WO2020088272A1 - Method for improving glass feeling of surface of diammonium phosphate - Google Patents

Method for improving glass feeling of surface of diammonium phosphate Download PDF

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WO2020088272A1
WO2020088272A1 PCT/CN2019/111876 CN2019111876W WO2020088272A1 WO 2020088272 A1 WO2020088272 A1 WO 2020088272A1 CN 2019111876 W CN2019111876 W CN 2019111876W WO 2020088272 A1 WO2020088272 A1 WO 2020088272A1
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diammonium phosphate
phosphoric acid
phosphate
particles
acid
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PCT/CN2019/111876
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French (fr)
Chinese (zh)
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王仁宗
杨慧萍
田楠
李淑华
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湖北富邦科技股份有限公司
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Publication of WO2020088272A1 publication Critical patent/WO2020088272A1/en

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    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/60Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05BPHOSPHATIC FERTILISERS
    • C05B7/00Fertilisers based essentially on alkali or ammonium orthophosphates
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity

Definitions

  • the present invention relates to the production field of diammonium phosphate, specifically, to the production field of diammonium phosphate granulation.
  • Improving the appearance quality of DAP products is one of the important means to establish the product image and user texture. Under the premise of ensuring the internal quality, the appearance quality of DAP product particles is usually tested and determined by the following indicators:
  • Particle size Use a test sieve with a pore size of 1.00 to 4.00mm to sieve the sample to calculate its fraction; and the degree to which the particle size tends to be consistent is called particle uniformity. At present, the particle size of diammonium phosphate is 90-92%
  • Roundness the degree to which the external arc of the particles is spherical.
  • a few companies use the sieving method to classify the particles with a particle size of 2.5-3.5mm first, and then randomly take dozens of particles from them, and the number of the particles that freely roll down to the preset reference distance on the inclined surface with a smooth surface accounts for the sampling number
  • the score (usually, the rounder particles are relatively free to fall off) is used as a measurement standard, and its value is generally 60% -80%. The larger the value, the more round the particles.
  • the roundness is the degree to which the particles visually feel their spherical shape and oiliness under light.
  • Particle strength Use a particle strength meter to measure the crushing pressure of particles. At present, the particle strength of DAP particles is 40-80 Newtons.
  • Translucency Pure ammonium phosphate is white crystals, and the product particles can intuitively feel its crystal clearness under the light. There is currently no quantitative standard to measure.
  • DAP diammonium phosphate
  • Patent "CN101891169B” is a method of using aluminum ions to improve the crystallinity of diammonium phosphate. It discloses that during the process of decomposing phosphate rock to phosphoric acid, the aluminum element accounts for 0 to 2.5% of the weight of the phosphate rock or has been generated. Adding 0 to 1.25% of aluminum by weight to phosphoric acid, and the addition amount of aluminum is not 0, so that the content of metal sesquioxide in diammonium phosphate is 1.5 to 3%, and phosphoric acid with good crystallinity can be obtained Diammonium particles.
  • diammonium phosphate Although the appearance of diammonium phosphate is improved and the particle strength is enhanced, due to the addition of aluminum, the sesquioxide content is high, which reduces the total nutrients of diammonium phosphate and affects the quality of diammonium phosphate. There are certain requirements for quality, and the use of phosphate rock is restricted to a certain extent.
  • the patent "CN1765734A” uses phosphoric acid with a high magnesium content to produce diammonium phosphate, which discloses the rapid neutralization of phosphoric acid and ammonia in the reactor: the phosphoric acid entering the tubular reactor to produce diammonium phosphate is non-neutralizing Phosphoric acid, the phosphoric acid that enters the pre-neutralization tank is washing acid.
  • the production load of the tubular reactor is controlled above 80% of the total production volume, and the production volume of the pre-neutralization tank is controlled below 20% of the total production volume.
  • This method can produce qualified diammonium phosphate products using wet-process phosphoric acid with a magnesium content of 1.5% to 2.5%, thereby broadening the application path of phosphate ores with high magnesium oxide content, and the produced products have a good crystallinity. Although the crystallization is very good, the product is not rounded, which makes the product easier to agglomerate, and it is limited to a specific process.
  • the patent "CN104193453A” discloses a production method containing trace elements of ammonium phosphate, which is characterized in that in the production process of ammonium phosphate, the method adopts the method of dissolving phosphoric acid and fully ammonizing the reaction of trace element oxides or salts, which will contain trace amounts
  • the oxides or salts of the elements are added to the acidolysis tank, the washing liquid from the ammonium phosphate washing system, phosphoric acid, and water are mixed and stirred to fully decompose the oxides or salts of trace elements into ions or complexes to form trace elements.
  • the phosphoric acid solution is transported by the feed pump into the tube counter acid tank, added with phosphoric acid, washing liquid, and process water to mix, rapidly ammoniated in the tubular reactor, sprayed and granulated in the granulator, and then dried , Sieving, cooling and wrapping to obtain ammonium phosphate compound fertilizer containing trace elements.
  • the ammonium phosphate compound fertilizer containing trace elements obtained by the method of the invention has good solubility.
  • the oxide or salt of the trace element is borax pentahydrate (Na 2 B 4 O 7 .5H 2 O), borax decahydrate (Na 2 B 4 O 7 .10H 2 O), zinc oxide (ZnO), zinc sulfate (ZnSO 4), zinc phosphate (Zn 3 (PO 4) 2 ), copper sulfate (CuSO 4 .5H 2 O), copper phosphate (Cu 3 (PO 4 ) 2 ), sodium phosphate (Na 3 PO 4 ), sodium selenite (Na 2 SeO 3 ), sodium selenite (Na 2 SeO 4 ), molybdenum trioxide (MoO 3 ), selenium oxide (SeO 2 ), Iron sulfate (Fe 2 (SO 4 ) 3 ), iron phosphate (FePO 4 ), iron oxide (Fe 2 O 3 ), manganese sulfate (MnSO 4 ),
  • the patent "CN101723733B" method for producing crystals of diammonium phosphate with added trace elements is to add proportionally to the diammonium phosphate product the soluble salt containing iodine, cobalt, selenium, zinc, copper, iron, manganese, boron.
