WO2015149703A1 - 铁酸钙的制备方法 - Google Patents

铁酸钙的制备方法 Download PDF

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WO2015149703A1
WO2015149703A1 PCT/CN2015/075680 CN2015075680W WO2015149703A1 WO 2015149703 A1 WO2015149703 A1 WO 2015149703A1 CN 2015075680 W CN2015075680 W CN 2015075680W WO 2015149703 A1 WO2015149703 A1 WO 2015149703A1
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gypsum
iron
calcium ferrite
pyrite
calcium
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French (fr)
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杨林
罗显明
张志业
罗蜀峰
王辛龙
马先林
陈晓东
付全军
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Sichuan University
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0036—Mixed oxides or hydroxides containing one alkaline earth metal, magnesium or lead

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  • the invention relates to a preparation method of calcium ferrite, and belongs to the technical field of dephosphorization agents.
  • phosphorus is usually a harmful element in steel. If the content is too high, the steel will become cold and brittle and affect the mechanical properties of the steel.
  • the dephosphorization agents calcium ferrite has obvious advantages. Because of its good fluidity, it can accelerate the dissolution of lime, so there is no need to use fluorite to help. In addition, calcium ferrite is more oxidizing. Compared with the oxide dephosphorization agent, the non-dephosphorization pathway consumes less oxygen, and has good dephosphorization kinetic conditions, achieving fluorine-free steelmaking, reducing lining erosion, and environmental protection. Reduced pollution.
  • the steel yield can be increased by about 1%.
  • Calcium ferrite can also effectively improve the converter smelting process, rapidly slag, and efficiently dephosphorize the rate, thereby achieving smelting. Time is shortened.
  • Chinese Patent Application No. CN201210226364.2 discloses a steelmaking dephosphorization agent and a preparation method thereof, which use industrial waste rich in calcium oxide and iron oxide as raw materials, crushed, mixed, stirred, and at 1500 ⁇ Melting at 1550 ° C, melting and cooling, and crystal cooling to obtain a calcium ferrite dephosphorization agent.
  • the invention processes a large amount of waste slag containing calcium oxide and iron oxide, a large amount of high-temperature waste slag is still obtained after being melted by a high-temperature reaction, and the waste slag cannot be effectively utilized, which not only causes waste of resources, but also may cause environmental pollution;
  • the reaction temperature of the process reaches 1500 ° C, and the energy consumption and production cost are high.
  • pyrite is mainly the main raw material for the production of sulfuric acid, especially as a by-product tailings in the non-ferrous metal industry.
  • the utilization rate of iron resources is very low, resulting in a large number of effective Waste of resources. Therefore, the development of new processes for pyrite applications is particularly important.
  • the main component of gypsum is calcium sulfate.
  • various industrial by-product gypsums have also increased rapidly, including desulfurization gypsum produced by coal-fired thermal power generation, phosphogypsum produced by wet-process phosphoric acid production, and salt gypsum and citric acid.
  • Gypsum, fluorogypsum, mirabilite gypsum and titanium gypsum, especially desulfurized gypsum and phosphogypsum have the largest emissions. Due to the presence of various harmful impurities, industrial by-product gypsum seriously affects and threatens the ecological environment of various regions. Therefore, the scale production of industrial by-product gypsum can not only contribute to the sustainable development of industry, but also avoid occupying valuable land resources and environmental pollution. Dyeing is of great significance.
  • the Chinese patent No. 201210226364.2 proposes a steelmaking dephosphorization agent and a preparation method thereof, which uses industrial waste rich in calcium oxide and iron oxide as raw materials, which is crushed, mixed, stirred, and at 1500 ⁇ Melting at a temperature of 1550 ° C, melting and exiting the furnace, and cooling the crystal to obtain a calcium ferrite dephosphorization agent.
  • the invention processes a large amount of waste slag containing calcium oxide and iron oxide, a large amount of high-temperature waste slag is still obtained after high-temperature reaction melting, and the waste slag cannot be effectively utilized, resulting in waste of resources and environmental pollution;
  • the reaction temperature reaches 1500 ° C, the energy consumption is higher, and the production cost is increased.
  • the Chinese patent No. 201210042150.X is a method for preparing sulfuric acid by using pyrite to reduce and decompose gypsum sulfuric acid and flue gas for producing sulfuric acid.
  • the patent application is a preliminary work of the applicant of the present invention, and the purpose thereof is to provide a method for preparing sulfuric acid.
  • the residue obtained by the method has a very large proportion of calcium oxide and a very low iron content, which does not meet the YBT4266-2011 standard, that is, the solid slag obtained by the application is not a pre-melted calcium ferrite, and cannot be used as a dephosphorization slag for steelmaking.
  • the agent can only be used as a cement raw material, and the utilization rate and added value are low.
  • European Patent Application No. EP0004568A1 proposes a sulfuric acid method using natural gypsum or phosphogypsum.
  • the reaction conditions are as follows: the product obtained at 700-1100 ° C is sulfur dioxide and cement clinker, wherein the main material of cement clinker is silicic acid III.
  • Calcium silicates such as calcium, dicalcium silicate and tetracalcium silicate.
  • calcium oxide and iron oxide are smelted at a temperature of 1500 to 1550 ° C to obtain calcium ferrite.
  • the invention mainly uses pyrite to react with gypsum to prepare sulfuric acid, and at the same time obtains cement clinker, in which sulfur element is fully utilized, but iron and calcium are used as cement clinker, the utilization value is low, and a lot of valuable resources are wasted.
  • Patent Application Publication No. discloses a preparation of a calcium-iron oxide composite particle for a hydrogen chloride scavenger; that is, the calcium-iron oxide provided by the application is a composite particle in which the main component is calcium oxide, three Ferric oxide, calcium ferrite, and used as a hydrogen chloride scavenger, it must satisfy a BET specific surface area of 0.1-100 m 2 /g, and is not included in the total amount of iron atoms contained in the calcium-iron oxide composite particles. Less than 50% of the iron atoms combine with the calcium atoms to form an iron ferrite phase.
