WO2021254072A1 - 一种含硫富过磷酸钙生产装置和制备方法 - Google Patents

一种含硫富过磷酸钙生产装置和制备方法 Download PDF

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WO2021254072A1
WO2021254072A1 PCT/CN2021/094479 CN2021094479W WO2021254072A1 WO 2021254072 A1 WO2021254072 A1 WO 2021254072A1 CN 2021094479 W CN2021094479 W CN 2021094479W WO 2021254072 A1 WO2021254072 A1 WO 2021254072A1
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sulfur
phosphoric acid
rich
superphosphate
liquid
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PCT/CN2021/094479
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English (en)
French (fr)
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纳达夫·特钠
曹光玲
施永辉
陈月舞
何利全
高刚
许江涛
赵熙碧
胡彬
王文平
陈斌
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云南磷化集团海口磷业有限公司
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Publication of WO2021254072A1 publication Critical patent/WO2021254072A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B1/00—Superphosphates, i.e. fertilisers produced by reacting rock or bone phosphates with sulfuric or phosphoric acid in such amounts and concentrations as to yield solid products directly
    • C05B1/02—Superphosphates
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B1/00—Superphosphates, i.e. fertilisers produced by reacting rock or bone phosphates with sulfuric or phosphoric acid in such amounts and concentrations as to yield solid products directly
    • C05B1/10—Apparatus for the manufacture of superphosphates

Definitions

  • the invention belongs to the technical field of phosphate fertilizer production, and specifically relates to a sulfur-containing rich superphosphate production device and a preparation method.
  • the nutrient elements necessary for the whole growth period of crops include macro elements, middle elements and trace elements.
  • the middle element is the nutrient element that is inferior to nitrogen, phosphorus, potassium and higher than the trace element in the crop growth process, and accounts for the dry matter weight of the crop. 0.1%-0.5% of, usually refers to the three elements of calcium, magnesium and sulfur.
  • Sulfur is one of the essential nutrient elements for the growth and development of crops, second only to nitrogen, phosphorus, and potassium, ranking fourth.
  • the average sulfur content in crops is 2.0g/kg, which is equivalent to the phosphorus content, which is about dry matter weight. 0.1% to 0.5% of the content, with an average of about 0.25%. Sulfur participates in protein synthesis, respiration, photosynthesis, biological nitrogen fixation, lipid synthesis, sugar metabolism and other physiological activities in crop growth, and is an important factor affecting crop growth.
  • Sulfur in the soil exists in organic and inorganic forms, and in various oxidation forms. In the surface layer of agricultural soil in my country, most of the sulfur exists in the organic form, accounting for more than 90% of the total sulfur in the soil. In the non-calcareous surface soil, organic sulfur accounts for 85% to 94%, and inorganic sulfur accounts for 6% to 15%. Sulfate is the main form of plant roots that absorb sulfur from the soil. It is greatly affected by transpiration, and its ability to transport upwards and downwards with water is very poor, that is, the ability to reuse it is poor, and the form of sulfate in the soil is easy to lose.
  • Patent CN108752097A discloses a preparation method of elemental sulfur-based ammonium phosphate slow-release fertilizer. By preparing sulfur sol, the sulfur sol is blended, granulated, wrapped, and washed to obtain elemental sulfur-containing ammonium phosphate slow-release fertilizer. In order to ensure the dispersion of elemental sulfur, emulsifiers, stabilizers, dispersants, etc. are used. The process is complicated and costly, uses a large number of additives that cannot be absorbed by crops, and is difficult to achieve large-scale production.
  • Patent CN104529625 A discloses a uniform addition method of elemental sulfur in ammonium phosphate.
  • Sulfur colloid is prepared by mixing sulfur and nonionic surfactant with water, and then sulfur suspension or sulfur colloid is added to the raw material phosphoric acid or ammonium phosphate.
  • sulfur suspension or sulfur colloid is added to the raw material phosphoric acid or ammonium phosphate.
  • these technologies add dispersants, surfactants and other ingredients, they can only disperse elemental sulfur to a certain extent, and the prepared products still have problems such as large fluctuations in sulfur content and difficulty in controlling, and they are often used as dispersants and stabilizers. It pollutes the soil to a certain extent, so how to add elemental sulfur to phosphate fertilizers evenly and stably has always been a problem in the industry.