  • the soluble salts containing iodine, cobalt, selenium, zinc, copper, iron, manganese, and boron are sodium iodide or potassium iodide, cobalt oxide, selenium oxide, zinc oxide, copper sulfate, iron sulfate, or ferrous sulfate, sulfuric acid Manganese, borax.
  • the purpose of the present invention is to provide a method for improving the surface glass feel of diammonium phosphate on the basis of the existing technology, improve the permeability, gloss, strength and other properties of diammonium phosphate particles, and improve the surface appearance of diammonium phosphate At the same time, the PH value of diammonium phosphate can be adjusted, and the selectivity to crops is broader.
  • a method for improving the surface glass feel of diammonium phosphate including the following steps:
  • a neutralizing tank is added with a mass of 0.05 ⁇ 0.20 of phosphoric acid in the neutralizing tank % Boric acid.
  • Boric acid is a weak acid.
  • a mixture of boric acid and ammonium borate is formed in the neutralization tank.
  • the ammonium borate contains crystal water and its molecular formula is NH 4 HB 4 O 7 ⁇ 3H 2 O.
  • the mixture of boric acid and ammonium borate is The surface of the diammonium phosphate forms a dense glass fiber and the crystallization mechanism of the boric acid and borate system, which not only enhances the gloss and firmness of the surface of the diammonium phosphate but also improves the particle strength, so that the surface of the diammonium phosphate has a clear glass feel.
  • the present invention can achieve the following points through the following tests:
  • Particle size Use a test sieve with a pore size of 2.00 to 4.00mm to sieve the sample to calculate its fraction; and the degree to which the particle size tends to be consistent is called particle uniformity.
  • the particle size of the diammonium phosphate prepared by the invention reaches more than 95%.
  • Roundness the degree to which the external arc of the particles is spherical.
  • the diammonium phosphate prepared by the present invention randomly takes dozens of particles from it, and the number of free rolls on a smooth surface inclined plate to a preset reference distance accounts for the fraction of the number of samples (usually, it is more round The distance at which the particles are free to roll off is relatively long) As a measure, the value is generally greater than 80%. The larger the value, the more round the particles.
  • the roundness is the degree to which the particles visually feel their spherical shape and oiliness under light.
  • Particle strength A particle strength meter is used to measure the crushing pressure of the particles, and the particle strength of the diammonium phosphate particles prepared by the present invention is 80-100 Newtons.
  • Ammonium phosphate is a crystal structure.
  • the diammonium phosphate product particles prepared by the present invention are visually clear and transparent under the light, and the glass feels strong.
  • the method of the present invention mainly improves the roundness, strong crystal sense, obvious glass feeling, high strength and other properties of the diammonium phosphate particles, makes the surface appearance of the diammonium phosphate have a glassy feel, and at the same time can make the diammonium phosphate contain boron trace elements.
  • Many crops have fertilizer effects that can improve crop quality and increase yield. It also has insecticidal and catalyst effects.
  • a diammonium phosphate enterprise in Hubei uses the traditional pre-neutralization-drum ammonia granulation method for production.
  • the specific process flow is: in the pre-neutralization tank, concentrated phosphoric acid and liquid ammonia are reacted at 120 ° C to produce a slurry with an N / P of 1.5, and the slurry is pumped into the granulator.
  • the slurry and ammonia are further reacted to produce DAP with an N / P of 1.8 to 1.9 and a moisture content of 3 to 4%, which is fed into a co-current rotary dryer and dried into a finished product. Due to the influence of impurities such as magnesium oxide phosphate, the produced diammonium phosphate particles have insufficient roundness, no glossiness, low strength, and easy agglomeration.
  • 0.06% boric acid with a purity of 99.8% by weight of phosphoric acid in the neutralization tank is added to the phosphoric acid pre-neutralization tank, and the reaction is performed to generate a slurry with an N / P of 1.5, and then the slurry is pumped into the granulator.
  • the produced diammonium phosphate particles are round, strong crystalline, obvious glass, high strength, and good flowability of the diammonium phosphate particles.
  • the tested particle size reaches 96%, the roundness reaches 80%, and the particle strength reaches 90 Newtons.
  • a diammonium phosphate enterprise in Gansu province uses the pre-neutralization + tube reactor mixing process for production.
  • the specific process flow is as follows: the concentrated acid in the wet phosphoric acid storage tank and the washing liquid (N / P is about 0.6) are prepared into a certain concentration of dilute phosphoric acid (N / P ⁇ 0.6), and then the prepared dilute phosphoric acid and The liquid ammonia in the integrated tank area reacts in the pre-neutralization reactor (120 ° C) + tubular reactor (140 ° C) to produce a diammonium phosphate slurry (N / P is about 1.5), and the slurry is sprayed to the The granulation is carried out in the granulator.
  • the slurry and ammonia are further reacted to produce DAP with an N / P of 1.9.
  • the material granulated by the granulator enters the dryer to dry the material into a finished product.
  • the tubular reactor can produce 60-70% of the total ammonium phosphate slurry required, and the remaining 30-40% is produced by the neutralization tank. Due to the limitation of ore quality, the produced sesquioxide phosphate has a high impurity content, and the produced diammonium phosphate particles have insufficient roundness, lack of permeability, and low strength. With the patent "CN101891169B", the product's nutrients are not up to the standard; with the patent "CN1765734A”, the capacity of the tubular reactor is limited.