  • the technical problem solved by the present invention is to provide a new preparation method of calcium ferrite.
  • the molar ratio of calcium sulfate in the gypsum: pyrite in the pyrite: iron in the iron supplement 1: 0.1 ⁇ 2.5: 0 ⁇ 2,
  • the molar ratio of the calorie mixture is: 1:1 to 2.5, the gypsum has a water content of less than 10% by weight, and the pyrite has a water content of 0.1 to 15% by weight;
  • the protective atmosphere is an inert atmosphere, a reducing atmosphere or an oxidizing atmosphere having an oxygen content of less than 5% by weight.
  • the iron supplement described in the present invention is a substance capable of providing iron.
  • the gypsum in the step (a) of the present invention is preferably anhydrous gypsum, hemihydrate gypsum, phosphogypsum, desulfurized gypsum, fluorogypsum, citrate gypsum, nickel gypsum, titanium dioxide by-product. At least one of gypsum, natural gypsum, and anhydrite.
  • the gypsum is hemihydrate gypsum having a water content of 0.1 to 10% by weight or an anhydrite.
  • the iron supplement is preferably a substance having an iron content of more than 25% by weight.
  • the iron extender preferably contains at least one of ferrous oxide, triiron tetroxide, iron oxide, iron carbonate, ferrous sulfate, iron sulfate, and iron.
  • iron element 1:0.3 to 1:0.5 to 1.
  • the calcination temperature is preferably from 1,000 to 1,200 ° C; and the calcination temperature is more preferably from 1,100 ° C.
  • the baking time is preferably from 1 to 2 hours.
  • the protective atmosphere is preferably at least one of nitrogen, carbon dioxide and sulfur dioxide.
  • the protective atmosphere is more preferably a mixed atmosphere of nitrogen, carbon monoxide and sulfur dioxide; or a mixed atmosphere of carbon dioxide, carbon monoxide and sulfur dioxide; or a mixed atmosphere of nitrogen, carbon dioxide, carbon monoxide and sulfur dioxide.
  • the protective atmosphere is also preferably a mixed atmosphere of gas A, oxygen, and sulfur dioxide, wherein the gas A is at least one of nitrogen, carbon dioxide, and carbon monoxide, and the content of the oxygen is less than 5% by weight.
  • the invention adopts pyrite reduction and decomposition gypsum to prepare calcium ferrite, and the reaction conversion rate thereof is high, and the purity of calcium ferrite is high, and the content of phosphorus sulfur sulfur impurities is low.
  • the invention adopts pyrite reduction and decomposition gypsum to prepare calcium ferrite, and the gypsum used can be industrial by-product gypsum, such as phosphogypsum, desulfurized gypsum, etc., and effectively utilizes a large amount of by-product industrial gypsum, and fully utilizes it.
  • Industrial waste, and the conversion rate of the raw material of the present invention is high.
  • the invention adopts pyrite reduction and decomposition gypsum to prepare calcium ferrite, and the reaction temperature is lower than the current process, and the process is simple and environmentally friendly.
  • the process of the invention is suitable for large-scale production, and has the characteristics of simple operation, easy control, resource recycling, and easy promotion.
  • the product obtained by the invention is calcium ferrite, sulfuric acid or sulfur, which not only can effectively utilize the sulfur element in the raw material, but also fully utilizes the calcium and iron elements in the raw material, and fully utilizes various elements in the raw material.
  • the gas phase is rich in SO 2 for sulfuric acid or sulfur, and the solid phase component is calcium ferrite.
  • the inclusion of a small amount of impurities such as silicon and aluminum will not affect the performance of calcium ferrite, but also improve the performance of dephosphorization and slagging.
  • the obtained calcium ferrite has a higher added value, and the utilization of the raw materials is fully utilized, and at the same time, it can provide a new route for utilization of pyrite, which is beneficial to the popularization and application of the process.
  • the applicant of the present invention has long been devoted to the research in the field of phosphorus chemical industry and metallurgy, and creatively uses the waste residue in the field of phosphorus chemical industry, gypsum, and the pyrite which has a very low utilization rate of iron resources (the by-product tailings in the non-ferrous metal industry).
  • the raw material successfully prepared a low-cost dephosphorization agent, calcium ferrite which is urgently needed in the metallurgical field (the cost of calcium ferrite produced by the method of the present invention is lower than that of the commercially available calcium ferrite) by 80%. It not only recycles the pyrite that has very low utilization rate of phosphogypsum and iron resources, but also solves the technical problem of providing low-cost calcium ferrite that steel companies have been eager to solve.
  • Example 1 is an XRD spectrum of a calcium ferrite product obtained in Example 1.
  • Fig. 2 is an XRD chart of the residue obtained by the method disclosed in Chinese Patent Application No. CN201210042150.X.
  • Example 3 is an XRD chart of the calcium ferrite product obtained in Example 3.
  • the protective atmosphere is an inert atmosphere, a reducing atmosphere or an oxidizing atmosphere having an oxygen content of less than 5% by weight.
  • the iron supplement described in the present invention is a substance capable of providing iron.
  • the gypsum in the step (a) of the present invention preferably contains anhydrous gypsum, hemihydrate gypsum, phosphogypsum, desulfurization gypsum, fluorogypsum, citrate gypsum, nickel gypsum, titanium dioxide by-product. At least one of gypsum, natural gypsum, and anhydrite.
  • the gypsum is hemihydrate gypsum having a water content of 0.1 to 10% by weight or an anhydrite.
