WO2019192328A1 - 聚磷酸钙镁肥料、以磷酸和磷尾矿为原料制备的聚磷酸钙镁肥料及其制备方法 - Google Patents

聚磷酸钙镁肥料、以磷酸和磷尾矿为原料制备的聚磷酸钙镁肥料及其制备方法 Download PDF

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WO2019192328A1
WO2019192328A1 PCT/CN2019/079027 CN2019079027W WO2019192328A1 WO 2019192328 A1 WO2019192328 A1 WO 2019192328A1 CN 2019079027 W CN2019079027 W CN 2019079027W WO 2019192328 A1 WO2019192328 A1 WO 2019192328A1
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calcium
phosphorus
magnesium
fertilizer
phosphoric acid
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PCT/CN2019/079027
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English (en)
French (fr)
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胡兆平
陈宏坤
刘永秀
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金正大诺泰尔化学有限公司
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Priority to US17/043,752 priority Critical patent/US11787748B2/en
Priority to EP19782443.6A priority patent/EP3778535A4/en
Publication of WO2019192328A1 publication Critical patent/WO2019192328A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B13/00—Fertilisers produced by pyrogenic processes from phosphatic materials
    • C05B13/06—Alkali and alkaline earth meta- or polyphosphate fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B13/00—Fertilisers produced by pyrogenic processes from phosphatic materials
    • C05B13/02—Fertilisers produced by pyrogenic processes from phosphatic materials from rock phosphates
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D3/00—Calcareous fertilisers
    • C05D3/02—Calcareous fertilisers from limestone, calcium carbonate, calcium hydrate, slaked lime, calcium oxide, waste calcium products
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D5/00—Fertilisers containing magnesium

Definitions

  • the invention belongs to the technical field of chemical fertilizer production, in particular to a calcium magnesium phosphate fertilizer, a calcium polyphosphate fertilizer prepared by using wet process phosphoric acid and phosphorus tailings as raw materials and a preparation method thereof.
  • Phosphorus tailings are solid waste that cannot be used when phosphorus ore flotation concentrates are discharged.
  • the grade of phosphate ore in China is not high, which causes the phosphorus chemical industry to discharge a large amount of phosphorus tailings in the flotation concentrate of phosphate rock. For each 3 tons of phosphate rock, one ton of phosphorus tailings should be discharged.
  • the massive accumulation of phosphorus tailings not only occupies a large amount of land, but also brings environmental pollution. With the continuous development of China's phosphorus chemical industry and the increasing demand of society, the accumulation of phosphorus tailings is becoming more and more serious.
  • phosphorus tailings are mainly reflected in the following aspects: First, the use of phosphorus tailings as raw materials for the preparation of building materials, building materials such as cement, aerated concrete and glass-ceramics, etc. The consumption of a part of the phosphorus tailings relieved the accumulation of the phosphorous tailings to a certain extent, but did not make full use of the phosphorus tailings, resulting in the waste of some useful elements in the phosphorus tailings.
  • the phosphorus tailings The secondary flotation process further utilizes the phosphorus in the phosphorus tailings, which can effectively reduce the phosphorus content in the phosphorus tailings, but the utilization of phosphorus in the phosphorus tailings is still low, and cannot be fundamentally solved.
  • Third, the preparation of calcium magnesium phosphate fertilizer by a certain technical means of phosphorus tailings, the prior art includes the following:
  • the Chinese patent publication No. CN 101367673 A discloses "a method for directly preparing phosphorus-magnesium fertilizer by using phosphate rock flotation by-product tailings", and the specific process uses flotation phosphorus tailings slurry as raw material to control the water content of 40-45%.
  • the mixture reaction is directly carried out with the sulfur-phosphorus mixed acid, the reaction temperature is controlled at 60-90 ° C, and the reaction time is 30-60 min, thereby preparing a powdery or granular compound fertilizer.
  • the Chinese patent publication No. CN 101618981 A discloses a method for producing a phosphorus-magnesium compound fertilizer by using phosphorus tailings to re-float by-product high-magnesium phosphorus tailings slag.
  • the specific process is to dry and pulverize the phosphorus tailings.
  • the powder is used as a raw material, and the mixed reaction is directly carried out with the sulfur-phosphorus mixed acid, the reaction time is 35 to 55 minutes, and the reaction temperature is 50 to 80 ° C, thereby preparing a powdery or granular compound fertilizer.
  • CN 102161602 A discloses "a method for preparing a phosphorus-magnesium compound fertilizer using a residual acid and a high-magnesium phosphorus tailings slag", comprising the steps of: 1001-1003 parts of P 2 O 5 mass fraction is 4-7%, MgO mass fraction is 15-19% high magnesium phosphorus tailings slag drying, pulverized with 700-1300 parts containing P 2 O 5 mass fraction 42-46%, MgO mass fraction 3-6% wet
  • the phosphoric acid purification by-product raffinate acid is mixed in the reactor, and 0.1002-1.002 parts of surfactant is added, the reaction time is 10-20 min, the reaction temperature is controlled at 40-60 ° C; the fresh phosphorus-magnesium composite obtained after the reaction is combined
  • the fertilizer is dried at 100 ⁇ 5°C; after being pulverized and directly packaged, a powdery phosphorus-magnesium composite fertilizer product is obtained.
  • the implementation of the above three patents can consume a certain amount of phosphorus tailings and prepare a phosphorus-magnesium compound fertilizer, but the products prepared are mostly sulfate or phosphate, and the effective calcium, magnesium and phosphorus are less. Moreover, the nutrient content is low, the product has a slow effect, and the agronomic application effect is poor.
  • Diammonium phosphate and monoammonium phosphate belong to the binary quick-acting compound fertilizer, and contain nutrients necessary for the growth of nitrogen and phosphorus plants. They have been widely used as the main phosphate fertilizer for many years. However, there are some problems in the application of monoammonium and diammonium, that is, phosphorus and calcium, aluminum or iron are prone to form a delayed state, and phosphorus availability is lowered, resulting in a low utilization rate of phosphorus in the current season. In view of the fact that phosphorus in phosphorus-containing fertilizers is easily fixed by the soil, patent documents are solved in the form of polymeric phosphorus. For example, the Chinese Patent Publication No.