  • Fertilizers such as calcium-rich fertilizers are basic fertilizers with low added value. In order to reduce production costs, it is necessary to increase the scale of production and increase corporate profits through high yields. Small-scale production is not suitable for the low-cost production requirements of basic fertilizers. High-cost raw materials such as chemical fertilizers and stabilizers cannot meet the low-cost production requirements of basic fertilizers.
  • Rich superphosphate is abbreviated as rich calcium, and its effective P 2 O 5 content is between super superphosphate and superphosphate.
  • the main components of the product are Ca(H 2 PO 4 ) 2. H 2 O and CaSO 4 , followed by There are also water-soluble P 2 O 5 , free acid and H 2 O.
  • the effective P 2 O 5 varies according to customer needs. There are mainly 24%, 26%, 28%, 30%, 32%, 34% and other specifications.
  • the manufacturing process of rich calcium mainly includes blending method and acid method. Among them, the blending method is divided into superphosphate, superphosphate blending or superphosphate blending, phosphogypsum blending and other methods.
  • the acid method can be divided into phosphoric acid method and mixed acid method.
  • the mixed acid method directly uses a mixed acid of phosphoric acid and sulfuric acid to decompose phosphate rock powder to produce calcium-rich.
  • the mixed acid method is currently the mainstream method of industrial production due to its low requirements on the grade of phosphate rock and relatively stable product quality.
  • phosphoric acid and phosphate rock powder are mixed in a semi-closed mixer with stirring blades and then sent to the chemical conversion chamber. After solidification in the chemical conversion chamber, it is cut into blocks by a cutting machine, and is sent to the mature warehouse by a belt. , Calcium-rich products can be obtained after the maturation is completed.
  • the residence time of phosphoric acid and phosphate rock in the mixer is extremely short and cannot be completely effectively mixed.
  • the mixture of phosphoric acid and phosphate rock after preliminary mixing is a solid-liquid mixture.
  • the state flows into the formation chamber directly below it by gravity, and gradually reacts in the formation chamber to transform from a liquid-solid mixture to a solid state.
  • the finished product is prepared by sieving and granulating. Since the turning of the pile during the later cutting and maturation process has the effect of further mixing, the production of calcium-rich production does not have high requirements for the uniformity and completeness of the mixing of the materials in the mixer.
  • the purpose of the present invention is to provide a sulfur-containing rich superphosphate production device and preparation method.
  • dispersing liquid sulfur into concentrated phosphoric acid spraying by liquid sulfur spray gun and circulating mixing by circulating pump, it effectively solves the problem of liquid sulfur. It is difficult to evenly disperse into the product, resulting in a calcium-rich product with uniform elemental sulfur content and stable quality.
  • Said production device for sulfur-rich superphosphate includes: sulfur melting furnace, liquid sulfur atomizing spray gun, dispersion tank, circulating pump, mixer, forming chamber, cutting machine, conveyor belt, spreader, and maturing chamber;
  • the sulfur melting furnace is connected to the dispersion tank through a pipe with a jacketed insulation through a liquid sulfur atomizing spray gun;
  • the circulating pump and the dispersion tank are connected by a pipe to form a circulation loop;
  • the dispersion tank is connected to the phosphate rock powder conveying pipe through the pipe, and passes
  • the phosphate rock powder conveying pipe is connected to the mixer;
  • the mixer is arranged above the forming chamber; the materials in the forming chamber are cut by the cutting machine and transported to the spreader through the conveyor belt, and sprayed to the maturation chamber by the spreader for maturation;
  • the method for producing sulfur-containing rich superphosphate by using the above-mentioned sulfur-containing rich superphosphate production device includes the following steps:
  • Liquid sulfur dispersion The liquid sulfur is pumped to the dispersion tank through the liquid sulfur spray gun, and the dispersion tank circulates the material under the action of the circulating pump to realize the conversion of liquid sulfur into powdered sulfur in concentrated phosphoric acid and uniformly disperse it. In concentrated phosphoric acid, sulfur-containing phosphoric acid is formed;
  • Formation chamber reaction the materials enter the formation chamber after preliminary mixing
  • liquid sulfur in step (1) is filtered and then transported.
  • step (3) preliminary mixing refers to that the sulfur-containing wet-process phosphoric acid with a concentration of 44-48% as P 2 O 5 and the phosphate rock powder with a fineness of 180-220 mesh are fully stirred and mixed in the mixing chamber.
