WO2017201911A1 - 一种由磷铁低温制备含FexPO4物质的方法 - Google Patents

一种由磷铁低温制备含FexPO4物质的方法 Download PDF

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WO2017201911A1
WO2017201911A1 PCT/CN2016/098012 CN2016098012W WO2017201911A1 WO 2017201911 A1 WO2017201911 A1 WO 2017201911A1 CN 2016098012 W CN2016098012 W CN 2016098012W WO 2017201911 A1 WO2017201911 A1 WO 2017201911A1
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iron
phosphorus
low temperature
ferrophosphorus
preparing
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王贵欣
许飞
邹江东
闫康平
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Sichuan University
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

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  • the invention relates to a method for preparing a material containing Fe x PO 4 from phosphorus iron at a low temperature, which overcomes the influence of impurities in the raw material, has high purity, fine particle size, easy to control the morphology, simple process and can be applied to the synthesis of chemical solid waste. Utilize and low-cost cleaner production of high-end phosphate materials.
  • Fe x PO 4 As a kind of iron phosphate, there are many kinds of Fe x PO 4 substances. Commonly, there are iron phosphate, ferrous phosphate, iron hydroxyphosphate, ferrous hydroxyphosphate, iron phosphate, and ferrous carbonate. , catalysts, ceramics, food additives and other fields have a wide range of applications.
  • the Fe x PO 4 -containing material itself can be used as an electrode material or as a raw material for preparing electrode materials such as LiFePO 4 , LiFeP 2 O 7 and Li 3 Fe 2 (PO 4 ) 3 . Since Fe and P have been dispersed relatively uniformly in the Fe x PO 4 -containing material, only Li + diffusion is required to obtain a lithium-containing electrode material.
  • the electrode material is prepared from the Fe x PO 4 -containing material. It is easy to carry out, so a large amount of Fe x PO 4 is currently used as an iron source and a phosphorus source to prepare electrode materials such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 .
  • commercial FePO 4 usually uses iron powder or iron salt and phosphoric acid or phosphate as raw materials, stirs the reaction under the condition of solution, and is dried at 90-100 ° C and then calcined at 600-800 ° C, and a large amount of waste is generated during the reaction.
  • the present invention proposes a new process route for preparing Fe x PO 4 using ferrophosphorus different from the above process, overcomes the shortcomings of the current Fe x PO 4 production process, and utilizes the magnetic properties of the ferrophosphorus to physically purify it.
  • Fe x PO 4 When Fe x PO 4 is prepared from ferrophosphorus, the phosphorus-iron raw material consumes a lot of water, consumes a large amount of energy, and the impurity type and content are uncertain, which makes it difficult to comprehensively purify the impurity element and the technical difficulty of controlling the particle size and morphology of the Fe x PO 4 product, simplifying
  • the present invention proposes a novel process completely different from the above invention: preparing Fe x PO 4 by reacting ferrophosphorus with an oxidizing substance under low temperature conditions, through raw material selection and process control
  • the Fe x PO 4 finished product can be obtained directly, and the finished product can be further used as a raw material for producing other materials, and the kind of by-products can be controlled.
  • the invention is innovative from the source, and creatively proposes a new process route for preparing iron phosphate from phosphorus iron as raw material with low energy consumption, the reaction condition is simple and easy, and the phosphorus and iron can be specifically purified by controlling raw materials and process parameters.
  • Fe x PO 4 can be granulated, the by-product type can be controlled and can be recycled.
  • the Fe x PO 4 product prepared by the invention has high purity, small particle size, easy to control morphology, low raw material cost and water consumption. Less, low energy consumption, less pollution, short reaction process, simple preparation process, clean and environmentally friendly, easy to operate, and good efficiency.
  • the object of the present invention is to solve the above problems, overcome the deficiencies of the prior art, simplify the reaction process for preparing Fe x PO 4 -containing substances from ferrophosphorus, and reduce the energy consumption and water consumption in the synthesis process, and creatively propose a Phosphorus iron reacts with oxidizing substances at low temperature to obtain a new process method containing Fe x PO 4 substances.
  • the chemical reaction process can be strengthened by different chemical measures.
  • the product can be granulated, and the temperature and reaction conditions can be controlled to control the composition of by-products.
  • the particle size and morphology of the product, the filtrate can be recycled after being treated, the power consumption is low, and the operation is simple.