  • CN 105481515 A discloses a production method comprising a magnesium polyphosphate compound fertilizer, comprising the following steps: (1) using a wet process phosphoric acid and a magnesium oxide powder to be proportionally added to the reactor for reaction. Obtaining a dilute magnesium phosphate solution; (2) adding one or more of urea, ammonium nitrate, calcium ammonium nitrate, and nitrophosphate to the dilute magnesium phosphate solution, and placing it in an evaporator to evaporate to obtain a slurry (3) The slurry is produced to form a polyphosphate-containing compound fertilizer.
  • the magnesium polyphosphate compound fertilizer uses wet process phosphoric acid and magnesium oxide powder as raw materials, and the cost is relatively high, and only a small amount of orthophosphate is converted into polyphosphate in this method, the conversion rate is low, and the magnesium content is low.
  • a fertilizer product has been developed which can fully utilize the useful elements in the phosphorus tailings to prepare a slow-release phosphorus, which is not easily fixed, and which is not easily leached by calcium and magnesium and is easily absorbed by the crop. Important economic and environmental significance.
  • the present invention provides a calcium polyphosphate fertilizer, a calcium polyphosphate fertilizer prepared by using wet process phosphoric acid and phosphorus tailings as a raw material, and a preparation method thereof, to solve a large accumulation of phosphorus tailings.
  • the environmental pollution caused by the invention and the technical problems of phosphorus, calcium and magnesium in the phosphorus-magnesium-calcium fertilizer prepared by using phosphorus tailings as raw materials in the prior art are not effective.
  • the effective phosphorus, effective magnesium and effective calcium in the present invention refer to phosphorus (as P 2 O 5 ) and magnesium which can be extracted by EDTA (ethylenediaminetetraacetic acid) under alkaline conditions of pH 12-13. Calcium content (calculated as CaO).
  • available phosphorus refers to soluble phosphorus and strontium-soluble phosphorus, and total phosphorus contains insoluble phosphorus in addition to available phosphorus.
  • the polymerization rate of the present invention refers to the percentage of available phosphorus (as P 2 O 5 ) minus the amount of phosphorus in the orthophosphate form (as P 2 O 5 ) to the available phosphorus (as P 2 O 5 ).
  • a calcium polyphosphate fertilizer calculated as P 2 O 5 , MgO, CaO, in the calcium magnesium phosphate fertilizer:
  • the polymerization rate of the calcium calcium magnesium phosphate fertilizer is ⁇ 50% based on P 2 O 5 .
  • the calcium polyphosphate fertilizer provided by the invention has the sustained release phosphorus, the phosphorus is not easily fixed, the calcium and magnesium are not easily leached, and are easily absorbed by the crop.
  • Calcium magnesium polyphosphate fertilizer includes a polyphosphate; phosphorus pentoxide (P 2 O 5) terms, the rate of polymerization of the poly magnesium phosphate fertilizers ⁇ 50%, preferably ⁇ 75%, e.g. 55- 90%.
  • the calcium calcium phosphate fertilizer comprises: 50-68% of total phosphorus, 47-66% of available phosphorus; further preferably 55-65% of total phosphorus and 54-64% of available phosphorus.
  • total magnesium phosphate polyphosphate fertilizer total magnesium 5-18%, effective magnesium 4-15%; further preferably total magnesium 8-15%, effective magnesium 8-14%.
  • total calcium 11%-20% effective calcium 10%-18%; further preferably total calcium 13%-20%, effective calcium 12%-17%. All of the above are by mass percentage; respectively, based on P 2 O 5 , magnesium oxide (MgO), and calcium oxide (CaO).
  • the effective content of phosphorus, calcium and magnesium in the phosphorus magnesium calcium fertilizer according to the embodiment of the invention is high, which is beneficial to the application.
  • the phosphorus in the product has sustained release property, and the product is applied into the soil, wherein the polymerized phosphorus is not quickly fixed, but the orthophosphate is slowly released to meet the crop demand, also due to the polyphosphoric acid.
  • the role of magnesium, calcium is not easy to be leached by water, especially suitable for crops with high demand for calcium and magnesium.
  • the polymerization rate of the calcium calcium magnesium phosphate fertilizer is ⁇ 50% based on P 2 O 5 .
  • the polyphosphate magnesium calcium fertilizer provided by the embodiment of the invention has the advantages of slow release phosphorus, phosphorus, calcium and magnesium, and the cost is relatively low, and can solve the environmental pollution problem caused by the massive accumulation of the phosphorus tailings.
  • the phosphorus tailings are one of the raw materials for preparing the calcium polyphosphate magnesium fertilizer, and the phosphorus tailings are the solid wastes which are discharged when the phosphate ore flotation concentrate is discharged.
  • the phosphorus tailings preferably have a mass percentage of phosphorus of 4 to 8% in terms of P 2 O 5 and a mass content of magnesium of 15 to 19% in terms of MgO.
  • the invention utilizes the characteristics of high content of calcium and magnesium in the phosphorous tailings, and fully utilizes these two elements.
  • Another raw material for preparing a calcium polyphosphate magnesium phosphate fertilizer according to an embodiment of the present invention is phosphoric acid, and the phosphoric acid is preferably wet phosphoric acid.
  • the component of the wet process phosphoric acid is phosphoric acid, and further contains trace amounts of other impurity ions; in the wet process phosphoric acid, the mass percentage of phosphorus is 15%-46%, further preferably 20%-30%, based on P 2 O 5 , More preferably, it is 22%-26%.
  • the polymerization rate of the calcium polyphosphate fertilizer is ⁇ 75% .
  • a method for preparing a calcium polyphosphate magnesium fertilizer by using wet process phosphoric acid and phosphorus tailings as raw materials comprises the following steps:
  • reaction mixture (1) mixing phosphorous tailings with phosphoric acid at room temperature to obtain a reaction mixture;
  • reaction mixture is polymerized under the action of hot air at a high temperature of 200-600 ° C, and the reaction is stopped when the polymerization rate of phosphoric acid (in terms of P 2 O 5 ) is ⁇ 50%, and the product is ground to obtain calcium polyphosphate.