  • the iron supplement is preferably a substance having an iron content of more than 25% by weight;
  • the iron extender preferably contains at least one of ferrous oxide, triiron tetroxide, iron oxide, iron carbonate, ferrous sulfate, iron sulfate, and iron.
  • iron element 1:0.3 to 1:0.5 to 1.
  • the calcination temperature is preferably from 1,000 to 1,200 ° C; and the calcination temperature is more preferably from 1,100 ° C.
  • the baking time is preferably from 1 to 2 hours.
  • the protective atmosphere is preferably at least one of nitrogen, carbon dioxide and sulfur dioxide.
  • the protective atmosphere is more preferably a mixed atmosphere of nitrogen, carbon monoxide and sulfur dioxide; or a mixed atmosphere of carbon dioxide, carbon monoxide and sulfur dioxide; or a mixed atmosphere of nitrogen, carbon dioxide, carbon monoxide and sulfur dioxide.
  • the protective atmosphere is also preferably a mixed atmosphere of gas A, oxygen, and sulfur dioxide, wherein the gas A is at least one of nitrogen, carbon dioxide, and carbon monoxide, and the content of the oxygen is less than 5% by weight.
  • sulfur dioxide as tail gas is obtained, and sulfur dioxide is used for producing sulfuric acid or sulfur.
  • the present invention actually solves the technical problem that people have been eager to solve but has never succeeded in providing a low cost calcium ferrite preparation method; it is well known to those skilled in the art that, relative to other dephosphorization agents, Calcium ferrite has obvious advantages as a dephosphorization agent (see the background art of the present invention).
  • iron and steel enterprises In order to smelt high-quality steel, iron and steel enterprises must use high-quality dephosphorization agent calcium ferrite, and currently produce dephosphorization slag agent iron according to the present invention.
  • the applicant of the present invention has long been devoted to the research in the field of phosphorus chemical industry and metallurgy, and creatively uses the waste residue in the field of phosphorus chemical industry, gypsum, and the pyrite which has a very low utilization rate of iron resources (the by-product tailings in the non-ferrous metal industry).
  • the raw material successfully prepared a low-cost dephosphorization agent, calcium ferrite which is urgently needed in the metallurgical field (the cost of calcium ferrite produced by the method of the present invention is lower than that of the commercially available calcium ferrite) by 80%. It not only recycles the pyrite that has very low utilization rate of phosphogypsum and iron resources, but also solves the technical problem of providing low-cost calcium ferrite that steel companies have been eager to solve.
  • some of the products obtained by the present invention are in the form of a block, and some are in the form of a powder, that is, there are no particular requirements on the particle size and specific surface area.
  • the patent application disclosed in the background art is CN1227190A, the purpose of which is to prepare a calcium-iron oxide composite particle for a hydrogen chloride purifying agent, the main components being calcium oxide, ferric oxide and calcium ferrite.
  • a hydrogen chloride purifying agent it must satisfy an iron atom having a BET specific surface area of 0.1 to 100 m 2 /g and not less than 50% by the total amount of iron atoms contained in the calcium-iron oxide composite particles.
  • the calcium atoms combine to form an iron ferrite phase; that is, the calcium-iron oxide in the application has certain requirements on the particle size and specific surface area and is a composite composed of a plurality of substances.
  • Example 1 is an XRD spectrum of the calcium ferrite product obtained in Example 1.
  • the calcium ferrite prepared by the present invention belongs to the calcium ferrite component alone (compared with the standard map of calcium ferrite in the figure, all peak forms are matched) That is, the calcium ferrite obtained by the present invention does not contain other mixed components such as calcium oxide and ferric oxide.
  • the calcium ferrite composite particles disclosed in the patent application disclosed in the publication No. CN1227190A are different substances, and their functions are completely different, and the application fields are completely different.
  • the Chinese patent application No. CN201210042150.X discloses a method for reducing and decomposing gypsum sulfuric acid by using pyrite, and the flue gas is used for producing sulfuric acid.
  • the patent application is a preliminary work of the applicant of the present invention, and the purpose thereof is to provide a The method for preparing sulfuric acid
  • FIG. 2 is the XRD spectrum of the residue obtained in the application, and it can be seen that the residue obtained by the method has a very large proportion of calcium oxide and a very low iron content, which does not meet the YBT4266-2011 standard, that is, the solid obtained by the application.
  • the slag is not a pre-melted calcium ferrite, and cannot be used as a dephosphorization slag-forming agent for steelmaking, but can only be used as a cement raw material.
  • the citrate gypsum having a water content of 5 wt% is uniformly ground with pyrite having a water content of 5 wt%, and the molar ratio of the active ingredient ferrous sulfide in the pyrite to the calcium sulfate in the gypsum is 1.5. :1, adding iron supplement is iron sulfate, the molar ratio of iron sulfate to gypsum in the gypsum is 0.1:1, to obtain a mixture;
  • the mixture was added to a reactor at a temperature of 1300 ° C, and calcined under a protective atmosphere (nitrogen, 4 wt% of oxygen and sulfur dioxide) for 1.5 h, and the solid phase was cooled to obtain calcium ferrite, and the resulting sulfur dioxide tail gas was made into sulfuric acid or sulfur.
  • a protective atmosphere nitrogen, 4 wt% of oxygen and sulfur dioxide
  • Example 3 is an XRD spectrum of the calcium ferrite product obtained in Example 3.
  • the calcium ferrite prepared by the present invention belongs to the calcium ferrite component alone (compared with the standard map of calcium ferrite in the figure, all peak forms are consistent) .