  • the residence time of the materials in step (4) in the formation chamber is 45-60 minutes.
  • step (6) is 3-5 days.
  • the present invention realizes liquid sulfur transportation by melting solid sulfur particles into liquid sulfur, and using jacketed insulation pipelines to transport after filtering; the liquid sulfur is atomized by the liquid sulfur spray gun and the pressure provided by the delivery pump is added to the In the dispersion tank, the liquid sulfur is transformed into the state of micro-particle powder and added to phosphoric acid uniformly and stably; a uniform mixture of solid powdered sulfur and concentrated phosphoric acid is formed, which is a uniform mixing reaction with phosphate rock powder in the mixer lay the foundation.
  • the uniform mixing of phosphoric acid and powdered solid sulfur can be effectively mixed with phosphate rock even in a mixer with normal pressure, semi-closed, and extremely short mixing time, and it can be mixed again in the subsequent cutting, maturation and turning process of calcium-rich production.
  • Effective dispersion; the present invention through the design of the production device, the improvement and optimization of the process, and the production characteristics of the mixed acid method of calcium-enrichment, through the control of the process conditions, the uniform, dispersed and effective addition of powdered sulfur in the calcium-enriched product is realized ,
  • the calcium-rich products produced have an elemental sulfur content of more than 4%.
  • the entire production process is simple, controllable, safe, and suitable for large-scale production. At present, it is running smoothly in our company’s 200,000 tons/year calcium-rich production. The product quality is stable, and the device operation rate is over 98%.
  • Figure 1 Schematic diagram of the device flow of the present invention
  • FIG. 1 The sedimentation effect test of the dispersion tank material (black and white);
  • FIG. 3 The sedimentation effect test of the dispersion tank (primary color).
  • the said one kind of sulfur-rich calcium superphosphate production device includes: sulfur melting furnace, liquid sulfur atomizing spray gun, dispersion tank, circulating pump, mixer, forming chamber, cutting machine, conveyor belt, spreader, maturing chamber, Screening and granulation system; the method for producing sulfur-containing rich superphosphate with this production device includes the following steps:
  • Sulfur liquefaction Melt solid sulfur into liquid sulfur in the sulfur melting furnace, and filter it with a filter to filter out impurities in the liquid sulfur to avoid the impurities in the liquid sulfur causing the liquid sulfur spray gun nozzle to block and liquid sulfur mist
  • the chemical effect is poor, and as a result, the liquid sulfur particles entering the phosphoric acid are coarse or lumpy.
  • the filtered liquid sulfur is transported to the dispersion tank by a liquid sulfur pump through a steam insulation jacket pipe with a temperature of 130-150°C.
  • the addition of liquid sulfur effectively avoids the explosion safety risk that currently exists in the use of powdered sulfur, and avoids environmental pollution and harm to the human body by sulfur dust.
  • Liquid sulfur dispersion The liquid sulfur is pumped to the dispersion tank, and sprayed into the dispersion tank through the liquid sulfur atomization spray gun. Under the action of the liquid sulfur atomization spray gun, the liquid sulfur drops in the dispersion tank. When it comes into contact with wet concentrated phosphoric acid ( calculated as P 2 O 5 , the concentration is 44-48%, the temperature is about 30-60° C.), it transforms into solid sulfur powder due to temperature drop. At the same time, under the circulating action of the circulating pump, the forced circulation of sulfur powder and concentrated phosphoric acid is completed. The mixed concentrated phosphoric acid is continuously delivered to the mixer, and fresh concentrated phosphoric acid is continuously replenished to achieve continuous mixing and continuous feeding of concentrated phosphoric acid and sulfur powder. Because the wet concentrated phosphoric acid itself has a certain viscosity, the powdered sulfur powder dispersed in the concentrated phosphoric acid is relatively stable and can maintain a better dispersion state during the transportation process.
  • wet concentrated phosphoric acid itself has
  • Reaction in the formation chamber the materials flow into the formation chamber after preliminary mixing; and the preliminary reaction and maturation are carried out in the formation chamber for 45-60 minutes.
  • the material is converted from the initial solid-liquid mixed state reaction into a solid state in the chemical conversion chamber, and the curing degree of the phosphoric acid and phosphate rock powder reaction material is controlled by controlling the curing time to facilitate the cutting of the cutting machine.