  • 0.18% boric acid with a purity of 99.8% by weight of phosphoric acid in the neutralization tank is added to the phosphoric acid pre-neutralization tank, and then the slurry is pumped into the granulator.
  • the produced diammonium phosphate particles are round, strong crystalline, obvious glass, high strength, and good flowability of the diammonium phosphate particles.
  • the tested particle size reaches 95%, the roundness reaches 81%, and the particle strength reaches 85 Newtons.
  • the specific technological process is as follows: the concentrated acid and washing liquid (N / P is about 0.8) in the wet phosphoric acid storage tank are prepared into a certain concentration of dilute phosphoric acid (N / P ⁇ 0.6), and then the prepared dilute phosphoric acid and The liquid ammonia in the integrated tank area reacts in the pre-neutralization reactor (120 ° C) + tubular reactor (140 ° C) to produce a diammonium phosphate slurry (N / P is about 1.5), and the slurry is sprayed to the The granulation is carried out in the granulator.
  • the slurry and ammonia are further reacted to produce DAP with an N / P of 1.9.
  • the material granulated by the granulator enters the dryer to dry the material into a finished product.
  • the tubular reactor can produce 60-70% of the total ammonium phosphate slurry required, and the remaining 30-40% is produced by the neutralization tank. Due to the limitation of ore quality, the produced sesquioxide phosphate has a high impurity content, and the produced diammonium phosphate particles have insufficient roundness, lack of permeability, and low strength. With the patent "CN101891169B", the product's nutrients are not up to the standard; with the patent "CN1765734A”, the capacity of the tubular reactor is limited.
  • the produced diammonium phosphate particles are round, strong crystalline, obvious glass, high strength, and good flowability of the diammonium phosphate particles.
  • the tested particle size reaches 96%, the roundness reaches 82%, and the particle strength reaches 90 Newtons.
  • a diammonium phosphate enterprise in Hubei uses the traditional pre-neutralization-drum ammonia granulation method for production.
  • the specific process flow is: In the pre-neutralization tank, concentrated phosphoric acid and liquid ammonia are reacted at 110-120 ° C to produce a slurry with an N / P of 1.5-1.8, which is pumped into the granulator by the slurry; in the granulator In the process, the slurry further reacts with ammonia to form DAP with N / P of 1.8 to 1.9 and moisture content of 3 to 4%, and enters the co-current rotary dryer to dry it into finished products. Due to the influence of impurities such as magnesium oxide phosphate, the produced diammonium phosphate particles have insufficient roundness, no glossiness, low strength, and easy agglomeration.

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  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plant Pathology (AREA)
  • Fertilizers (AREA)

Abstract

Disclosed by the present invention is a method for improving the glass feeling of the surface of diammonium phosphate, comprising the following steps: in a conventional method for producing diammonium phosphate by using phosphoric acid, boric acid which accounts for 0.05-0.20% by mass of the phosphoric acid in a neutralization tank is added into the neutralization tank, the boric acid being a weak acid. The method according to the present invention is mainly used for improving properties such as transparency, luster and strength of diammonium phosphate particles, and may simultaneously allow the diammonium phosphate to contain boron microelements, have fertilizer efficiency to many crops, improve the crop quality, increase yield, and have insecticidal and catalyst effects.

Description

一种提高磷酸二铵的表面玻璃感的方法Method for improving surface glass feeling of diammonium phosphate 技术领域Technical field
本发明涉及磷酸二铵的生产领域,具体来说,涉及磷酸二铵造粒的生产领域。The present invention relates to the production field of diammonium phosphate, specifically, to the production field of diammonium phosphate granulation.
背景技术Background technique
随着市场不断发展,用户对磷酸二铵产品的质量要求也不断提升。特别是对磷酸二铵的外观质量要求很高,对于控制好产品粒度、圆润度、色度、结晶感将成为磷酸二铵产品质量的直观标准。With the continuous development of the market, the quality requirements of users for diammonium phosphate products have also been continuously improved. In particular, the appearance quality of diammonium phosphate is very high, and it will become an intuitive standard for the quality of diammonium phosphate to control the product particle size, roundness, color and crystallinity.
提升DAP产品外观质量是树立产品形象和用户质感的重要手段之一,在保证内在质量的前提下,通常DAP产品粒子外观质量由以下几项指标进行检验、判定:Improving the appearance quality of DAP products is one of the important means to establish the product image and user texture. Under the premise of ensuring the internal quality, the appearance quality of DAP product particles is usually tested and determined by the following indicators:
1、粒度:用孔径为1.00-4.00mm的试验筛筛分样品计算其所占的分率;而粒子大小规格趋于一致的程度,称为粒子均匀度。目前磷酸二铵粒度在90-92%1. Particle size: Use a test sieve with a pore size of 1.00 to 4.00mm to sieve the sample to calculate its fraction; and the degree to which the particle size tends to be consistent is called particle uniformity. At present, the particle size of diammonium phosphate is 90-92%
2、圆整度:颗粒外表轮廓圆弧呈球形的程度。少数企业用筛分法先将样品粒度2.5-3.5mm的粒子分级出来,然后从中随机取数十颗粒子,以其在表面光滑的斜板上自由滚落到预设基准距离的数量占抽样数的分率(通常情况下,较圆的粒子自由滚落的距离相对远一些)作为衡量标准,其数值一般在60%-80%,数值越大,说明粒子越圆。而圆润度则是颗粒在光线下肉眼直观感觉其球形和油润性的程度。2. Roundness: the degree to which the external arc of the particles is spherical. A few companies use the sieving method to classify the particles with a particle size of 2.5-3.5mm first, and then randomly take dozens of particles from them, and the number of the particles that freely roll down to the preset reference distance on the inclined surface with a smooth surface accounts for the sampling number The score (usually, the rounder particles are relatively free to fall off) is used as a measurement standard, and its value is generally 60% -80%. The larger the value, the more round the particles. The roundness is the degree to which the particles visually feel their spherical shape and oiliness under light.