  • the basic idea of the present invention is that the present invention utilizes oxygen in an oxidizing substance to oxidize P of ferrophosphorus to PO 4 3- under low temperature conditions, thereby saving water and energy, and purifying and strengthening the ferrophosphorus by simple chemical measures. Process, purity, morphology and particle size and by-product type of Fe x PO 4 containing materials prepared by raw material selection and process parameters.
  • the method for preparing a material containing Fe x PO 4 from ferrophosphorus according to the present invention has the following specific steps; mixing phosphorus iron with an oxidizing substance, supplementing the phosphorus source or the iron source according to the composition of the ferrophosphorus, and reacting at a low temperature to obtain Fe-containing x PO 4 substance.
  • the oxidizing substance means an oxygen-containing substance.
  • the low temperature means that the temperature supplied to the reaction system by the outside does not exceed 600 °C.
  • the supplemental phosphorus source refers to a substance containing phosphorus.
  • the supplemental iron source refers to a substance containing iron.
  • the Fe x PO 4 -containing substance means a substance containing Fe x PO 4 in the composition.
  • iron phosphate in the Fe x PO 4 -containing material, 0 ⁇ x ⁇ 2, in particular, iron phosphate, ferrous phosphate, iron hydroxyphosphate, ferrous hydroxyphosphate, iron phosphate, and ferrous phosphate.
  • the influence of impurities in the raw material on the product, the strengthening of the reaction process, and the promotion of the reaction in the desired direction can be eliminated in accordance with the magnetic properties of the ferrophosphorus and the solubility of the product.
  • the morphology, crystallinity, particle size and distribution of the material containing Fe x PO 4 can be controlled by the process conditions, and the product can be subjected to ball milling, jet milling, modification, etc., as needed.
  • the invention realizes the technical problem of preparing Fe x PO 4 -containing material by phosphorus iron under low temperature condition, and solves the impurity element pair of ferrophosphorus raw material when preparing Fe x PO 4 material from ferrophosphorus
  • the influence of the product and the series of technical problems that are difficult to control the particle size and morphology of the Fe x PO 4 material overcome the problem of difficult raw material ratio caused by the diversity of ferrophosphorus composition, eliminating the high energy consumption and equipment ease of phosphorus iron oxidation.
  • Figure 1 is a flow chart of a process for preparing a Fe x PO 4 -containing material from a ferrophosphorus low temperature by a solvothermal method.
  • Figure 2 is an XRD pattern of the Fe x PO 4 containing material prepared from phosphorus iron at a low temperature.
  • water or other solvent may be added and reacted at 50 ° C to 300 ° C for 5 to 75 hours to obtain an aqueous solution of Fe 5 (PO 4 ) 4 (OH) 3 , and the morphology and particle size of the product are regulated by a concentration process, and dried.
  • the reaction equation is as follows:
  • phosphoric acid is used as a supplemental phosphorus source
  • hydrogen peroxide is used as an oxidant
  • the reaction is not more than 300 ° C.
  • the product is iron phosphate Fe 5 (PO 4 ) 4 (OH) 3 and water H 2 O, and no other harmful by-products are formed. Evaporative condensation can be used to achieve green and clean production.
  • iron phosphate FePO 4 is prepared from ferrophosphorus Fe 2 P, and the ferrophosphorus Fe 2 P is pulverized to a particle size of 1000 mesh or more, and then the phosphorus source P 2 O 5 powder is in a dry atmosphere.
  • the mixture is uniformly mixed and transferred into a closed heating vessel with a pressure reducing valve.
  • a certain amount of air is introduced to bring the powder to a boiling state, and the external magnetic field of 1T to 10T is used to enhance the transfer process of the ferrophosphorus powder in the reaction vessel.
  • the reaction is carried out at 100 ° C to 500 ° C for 10 to 35 hours to obtain a FePO 4 finished product.
  • the reaction equation is as follows:
  • P 2 O 5 is used as a supplemental phosphorus source
  • O 2 in the air is an oxidant
  • the product is only ferric phosphate FePO 4 , and no other by-products are formed, which realizes green and clean production, and the difference in density between products and raw materials.
  • oxygen O 2 may be replaced by ozone O 3 .
  • the iron phosphate FePO 4 was prepared from the ferrophosphorus FeP by plasma method, the plasma-forming device was composed of the solution of the aluminum-plated stainless steel as the anode, the stainless steel tank wall as the cathode and the distilled water as the electrolyte, and the ferro-Fe Fe was placed in the titanium basket. Oxidation in the anode region where the plasma is generated for 0.5 to 5 hours, regulating the voltage and current of the plasma source to regulate the composition of the oxidation product, adjusting the composition of the solution to regulate the solubility of the phosphate oxidation product, and utilizing the solubility of the phosphate to the product Purification, adjustment of particle size and morphology by concentration, drying to obtain FePO 4 finished product. In addition, the in-situ doping modification of the ferrophosphorus can be performed by adjusting the electrolyte.