  • phosphoric acid in terms of P 2 O 5
  • phosphorus tailings and phosphoric acid are mixed and reacted in a reactor at normal temperature.
  • the mass percentage of phosphorus is 4-8% in terms of P 2 O 5 ; and the mass content of magnesium in terms of MgO is 13-19%, based on CaO, the calcium content is 28% -38%.
  • the phosphoric acid is preferably wet-process phosphoric acid, and the mass percentage of phosphorus in the wet-process phosphoric acid is from 15% to 40%, more preferably from 20% to 30%, based on P 2 O 5 .
  • the ratio of the phosphorus tailings to the phosphoric acid in the step (1) preferably satisfies the reaction mixture: the molar ratio of P 2 O 5 :(CaO+MgO) is 1:1.2-1.8; further preferably, the phosphorus tailings and The proportion of phosphoric acid added is such that the molar ratio of P 2 O 5 :(CaO+MgO) is 1:1.25-1.45.
  • the preparation method of the invention must strictly control the ratio of phosphorus tailings to phosphoric acid in the system.
  • the molar ratio of P 2 O 5 :(CaO+MgO) in phosphorus tailings mixed with phosphoric acid is lower than 1:1.8, that is, the extraction efficiency of phosphorus, calcium and magnesium in phosphorous tailings is too much when phosphorus tailings are excessive. Will decrease, and excessive phosphorus tailings will reduce the effective nutrient content of the final product and reduce the polymerization efficiency.
  • the molar ratio of P 2 O 5 :(CaO+MgO) is higher than 1:1.2, that is, when the phosphoric acid is too much, the quality of the final product is lowered, the viscosity is increased, and the commerciality of the product is lowered.
  • the mixing reaction of the phosphorous tailings with phosphoric acid at room temperature in the step (1) is preferably from 1 to 3 h, more preferably from 1 h to 2.5 h.
  • the present invention preferably concentrates it to obtain a concentrate, followed by calcination.
  • the reaction mixture is concentrated at a temperature of 60-100 ° C and a pressure of 10-90 kPa, and concentrated to a mass percentage of water of 35-45% in the slurry. Then, the calcination reaction is carried out.
  • the above concentrated liquid may be concentrated and polymerized under the action of high temperature hot air to obtain a calcium polyphosphate fertilizer.
  • the temperature of the calcination reaction in the step (2) is from 350 to 450 °C.
  • the polymerization rate of phosphate P 2 O 5 in the count
  • the calcination reaction is stopped.
  • the product obtained by the calcination reaction can be ground to obtain a calcium polyphosphate fertilizer.
  • the preparation method of the present invention when the temperature is lower than 200 ° C, the polymerization rate of the product is greatly reduced, and when the temperature is higher than 600 ° C, the phosphoric acid phosphate in the product grows slowly, and the energy consumption cost is increased, and the production control is increased. Difficulty.
  • the polymerization rate can be ⁇ 75%.
  • the phosphoric acid and phosphorus tailings are directly mixed as raw materials, and the final product is obtained by high-temperature polymerization; the effective phosphorus, effective calcium and effective magnesium content of the product of the invention are high, wherein the total phosphorus is 50-68%. , effective phosphorus 47-66%, total magnesium 5-18%, effective magnesium 4-15%, total calcium 11% -20%, effective calcium 10% -18%, are all mass percentage; based on P 2 O 5 The polymerization rate of the calcium polyphosphate fertilizer is ⁇ 50%.
  • the polymeric phosphorus, the polymeric calcium, and the polymeric magnesium in the product prepared by the invention have sustained release property, and the product is applied to the soil, wherein the calcium polyphosphate is not rapidly fixed, but slowly releases calcium in the form of orthophosphoric acid.
  • magnesium to meet the needs of crops, improve the absorption and utilization of phosphorus, calcium, magnesium; also due to the role of polyphosphate, magnesium, calcium is not easily leached by water.
  • the invention converts phosphoric acid and phosphorus tailings into chemical fertilizers, can cure the pollution problem of phosphorus tailings slag, turn waste into treasure, and is an effective way to improve the comprehensive utilization rate of resources, and ensure the sustainable development of agricultural development and phosphorus chemical industry. Has important practical significance.
  • the invention has wide sources of raw materials, low energy consumption, simple production process, reliable product quality and good effect.
  • a method for preparing calcium polyphosphate calcium phosphate fertilizer by using wet process phosphoric acid and phosphorus tailings as raw materials, and the raw material indexes used are as follows:
  • Phosphorus tailings w(P 2 O 5 )7.07%, w(MgO) 16.2%, w(CaO) 35.11%;
  • reaction mixture (1) mixing 100 kg of phosphorous tailings with 400 kg of wet-process phosphoric acid in a reactor at room temperature for 1.5 h to obtain a reaction mixture;
  • a method for preparing calcium polyphosphate calcium phosphate fertilizer by using wet process phosphoric acid and phosphorus tailings as raw materials, and the raw material indexes used are as follows:
  • Phosphorus tailings w (P 2 O 5 ) 6.18%, w (MgO) 15.23%, w (CaO) 34.32%;
  • reaction mixture 100 kg of phosphorous tailings with 520 kg of phosphoric acid in a reactor at room temperature for 2 h to obtain a reaction mixture;
  • a method for preparing calcium polyphosphate calcium phosphate fertilizer by using wet process phosphoric acid and phosphorus tailings as raw materials, and the raw material indexes used are as follows:
  • WPA by: w (P 2 O 5) 22.39%, w (MgO) 1.33%, w (CaO) 0.19%;
  • Phosphorus tailings w (P 2 O 5 ) 7.02%, w (MgO) 17.23%, w (CaO) 33.35%;
  • reaction mixture 100 kg of phosphorous tailings with 580 kg of phosphoric acid in a reactor at room temperature for 1 h to obtain a reaction mixture;
  • a method for preparing calcium polyphosphate calcium phosphate fertilizer by using wet process phosphoric acid and phosphorus tailings as raw materials, and the raw material indexes used are as follows:
  • Phosphorus tailings w (P 2 O 5 ) 5.02%, w (MgO) 17.03%, w (CaO) 32.15%;
  • reaction mixture 100 kg of phosphorous tailings with 500 kg of phosphoric acid in a reactor at room temperature for 1 h to obtain a reaction mixture;
  • a method for preparing calcium polyphosphate calcium phosphate fertilizer by using wet process phosphoric acid and phosphorus tailings as raw materials, and the raw material indexes used are as follows:
  • Phosphorus tailings w (P 2 O 5 ) 5.91%, w (MgO) 18.33%, w (CaO) 31.35%;
  • reaction mixture 100 kg of phosphorous tailings with 500 kg of phosphoric acid in a reactor at room temperature for 1.5 h to obtain a reaction mixture;
  • reaction mixture is pumped into the top of the spray tower to be sprayed, and hot air of 450 ° C is introduced into the spray tower, and the mixed solution is concentrated and polymerized by hot air to obtain a calcium polyphosphate product.