  • the phosphogypsum having a water content of 0.5% by weight is uniformly ground with pyrite having a water content of 3 wt%, and the molar ratio of the active ingredient in the pyrite, the active ingredient in the ferrous sulfide and the phosphogypsum, is 1:1, adding iron supplement is ferrous sulfate, the molar ratio of ferrous sulfate to gypsum in the gypsum is 0.5:1, to obtain a mixture;

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Abstract

本发明涉及铁酸钙的制备方法，属于冶金技术领域，本发明所要解决的技术问题是提供一种铁酸钙的制备方法，该方法包括如下步骤：（a）取石膏、硫铁矿和铁补充剂，混合得到混合物料；其中，按摩尔比石膏中硫酸钙：硫铁矿中二硫化亚铁：铁补充剂中铁元素＝1：0.1～2.5：0～2，并且按摩尔比混合物料中钙元素：铁元素＝1∶1～2.5，所述石膏的含水率小于10wt％，所述硫铁矿的含水率为0.1～15wt％；（b）于保护气氛下将混合物料进行焙烧，焙烧温度为900～1500℃，焙烧时间为0.1～4h，焙烧完毕，冷却得到铁酸钙；其中，所述保护气氛为惰性气氛、还原性气氛或氧气含量小于5wt％的弱氧化性气氛。

Description

铁酸钙的制备方法 技术领域
本发明涉及铁酸钙的制备方法，属于脱磷剂技术领域。
背景技术
众所周知，磷在钢中通常是有害元素，含量过高会使钢产生冷脆现象而影响钢材机械性能。目前脱磷剂中，铁酸钙具有较为明显的优势，由于其具有较好的流动性，可加速石灰的溶解，因而无须再用萤石助熔。另外，铁酸钙氧化性较强，与氧化物脱磷剂相比，非脱磷途径耗氧量少，且具有良好的脱磷动力学条件，实现无氟炼钢，炉衬侵蚀减少，对环境污染减轻。同时，由于铁酸钙化渣好、冶炼平稳、减少钢水喷溅，从而可以提高钢收率1％左右，铁酸钙还能够有效改善转炉冶炼工艺，快速化渣，高效脱磷率，从而实现冶炼时间缩短。
申请号CN201210226364.2的中国专利申请公开了一种炼钢脱磷剂及其制备方法，其采用富含氧化钙和氧化铁的工业废弃物作为原料，经破碎、混合、搅拌，并在1500～1550℃下熔炼，熔融出炉后结晶冷却得到铁酸钙脱磷剂。该发明虽然处理了大量含氧化钙和氧化铁的废渣，但经高温反应熔出后依然会得到大量的高温废渣，而废渣不能得到有效的利用，不仅造成资源浪费，还可能造成环境污染；同时该工艺反应温度达到1500℃，能耗和生产成本较高。
因此，如何降低能耗和生产成本，同时避免资源浪费和环境污染的炼钢脱磷剂制备方法成为本领域迫切需要解决的技术难题。
俄罗斯、巴西、加拿大、澳大利亚、印度、美国和中国等国的硫铁矿资源丰富，占世界大部分的总储量。硫铁矿的主要成分为二硫化亚铁，长期以来硫铁矿都主要是生产硫酸的主要原料，尤其作为有色金属行业中的副产尾矿，其中铁资源利用率非常低，造成大量的有效资源浪费。因此，开发硫铁矿应用的新工艺就显得尤为重要。
石膏中主要成分为硫酸钙，随着各国工业的发展，各种工业副产石膏产量也迅速增加，包括燃煤火力发电产生的脱硫石膏，湿法磷酸生产排放的磷石膏及盐石膏、柠檬酸石膏、氟石膏、芒硝石膏和钛石膏等，尤其是脱硫石膏和磷石膏的排放量最为巨大。工业副产石膏由于含有各种有害杂质，其大量堆存严重影响和威胁各地区的生态环境。因此工业副产石膏规模化处理不仅可为实现工业的可持续发展做出贡献，还能避免占用宝贵的土地资源和环境污 染，意义十分重大。
与本发明具有典型对比的技术文件如下：
其中，申请号为201210226364.2的中国专利提出了一种炼钢脱磷剂及其制备方法，其采用富含氧化钙和氧化铁的工业废弃物作为原料，经破碎、混合、搅拌，并在1500～1550℃温度下熔炼，熔融出炉后结晶冷却得到铁酸钙脱磷剂。该发明虽然处理了大量含氧化钙和氧化铁的废渣，经高温反应熔出后依然会得到大量的高温废渣，该废渣不能得到有效的利用，造成资源浪费，还可能造成环境污染；同时该工艺反应温度达到1500℃，能耗较高，增加生产成本。
申请号为201210042150.X的中国专利是采用硫铁矿还原分解石膏制硫酸，烟气用于制硫酸，该专利申请作为本发明申请人的前期工作，其目的是提供一种制备硫酸的方法，而利用该方法得到的残渣中氧化钙比例非常大，铁含量非常低，不符合YBT4266-2011标准，即该申请得到的固体渣不是预熔型铁酸钙，不能作为炼钢用脱磷造渣剂，而只能用作水泥原料，利用率和附加值都较低。