  • the Fe 2 P ferrophosphorus prepared iron phosphate FePO 4 first ferrophosphorus Fe 2 P pulverized to a particle size of 800 mesh or more, the ferrophosphorus powder is then transferred into an aqueous solution of phosphoric acid in a concentration of Oxidation by ozone for 1 ⁇ 3h, using phosphoric acid to adjust the pH of the solution below 1.5, to obtain FePO 4 solution, adjust the solubility of the product in solution by the pH of the solution to promote the reaction to move toward the formation of FePO 4 , and add ammonia after the reaction is completed.
  • the pH of the solution was adjusted to be between 2.5 and 4.0, and FePO 4 was precipitated and precipitated, filtered, washed and dried to obtain a finished FePO 4 product.
  • the pH is adjusted by the raw material phosphoric acid in the early stage, and the ammonia is added to adjust the pH in the later stage.
  • the entire reaction by-product is an aqueous solution of ammonium phosphate, which can be used as a chemical fertilizer, and the reaction process is used to remove impurities, thereby achieving green and environmentally clean production.
  • the iron phosphate FePO 4 is prepared from phosphorus iron FeP by gas-solid oxidation method.
  • the ferro-phosphorus FeP is pulverized to a particle size of more than 2000 mesh, then the ferro-phosphorus powder is transferred into a boiling furnace, and the air is introduced into a boiling state, and then the ozone is introduced. Oxidation at 300 ° C ⁇ 500 ° C for 1 ⁇ 3h, through the ozone content and boiling furnace temperature control reaction process, so that it is safe and stable operation, using the difference in density of raw materials and products to separate the product, to obtain FePO 4 finished product.
  • the reaction equation is as follows:
  • Fe 3 (PO 4 ) 2 is prepared by using phosphorus iron Fe 3 P as iron source and part of phosphorus source, and the phosphorus iron and the supplementary phosphorus source P 2 O 5 powder are uniformly mixed in proportion, and transferred into an atmosphere furnace and introduced into CO 2 .
  • the reaction process is strengthened by applying a magnetic field of 1 to 10 T, and the reaction is carried out at 200 ° C to 400 ° C for 1 to 10 h, and air is introduced into the generated hot exhaust gas, and then the treated tail gas is re-introduced into the reaction system for recycling, and the phosphoric acid is obtained after cooling. Finished iron.
  • the reaction equation is as follows:
  • Fe 3 (PO 4 ) 2 was prepared by using FeFe iron as iron source and part of phosphorus source, and the ferrophosphorus and supplemental phosphorus source (NH 4 ) 2 HPO 4 powder were mixed uniformly in proportion, and then with a certain amount of biomass magnolia powder After mixing, it is transferred into an atmosphere furnace and reacted in an inert atmosphere at 200 ° C to 550 ° C for 1 to 5 hours. The generated hot tail gas is oxidized by air and then re-introduced into the reaction system to obtain a finished ferrous phosphate product after cooling.
  • Fe 3 (PO 4 ) 2 is prepared by using iron and iron Fe 2 P as iron source and part of phosphorus source, and the ferrophosphorus and supplemental phosphorus source (NH 4 ) 2 HPO 4 powder are mixed uniformly in proportion, and then mixed with a certain amount of bagasse After uniform ball milling for 1 ⁇ 10h, transferred into the atmosphere furnace, treated with 300 ⁇ 600W microwave oven for 0.5 ⁇ 5h, after cooling to obtain the finished ferrous phosphate.