  • a method for preparing calcium polyphosphate calcium phosphate fertilizer by using wet process phosphoric acid and phosphorus tailings as raw materials, and the raw material indexes used are as follows:
  • Phosphorus tailings w (P 2 O 5 ) 5.91%, w (MgO) 18.33%, w (CaO) 31.35%;
  • reaction mixture 100 kg of phosphorous tailings with 500 kg of phosphoric acid in a reactor at room temperature for 2 h to obtain a reaction mixture;
  • Example 2 The materials and methods were the same as in Example 1, except that the amount of the wet process phosphoric acid in the step (1) was changed to 350 kg.
  • Example 2 The materials and methods were the same as in Example 1, except that the reaction temperature of the step (2) was changed to 150 ° C for calcination.
  • Example 3 The materials and methods were the same as in Example 3, except that the amount of the wet process phosphoric acid in the step (1) was changed to 650 kg.
  • the products obtained in this comparative example have a large amount of phosphoric acid, and the viscosity of the material in the production process increases, the production is limited, and the commercial property is poor.
  • Raw materials urea (N 46%), potassium nitrate (N 13.5%, K 2 O 46%), monoammonium phosphate (N 11%, P 2 O 5 49%), calcium nitrate (N 11%, CaO 23%)
  • urea N 46%), potassium nitrate (N 13.5%, K 2 O 46%), monoammonium phosphate (N 11%, P 2 O 5 49%), calcium nitrate (N 11%, CaO 23%)
  • Magnesium sulfate heptahydrate (MgO 16%), ammonium polyphosphate (11-44-0) and water soluble fertilizer (16-8-34) are all commercially available products.
  • Test time and place The test was conducted in December 2016 in the watermelon greenhouse in Feixian County, Linyi City, Shandong province.
  • Treatment 1 18.5 kg of monoammonium phosphate, 16 kg of urea, 16 kg of potassium nitrate, 10 kg of calcium nitrate, 8.8 kg of magnesium sulfate heptahydrate as the base fertilizer, and when the watermelon grows to the egg size in the fruit-expanding period, 5 kg of water-soluble fertilizer is applied (16- 8-34), apply 5 kg after 10 days.
  • Treatment 2 14 kg of calcium polyphosphate obtained in Example 2, 16 kg of urea, and 16 kg of potassium nitrate were used as the base fertilizer. When the watermelon was grown to the egg size in the fruit-expanding period, 5 kg of water-soluble fertilizer was applied (16-8-34). 5 kg will be applied after 10 days.
  • Treatment 3 20 kg of calcium polyphosphate product prepared in Comparative Example 2, 16 kg of urea, and 16 kg of potassium nitrate were used as the base fertilizer. When the watermelon was grown to the egg size in the fruit-expanding period, 5 kg of water-soluble fertilizer was applied (16-8-34). ), apply 5kg after 10 days.
  • Treatment 4 19 kg of ammonium polyphosphate (11-44-0), 16 kg of urea, 16 kg of potassium nitrate, 10 kg of calcium nitrate, 8.8 kg of magnesium sulfate heptahydrate as a base fertilizer, when the watermelon grows to the size of the egg during the expansion period, the application 5kg water-soluble fertilizer (16-8-34), apply 5kg after 10 days.
  • treatment 4 applied ammonium polyphosphate instead of monoammonium phosphate, can increase yield by 7.3% compared with treatment 1, but it still increased by 8.9% less than treatment 2, indicating that ammonium polyphosphate and calcium fertilizers are difficult to reach the calcium magnesium phosphate of the present invention. effect.