  • Sulfur liquefaction Melt solid sulfur into liquid sulfur in a sulfur melting furnace, and filter it with a filter to filter out impurities in the liquid sulfur.
  • the filtered liquid sulfur is insulated by a liquid sulfur pump with steam at 130-150°C.
  • the steam insulation jacket pipe is transported to the dispersion tank.
  • Liquid sulfur dispersion pump liquid sulfur to the dispersion tank, and spray it into the dispersion tank through a liquid sulfur spray gun.
  • the outlet pressure of the liquid sulfur spray gun is controlled to: 0.8-1.2MPa, and the circulation volume of the circulating pump is in the dispersion tank 270-300% of the total volume of concentrated phosphoric acid, the liquid sulfur can be effectively dispersed under the combined action of the liquid sulfur spray gun and the circulating pump.
  • the obtained sulfur powder and concentrated phosphoric acid mixture is filtered and dried , The particle size of the solids measured is ⁇ 100 ⁇ m. Use a 1000 mL graduated cylinder to take 1000 mL of sulfur-containing concentrated phosphoric acid for the sedimentation test.
  • reaction in the formation chamber the materials flow into the formation chamber after preliminary mixing; and the preliminary reaction and maturation are carried out in the formation chamber for 45-60 minutes. Initially react and mature in the chemical conversion chamber for 45-60 minutes to complete the reaction and solidification of phosphoric acid and phosphate rock powder.
  • the product indicators obtained are:

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Abstract