3、颗粒强度:使用颗粒强度仪测量粒子的破碎压力,目前磷酸二铵粒子颗粒强度在40-80牛顿。3. Particle strength: Use a particle strength meter to measure the crushing pressure of particles. At present, the particle strength of DAP particles is 40-80 Newtons.
4、透感:纯磷酸铵盐是白色晶体,产品颗粒在光线下肉眼直观感觉其晶莹剔透性,目前无定量标准衡量。4. Translucency: Pure ammonium phosphate is white crystals, and the product particles can intuitively feel its crystal clearness under the light. There is currently no quantitative standard to measure.
国内很多科研院所和企业做了大量工作,依据磷酸二铵(DAP)的造粒(成粒)机理,从造粒工序的原料、工艺、设备三方面分析了影响DAP造粒的各因素,从料浆中和度、中和温度、含水量、粘度、造粒工序的返料比、洗涤液、母料粒度分布、喷浆量和通氨量,以及造粒机内的料浆分布器、氨分布器和橡胶衬板等方面探讨了对造粒的影响,并取得一定的成效。Many domestic research institutes and enterprises have done a lot of work. Based on the granulation (granulation) mechanism of diammonium phosphate (DAP), the factors influencing the granulation of DAP are analyzed from the raw material, process and equipment of the granulation process. From the slurry neutralization degree, neutralization temperature, water content, viscosity, granulation process return ratio, washing liquid, masterbatch particle size distribution, spray volume and ammonia flux, and the slurry distributor in the granulator , Ammonia distributor and rubber liner etc. discussed the impact on granulation, and achieved certain results.
专利《CN101891169B》一种利用铝离子改善磷酸二铵结晶感的方法,公开了在磷矿 石被分解生成磷酸的过程中添加占磷矿石重量的0~2.5%的铝元素或在已经生成的磷酸中添加占磷酸重量的0~1.25%的铝元素,并且其中铝元素的添加量不为0,使磷酸二铵中金属倍半氧化物含量在1.5~3%,可以得到结晶感好的磷酸二铵粒子。虽然改善了磷酸二铵外观,增强了粒子强度,但由于添加了铝元素,倍半氧化物含量高,降低了磷酸二铵总养分,影响了磷酸二铵的品质;再者,对磷矿石品质有一定要求,在一定程度上限制对磷矿石的使用。Patent "CN101891169B" is a method of using aluminum ions to improve the crystallinity of diammonium phosphate. It discloses that during the process of decomposing phosphate rock to phosphoric acid, the aluminum element accounts for 0 to 2.5% of the weight of the phosphate rock or has been generated. Adding 0 to 1.25% of aluminum by weight to phosphoric acid, and the addition amount of aluminum is not 0, so that the content of metal sesquioxide in diammonium phosphate is 1.5 to 3%, and phosphoric acid with good crystallinity can be obtained Diammonium particles. Although the appearance of diammonium phosphate is improved and the particle strength is enhanced, due to the addition of aluminum, the sesquioxide content is high, which reduces the total nutrients of diammonium phosphate and affects the quality of diammonium phosphate. There are certain requirements for quality, and the use of phosphate rock is restricted to a certain extent.
专利《CN1765734A》用含镁量高的磷酸生产磷酸二铵的方法,公开了将磷酸和氨在反应器中迅速进行中和:进入管式反应器生产磷酸二铵的磷酸为无中和度的磷酸,进入预中和槽的磷酸为洗涤酸。管式反应器的生产负荷控制在总生产量的80%以上,预中和槽生产量控制在总生产量的20%以下。该方法可以使用含镁量在1.5%~2.5%的湿法磷酸生产出合格的磷酸二铵产品,从而拓宽了氧化镁含量高的磷矿石的应用途径,而且生产的产品结晶感很好。虽结晶感很好,但产品不太圆润,导致产品较易结块,同时受限于特定的工艺流程。The patent "CN1765734A" uses phosphoric acid with a high magnesium content to produce diammonium phosphate, which discloses the rapid neutralization of phosphoric acid and ammonia in the reactor: the phosphoric acid entering the tubular reactor to produce diammonium phosphate is non-neutralizing Phosphoric acid, the phosphoric acid that enters the pre-neutralization tank is washing acid. The production load of the tubular reactor is controlled above 80% of the total production volume, and the production volume of the pre-neutralization tank is controlled below 20% of the total production volume. This method can produce qualified diammonium phosphate products using wet-process phosphoric acid with a magnesium content of 1.5% to 2.5%, thereby broadening the application path of phosphate ores with high magnesium oxide content, and the produced products have a good crystallinity. Although the crystallization is very good, the product is not rounded, which makes the product easier to agglomerate, and it is limited to a specific process.