申请号为EP0004568A1的欧洲专利提出了一种采用天然石膏或者磷石膏制硫酸方法，其反应条件是在700～1100℃得到的产物为二氧化硫和水泥熟料，其中水泥熟料主要物质为硅酸三钙、硅酸二钙和硅酸四钙等硅酸钙盐。对比上述申请号为201210226364.2的中国专利，氧化钙和氧化铁在1500～1550℃温度下熔炼可以得到铁酸钙。该发明主要是采用硫铁矿与石膏反应制备硫酸，同时得到水泥熟料，其中硫元素得到了充分的利用，但是铁和钙作为水泥熟料，利用价值较低，浪费大量有价值的资源。
公开号为(CN1227190A)的专利申请公开了一种制备用于氯化氢净化剂的钙-铁氧化物复合颗粒；即该申请提供的钙-铁氧化物是复合颗粒，其中主要成分是氧化钙、三氧化二铁、铁酸钙，并且是作为氯化氢净化剂使用，那么其必须满足BET比表面积为0.1-100m2/g、且以包含在钙-铁氧化物复合颗粒中的铁原子全部数量计不低于50％的铁原子与钙原子结合在一起形成铁酸钙铁相。
发明内容
本发明解决的技术问题是提供一种铁酸钙的新的制备方法。
本发明铁酸钙的制备方法，其特征在于：包括如下步骤：
(a)取石膏、硫铁矿和铁补充剂，混合得到混合物料；
其中，按摩尔比石膏中硫酸钙:硫铁矿中二硫化亚铁:铁补充剂中铁元素＝1:0.1～2.5:0～2， 并且按摩尔比混合物料中钙元素:铁元素＝1:1～2.5，所述石膏的含水率小于10wt％，所述硫铁矿的含水率为0.1～15wt％；
(b)于保护气氛下将混合物料进行焙烧，焙烧温度为900～1500℃，焙烧时间为0.1～4h，焙烧完毕，冷却得到铁酸钙；
其中，所述保护气氛为惰性气氛、还原性气氛或氧气含量小于5wt％的氧化性气氛。
本发明中所述铁补充剂即为能够提供铁元素的物质。
本发明步骤(a)中硫铁矿中铁元素与石膏中钙元素的含量达到了制备铁酸钙的要求，即按摩尔比混合物料中钙元素:铁元素＝1:1～2.5，则可以不加入铁补充剂；若硫铁矿中铁元素与石膏中钙元素的含量未达到制备硫铁矿的要求，即铁元素的量较少时，即按摩尔比混合物料中钙元素:铁元素小于1:1，则需要加入铁补充剂，补充铁元素，以达到制备铁酸钙的要求，即按摩尔比混合物料中钙元素:铁元素＝1:1～2.5。
为了充分利用各种副产品石膏，优选本发明步骤(a)中的所述石膏优选为无水石膏、半水石膏、磷石膏、脱硫石膏、氟石膏、柠檬酸石膏、镍石膏、钛白粉副产石膏、天然石膏和硬石膏中的至少一种。
更进一步地，优选所述石膏为含水率为0.1～10wt％的半水石膏或为无水石膏。
为了充分利用石膏中的钙元素，所述铁补充剂优选为铁元素的含量大于25wt％的物质。
更进一步地，铁补充剂优选含氧化亚铁、四氧化三铁、氧化铁、碳酸铁、硫酸亚铁、硫酸铁和铁中的至少一种。
为了充分利用铁元素和钙元素，按摩尔比所述混合物料中优选钙元素:铁元素＝1:0.3～1:0.5～1。
为了节约能源，所述焙烧温度优选为1000～1200℃；焙烧温度更优选为1100℃。所述焙烧时间优选为1～2h。
考虑到保护气氛的来源，优选易得的气体，故所述保护气氛优选为氮气、二氧化碳和二氧化硫中的至少一种。
所述保护气氛更优选为氮气、一氧化碳和二氧化硫的混合气氛；或为二氧化碳、一氧化碳和二氧化硫的混合气氛；或为氮气、二氧化碳、一氧化碳和二氧化硫的混合气氛。
所述保护气氛还优选为气体A、氧气和二氧化硫的混合气氛，其中，所述气体A为氮气、二氧化碳和一氧化碳中的至少一种，所述氧气的含量小于5wt％。
本发明铁酸钙的制备方法中，焙烧后除了得到铁酸钙，还得到尾气二氧化硫，二氧化硫 用于制硫酸或硫磺。
本发明铁酸钙的制备方法具有以下优点：
1、本发明采用的是硫铁矿还原分解石膏制备铁酸钙，其反应转化率高，得到铁酸钙纯度高，磷硫氟杂质含量低。
2、本发明采用的是硫铁矿还原分解石膏制备铁酸钙，所采用的石膏可以为工业副产品石膏，如磷石膏、脱硫石膏等，有效利用了大量的副产工业石膏，充分的利用了工业废渣，而且本发明原料的转化率高。
3、本发明采用的是硫铁矿还原分解石膏制备铁酸钙，其反应温度相比目前工艺较低，同时工艺简单，对环境友好。
4、本发明工艺适合于大规模的生产，它具有操作简单，易于控制，资源循环利用，便于推广等特点。
5、本发明得到的产品为铁酸钙、硫酸或硫磺，其不仅能有效利用原料中的硫元素，还充分利用了原料中的钙和铁两种元素，充分利用原料中的各种元素，气相富含SO2用于制硫酸或硫磺，固相组分为铁酸钙产品，其中含有少量的硅、铝等杂质不仅不会影响铁酸钙性能，还能提高其脱磷造渣性能，得到的铁酸钙附加值较高，实现的原料的充分利用，同时又能够提供一条硫铁矿利用的新途径，有利于该工艺的推广应用。