本发明涉及一种含硫富过磷酸钙生产装置和制备方法，属于磷肥生产技术领域，所述的含硫富过磷酸钙生产装置包括：熔硫炉、液硫雾化喷枪、分散槽、循环泵、混合器、化成室、切削机、输送皮带、撒扬机、熟化室；本发明结合混酸法富钙生产装置的特点，通过液硫喷枪将液硫分散到浓磷酸中，得到粉状硫磺与浓磷酸混合物，通过液硫喷枪的雾化作用，使液硫固化为固态粉状硫磺混入湿法浓磷酸中，湿法浓磷酸的粘度结合循环泵的使用，能使固态粉状硫磺在浓磷酸中均匀分散，有效解决了硫磺粉难以均匀分散到产品中的难题，将硫磺粉与浓磷酸混合物在混合器内初步混合、化成等工序制备出单质硫含量均匀的含硫富钙，有效解决了单质硫无法在富钙产品中均匀分散的问题。

Description

一种含硫富过磷酸钙生产装置和制备方法 技术领域
本发明属于磷肥生产技术领域，具体的说，涉及一种含硫富过磷酸钙生产装置和制备方法。
背景技术
作物整个生长期所必须的营养元素有大量元素﹑中量元素和微量元素，中量元素是作物生长过程中需要量次于氮、磷、钾而高于微量元素的营养元素，占作物干物重的0.1％-0.5％，通常指钙、镁、硫三种元素。硫是作物生长发育必须的营养元素之一，仅次于氮、磷、钾，位于第四位，在作物体内硫的含量平均为2.0g/kg，与磷的含量相当，约为干物质重的0.1％～0.5％，平均为0.25％左右。硫在作物生长中参与蛋白质合成、呼吸作用、光合作用、生物固氮、脂类合成、糖代谢等生理活动，是影响作物生长的重要因素。
土壤中硫以有机、无机多种形态存在，呈多种氧化形态，我国农业土壤表层中，大部分硫以有机态存在，占土壤全硫的90％以上，我国南方多数湿润和半湿润地区的非石灰性表层土壤中，有机硫占85％～94％，无机硫占6％～15％。硫酸根是植物根系从土壤中吸收硫的主要形态，受蒸腾作用影响较大，随水向上运输，向下运输的能力很差，即再利用能力很差，加之土壤中硫酸根形态容易流失。故土壤缺硫的情况下，增施硫肥是现代农业解决土壤缺硫导致作物缺硫的有效措施，但补充的硫肥除含硫酸根硫外，还需其他形态的硫，如单质硫，单质硫需氧化成硫酸根才能被作物吸收利用，硫营养逐步释放，具有缓释的效果，能满足作物整个生育期的需求。
我国氮肥和磷肥的过度施用，硫肥的忽视，提升作物产量的同时，也造成土壤中硫元素的大量耗竭。此外，随着化肥结构的不断优化，过磷酸钙、重过磷酸钙、富钙等含硫肥量的用量逐年减少，导致土壤中硫元素缺乏已成为农业生产中的制约因素。研究表明：我国土壤缺硫状况日益严重，耕地土壤缺硫面积约占30％，超过20％的耕地土壤潜在缺硫。
目前，向化肥中添加单质硫制备含硫化肥的研究较多，但由于单质硫一般以较小颗粒状的形式均匀存在于肥料中才能被作物有效吸收，因此需要将细粉状硫磺粉均匀混入肥料中才能实现。由于硫磺粉有爆炸风险且很难分散，若直接在磷肥生产中添加硫磺粉，存在极大的粉尘爆炸风险，且在添加过车中硫磺粉极易团聚成块，加入系统后很难在肥料中均匀分散，制备出的含硫产品硫含量波动大。得到保证硫分散均匀的肥料产品，一直是行业同仁的研究方向。专利CN108752097A公开了一种单质硫基磷铵缓释肥的制备方法，通过制硫磺溶 胶，将硫磺溶胶通过掺混、造粒、包裹、清洗得到含单质硫的磷铵缓释肥，制作过程中为保证单质硫的分散，使用乳化剂、稳定剂、分散剂等，该工艺制作工艺复杂、成本高，使用大量不能被作物吸收的添加剂，且难以实现规模化生产。专利CN104529625 A公开了一种单质硫在磷铵中的均匀添加方式，通过将硫磺与非离子表面活性剂与水混合制备硫磺胶体，再把硫磺悬浮液或硫磺胶体加入到原料磷酸或被铵中和的料浆中，该方法制备出的含硫肥料，很难保证单质硫在肥料中的均匀性。这些技术虽然通过添加分散剂、表面活性剂等成分，但这只能在一定程度上分散单质硫，制备出的产品仍然存在硫含量波动大，难以控制等问题，且多用的分散剂、稳定剂对土壤有一定污染，因此如何将单质硫均匀、稳定地添加至磷肥中，一直是行业内的难题。
富钙等化肥属于低附加值的基础化肥，为了降低生产成本，需要通过加大生产规模，通过高产量来提高企业利润，小规模的生产不适应于基础化肥的低成本生产要求，而添加分散剂、稳定剂等高成本原料更是无法满足基础化肥的低成本生产要求。