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Abstract

一种由磷铁低温制备含Fe xPO 4物质的方法，以磷铁为原料，x为不同化学组成所确定的系数，其步骤如下：将磷铁与氧化性物质混合，根据磷铁组成补充磷源或铁源，在低温下反应，得到含Fe xPO 4物质。

Description

一种由磷铁低温制备含FexPO4物质的方法 技术领域
本发明涉及一种由磷铁低温制备含FexPO4物质的方法，克服原料中杂质的影响，产物的纯度高、粒度细、形貌易控制，工艺简单，可应用于化工固体废物的综合利用和高端磷酸盐材料的低成本清洁生产。
背景技术
作为铁的一种磷酸盐，含FexPO4物质的种类较多，常见的有磷酸铁、磷酸亚铁、羟基磷酸铁、羟基磷酸亚铁、碳酸磷酸铁、碳酸磷酸亚铁，在能源材料、催化剂、陶瓷、食品添加剂等领域有广泛的应用。在能源材料领域，含FexPO4物质本身既可用作电极材料，又可作为制备LiFePO4，LiFeP2O7和Li3Fe2(PO4)3等电极材料的原料。由于Fe与P在含FexPO4物质中已经分散比较均匀，只需要Li+扩散进去就能得到含锂电极材料，从理论和实践结果来说，由含FexPO4物质制备电极材料更容易进行，因此目前大量采用FexPO4同时作为铁源和磷源制备LiFePO4和Li3Fe2(PO4)3等电极材料。目前商业化FePO4通常以铁粉或铁盐与磷酸或磷酸盐为原料，在溶液状态下搅拌反应，经90～100℃烘干后再在600～800℃焙烧得到，反应过程中产生大量废液，存在反应过程难以控制、原料单一、设备腐蚀严重、废液处理难度大、能耗高等问题，制备成本较高，导致目前FePO4的市场价格较高(约3万/吨)，从而导致由磷酸铁制备磷酸亚铁锂的价格较高。
磷铁是磷与铁形成的合金，略有金属光泽，比重较大，资源丰富，来源广泛，可以是矿物或其冶炼产物，也可以是黄磷或钙镁磷肥等磷化工和硅酸盐化工等生产中的副产物，也可自制，产量较大，仅电炉法生产磷工艺中，生产1吨黄磷副产磷铁80-150公斤，其中，w(P)＝18％-26％，w(Fe)＝70％。我国的磷铁资源丰富，应用领域不广，市场价格比较低，大部分廉价出口或被商贸部门以粗品收购。
为了扩展磷铁的应用领域，提高磷铁资源的高值利用，我们对磷铁开展了大量工作，率先提出了利用来源丰富的价廉磷铁制备电极材料的新思路[中国专利ZL200810045243.1，CN101602500A，CN101659408A，200910263487.1，20091063486.7，200910263552.0，200910263553.5，201010126920.X.]和由磷铁制备磷酸铁的特殊实施工艺[中国专利CN101659406A，CN102051629A]。在这些方法中，由磷铁制备电极材料与由磷铁制备磷酸铁的工艺方法不同。而我们原来由磷铁制备磷酸铁的特殊实施工艺[中国专利CN101659406A] 中，依靠磷铁在干燥含氧气氛中氧化为Fe2O3和P2O5后再次反应来降低磷铁中的杂质元素对产物的影响，中国专利CN102051629A中通过对磷铁进行电解除杂、调整溶液pH沉淀、洗涤、过滤等工艺过程制备磷酸铁，与本申请显然不同。文献报道的利用微波消解磷铁制备磷酸铁中[无机盐工业，2015,4(3):23-26]，利用硝酸和磷酸溶液，产生氮氧化物和大量废液，而且反应工艺过程复杂，也与本申请显然不同。另外，不同地域、不同工艺得到的磷铁中的杂质种类及含量不同，而这些杂质会对产物的性能有不同程度的影响，需要对其进行一定的提纯处理。另外，直接由磷铁制备磷酸铁时，产物的粒度受磷铁原料的粒度影响较大。
在此，本发明提出了与上述工艺不同的利用磷铁制备含FexPO4的全新工艺路线，克服目前FexPO4生产工艺的不足，利用磷铁的磁特性对其进行物理提纯，解决由磷铁制备FexPO4时磷铁原料中耗水多、耗能高、杂质种类及含量不确定导致难以全面提纯杂质元素和FexPO4产物粒度与形貌难以控制的技术难题，简化制备工艺，减少能耗和废物排放，本发明提出了一种与上述发明完全不同的新型工艺方法：由磷铁与氧化性物质在低温条件下反应制备FexPO4，通过原料选择和工艺控制可以直接得到FexPO4成品，该成品可以进一步作为生产其他材料的原料，副产物的种类可控。本发明从源头上创新，创造性的提出一种由磷铁为原料低能耗制备磷酸铁的全新工艺路线，反应条件简单易行，同时可以通过控制原料和工艺参数对磷铁进行针对性提纯，也可以对FexPO4进行造粒处理，副产物种类可控并且可以加以回收利用，由该发明制备的FexPO4产物的纯度高、粒度小、形貌易控制，原料成本低，耗水少，能耗低，污染少，反应流程短，制备方法工艺简单，清洁环保，反应易操作，效益好。