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Abstract

本发明涉及一种以磷酸和磷尾矿为原料制备的聚磷酸钙镁肥料及其制备方法，该聚磷酸钙镁肥料，以磷尾矿和磷酸为原料制备得到，以P2O5、MgO、CaO计，该聚磷酸钙镁肥料中：总磷50-68％、有效磷47-66％、总镁5-18％、有效镁4-15％、总钙11％-20％、有效钙10％-18％，均为质量百分比；以P2O5计，该聚磷酸钙镁肥料的聚合率≥50％。本发明还提供上述肥料的制备方法。本发明所制备产品中的磷具有缓释性，本产品施入土壤中，其中的磷不会被迅速固定，而是缓慢释放出正磷酸盐，以满足作物需求，同样因聚磷酸的作用，镁，钙不易被水大量淋溶，特别适用于对钙、镁需求较高的作物。

Description

聚磷酸钙镁肥料、以磷酸和磷尾矿为原料制备的聚磷酸钙镁肥料及其制备方法
本申请要求于2018年04月02日提交中国专利局、申请号为201810281139.6、发明名称为“一种以磷酸和磷尾矿为原料制备的聚磷酸钙镁肥料及其制备方法”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
本发明属于化肥生产技术领域，具体的说是涉及一种聚磷酸钙镁肥料、一种以湿法磷酸和磷尾矿为原料制备的聚磷酸钙镁肥料及其制备方法。
背景技术
磷尾矿是磷矿浮选精矿时排出的未能加以利用的固体废料。我国磷矿石原矿的品位均不高，造成了磷化工行业在磷矿浮选精矿时都要向外排放大量的磷尾矿，每产3吨磷矿，要排放1吨磷尾矿，磷尾矿的大量堆积，不仅占用大量的土地，而且还会带来环境污染。随着我国磷化工产业的不断发展和社会需求的不断增加，磷尾矿的堆积问题越来越严重。
目前，我国对磷尾矿的利用主要体现在以下几个方面：第一，将磷尾矿用作制备建筑材料的原料，建筑材料如水泥、加气混凝土以及微晶玻璃等，上述途径虽然能消耗一部分磷尾矿，在一定程度上缓解了磷尾矿大量堆积的状况，但没有对磷尾矿进行充分的利用，造成了磷尾矿中部分有用元素的浪费；第二，将磷尾矿进行二次浮选，该方法对磷尾矿中的磷进一步进行利用，可有效降低磷尾矿中的磷含量，但对磷尾矿中磷的利用率依然偏低，且不能从根本上解决磷尾矿大量堆积的现状；第三，将磷尾矿通过一定的技术手段制备钙镁磷肥，其中已有技术包括以下几项：
公开号为CN 101367673 A的中国专利文献公开了“利用磷矿浮选副产尾矿直接制备磷镁肥料的方法”，具体过程以浮选磷尾矿浆为原料，控制其含水量40-45％，与硫磷混酸直接进行混合反应，反应温度控制60-90℃，反应时间30-60min，从而制得粉状或粒状复合肥。公开号为CN 101618981 A的中国专利文献公开了一种“利用磷尾矿再浮选副产高镁磷尾矿渣生产磷镁复合肥的方 法”，具体过程是以烘干粉碎后的磷尾矿粉为原料，与硫磷混酸直接进行混合反应，反应时间35～55min，反应温度在50～80℃，从而制得粉状或粒状复合肥。公开号为CN 102161602 A的中国专利文献公开了“一种利用萃余酸和高镁磷尾矿渣制备磷镁复合肥料的方法”，包括以下步骤：将1001-1003份P 2O 5质量分数为4-7％、MgO质量分数为15-19％高镁磷尾矿渣烘干、粉碎后与700-1300份含P 2O 5质量分数为42-46％、MgO质量分数为3-6％湿法磷酸净化副产萃余酸在反应器中混合反应，并添加0.1002-1.002份表面活性剂，反应时间为10-20min，反应温度控制在40-60℃；将反应后所得的新鲜磷镁复合肥料在100±5℃下烘干；经过粉碎直接包装后得到粉状磷镁复合肥料产品。
上述三篇专利的实施都能消耗掉一定量的磷尾矿，并制备出了磷镁复合肥，但所制备的产品中多为硫酸盐或磷酸盐，有效的钙、镁、磷较少，并且养分含量较低，产品起效慢，农学施用效果较差。
磷酸二铵、磷酸一铵属于二元速效复合肥，含有氮、磷二种植物生长必需的营养元素，多年来作为主要的磷肥广泛使用。但施用一铵和二铵也存在一些问题，即其中的磷和钙、铝或铁易形成迟效态，磷有效性降低，造成磷的当季利用率很低。针对含磷肥料中磷元素容易被土壤固定的问题，有专利文件采用聚合磷的形式解决。例如：公开号为CN 105481515 A的中国专利文件公开了一种含聚磷酸镁复肥的生产方法，包括以下步骤：(1)采用湿法磷酸和氧化镁粉按比例加入到反应器中反应，得到稀磷酸二氢镁溶液；(2)在稀磷酸二氢镁溶液中加入尿素、硝酸铵、硝酸铵钙、硝酸磷肥中的一种或几种，并置入蒸发器中加热蒸发，得到浆料；(3)将浆料进行生产形成含聚磷酸镁复肥。然而，该聚磷酸镁复合肥是采用湿法磷酸和氧化镁粉为原料，成本相对较高，且此方法仅有少量正磷酸根转化为聚磷酸根，转化率低，且镁含量较低。
综上所述，研发出一种能够将磷尾矿中有用元素充分利用，制备一种具有缓释磷，磷不易被固定，钙、镁不易被淋溶且易被作物吸收的化肥产品，具有重要的经济和环保意义。
发明内容
针对现有技术的不足，本发明提供一种聚磷酸钙镁肥料、一种以湿法磷酸 和磷尾矿为原料制备的聚磷酸钙镁肥料及其制备方法，以解决磷尾矿大量堆积带来的环境污染，以及现有技术中使用磷尾矿为原料制备的磷镁钙肥中磷、钙、镁有效性不高的技术问题。
术语说明：
本发明中的有效磷、有效镁、有效钙是指在pH值12-13的碱性条件下，通过EDTA(乙二胺四乙酸)可提取的磷(以P 2O 5计)、镁(以MgO计)、钙含量(以CaO计)。以磷为例，有效磷是指可溶性磷和枸溶性磷，总磷除了有效磷还包含难溶磷。
本发明的聚合率是指产品有效磷(以P 2O 5计)减去正磷酸根形式的磷(以P 2O 5计)后与有效磷(以P 2O 5计)的百分比。
本发明的技术方案如下：