富过磷酸钙简称富钙，其有效P 2O 5含量介于重过磷酸钙和过磷酸钙之间，产品的主要成分是Ca(H 2PO 4) 2.H 2O和CaSO 4，其次还有水溶P 2O 5﹑游离酸和H 2O，有效P 2O 5根据客户需求不同，主要有24％﹑26％﹑28％﹑30％﹑32％﹑34％等规格。富钙的制造工艺主要有掺混法和酸法。其中，掺混法又分过磷酸钙﹑重过磷酸钙掺混或重过磷酸钙﹑磷石膏掺混等方法。酸法又可分为磷酸法和混酸法，混酸法是直接采用磷酸和硫酸的混合酸分解磷矿粉生产富钙。在这些制备工艺中，混酸法由于对磷矿的品位要求不高，且产品质量较为稳定的特点，是目前工业生产的主流方法。混酸法工艺中，将磷酸和磷矿粉在带有搅拌桨叶的半封闭的混合器内混合后送入化成室、在化成室凝固后经切削机切削呈块状，由皮带送至熟化库，熟化完成后即得到富钙产品。在半封闭的常压混合器内，磷酸与磷矿在混合器内停留时间极短，不能完全有效混合，我们姑且称之为初步混合，初步混合后的磷酸与磷矿混合物料以固液混合物状态以重力作用淌入位于其正下方的化成室，并在化成室内逐渐反应由液固混合物转变为固态，在化成室转动一周后由切削机切削成块状，进而送至熟化库熟化后，筛分造粒制备为成品。由于后期的切削、熟化过程中的翻堆，均有进一步混合的作用，因此，富钙的生产对混合器内物料的混合是否均匀、是否完全的要求不高。
发明内容
发明人经过大量试验研究，根据富钙生产的工艺特点，在熟化库内添加单质硫会产生大量硫磺粉尘，安全风险极大，且不能保证单质硫的均匀分散，封闭的、物料逐渐固化的化成室内无法实现单质硫的添加。在半封闭的混合器内添加单质硫，采用粉状添加无法实现 单质硫的均匀分散，采用液态硫磺添加，由于在混合器内磷矿和磷酸的温度均较低，在液态硫加入的瞬间，迅速凝固呈块状，不仅容易堵塞管道，且冷却后的硫磺颗粒极大，无法实现粉状添加，且如果液态硫的输送压力过大，很容易从半封闭的混合器中喷出，安全隐患极大。
基于以上研究，本发明的目的在于提供含硫富过磷酸钙生产装置和制备方法，通过将液硫分散到浓磷酸中，经过液硫喷枪的喷洒及循环泵的循环混合，有效解决了液硫难以均匀分散到产品中的难题，得到了单质硫含量均匀、质量稳定的富钙产品。
本发明的目的是通过以下技术方案实现的。
所述的一种含硫富过磷酸钙生产装置包括：熔硫炉、液硫雾化喷枪、分散槽、循环泵、混合器、化成室、切削机、输送皮带、撒扬机、熟化室；其中熔硫炉通过带有夹套保温管道经液硫雾化喷枪连通至分散槽；循环泵与分散槽通过管道连接为循环回路；所述分散槽通过管道连通至磷矿粉输送管，并通过磷矿粉输送管连通至混合器；混合器设置在化成室的上方；化成室内物料经切削机切削后经输送皮带输送至撒扬机，经撒扬机喷洒至熟化室熟化；
用上述含硫富过磷酸钙生产装置生产含硫富过磷酸钙的方法包括如下步骤：
(1)硫磺液化：将硫磺融化为液态硫磺；
(2)液硫分散：将液态硫磺用泵通过液硫喷枪输送至分散槽，分散槽在循环泵的作用下进行物料循环，实现液硫在浓磷酸中转变为粉状硫磺，并均匀分散在浓磷酸中，形成含硫磷酸；
(3)初步混合：将分散后的含硫磷酸用泵输送至混合器，使含硫磷酸和磷矿粉初步混合；
(4)化成室反应：初步混合后物料进入化成室；
(5)切削：化成室内物料经切削机切削后输送至撒扬机；
(6)熟化：物料经撒扬机送至熟化库熟化。
进一步地，所述的物料熟化后，再进行筛分、造粒，制备成粒状产品。
进一步地，步骤(1)的液态硫磺进行过滤再输送。
进一步地，步骤(3)初步混合是指以P 2O 5计浓度为44-48％的含硫湿法磷酸、细度为180-220目的磷矿粉在混合室充分搅拌混合。
进一步地，步骤(4)物料在化成室停留时间为45-60min。
进一步地，步骤(6)的熟化时间为3-5天。
进一步地，所生产出的富钙产品各成分含量为：
总磷(以P 2O 5计)：36％～41％
有效磷(以P 2O 5计)：34％～38％
水溶磷(以P 2O 5计)：27％～32％
单质S(以S计)：≥4％
SO 2- 4(以S计)：2％～6％
总硫(以S计)：≥8％
游离酸：≤5.5％
游离水：≤5％。
本发明的有益效果：