专利《CN104193453A》公开了一种含有微量元素磷酸铵的生产方法,其特征是该方法在磷酸铵生产过程中,采用磷酸溶解并充分氨化反应微量元素氧化物或盐类的方式,将含有微量元素的氧化物或盐类添加于酸解槽,回收来自磷酸铵洗涤系统的洗涤液、磷酸、水混合搅拌,将微量元素的氧化物或盐类充分分解成为离子或复合物,形成含有微量元素的磷酸溶液,由给料泵输送进入管反配酸槽,添加磷酸、洗涤液、工艺水混合,在管式反应器中快速氨化,并在造粒机中喷浆造粒,再经干燥、筛分、冷却、包裹得到含有微量元素的磷酸铵复合肥。采用本发明方法得到的含有微量元素的磷酸铵复合肥有良好的可溶性。The patent "CN104193453A" discloses a production method containing trace elements of ammonium phosphate, which is characterized in that in the production process of ammonium phosphate, the method adopts the method of dissolving phosphoric acid and fully ammonizing the reaction of trace element oxides or salts, which will contain trace amounts The oxides or salts of the elements are added to the acidolysis tank, the washing liquid from the ammonium phosphate washing system, phosphoric acid, and water are mixed and stirred to fully decompose the oxides or salts of trace elements into ions or complexes to form trace elements. The phosphoric acid solution is transported by the feed pump into the tube counter acid tank, added with phosphoric acid, washing liquid, and process water to mix, rapidly ammoniated in the tubular reactor, sprayed and granulated in the granulator, and then dried , Sieving, cooling and wrapping to obtain ammonium phosphate compound fertilizer containing trace elements. The ammonium phosphate compound fertilizer containing trace elements obtained by the method of the invention has good solubility.
权利要求所述的含有微量元素磷酸铵的生产方法中所述微量元素的氧化物或盐类为五水硼砂(Na 2B 4O 7.5H 2O)、十水硼砂(Na 2B 4O 7.10H 2O)、氧化锌(ZnO)、硫酸锌(ZnSO 4)、磷酸锌(Zn 3(PO 4) 2)、硫酸铜(CuSO 4.5H 2O)、磷酸铜(Cu 3(PO 4) 2)、磷酸钠(Na 3PO 4)、亚硒酸钠(Na 2SeO 3)、硒酸钠(Na 2SeO 4)、三氧化钼(MoO 3)、氧化硒(SeO 2)、硫酸铁(Fe 2(SO 4) 3)、磷酸铁(FePO 4)、氧化铁(Fe 2O 3)、硫酸锰(MnSO 4)、氧化锰(MnO)、硫酸钠(Na 2SO 4)、碘化钠(NaI)、碘酸钠(NaIO 3)的一种或多种。 In the production method of the trace element-containing ammonium phosphate according to claim, the oxide or salt of the trace element is borax pentahydrate (Na 2 B 4 O 7 .5H 2 O), borax decahydrate (Na 2 B 4 O 7 .10H 2 O), zinc oxide (ZnO), zinc sulfate (ZnSO 4), zinc phosphate (Zn 3 (PO 4) 2 ), copper sulfate (CuSO 4 .5H 2 O), copper phosphate (Cu 3 (PO 4 ) 2 ), sodium phosphate (Na 3 PO 4 ), sodium selenite (Na 2 SeO 3 ), sodium selenite (Na 2 SeO 4 ), molybdenum trioxide (MoO 3 ), selenium oxide (SeO 2 ), Iron sulfate (Fe 2 (SO 4 ) 3 ), iron phosphate (FePO 4 ), iron oxide (Fe 2 O 3 ), manganese sulfate (MnSO 4 ), manganese oxide (MnO), sodium sulfate (Na 2 SO 4 ), One or more of sodium iodide (NaI) and sodium iodide (NaIO 3 ).
专利《CN101723733B》生产加有微量元素的磷酸二铵产晶的方法是在磷酸二铵产 品中按比例添加由含碘、钴、硒、锌、铜、铁、锰、硼元素的可溶性盐中的一种或几种,并与磷酸二铵料浆混合,经常规工艺造粒、干燥制成。所述含碘、钴、硒、锌、铜、铁、锰、硼元素的可溶性盐分别是碘化钠或碘化钾、氧化钴、氧化硒、氧化锌、硫酸铜、硫酸铁或硫酸亚铁、硫酸锰、硼砂。The patent "CN101723733B" method for producing crystals of diammonium phosphate with added trace elements is to add proportionally to the diammonium phosphate product the soluble salt containing iodine, cobalt, selenium, zinc, copper, iron, manganese, boron. One or more kinds, mixed with diammonium phosphate slurry, made by conventional granulation and drying. The soluble salts containing iodine, cobalt, selenium, zinc, copper, iron, manganese, and boron are sodium iodide or potassium iodide, cobalt oxide, selenium oxide, zinc oxide, copper sulfate, iron sulfate, or ferrous sulfate, sulfuric acid Manganese, borax.
磷肥与复肥2015年4月第30卷第4期论文《用三元相图控制磷酸二铵产品外观质量的研究》,探讨矿物杂质含量与产品外观质量结晶感的关系,通过对产品中的AI 2O 3、CaO、MgO、SiO 2、Fe 2O 3杂质构成三元相图的研究,找到了最合适的控制区间为AI 2O 3含量在1.65-2.20%;MgO含量不大于1.44%;SiO 2含量在不大于0.55%,以达到提高产品外观质量的目的。 Phosphate Fertilizer and Compound Fertilizer, Volume 30, Issue 4, April 2015, "Study on Controlling Appearance Quality of Diammonium Phosphate Products with Ternary Phase Diagram", explores the relationship between mineral impurity content and product appearance quality crystallinity, through the AI 2 O 3 , CaO, MgO, SiO 2 , and Fe 2 O 3 impurities constitute a ternary phase diagram, and the most suitable control interval is found for AI 2 O 3 content of 1.65-2.20%; MgO content is not greater than 1.44% ; SiO 2 content is not more than 0.55%, in order to achieve the purpose of improving product appearance quality.
硫磷设计与粉体工程2016年第3期论文《浅析影响DAP产品结晶感的因素》,文章分析了影响DAP产品结晶感的主要原因,提出了磷矿石和磷酸中的AI 2O 3、MgO杂质及固含量(淤泥含量)主要控制参数。 Sulphur and Phosphorus Design and Powder Engineering The third issue of 2016, "Analysis of Factors Affecting the Crystallinity of DAP Products", the article analyzes the main factors affecting the crystallinity of DAP products, and proposes AI 2 O 3 in phosphate rock and phosphoric acid. The main control parameters of MgO impurities and solid content (silt content).