一种聚磷酸钙镁肥料，以P 2O 5、MgO、CaO计，该聚磷酸钙镁肥料中：
总磷50-68％、有效磷47-66％、总镁5-18％、有效镁4-15％、总钙11％-20％、有效钙10％-18％，均为质量百分比；以P 2O 5计，该聚磷酸钙镁肥料的聚合率≥50％。
本发明提供的聚磷酸钙镁肥料具有缓释磷，磷不易被固定，钙、镁不易被淋溶，且易被作物吸收。
本发明实施例提供的聚磷酸钙镁肥料包括聚磷酸根；以五氧化二磷(P 2O 5)计，该聚磷酸钙镁肥料的聚合率≥50％，优选≥75％，例如55-90％。
在本发明的实施例中，该聚磷酸钙镁肥料中：总磷50-68％、有效磷47-66％；进一步优选总磷55-65％、有效磷54-64％。该聚磷酸钙镁肥料中：总镁5-18％、有效镁4-15％；进一步优选总镁8-15％、有效镁8-14％。该聚磷酸钙镁肥料中：总钙11％-20％，有效钙10％-18％；进一步优选总钙13％-20％，有效钙12％-17％。以上均为质量百分比；分别以P 2O 5、氧化镁(MgO)、氧化钙(CaO)计。本发明实施例所述的磷镁钙肥中磷、钙、镁有效含量较高，利于应用。
本发明实施例该产品中的磷具有缓释性，本产品施入土壤中，其中的聚合态磷不会被迅速固定，而是缓慢释放出正磷酸盐，以满足作物需求，同样因聚磷酸的作用，镁，钙不易被水大量淋溶，特别适用于对钙、镁需求较高的作物。
本发明优选实施例的技术方案如下：
一种聚磷酸钙镁肥料，以磷尾矿和磷酸为原料制备得到，以P 2O 5、MgO、CaO计，该聚磷酸钙镁肥料中：
总磷50-68％、有效磷47-66％、总镁5-18％、有效镁4-15％、总钙11％-20％、有效钙10％-18％，均为质量百分比；以P 2O 5计，该聚磷酸钙镁肥料的聚合率≥50％。
本发明实施例提供的聚磷镁钙肥中具有缓释磷，磷、钙、镁的有效性较高，并且成本相对较低，还能解决磷尾矿大量堆积带来的环境污染问题。
本发明实施例以磷尾矿为制备聚磷酸钙镁肥料的原料之一，磷尾矿是磷矿浮选精矿时排出的未能加以利用的固体废料。根据本发明，优选的，所述的磷尾矿中以P 2O 5计，磷的质量百分含量为4-8％、以MgO计，镁的质量含量为15-19％。本发明利用了磷尾矿中钙镁含量高的特点，将这两种元素充分进行了利用。
本发明实施例制备聚磷酸钙镁肥料的另一原料是磷酸，所述的磷酸优选湿法磷酸。所述湿法磷酸的成分就是磷酸，此外含有微量的其他杂质离子；湿法磷酸中以P 2O 5计，磷的质量百分含量为15％-46％，进一步优选20％-30％，更优选22％-26％。
在本发明的实施例中，以P 2O 5、MgO、CaO计，以磷尾矿和磷酸为原料制得的聚磷酸钙镁肥料中，进一步优选总磷55-65％、有效磷54-64％、总镁8-15％、有效镁8-14％、总钙13％-20％、有效钙12％-17％，均为质量百分比；该聚磷酸钙镁肥料的聚合率≥75％。
相应地，一种以湿法磷酸和磷尾矿为原料制备聚磷酸钙镁肥料的方法，包括步骤如下：
(1)将磷尾矿与磷酸在常温下混合反应，得反应混合液；
(2)将反应混合液在200-600℃下煅烧反应，当磷酸聚合率(以P 2O 5计)≥50％时停止反应，将产物粉磨，即得聚磷酸钙镁肥料；
或者，将反应混合液在200-600℃的高温下，在热风作用下聚合，当磷酸聚合率(以P 2O 5计)≥50％时停止反应，将产物粉磨，即得聚磷酸钙镁肥料。
本发明实施例将磷尾矿与磷酸在反应器中，在常温下混合反应。根据本发 明的制备方法，优选的，步骤(1)中所述的磷尾矿中以P 2O 5计，磷的质量百分含量为4-8％；以MgO计，镁的质量含量为13-19％，以CaO计，钙的质量含量为28％-38％。
并且，所述的磷酸优选湿法磷酸，湿法磷酸中以P 2O 5计，磷的质量百分含量为为15％-40％，进一步优选20％-30％。
所述步骤(1)中的磷尾矿与磷酸的加入比例优选满足反应混合液中：P 2O 5：(CaO+MgO)的摩尔比为1:1.2-1.8；进一步优选，磷尾矿与磷酸的加入比例满足反应混合液中：P 2O 5：(CaO+MgO)的摩尔比为1:1.25-1.45。
本发明的制备方法，须严格控制体系中磷尾矿与磷酸的配比。当磷尾矿与磷酸混合后其中的P 2O 5：(CaO+MgO)摩尔配比低于1:1.8，即磷尾矿过多时，磷酸对磷尾矿中磷、钙、镁的提取效率会降低，而且过量的磷尾矿会降低最终产品的有效养分含量，并降低聚合效率。当磷尾矿与磷酸混合后其中的P 2O 5：(CaO+MgO)摩尔配比高于1:1.2，即磷酸过多时，会使最终产品品质降低，粘度增大，产品商品性降低。
根据本发明的制备方法，优选的，步骤(1)中磷尾矿与磷酸在常温下混合反应的时间优选为1-3h，更优选为1h-2.5h。
得到反应混合液后，本发明实施例优选将其进行浓缩，得到浓缩液，再进行煅烧反应。根据本发明的制备方法，优选的，步骤(2)中，将反应混合液在温度60-100℃、压力10-90kPa下浓缩，浓缩到料浆中水的质量百分含量为35-45％，再进行煅烧反应。此外，还可将上述浓缩液在高温热风作用下，浓缩聚合，得到聚磷酸钙镁肥料。
根据本发明的制备方法，优选的，步骤(2)中煅烧反应的温度为350-450℃。本发明实施例当磷酸聚合率(以P 2O 5计)≥50％、优选≥75％时，停止煅烧反应。本发明实施例可将煅烧反应得到的产物粉磨，即得聚磷酸钙镁肥料。
根据本发明的制备方法，当温度低于200℃时，产品聚合率会大大降低，而当温度高于600℃时，产品中磷酸聚合磷增长缓慢，且会增加能耗成本，增大生产控制难度。
本发明的温度控制在350-450℃时，聚合率能够≥75％。
与现有技术相比，本发明实施例有益效果如下：
