒直径约 1.5mm的钢渣磷肥，它以钢渣磷肥质量计含有 P205 18 %、 CaO 40%、 MgO 3%、 Si02 5%、 FeO 10%、 MnO 3%, 称取 100 Kg 这种钢渣磷肥加入到有效容积为 0.2m3的反应器中， 构成一种固定床。 Select steel slag phosphate with a particle diameter of about 1.5 mm, which contains P 2 0 5 18 %, CaO 40%, MgO 3%, Si0 2 5%, FeO 10%, MnO 3%, and weigh 100 Kg. The steel slag phosphate fertilizer is added to a reactor having an effective volume of 0.2 m 3 to form a fixed bed.
按下述比例称取原料， 配制活化剂溶液： 5kg硝酸钾， 5kg 98%硫 酸， 25kg氯化铵， 200公斤水。 将这种活化剂装入有效容积为 0.3 m3 的储罐中。 The raw materials were weighed in the following proportions to prepare an activator solution: 5 kg of potassium nitrate, 5 kg of 98% sulfuric acid, 25 kg of ammonium chloride, and 200 kg of water. The activator is loaded into an effective volume of 0.3 m 3 In the tank.
从灌溉***中以流量为 10 m3/h的灌溉用水，按照 300: 1的比例加 到活化剂溶液中得到一种稀释的活化剂溶液，让这种稀释的活化剂溶液 通过上述固定床后得一种灌溉水， 这种灌溉水含有以质量计 P2O5 30 mg/kg、 N 100 mg/kg> K20 37 mg/kg、 CaO 65mg/kg、 MgO 5 mg/kg、 Si02 8 mg/kg、 FeO 10 mg/kg、 MnO 5 mg/kg、 S 26 mg/kg。 From the irrigation system, the irrigation water with a flow rate of 10 m 3 /h is added to the activator solution in a ratio of 300:1 to obtain a diluted activator solution, and the diluted activator solution is passed through the above fixed bed. An irrigation water containing P 2 O 5 30 mg/kg, N 100 mg/kg > K 2 0 37 mg/kg, CaO 65 mg/kg, MgO 5 mg/kg, Si0 2 8 mg/kg, FeO 10 mg/kg, MnO 5 mg/kg, S 26 mg/kg.
使用得到的灌溉水进行了玉米的田间试验。 经 66.7 公顷的玉米试 验表明， 在获得玉米产量相同的情况下， 比传统施肥量节省 50%。  A field trial of corn was carried out using the obtained irrigation water. The 66.7 hectare corn test showed a 50% savings over conventional fertilization with the same corn yield.
由于土壤、 气候、 作物品种及其不同生长期等诸多因素， 作物对这 些营养元素的需求是不一样的。因此，人们施肥就应当适应于这些变化。 本发明的灌溉施肥法所产生的灌溉水中营养元素含量可在很大幅度范 围内变动正好适应于这种变化。  Due to factors such as soil, climate, crop varieties and their different growth stages, the demand for these nutrients varies from crop to crop. Therefore, people should adapt to these changes. The nutrient content of the irrigation water produced by the fertigation method of the present invention can be varied within a large range to accommodate this change.
釆用本发明的灌溉施肥方法可使肥料用量比传统施肥方法节省 30-60%, 可使肥料利用率达到 70-90%, 属于水、 肥高利用率的现代农 业方法。 此外， 还有利于实现农业产业化。  The fertigation method of the invention can save the fertilizer amount by 30-60% compared with the traditional fertilization method, and the fertilizer utilization rate can reach 70-90%, which is a modern agricultural method for water and fertilizer utilization. In addition, it is also conducive to the realization of agricultural industrialization.