发明内容Summary of the invention
本发明目的是在现有技术基础上,提供一种提高磷酸二铵的表面玻璃感的方法,提高磷酸二铵粒子的透感、光泽、强度等性能,提高磷酸二铵表面外观具有玻璃感的同时能够调节磷酸二铵PH值,对作物选择性更宽广。The purpose of the present invention is to provide a method for improving the surface glass feel of diammonium phosphate on the basis of the existing technology, improve the permeability, gloss, strength and other properties of diammonium phosphate particles, and improve the surface appearance of diammonium phosphate At the same time, the PH value of diammonium phosphate can be adjusted, and the selectivity to crops is broader.
本发明的技术方案为:The technical solution of the present invention is:
一种提高磷酸二铵的表面玻璃感的方法,包括以下步骤:在磷酸生产磷酸二铵的常规方法中,其特征在于:在中和槽中添加一种占中和槽磷酸质量的0.05~0.20%的硼酸。A method for improving the surface glass feel of diammonium phosphate, including the following steps: In the conventional method for producing diammonium phosphate in phosphoric acid, it is characterized in that: a neutralizing tank is added with a mass of 0.05 ~ 0.20 of phosphoric acid in the neutralizing tank % Boric acid.
硼酸是一种弱酸,在中和槽中形成硼酸和硼酸铵盐的混合物,硼酸铵盐含有结晶水,其分子式是NH 4HB 4O 7·3H 2O,硼酸和硼酸铵盐的混和物在磷酸二铵的表面形成致密的玻璃纤维和硼酸和硼酸盐体系的结晶机理,不但增强了磷酸二铵表面的光泽和坚固性能还提高粒子强度,使磷酸二铵表面具有明显的玻璃感。 Boric acid is a weak acid. A mixture of boric acid and ammonium borate is formed in the neutralization tank. The ammonium borate contains crystal water and its molecular formula is NH 4 HB 4 O 7 · 3H 2 O. The mixture of boric acid and ammonium borate is The surface of the diammonium phosphate forms a dense glass fiber and the crystallization mechanism of the boric acid and borate system, which not only enhances the gloss and firmness of the surface of the diammonium phosphate but also improves the particle strength, so that the surface of the diammonium phosphate has a clear glass feel.
本发明通过以下测试,能做到以下几点:The present invention can achieve the following points through the following tests:
1、粒度:用孔径为2.00-4.00mm的试验筛筛分样品计算其所占的分率;而粒子大小规格趋于一致的程度,称为粒子均匀度。通过本发明制得的磷酸二铵粒度达到在95%以上。1. Particle size: Use a test sieve with a pore size of 2.00 to 4.00mm to sieve the sample to calculate its fraction; and the degree to which the particle size tends to be consistent is called particle uniformity. The particle size of the diammonium phosphate prepared by the invention reaches more than 95%.
2、圆整度:颗粒外表轮廓圆弧呈球形的程度。通过本发明制得的磷酸二铵,从中随机取数十颗粒子,以其在表面光滑的斜板上自由滚落到预设基准距离的数量占抽样数的分率(通常情况下,较圆的粒子自由滚落的距离相对远一些)作为衡量标准,其数值一般在大于80%,数值越大,说明粒子越圆。而圆润度则是颗粒在光线下肉眼直观感觉其球形和油润性的程度。2. Roundness: the degree to which the external arc of the particles is spherical. The diammonium phosphate prepared by the present invention randomly takes dozens of particles from it, and the number of free rolls on a smooth surface inclined plate to a preset reference distance accounts for the fraction of the number of samples (usually, it is more round The distance at which the particles are free to roll off is relatively long) As a measure, the value is generally greater than 80%. The larger the value, the more round the particles. The roundness is the degree to which the particles visually feel their spherical shape and oiliness under light.
3、颗粒强度:使用颗粒强度仪测量粒子的破碎压力,通过本发明制得的磷酸二铵粒子颗粒强度在80-100牛顿。3. Particle strength: A particle strength meter is used to measure the crushing pressure of the particles, and the particle strength of the diammonium phosphate particles prepared by the present invention is 80-100 Newtons.
4、透感:磷酸铵盐是一种晶体结构,通过本发明制得的磷酸二铵产品颗粒在光线下肉眼直观感觉明显的晶莹剔透,玻璃感强烈。4. Translucency: Ammonium phosphate is a crystal structure. The diammonium phosphate product particles prepared by the present invention are visually clear and transparent under the light, and the glass feels strong.
本发明方法主要改善磷酸二铵粒子的圆润度、结晶感强、具有明显的玻璃感、强度高等性能,使磷酸二铵表面外观具有玻璃感,同时能够使磷酸二铵中含硼微量元素,对许多作物有肥效,能增进作物品质和提高产量。而且还具有杀虫和催化剂效果。The method of the present invention mainly improves the roundness, strong crystal sense, obvious glass feeling, high strength and other properties of the diammonium phosphate particles, makes the surface appearance of the diammonium phosphate have a glassy feel, and at the same time can make the diammonium phosphate contain boron trace elements. Many crops have fertilizer effects that can improve crop quality and increase yield. It also has insecticidal and catalyst effects.