本发明通过将固态硫磺颗粒熔融后变成液硫，经过滤后使用夹套保温管道输送，实现了液硫输送；通过液硫喷枪并借助输送泵提供的压力将液硫进行雾化后加入到分散槽中，实现了液硫液态形势转变了微颗粒粉状状态并均匀稳定加入到磷酸中；形成均匀的固态粉状硫磺与浓磷酸混合物，为在混合器内与磷矿粉的均匀混合反应打下基础。磷酸与粉状固态硫磺的均匀混合，即使在常压、半封闭、混合时间极短的混合器内也能与磷矿得到有效混合，并在富钙生产后续的切削、熟化翻堆过程中再次有效分散；本发明的通过生产装置的设计、工艺的改进优化，并针对混酸法富钙的生产特点，通过工艺条件的控制，实现了粉状硫磺在富钙产品中的均匀、分散、有效添加，生产出的富钙产品，单质硫含量达4％以上，整个生产过程简单、可控，安全性高，能适应规模化生产，目前在我公司20万吨/年富钙生产中运行平稳，产品质量稳定，装置运行率达98％以上。
附图说明：
图1：本发明的装置流程示意图；
图2：分散槽物料沉降效果试验(黑白色)；
图3：分散槽物料沉降效果试验(原色)。
备注：因黑白色图片不能准确看出分散槽的分散效果，故增加了未经颜色处理的原色图。
具体实施方式
为了使本发明的目的、技术方案和有益效果更加清楚，下面将对本发明的优选实施例进行详细的说明，以方便技术人员理解。
所述的一种含硫富过磷酸钙生产装置包括：熔硫炉、液硫雾化喷枪、分散槽、循环泵、混合器、化成室、切削机、输送皮带、撒扬机、熟化室、筛分和造粒系统；用该生产装 置生产含硫富过磷酸钙的方法包括如下步骤：
(1)硫磺液化：在熔硫炉内将固态硫磺融化为液态硫磺，并用过滤器过滤，滤去液硫中的杂质，以避免液硫中存在的杂质导致液硫喷枪喷口堵塞以及液硫雾化效果差，并因此导致进入磷酸中的液硫颗粒偏粗或成块状。过滤后的液硫用液硫泵经130～150℃的蒸汽保温的蒸汽保温夹套管输送至分散槽。用液硫加料有效避免了目前采用粉状硫磺加料所存在的爆炸安全风险，且避免了硫磺粉尘对环境的污染和对人体的伤害。
(2)液硫分散：将液态硫磺用泵输送至分散槽，并经液硫雾化喷枪喷入分散槽内，经液硫雾化喷枪雾化作用下，在分散槽内，液硫液滴在与湿法浓磷酸(以P 2O 5计，浓度为44-48％，温度约为30-60℃)接触时由于温降转变为固态硫磺粉。同时在循环泵的循环作用下，完成硫磺粉与浓磷酸的强制循环，混合后的浓磷酸不断输送至混合器，新鲜浓磷酸不断补充，实现浓磷酸与硫磺粉的连续混合、连续供料。由于湿法浓磷酸本身具有一定的粘度，在浓磷酸中分散的粉状硫磺粉相对比较稳定，在输送过程中能保持较好的分散状态。
(3)初步混合：将硫磺粉与浓磷酸混合物用泵输送至混化装置的混合室，与细度为180-220目磷矿粉初步混合；在混合室，混有硫磺粉的浓磷酸、磷矿粉初步混合。经物料沉降实现，分散槽中部物料较为稳定，输送泵从分散槽中部进料输送至混合室。
(4)化成室反应：初步混合后物料淌入化成室；并在化成室内初步反应熟化45-60min。在富钙生产过程中，物料在化成室内由最初的固液混合状态反应转化为固态，通过控制熟化时间控制磷酸与磷矿粉反应物料的固化程度，以便于切削机切削。
(5)熟化：化成室物料经切削机切削为块状后，用皮带输送至撒扬机，经撒扬机再次破碎后撒扬至熟化室，在熟化室内推存熟化3-5天，为维持熟化温度，并保证物料指标的均匀，混化过程中用抓斗或铲车进行翻堆。
(6)造粒：完成熟化后物料，经筛分，造粒制备出单质硫含量为4％～7％的含硫富钙产品。
实施例1
(1)硫磺液化：在熔硫炉内将固态硫磺融化为液态硫磺，并用过滤器过滤，滤去液硫中的杂质，过滤后的液硫用液硫泵经130～150℃的蒸汽保温的蒸汽保温夹套管输送至分散槽。
(2)液硫分散：将液态硫磺用泵输送至分散槽，并经液硫喷枪喷入分散槽，液硫喷枪的出口压力控制为：0.8-1.2MPa，循环泵的循环量为分散槽内浓磷酸体积总量的270-300％，液硫在液硫喷枪和循环泵的共同作用下得以有效分散，为检测浓磷酸中固态硫磺情况，将得到的硫磺粉与浓磷酸混合物经过滤、干燥，测得固态物的粒径为＜100μm。用 1000mL量筒取1000mL含硫浓磷酸做沉降试验，使用2000ml量筒，取1900ml含硫磷酸进行沉降试验，沉降20分钟后，底部含有较大颗粒混合物约300ml，顶部含有悬浮颗粒混合物约200ml，硫磺与浓磷酸均匀混合物在中层，约1400ml，分层边界不明显。说明硫磺粉和浓磷酸在分散槽得到了较为稳定的分散，沉降效果图见附图2和附图3。