Claims

权 利 要 求 Rights request
1. 一种农业灌溉施肥方法， 其特征在于： 该方法包括下述步骤：An agricultural fertigation method, characterized in that: the method comprises the steps of:
(i)把一种或多种选自磷矿粉、酸制磷肥和热制磷肥的非水溶性磷肥 颗粒作为磷源， 与非水溶性的中微量元素肥料或矿物颗粒混合后装入容 器中， 制备一种肥料颗粒固定床， 所述的非水溶性磷肥颗粒与所述的中 微量元素肥料颗粒混合比是 100: 0-2; (i) one or more water-insoluble phosphate fertilizer particles selected from the group consisting of phosphate rock, acid phosphate fertilizer and hot phosphate fertilizer as phosphorus source, mixed with water-insoluble medium and trace element fertilizer or mineral particles, and then placed in a container a fixed bed of fertilizer granules, wherein the mixing ratio of the water-insoluble phosphate fertilizer particles to the medium-micro element fertilizer granules is 100: 0-2;
(ii)将一种或多种选自无机酸、有机酸、无机盐和酰胺态氮肥的活化 剂溶于水中制备一种活化剂水溶液， 所述活化剂水溶液的质量浓度是 5-30%;  (ii) preparing an activator aqueous solution by dissolving one or more activators selected from the group consisting of inorganic acids, organic acids, inorganic salts and amide nitrogen fertilizers, the aqueous solution of the activator having a mass concentration of 5-30%;
(iii)让在步骤 (ii)制备的所述活化剂水溶液与水混合得到一种稀释的 活化剂溶液， 然后让所述稀释的活化剂溶液通过在步骤 (i)制备的所述肥 料颗粒固定床得到一种灌溉水， 所述的灌溉水含有磷以及多种中、 微量 元素， 这种灌溉水可直接灌溉作物；  (iii) mixing the aqueous solution of the activator prepared in the step (ii) with water to obtain a diluted activator solution, and then allowing the diluted activator solution to be fixed by the fertilizer granule prepared in the step (i) The bed receives an irrigation water, the irrigation water contains phosphorus and a plurality of medium and trace elements, and the irrigation water can directly irrigate the crop;
其中所述活化剂水溶液与水的混合比以体积计是 1:1000至 1:100; 所述稀释的活化剂溶液通过所述肥料颗粒固定床的线速度是 0.1-5 厘米 /秒；  Wherein the mixing ratio of the aqueous solution of the activator to water is 1:1000 to 1:100 by volume; the linear velocity of the diluted activator solution through the fixed bed of fertilizer particles is 0.1-5 cm / sec;
通过选择所述的非水溶性磷肥、 活化剂类型、 控制所述活化剂水溶 液与水的混合比与所述稀释的活化剂溶液的线速度，使得所述灌溉水的 质量浓度是 P205 1-200 mg/kg、 CaO 2-300 mg/kg, MgO 1-300 mg/kg、 Si02 1-300 mg/kg、 Fe 1-100 mg/kg、 Cu 0-5 mg/kg、 Zn 0-5 mg/kg、 Mn 0-5 mg/kg B203 0-5 mg/kg ^ N 0-400 mg/kg、 S 0-300 mg/kg和 K20 0-200 mg/kg The mass concentration of the irrigation water is P 2 0 5 by selecting the water-insoluble phosphate fertilizer, the type of activator, controlling the mixing ratio of the aqueous solution of the activator to water, and the linear velocity of the diluted activator solution. 1-200 mg/kg, CaO 2-300 mg/kg, MgO 1-300 mg/kg, Si0 2 1-300 mg/kg, Fe 1-100 mg/kg, Cu 0-5 mg/kg, Zn 0 -5 mg/kg, Mn 0-5 mg/kg B 2 0 3 0-5 mg/kg ^ N 0-400 mg/kg, S 0-300 mg/kg and K 2 0 0-200 mg/kg
2. 根据杈利要求 1所述的方法， 其特征在于所述的酸制磷肥是沉 淀磷酸钙； 所述的热制磷肥选自脱氟磷肥、 烧结钙钠磷肥、 偏磷酸钙、 钢渣磷肥或钙镁磷肥。  2. The method according to claim 1, characterized in that the acid phosphate fertilizer is precipitated calcium phosphate; the hot phosphate fertilizer is selected from the group consisting of defluorinated phosphate fertilizer, sintered calcium sodium phosphate fertilizer, calcium metaphosphate, steel slag phosphate fertilizer or Calcium magnesium phosphate fertilizer.
3. 根据杈利要求 1 所述的方法， 其特征在于所述含中微量元素的 肥料或矿物是一种或多种选自非水溶性的含钙、 镁、 硫、 硼、 钼、 锌、 锰、 铁和铜的肥料或矿物。 3. The method according to claim 1, characterized in that the fertilizer or mineral containing medium and trace elements is one or more selected from the group consisting of calcium, magnesium, sulfur, boron, molybdenum and zinc. Manganese, iron and copper fertilizers or minerals.
4. 根据权利要求 1-3 中任一杈利要求所述的方法， 其特征在于所 述的磷矿粉、 磷肥、 含中微量元素的肥料或矿物的粒度是 0.5亳米至 3 亳米。  The method according to any one of claims 1 to 3, characterized in that the phosphate rock, the phosphate fertilizer, the fertilizer containing a medium trace element or the mineral has a particle size of from 0.5 to 3 mm.
5. 根据权利要求 1 所述的方法， 其特征在于所述的无机酸是一种 或多种选自盐酸、 硝酸和硫酸的无机酸。  The method according to claim 1, wherein the inorganic acid is one or more inorganic acids selected from the group consisting of hydrochloric acid, nitric acid and sulfuric acid.
6. 根据杈利要求 1 所述的方法， 其特征在于所述的有机酸是一种 或多种选自草酸、 柠檬酸、 甲酸和苯甲酸的有机酸。  6. The method according to claim 1, wherein the organic acid is one or more organic acids selected from the group consisting of oxalic acid, citric acid, formic acid and benzoic acid.
7. 根据权利要求 1 所述的方法， 其特征在于所述的无机盐是一种 或多种选自硫酸氢钠、 硫酸氢钾、 尿素、 硝酸铵、 硫酸镁、 硫酸钾、 硫 酸铵、 氯化铵、 氯化钾或硝酸钾的无机盐。  7. The method according to claim 1, wherein the inorganic salt is one or more selected from the group consisting of sodium hydrogen sulfate, potassium hydrogen sulfate, urea, ammonium nitrate, magnesium sulfate, potassium sulfate, ammonium sulfate, chlorine. An inorganic salt of ammonium, potassium chloride or potassium nitrate.
8. 根据权利要求 1 所述的方法， 其特征在于所述的酰胺态氮肥是 尿素。  8. Process according to claim 1, characterized in that the amide nitrogen fertilizer is urea.
9. 根据权利要求 1 所述的方法， 其特征在于所述活化剂水溶液与 灌溉用水的混合比以体积计是 1 :500至 1 : 100。  9. The method according to claim 1, wherein the mixing ratio of the aqueous solution of the activator to the irrigation water is from 1:500 to 1:100 by volume.
10. 根据杈利要求 1所述的方法， 其特征在于所述稀释的活化剂溶 液通过所述肥料颗粒固定床的线速度是 0.5-2厘米 /秒。  10. The method according to claim 1, characterized in that the linear velocity of the diluted activator solution through the fixed bed of fertilizer granules is 0.5-2 cm/sec.
PCT/CN2006/001167 2005-06-09 2006-05-31 Fertilizing method for agricultural irrigation WO2006131056A1 (en)

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