具体实施方式detailed description
以下通过具体实施案例,进一步说明本发明The following further illustrates the present invention through specific implementation cases
实施案例1Implementation Case 1
湖北某磷酸二铵企业,采用传统的预中和-转鼓氨化粒化法生产。具体工艺流程为:在预中和槽中,浓磷酸与液氨在120℃下进行反应生成N/P为1.5的料浆,由料浆泵入造粒机。在造粒机中,料浆与氨进一步反应生成N/P为1.8~1.9、湿含量为3~4%的DAP,进入并流回转干燥机干燥成成品。由于磷酸氧化镁等杂质含量影响,生产出来的磷酸二铵粒子圆润度不够,没有光泽感,强度低,容易结块。A diammonium phosphate enterprise in Hubei uses the traditional pre-neutralization-drum ammonia granulation method for production. The specific process flow is: in the pre-neutralization tank, concentrated phosphoric acid and liquid ammonia are reacted at 120 ° C to produce a slurry with an N / P of 1.5, and the slurry is pumped into the granulator. In the granulator, the slurry and ammonia are further reacted to produce DAP with an N / P of 1.8 to 1.9 and a moisture content of 3 to 4%, which is fed into a co-current rotary dryer and dried into a finished product. Due to the influence of impurities such as magnesium oxide phosphate, the produced diammonium phosphate particles have insufficient roundness, no glossiness, low strength, and easy agglomeration.
采用本发明方法,在磷酸预中和槽中加入占中和槽磷酸重量的0.06%纯度99.8%硼酸,进行反应生成N/P为1.5的料浆,再由料浆泵入造粒机中。在其它工艺条件不变并与湖北某磷酸二铵企业相同情况下,生产出来的磷酸二铵粒子圆润、结晶感强、具有明显的玻璃感,强度高,磷酸二铵粒子流动性好。经测试粒度达96%,圆整度达80%,颗粒强度达90牛顿。Using the method of the present invention, 0.06% boric acid with a purity of 99.8% by weight of phosphoric acid in the neutralization tank is added to the phosphoric acid pre-neutralization tank, and the reaction is performed to generate a slurry with an N / P of 1.5, and then the slurry is pumped into the granulator. Under the same conditions of other processes and the same situation as a diammonium phosphate enterprise in Hubei, the produced diammonium phosphate particles are round, strong crystalline, obvious glass, high strength, and good flowability of the diammonium phosphate particles. The tested particle size reaches 96%, the roundness reaches 80%, and the particle strength reaches 90 Newtons.
实施案例2Implementation Case 2
甘肃某磷酸二铵企业,采用预中和+管式反应器混合工艺生产。具体工艺流程为: 将湿法磷酸贮槽内的浓酸与洗涤液(N/P约为0.6)配制成一定浓度的稀磷酸(N/P≤0.6),再将配好的稀磷酸与来自综合罐区的液氨在预中和反应器(120℃)+管式反应器(140℃)内反应,生成磷酸二铵料浆(N/P约为1.5),料浆喷浆洒到造粒机内进行喷浆造粒。在造粒机中,料浆与氨进一步反应生成N/P为1.9的DAP,经造粒机造粒后的物料进入干燥机对物料进行干燥成成品。管式反应器可生产所需磷酸铵料浆总量的60~70%,其余的30~40%由中和槽生产。受矿石品质的限制,生产的磷酸倍半氧化物杂质含量较高,生产出来的磷酸二铵粒子圆润度不够,缺乏透感,强度低。采用专利《CN101891169B》,产品养分不达标;采用专利《CN1765734A》,管式反应器产能受限制。A diammonium phosphate enterprise in Gansu province uses the pre-neutralization + tube reactor mixing process for production. The specific process flow is as follows: the concentrated acid in the wet phosphoric acid storage tank and the washing liquid (N / P is about 0.6) are prepared into a certain concentration of dilute phosphoric acid (N / P≤0.6), and then the prepared dilute phosphoric acid and The liquid ammonia in the integrated tank area reacts in the pre-neutralization reactor (120 ° C) + tubular reactor (140 ° C) to produce a diammonium phosphate slurry (N / P is about 1.5), and the slurry is sprayed to the The granulation is carried out in the granulator. In the granulator, the slurry and ammonia are further reacted to produce DAP with an N / P of 1.9. The material granulated by the granulator enters the dryer to dry the material into a finished product. The tubular reactor can produce 60-70% of the total ammonium phosphate slurry required, and the remaining 30-40% is produced by the neutralization tank. Due to the limitation of ore quality, the produced sesquioxide phosphate has a high impurity content, and the produced diammonium phosphate particles have insufficient roundness, lack of permeability, and low strength. With the patent "CN101891169B", the product's nutrients are not up to the standard; with the patent "CN1765734A", the capacity of the tubular reactor is limited.
采用本发明方法,在磷酸预中和槽中加入占中和槽磷酸重量的0.18%纯度99.8%硼酸,再由料浆泵入造粒机中。在其它工艺条件不变并与甘肃某磷酸二铵企业相同情况下,生产出来的磷酸二铵粒子圆润、结晶感强、具有明显的玻璃感,强度高,磷酸二铵粒子流动性好。经测试粒度达95%,圆整度达81%,颗粒强度达85牛顿。Using the method of the present invention, 0.18% boric acid with a purity of 99.8% by weight of phosphoric acid in the neutralization tank is added to the phosphoric acid pre-neutralization tank, and then the slurry is pumped into the granulator. Under the same conditions of other processes and the same situation as a diammonium phosphate enterprise in Gansu, the produced diammonium phosphate particles are round, strong crystalline, obvious glass, high strength, and good flowability of the diammonium phosphate particles. The tested particle size reaches 95%, the roundness reaches 81%, and the particle strength reaches 85 Newtons.