本发明申请人长期致力于磷化工、冶金领域的研究，创造性地将磷化工领域的废渣——石膏，同时采用铁资源利用率非常低的硫铁矿(有色金属行业中副产尾矿)为原料首次成功地制备了冶金领域急需的低成本脱磷剂——铁酸钙(利用本发明方法制得的铁酸钙较现市售铁酸钙的成本降低了80％)，可见，本发明不仅回收利用了磷石膏和铁资源利用率非常低的硫铁矿，而且解决了钢铁企业一直渴望解决的提供低成本铁酸钙的技术难题。
附图说明
图1为实施例1所得铁酸钙产品的XRD谱图。
图2为利用申请号CN201210042150.X的中国专利申请公开的方法所得残渣的XRD谱图。
图3为实施例3所得铁酸钙产品的XRD谱图。
具体实施方式
本发明铁酸钙的制备方法，其特征在于：包括如下步骤：
(a)取石膏、硫铁矿和铁补充剂，混合得到混合物料；
其中，按摩尔比石膏中硫酸钙:硫铁矿中二硫化亚铁:铁补充剂中铁元素＝1:0.1～2.5:0～2，并且按摩尔比混合物料中钙元素:铁元素＝1:1～2.5，所述石膏的含水率小于10wt％，所述硫铁矿的含水率为0.1～15wt％；
(b)于保护气氛下将混合物料进行焙烧，焙烧温度为900～1500℃，焙烧时间为0.1～4h，焙烧完毕，冷却得到铁酸钙；
其中，所述保护气氛为惰性气氛、还原性气氛或氧气含量小于5wt％的氧化性气氛。
本发明中所述铁补充剂即为能够提供铁元素的物质。
本发明步骤(a)中硫铁矿中铁元素与石膏中钙元素的含量达到了制备铁酸钙的要求，即按摩尔比混合物料中钙元素:铁元素＝1:1～2.5，则可以不加入铁补充剂；若硫铁矿中铁元素与石膏中钙元素的含量未达到制备硫铁矿的要求，即铁元素的量较少时，即按摩尔比混合物料中钙元素:铁元素小于1:1，则需要加入铁补充剂，补充铁元素，以达到制备铁酸钙的要求，即按摩尔比混合物料中钙元素:铁元素＝1:1～2.5。
为了充分利用各种副产品石膏，优选本发明步骤(a)中的所述石膏优选含无水石膏、半水石膏、磷石膏、脱硫石膏、氟石膏、柠檬酸石膏、镍石膏、钛白粉副产石膏、天然石膏和硬石膏中的至少一种。
更进一步地，优选所述石膏为含水率为0.1～10wt％的半水石膏或为无水石膏。
为了充分利用石膏中的钙元素，所述铁补充剂优选为铁元素的含量大于25wt％的物质；
更进一步地，铁补充剂优选含氧化亚铁、四氧化三铁、氧化铁、碳酸铁、硫酸亚铁、硫酸铁和铁中的至少一种。
为了充分利用铁元素和钙元素，按摩尔比所述混合物料中优选钙元素:铁元素＝1:0.3～1:0.5～1。
为了节约能源，所述焙烧温度优选为1000～1200℃；焙烧温度更优选为1100℃。所述焙烧时间优选为1～2h。
考虑到保护气氛的来源，优选易得的气体，故所述保护气氛优选为氮气、二氧化碳和二氧化硫中的至少一种。
所述保护气氛更优选为氮气、一氧化碳和二氧化硫的混合气氛；或为二氧化碳、一氧化碳和二氧化硫的混合气氛；或为氮气、二氧化碳、一氧化碳和二氧化硫的混合气氛。
所述保护气氛还优选为气体A、氧气和二氧化硫的混合气氛，其中,所述气体A为氮气、二氧化碳和一氧化碳中的至少一种，所述氧气的含量小于5wt％。
本发明铁酸钙的制备方法中，焙烧后除了得到铁酸钙，还得到尾气二氧化硫，二氧化硫用于制硫酸或硫磺。
本发明实际上解决了人们一直渴望解决但始终未能获得成功的技术难题——即提供一种成本低廉的铁酸钙的制备方法；本领域技术人员公知，相对于其他脱磷剂而言，铁酸钙作为脱磷剂使用具有较为明显的优势(参见本发明背景技术部分)，钢铁企业为了冶炼优质钢必须选用高品质脱磷剂铁酸钙，目前关于本发明生产脱磷造渣剂铁酸钙的制备方法的报道几乎没有，而铁酸钙的售价较高，这给钢铁企业造成了很大的经济压力，因此钢铁企业一直渴望出现成本低廉的预熔型铁酸钙(符合YBT4266-2011标准的铁酸钙产品)。本发明申请人长期致力于磷化工、冶金领域的研究，创造性地将磷化工领域的废渣——石膏，同时采用铁资源利用率非常低的硫铁矿(有色金属行业中副产尾矿)为原料首次成功地制备了冶金领域急需的低成本脱磷剂——铁酸钙(利用本发明方法制得的铁酸钙较现市售铁酸钙的成本降低了80％)，可见，本发明不仅回收利用了磷石膏和铁资源利用率非常低的硫铁矿，而且解决了钢铁企业一直渴望解决的提供低成本铁酸钙的技术难题。
下面结合实施例对本发明的具体实施方式做进一步的描述，并不因此将本发明限制在所述的实施例范围之中。
实施例1铁酸钙的制备
(a)将含水率为3wt％的半水磷石膏与含水率为15wt％的硫铁矿研磨均匀，硫铁矿中的有效成分二硫化亚铁和磷石膏中的有效成分硫酸钙的摩尔比为0.4:1，添加铁补充剂为四氧化三铁，四氧化三铁与石膏中硫酸钙摩尔比为0.5:1，得到混合物料；
(b)将该混合物料加入温度950℃的反应器中，在保护气氛(氮气、一氧化碳和二氧化硫)下，焙烧4h，固相经冷却得到铁酸钙，产生的二氧化硫尾气制硫酸或硫磺。
经测定，实施例1中硫铁矿分解率为95％，磷石膏的分解率为90％，制得的铁酸钙中按摩尔比铁元素:钙元素＝2.1:1。