从以上技术方案可知，采用磷酸和磷尾矿为原料直接混合反应，并通过高温聚合方式，得到最终产品；本发明该产品有效磷、有效钙、有效镁含量高，其中总磷50-68％、有效磷47-66％、总镁5-18％、有效镁4-15％、总钙11％-20％、有效钙10％-18％，均为质量百分比；以P 2O 5计，该聚磷酸钙镁肥料的聚合率≥50％。且本发明所制备产品中的聚合磷、聚合钙、聚合镁具有缓释性，本产品施入土壤中，其中的聚磷酸钙镁不会被迅速固定，而是缓慢释放出正磷酸形式的钙、镁，以满足作物需求，提高了磷、钙、镁的吸收利用率；同样因聚磷酸根的作用，镁，钙不易被水大量淋溶。
本发明将磷酸与磷尾矿转化为化学肥料，能够根治磷尾矿渣的污染问题，使其变废为宝，又是提高资源综合利用率的有效途径，对保证农业发展及磷化工可持续发展具有重要的现实意义。本发明原料来源广、能耗低、生产流程简单、产品质量可靠，效果好。
具体实施方式
下面通过具体实施例对本发明作进一步说明，但不限于此。
实施例中“％”均为质量百分含量。
实施例1：
一种以湿法磷酸和磷尾矿为原料制备聚磷酸钙镁肥料的方法，所用原料指标如下：
湿法磷酸：w(P 2O 5)23.39％，w(MgO)1.01％，w(CaO)0.12％；
磷尾矿：w(P 2O 5)7.07％，w(MgO)16.2％，w(CaO)35.11％；
包括步骤如下：
(1)将100kg磷尾矿与400kg湿法磷酸在反应器中常温下混合反应1.5h，得反应混合液；
(2)将上述所得反应混合液在350℃下煅烧3.5h，粉磨后即可得聚磷酸钙镁产品。
产品分析结果如下：
Figure PCTCN2019079027-appb-000001
实施例2：
一种以湿法磷酸和磷尾矿为原料制备聚磷酸钙镁肥料的方法，所用原料指标如下：
湿法磷酸：w(P 2O 5)22.39％，w(MgO)1.23％，w(CaO)0.15％；
磷尾矿：w(P 2O 5)6.18％，w(MgO)15.23％，w(CaO)34.32％；
包括步骤如下：
(1)将100kg磷尾矿与520kg磷酸在反应器中常温下混合反应2h，得反应混合液；
(2)将上述反应混合液在80℃，30kPa浓缩，得到料浆中水的质量含量44-45％的浓缩液；
(3)将上述所得浓缩液在450℃下煅烧3h，粉磨后即可得聚磷酸钙镁产品。
产品分析结果如下：
Figure PCTCN2019079027-appb-000002
实施例3：
一种以湿法磷酸和磷尾矿为原料制备聚磷酸钙镁肥料的方法，所用原料指标如下：
湿法磷酸：w(P 2O 5)22.39％，w(MgO)1.33％，w(CaO)0.19％；
磷尾矿：w(P 2O 5)7.02％，w(MgO)17.23％，w(CaO)33.35％；
包括步骤如下：
(1)将100kg磷尾矿与580kg磷酸在反应器中常温下混合反应1h，得反应混合液；
(2)将上述反应混合液在90℃，30kPa浓缩，得到料浆中水的质量含量35-36％的浓缩液；
(3)将上述所得浓缩液在600℃下煅烧2h，粉磨后即可得聚磷酸钙镁产品。
产品分析结果如下：
Figure PCTCN2019079027-appb-000003
实施例4：
一种以湿法磷酸和磷尾矿为原料制备聚磷酸钙镁肥料的方法，所用原料指标如下：
湿法磷酸：w(P 2O 5)22.39％，w(MgO)1.33％，w(CaO)0.19％；
磷尾矿：w(P 2O 5)5.02％，w(MgO)17.03％，w(CaO)32.15％；
包括步骤如下：
(1)将100kg磷尾矿与500kg磷酸在反应器中常温下混合反应1h，得反应混合液；
(2)将上述反应混合液在90℃，30kPa浓缩，得到料浆中水的质量含量35-36％的浓缩液；
(3)将上述所得浓缩液在200℃下煅烧4h，粉磨后即可得聚磷酸钙镁产品。
产品分析结果如下：
Figure PCTCN2019079027-appb-000004
实施例5：
一种以湿法磷酸和磷尾矿为原料制备聚磷酸钙镁肥料的方法，所用原料指标如下：
湿法磷酸：w(P 2O 5)25.41％，w(MgO)1.41％，w(CaO)0.23％；
磷尾矿：w(P 2O 5)5.91％，w(MgO)18.33％，w(CaO)31.35％；
包括步骤如下：
(1)将100kg磷尾矿与500kg磷酸在反应器中常温下混合反应1.5h，得反应混合液；
(2)将上述反应混合液泵入喷雾塔顶端喷出，向喷雾塔内通入450℃的热风，在热风作用下，混合溶液浓缩聚合，得到聚磷酸钙镁产品。
产品分析结果如下：
Figure PCTCN2019079027-appb-000005
实施例6：
一种以湿法磷酸和磷尾矿为原料制备聚磷酸钙镁肥料的方法，所用原料指标如下：
湿法磷酸：w(P 2O 5)22.39％，w(MgO)1.33％，w(CaO)0.19％；
磷尾矿：w(P 2O 5)5.91％，w(MgO)18.33％，w(CaO)31.35％；
包括步骤如下：
(1)将100kg磷尾矿与500kg磷酸在反应器中常温下混合反应2h，得反应混合液；
(2)将上述反应混合液在90℃，30kPa浓缩，得到料浆中水的质量含量35-36％的浓缩液；
(3)将上述所得浓缩液在250℃下煅烧5h，粉磨后即可得聚磷酸钙镁产品。
产品分析结果如下：
Figure PCTCN2019079027-appb-000006
对比例1
原料和方法与实施例1相同，不同的是将步骤(1)中湿法磷酸的用量改为350kg。
产品分析结果如下：
Figure PCTCN2019079027-appb-000007
对比例2
原料和方法与实施例1相同，不同的是将步骤(2)的反应温度改为150℃下煅烧。
产品分析结果如下：
Figure PCTCN2019079027-appb-000008