实施案例3Implementation Case 3
贵州某磷酸二铵企业,采用预中和+管式反应器混合工艺生产。具体工艺流程为:将湿法磷酸贮槽内的浓酸与洗涤液(N/P约为0.8)配制成一定浓度的稀磷酸(N/P≤0.6),再将配好的稀磷酸与来自综合罐区的液氨在预中和反应器(120℃)+管式反应器(140℃)内反应,生成磷酸二铵料浆(N/P约为1.5),料浆喷浆洒到造粒机内进行喷浆造粒。在造粒机中,料浆与氨进一步反应生成N/P为1.9的DAP,经造粒机造粒后的物料进入干燥机对物料进行干燥成成品。管式反应器可生产所需磷酸铵料浆总量的60~70%,其余的30~40%由中和槽生产。受矿石品质的限制,生产的磷酸倍半氧化物杂质含量较高,生产出来的磷酸二铵粒子圆润度不够,缺乏透感,强度低。采用专利《CN101891169B》,产品养分不达标;采用专利《CN1765734A》,管式反应器产能受限制。A diammonium phosphate enterprise in Guizhou, using pre-neutralization + tube reactor mixed process production. The specific technological process is as follows: the concentrated acid and washing liquid (N / P is about 0.8) in the wet phosphoric acid storage tank are prepared into a certain concentration of dilute phosphoric acid (N / P≤0.6), and then the prepared dilute phosphoric acid and The liquid ammonia in the integrated tank area reacts in the pre-neutralization reactor (120 ° C) + tubular reactor (140 ° C) to produce a diammonium phosphate slurry (N / P is about 1.5), and the slurry is sprayed to the The granulation is carried out in the granulator. In the granulator, the slurry and ammonia are further reacted to produce DAP with an N / P of 1.9. The material granulated by the granulator enters the dryer to dry the material into a finished product. The tubular reactor can produce 60-70% of the total ammonium phosphate slurry required, and the remaining 30-40% is produced by the neutralization tank. Due to the limitation of ore quality, the produced sesquioxide phosphate has a high impurity content, and the produced diammonium phosphate particles have insufficient roundness, lack of permeability, and low strength. With the patent "CN101891169B", the product's nutrients are not up to the standard; with the patent "CN1765734A", the capacity of the tubular reactor is limited.
采用本发明方法,在造粒机中加入占中和槽料浆质量的0.05%纯度99.9%硼酸。在其它工艺条件不变并与贵州某磷酸二铵企业相同情况下,生产出来的磷酸二铵粒子圆润、结晶感强、具有明显的玻璃感,强度高,磷酸二铵粒子流动性好。经测试粒度达96%,圆整度达82%,颗粒强度达90牛顿。Using the method of the invention, 0.05% purity 99.9% boric acid, which accounts for the mass of the neutralizing tank slurry, is added to the granulator. Under the same conditions of other processes and the same situation as a diammonium phosphate enterprise in Guizhou, the produced diammonium phosphate particles are round, strong crystalline, obvious glass, high strength, and good flowability of the diammonium phosphate particles. The tested particle size reaches 96%, the roundness reaches 82%, and the particle strength reaches 90 Newtons.
实施案例4Implementation Case 4
湖北某磷酸二铵企业,采用传统的预中和-转鼓氨化粒化法生产。具体工艺流程为: 在预中和槽中,浓磷酸与液氨在110-120℃下进行反应生成N/P为1.5-1.8的料浆,由料浆泵入造粒机;在造粒机中,料浆与氨进一步反应生成N/P为1.8~1.9、湿含量为3~4%的DAP,进入并流回转干燥机干燥成成品。由于磷酸氧化镁等杂质含量影响,生产出来的磷酸二铵粒子圆润度不够,没有光泽感,强度低,容易结块。A diammonium phosphate enterprise in Hubei uses the traditional pre-neutralization-drum ammonia granulation method for production. The specific process flow is: In the pre-neutralization tank, concentrated phosphoric acid and liquid ammonia are reacted at 110-120 ° C to produce a slurry with an N / P of 1.5-1.8, which is pumped into the granulator by the slurry; in the granulator In the process, the slurry further reacts with ammonia to form DAP with N / P of 1.8 to 1.9 and moisture content of 3 to 4%, and enters the co-current rotary dryer to dry it into finished products. Due to the influence of impurities such as magnesium oxide phosphate, the produced diammonium phosphate particles have insufficient roundness, no glossiness, low strength, and easy agglomeration.
采用本发明方法,在造粒机中加入占中和槽料浆质量的0.2%纯度纯度99.9%硼酸,在其它工艺条件不变并与湖北某磷酸二铵企业相同情况下,生产出来的磷酸二铵粒子圆润、结晶感强、具有明显的玻璃感,强度高,磷酸二铵粒子流动性好。经测试粒度达96%,圆整度达81%,颗粒强度达80牛顿。By adopting the method of the present invention, 0.2% purity and 99.9% boric acid with a mass of neutralizing tank slurry is added to the granulator. Under the same conditions of other processes and the same situation as a diammonium phosphate enterprise in Hubei, the diphosphoric acid produced The ammonium particles are round, strong in crystallization, have obvious glass feeling, high in strength, and the fluidity of the diammonium phosphate particles is good. The tested particle size reaches 96%, the roundness reaches 81%, and the particle strength reaches 80 Newtons.
以上所述,仅是本发明的实施例而已,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。The above is only an embodiment of the present invention, and does not limit the present invention in any form. Any simple modification or equivalent change made to the above embodiment based on the technical essence of the present invention without departing from the technical solution content of the present invention And modifications are still within the scope of the technical solution of the present invention.

Claims (1)

  1. 一种提高磷酸二铵的表面玻璃感的方法,包括以下步骤:在磷酸生产磷酸二铵的常规方法中,其特征在于:在中和槽中添加一种占中和槽磷酸质量的0.05~0.20%的硼酸。A method for improving the surface glass feel of diammonium phosphate, including the following steps: In the conventional method for producing diammonium phosphate in phosphoric acid, it is characterized in that: a neutralizing tank is added with a mass of 0.05 ~ 0.20 of phosphoric acid in the neutralizing tank % Boric acid.
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