此外，本发明得到的产品中有的是块状的，有的是粉末状的，即其对粒径和比表面积均没有特别的要求。而背景技术中提及的公开号为CN1227190A的专利申请，其目的在于制备一种用于氯化氢净化剂的钙-铁氧化物复合颗粒，主要成分是氧化钙、三氧化二铁、铁酸钙，并且是作为氯化氢净化剂使用，那么其必须满足BET比表面积为0.1-100m2/g、且以包含在钙-铁氧化物复合颗粒中的铁原子全部数量计不低于50％的铁原子与钙原子结合在一起形成铁酸钙铁相；即该申请中钙-铁氧化物对粒径及比表面积有一定的要求且是由多种物质组成的复合物。
图1为实施例1所得铁酸钙产品的XRD谱图，由图1可知，本发明制备的铁酸钙属于单独铁酸钙组分(与图中铁酸钙标准图谱对比，所有峰型吻合)，即本发明所得铁酸钙中不存在氧化钙和三氧化二铁等其他混合组分。可见，本发明所制备的铁酸钙与公开号为CN1227190A的专利申请中公开的钙-铁氧化物复合颗粒是不同的物质，其作用完全不同，应用领域也完全不同。
申请号CN201210042150.X的中国专利申请公开了一种采用硫铁矿还原分解石膏制硫酸的方法，其烟气用于制硫酸，该专利申请作为本发明申请人的前期工作，其目的是提供一种制备硫酸的方法，图2为该申请所得残渣的XRD谱图，可见利用该方法得到的残渣中氧化钙比例非常大，铁含量非常低，不符合YBT4266-2011标准，即该申请得到的固体渣不是预熔型铁酸钙，不能作为炼钢用脱磷造渣剂，而只能用作水泥原料。
实施例2铁酸钙的制备
(a)将含水率为0.1wt％的无水磷石膏与含水率为10wt％的硫铁矿研磨均匀，硫铁矿中的有效成分二硫化亚铁和磷石膏中的有效成分硫酸钙的摩尔比为0.1:1，添加铁补充剂为氧化亚铁，氧化亚铁与石膏中硫酸钙摩尔比为2:1，得到混合物料；
(b)将该混合物料加入温度1100℃的反应器中，在保护气氛(氮气、二氧化碳和二氧化硫)下，焙烧2.0h，固相经冷却得到铁酸钙，产生的二氧化硫尾气制硫酸或硫磺。
经测定，实施例2中硫铁矿分解率为99％，磷石膏的分解率为95％，制得的铁酸钙中按摩尔比铁元素:钙元素＝2.21:1。
实施例3铁酸钙的制备
(a)将含水率为5wt％的柠檬酸石膏与含水率为5wt％的硫铁矿研磨均匀，硫铁矿中的有效成分二硫化亚铁和石膏中的有效成分硫酸钙的摩尔比为1.5:1，添加铁补充剂为硫酸铁，硫酸铁与石膏中硫酸钙摩尔比为0.1:1，得到混合物料；
将该混合物料加入温度1300℃的反应器中，在保护气氛(氮气、4wt％氧气和二氧化硫)下，焙烧1.5h，固相经冷却得到铁酸钙，产生的二氧化硫尾气制硫酸或硫磺。
经测定，实施例3中硫铁矿分解率为90％，柠檬酸石膏的分解率为97％，制得的铁酸钙中按摩尔比铁元素:钙元素＝1.45:1。
图3为实施例3所得铁酸钙产品的XRD谱图，由图3可知，本发明制备的铁酸钙属于单独铁酸钙组分(与图中铁酸钙标准图谱对比，所有峰型吻合)。
实施例4铁酸钙的制备
(a)将含水率为8wt％的钛白粉副产石膏与含水率为1wt％的硫铁矿研磨均匀，硫铁矿中的有效成分二硫化亚铁和石膏中的有效成分硫酸钙的摩尔比为2:1，得到混合物料；
(b)将该混合物料加入温度1400℃的反应器中，在保护气氛(氮气、4wt％氧气和二氧化硫)下，焙烧1.0h，固相经冷却得到铁酸钙，产生的二氧化硫尾气制硫酸或硫磺。
经测定，实施例4中硫铁矿分解率为90％，钛白粉副产石膏的分解率为99.5％，制得的铁酸钙中按摩尔比铁元素:钙元素＝1.79:1。
实施例5铁酸钙的制备
(a)将含水率为0.1wt％的硬石膏与含水率为1wt％的硫铁矿研磨均匀，硫铁矿中的有效成分二硫化亚铁和石膏中的有效成分硫酸钙的摩尔比为0.3:1，添加铁补充剂为氧化铁，氧化铁与石膏中硫酸钙摩尔比为0.4:1，得到混合物料；
(b)将该混合物料加入温度1100℃的反应器中，在保护气氛(氮气、二氧化碳和二氧化硫)下，焙烧4h，固相经冷却得到铁酸钙，产生的二氧化硫尾气制硫酸或硫磺。
经测定，实施例5中硫铁矿分解率为98％，硬石膏的分解率为97％，制得的铁酸钙中按摩尔比铁元素:钙元素＝1.12:1。
实施例6铁酸钙的制备
(a)将含水率为10wt％的镍石膏与含水率为0.2wt％的硫铁矿研磨均匀，硫铁矿中的有效成分二硫化亚铁和石膏中的有效成分硫酸钙的摩尔比为2.5:1，得到混合物料；
(b)将该混合物料加入温度1500℃的反应器中，在保护气氛(氮气、2wt％氧气、二氧化碳和二氧化硫)下，焙烧2h，固相经冷却得到铁酸钙，产生的二氧化硫尾气制硫酸或硫磺。
经测定，实施例6中硫铁矿分解率为90％，镍石膏的分解率为98％，制得的铁酸钙中按摩尔比铁元素:钙元素＝2.3:1。
实施例7铁酸钙的制备
(a)将含水率为0.5wt％的氟石膏与含水率为3wt％的硫铁矿研磨均匀，硫铁矿中的有效成分二硫化亚铁和氟石膏中的有效成分硫酸钙的摩尔比为0.8:1，添加铁补充剂为硫酸亚铁，硫酸亚铁与石膏中硫酸钙摩尔比为0.8:1，得到混合物料；