(3)初步混合：将硫磺粉与浓磷酸混合物用泵输送至混化装置的混合室，浓磷酸与细度为180-220目磷矿粉初步混合。
(4)化成室反应：初步混合后物料淌入化成室；并在化成室内初步反应熟化45-60min。在化成室内初步反应、熟化45-60min，完成磷酸与磷矿粉的反应固化。
(5)熟化：化成室固化后物料经切削机切削为块状后，用皮带输送至撒扬机撒扬至熟化室，在熟化室内推存熟化3-5天，为维持熟化温度，并保证物料指标的均匀，混化过程中进行翻堆。
(6)造粒：完成熟化后物料，经筛分，造粒制备出单质硫含量为4％～7％的含硫富钙产品。
所得产品指标为：
总磷(以P 2O 5计)：40.42％、有效磷(以P 2O 5计)：40.06％、水溶磷(以P 2O 5计)：35.26％、单质S(以S计)：5.78％、SO 2- 4(以S计)：2.28％、总硫(以S计)：8.06％、游离酸：3.23％、游离水：2.4％、粒径：2-4mm≥90％、颗粒平均抗压强度：30.5N/粒。
最后说明的是，以上优选实施例仅用于说明本发明的技术方案而非限制，尽管通过上述优选实施例已经对本发明进行了详细的描述，但本领域技术人员应当理解，可以在形式上和细节上对其作出各种各样的改变，而不偏离本发明权利要求书所限定的范围，本说明书在未做特殊说明时，所述百分含量均指质量百分含量。
本说明书在未做特殊说明时，所述百分含量均指质量百分含量。

Claims (8)

  1. 一种含硫富过磷酸钙生产装置，其特征在于：所述的一种含硫富过磷酸钙生产装置包括：熔硫炉、液硫雾化喷枪、分散槽、循环泵、混合器、化成室、切削机、输送皮带、撒扬机、熟化室；其中熔硫炉通过带有夹套保温管道经液硫雾化喷枪连通至分散槽；循环泵与分散槽通过管道连接成循环回路；所述分散槽通过管道连通至磷矿粉输送管，并通过磷矿粉输送管连通至混合器；混合器设置在化成室的上方；化成室内物料经切削机切削后经输送皮带输送至撒扬机，经撒扬机喷洒至熟化室熟化。
  2. 一种利用权利要求1所述的含硫富过磷酸钙生产装置制备含硫富过磷酸钙的方法，其特征在于：所述制备含硫富过磷酸钙的方法包括如下步骤：
    (1)硫磺液化：将硫磺熔化为液态硫磺；
    (2)液硫分散：将液态硫磺用泵通过液硫喷枪输送至分散槽，分散槽在循环泵的作用下进行物料循环，实现液硫在浓磷酸中转变为粉状硫磺，并均匀分散在浓磷酸中，形成含硫磷酸；
    (3)初步混合：将分散后的含硫磷酸用泵输送至混合器，使含硫磷酸和磷矿粉初步混合；
    (4)化成室反应：初步混合后物料进入化成室；
    (5)切削：化成室内物料经切削机切削后输送至撒扬机；
    (6)熟化：物料经撒扬机送至熟化库熟化。
  3. 根据权利要求2所述的一种含硫富过磷酸钙的制备方法，其特征在于：所述的物料熟化后，再进行筛分、造粒，制备成粒状产品。
  4. 根据权利要求2所述的一种含硫富过磷酸钙的制备方法，其特征在于：步骤(1)的液态硫磺进行过滤再输送。
  5. 根据权利要求2-4任一项所述的一种含硫富过磷酸钙的制备方法，其特征在于：步骤(3)初步混合是指以P 2O 5计浓度为44-48％的含硫湿法磷酸、细度为180-220目的磷矿粉在混合室搅拌混合。
  6. 根据权利要求5所述的一种含硫富过磷酸钙的制备方法，其特征在于：步骤(4)物料在化成室停留时间为45-60min。
  7. 根据权利要求6所述的一种含硫富过磷酸钙的制备方法，其特征在于：步骤(6)的熟化时间为3-5天。
  8. 根据权利要求2所述的含硫富过磷酸钙生产装置，其特征在于：所生产出的富钙产品指标为：
    总磷(以P 2O 5计)：36％～41％
    有效磷(以P 2O 5计)：34％～38％
    水溶磷(以P 2O 5计)：27％～32％
    单质S(以S计)：4％～7％
    SO 2- 4(以S计)：4％～6％
    总硫(以S计)：≥8％
    游离酸：≤5.5％
    游离水：≤5％。
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