对比例3
原料和方法与实施例3相同，不同的是将步骤(1)湿法磷酸的用量改为650kg。
产品分析结果如下：
Figure PCTCN2019079027-appb-000009
本对比例所得产品由于磷酸过量较多，生产过程物料黏度增大，生产受限，商品性较差。
试验例：
原料：尿素(N 46％)、硝酸钾(N 13.5％，K 2O 46％)、磷酸一铵(N 11％，P 2O 5 49％)、硝酸钙(N 11％，CaO 23％)、七水硫酸镁(MgO 16％)、聚磷酸铵(11-44-0)和水溶肥(16-8-34)皆为市售产品。
试验时间及地点：试验于2016年12月在山东省临沂市费县西瓜大棚内进行。
试验处理如下：
处理1：将18.5kg磷酸一铵，16kg尿素，16kg硝酸钾，10kg硝酸钙，8.8kg七水硫酸镁作为底肥施用，在膨果期西瓜长至鸡蛋大小时，冲施5kg水溶肥(16-8-34)，隔10天后再冲施5kg。
处理2：将14kg实施例2所制得的聚磷酸钙镁，16kg尿素，16kg硝酸钾作为底肥施用，在膨果期西瓜长至鸡蛋大小时，冲施5kg水溶肥(16-8-34)，隔10天后再冲施5kg。
处理3：将20kg对比例2所制得的聚磷酸钙镁产品，16kg尿素，16kg硝酸钾作为底肥施用，在膨果期西瓜长至鸡蛋大小时，冲施5kg水溶肥(16-8-34)，隔10天后再冲施5kg。
处理4：将19kg聚磷酸铵(11-44-0)，16kg尿素，16kg硝酸钾，10kg硝酸钙，8.8kg七水硫酸镁作为底肥施用，在膨果期西瓜长至鸡蛋大小时，冲施5kg水溶肥(16-8-34)，隔10天后再冲施5kg。
每个处理设3个重复组，取平均值，只计算头茬瓜的产量。试验结果参见
表1：
表1不同施肥处理对大棚西瓜的影响
肥料类型 Spad 可溶性固形物(g) 亩产(Kg) 增产比例(％)
处理1 68.6 9.5％ 2320 -
处理2 72.1 10.3％ 2695 16.2％
处理3 69.0 10.1％ 2425 4.5％
处理4 69.7 9.6％ 2489 7.3％
通过表1可以明显看出本发明的产品具有明显的提质增产的效果，另外处理3中施用的有效磷的用量虽然和处理2一样，但是因为处理3中磷的聚合率低，所以其比处理2少增产11.7％。表1中，Spad代表叶绿素测量值。
另外，处理4施用聚磷酸铵替代磷酸一铵，可比处理1增产7.3％，但是其仍然比处理2少增产8.9％，说明聚磷酸铵加钙肥和镁肥料难以达到本发明聚磷酸钙镁的效果。
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，任何未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。

Claims (10)

  1. 一种聚磷酸钙镁肥料，其特征在于，以P 2O 5、MgO、CaO计，该聚磷酸钙镁肥料中：
    总磷50-68％、有效磷47-66％、总镁5-18％、有效镁4-15％、总钙11％-20％、有效钙10％-18％，均为质量百分比；以P 2O 5计，该聚磷酸钙镁肥料的聚合率≥50％。
  2. 一种聚磷酸钙镁肥料，其特征在于，该肥料以磷尾矿和磷酸为原料制备得到，以P 2O 5、MgO、CaO计，该聚磷酸钙镁肥料中：
    总磷50-68％、有效磷47-66％、总镁5-18％、有效镁4-15％、总钙11％-20％、有效钙10％-18％，均为质量百分比；以P 2O 5计，该聚磷酸钙镁肥料的聚合率≥50％；
    优选的，该聚磷酸钙镁肥料中：总磷55-65％、有效磷54-64％、总镁8-15％、有效镁8-14％、总钙13％-20％、有效钙12％-17％，均为质量百分比；该聚磷酸钙镁肥料的聚合率≥75％。
  3. 根据权利要求2所述的聚磷酸钙镁肥料，其特征在于，所述的磷尾矿中以P 2O 5计，磷的质量百分含量为4-8％、以MgO计，镁的质量含量为15-19％；
    优选的，所述的磷酸为湿法磷酸；以P 2O 5计，湿法磷酸中磷的质量百分含量为15％-46％。
  4. 权利要求2-3任一项所述以湿法磷酸和磷尾矿为原料制备聚磷酸钙镁肥料的方法，包括步骤如下：
    (1)将磷尾矿与磷酸在常温下混合反应，得反应混合液；
    (2)将反应混合液在200-600℃的高温下，煅烧反应或在热风作用下聚合，当磷酸聚合率(以P 2O 5计)≥50％时停止反应，即得聚磷酸钙镁肥料。
  5. 根据权利要求4所述的制备方法，其特征在于，步骤(1)中磷尾矿与磷酸在常温下混合反应的时间为1-3h。
  6. 根据权利要求4所述的制备方法，其特征在于，步骤(1)中所述的磷尾矿中以P 2O 5计，磷的质量百分含量为4-8％；以MgO计，镁的质量含量为15-19％，以CaO计，钙的质量含量为28％-38％。
  7. 根据权利要求4所述的制备方法，其特征在于，所述步骤(1)中的磷尾矿与磷酸的加入比例满足反应混合液中P 2O 5：(CaO+MgO)的摩尔比为1:1.2-1.8。
  8. 根据权利要求7所述的制备方法，其特征在于，所述步骤(1)中的磷尾矿与磷酸的加入比例满足反应混合液中P 2O 5：(CaO+MgO)的摩尔比为1:1.25-1.45。
  9. 根据权利要求4所述的制备方法，其特征在于，步骤(2)中煅烧反应的温度为350-450℃。
  10. 根据权利要求4所述的制备方法，其特征在于，步骤(2)中将反应混合液在温度60-100℃，压力10-90kPa下浓缩到料浆中水的质量百分含量为35-45％，再进行煅烧反应。
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