(b)将该混合物料加入温度1100℃的反应器中，在保护气氛(氮气、一氧化碳和二氧化硫)下，焙烧2h，固相经冷却得到铁酸钙，产生的二氧化硫尾气制硫酸或硫磺。
经测定，实施例7中硫铁矿分解率为96％，氟石膏的分解率为99％，制得的铁酸钙中按摩尔比铁元素:钙元素＝1.68:1。
实施例8铁酸钙的制备
(a)将含水率为0.5wt％的磷石膏与含水率为3wt％的硫铁矿研磨均匀，硫铁矿中的有效成分二硫化亚铁和磷石膏中的有效成分硫酸钙的摩尔比为1:1，添加铁补充剂为硫酸亚铁，硫酸亚铁与石膏中硫酸钙摩尔比为0.5:1，得到混合物料；
(b)将该混合物料加入温度1200℃的反应器中，在保护气氛(氮气、一氧化碳和二氧化硫)下，焙烧1h，固相经冷却得到铁酸钙，产生的二氧化硫尾气制硫酸或硫磺。
经测定，实施例8中硫铁矿分解率为97％，磷石膏的分解率为98％，制得的铁酸钙中按摩尔比铁元素:钙元素＝1.48:1。
实施例9铁酸钙的制备
(a)将含水率为0.5wt％的氟石膏与含水率为3wt％的硫铁矿研磨均匀，硫铁矿中的有效成分二硫化亚铁和氟石膏中的有效成分硫酸钙的摩尔比为0.3:1，添加铁补充剂为氧化亚铁，氧化亚铁与石膏中硫酸钙摩尔比为1:1，得到混合物料；
(b)将该混合物料加入温度1000℃的反应器中，在保护气氛(氮气、一氧化碳和二氧化硫)下，焙烧2h，固相经冷却得到铁酸钙，产生的二氧化硫尾气制硫酸或硫磺。
经测定，实施例9中硫铁矿分解率为98％，氟石膏的分解率为98％，制得的铁酸钙中按摩尔比铁元素:钙元素＝1.3:1。

Claims (15)

  1. 铁酸钙的制备方法，其特征在于：包括如下步骤：
    (a)取石膏、硫铁矿和铁补充剂，混合得到混合物料；
    其中，按摩尔比石膏中硫酸钙:硫铁矿中二硫化亚铁:铁补充剂中铁元素＝1:0.1～2.5:0～2，并且按摩尔比混合物料中钙元素:铁元素＝1:1～2.5，所述石膏的含水率小于10wt％，所述硫铁矿的含水率为0.1～15wt％；
    (b)于保护气氛下将混合物料进行焙烧，焙烧温度为900～1500℃，焙烧时间为0.1～4h，焙烧完毕，冷却得到铁酸钙；
    其中，所述保护气氛为惰性气氛、还原性气氛或氧气含量小于5wt％的氧化性气氛。
  2. 根据权利要求1所述的铁酸钙的制备方法，其特征在于：所述石膏为无水石膏、半水石膏、磷石膏、脱硫石膏、氟石膏、柠檬酸石膏、镍石膏、钛白粉副产石膏、天然石膏和硬石膏中的至少一种。
  3. 根据权利要求2所述的铁酸钙的制备方法，其特征在于：所述石膏为含水率为0.1～10wt％的半水石膏或为无水石膏。
  4. 根据权利要求1所述的铁酸钙的制备方法，其特征在于：所述铁补充剂为铁元素的含量大于25wt％的物质。
  5. 根据权利要求4所述的铁酸钙的制备方法，其特征在于：所述铁补充剂为氧化亚铁、四氧化三铁、氧化铁、碳酸铁、硫酸亚铁、硫酸铁和铁中的至少一种。
  6. 据权利要求1所述的铁酸钙的制备方法，其特征在于：按摩尔比石膏中硫酸钙:硫铁矿中二硫化亚铁:铁补充剂中铁元素＝1:0.3～1:0.5～1。
  7. 据权利要求2所述的铁酸钙的制备方法，其特征在于：按摩尔比石膏中硫酸钙:硫铁矿中二硫化亚铁:铁补充剂中铁元素＝1:0.3～1:0.5～1。
  8. 据权利要求3所述的铁酸钙的制备方法，其特征在于：按摩尔比石膏中硫酸钙:硫铁矿中二硫化亚铁:铁补充剂中铁元素＝1:0.3～1:0.5～1。
  9. 据权利要求4所述的铁酸钙的制备方法，其特征在于：按摩尔比石膏中硫酸钙:硫铁矿中二硫化亚铁:铁补充剂中铁元素＝1:0.3～1:0.5～1。
  10. 据权利要求5所述的铁酸钙的制备方法，其特征在于：按摩尔比石膏中硫酸钙:硫铁矿中二硫化亚铁:铁补充剂中铁元素＝1:0.3～1:0.5～1。
  11. 根据权利要求1所述的铁酸钙的制备方法，其特征在于：所述焙烧温度为1000～ 1200℃。
  12. 根据权利要求1所述的铁酸钙的制备方法，其特征在于：所述焙烧时间为1～2h。
  13. 根据权利要求1所述的铁酸钙的制备方法，其特征在于：所述保护气氛为氮气、二氧化碳和二氧化硫中的至少一种。
  14. 根据权利要求1所述的铁酸钙的制备方法，其特征在于：所述保护气氛为氮气、一氧化碳和二氧化硫的混合气氛；或为二氧化碳、一氧化碳和二氧化硫的混合气氛；或为氮气、二氧化碳、一氧化碳和二氧化硫的混合气氛。
  15. 根据权利要求1所述的铁酸钙的制备方法，其特征在于：所述保护气氛为气体A、氧气和二氧化硫的混合气氛，其中，所述气体A为氮气、二氧化碳和一氧化碳中的至少一种，所述氧气的含量小于5wt％。
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