发明内容
本发明的目的是为了解决上述问题，克服现有技术的不足，简化由磷铁制备含FexPO4物质的反应工艺流程，降低合成过程中的能耗和水耗，创造性的提出一种由磷铁在低温下与氧化性物质反应获得含FexPO4物质的全新工艺方法，利用不同的化工措施强化反应过程，可以对产物进行造粒处理，控制温度和反应工艺条件可以调控副产物组成、产物的粒度和形貌，滤液经处理后可以循环使用，耗电量低，操作简便。
本发明的基本构思在于：本发明利用氧化性物质中的氧在低温条件下将磷铁的P氧化为PO4 3-，节约水和能量，利用简便的化工措施对磷铁进行提纯和强化反应过程，通过原料选择和工艺参数调控制备的含FexPO4物质纯度、形貌与粒度及副产物类型。
本发明所述由磷铁制备含FexPO4物质的方法，具体工艺步骤如下；将磷铁与氧化性物质混合，根据磷铁组成补充磷源或铁源，在低温下反应，得到含FexPO4物质。
本发明中，所述的氧化性物质指含氧的物质。
本发明中，所述的低温指外界提供给反应体系的温度不超过600℃。
本发明中，所述的补充磷源指含磷的物质。
本发明中，所述的补充铁源指含铁的物质。
本发明中，所述的含FexPO4物质指组成中含有FexPO4的物质。
本发明中，所述的含FexPO4物质中，0<x≤2，尤其指磷酸铁、磷酸亚铁、羟基磷酸铁、羟基磷酸亚铁、碳酸磷酸铁、碳酸磷酸亚铁。
本发明中，可以根据磷铁的磁性和产物的溶解性消除原料中杂质对产物的影响、强化反应过程、促进反应朝期待的方向发生。
本发明中，可以通过工艺条件来控制含FexPO4物质的形貌、结晶度和粒径大小及分布等，也可以根据需要对产物进行球磨或气流粉碎、改性等后处理。
本发明与现有技术相比，本发明实现了由磷铁在低温条件下制备含FexPO4物质的技术难题，解决了由磷铁制备含FexPO4物质时磷铁原料杂质元素对产物的影响和含FexPO4物质粒度与形貌难以控制的系列技术难题，克服了由磷铁组成多样性引起的原料配比难的问题，消除了磷铁氧化时能耗高和设备易腐蚀及气固反应速度慢的不足，创造性的提出“利用氧化性物质中的氧给磷铁中的P提供氧源，实现磷铁和氧化性物质发生氧化还原反应的物料平衡”的新型低成本制备方法，不需要另外补充其他氧源，利用原料的磁性和产物溶解性可以对原料提纯、降低杂质元素影响和对产物进行造粒，具有以下优点和突出性效果：反应工艺独特，通过对反应进行设计，可以调控副产物的种类和含FexPO4物质的粒度与形貌，实现磷铁在低温下较容易得到含FexPO4物质，成本低；通过原料的选择和工艺的控制，可以不产生副产物，也可以调控仅副产水，实现绿色环保清洁生产；能够消除原料中杂质元素对产物的影响，通过控制磁场强度对磷铁进行针对性提纯；耗水或其他溶剂少，不产生有害的副产物，实现节能降耗；能够有效控制FexPO4产物的形貌和粒度分布，通过对含FexPO4物质溶液进行造粒、结晶等能有效控制含FexPO4物质的形貌和粒度分布，容易得到纳微尺度的球形材料；工艺流程简单，易操作，生产成本低廉，无三废污染，清洁环保，资源利用率高，投资少，效益好。
附图说明
图1用溶剂热法由磷铁低温制备含FexPO4物质的工艺流程图。
图2由磷铁低温制备含FexPO4物质的XRD图。
具体实施方式
以下结合实施例及附图对本发明作进一步说明，所述内容仅为本发明构思下的基本说明， 但是本发明不局限于下面例子，依据本发明的技术方案所作的任何等效变换，均属于本发明的保护范围。
实施例1
采用溶剂热法由磷铁Fe1.5P制备羟基磷酸铁Fe5(PO4)4(OH)3，将磷铁渣Fe1.5P粉碎至粒度在400目以上，根据磷铁与杂质的磁性不同利用磁浮选法将高纯度磷铁转移入一个干净容器中，从而提高原料磷铁的纯度，将高纯度磷铁放入带泄压阀的水热釜中，按比例添加磷酸和双氧水，根据需要，可以添加水或其他溶剂，在50℃～300℃反应5～75h，得到Fe5(PO4)4(OH)3水溶液，通过浓缩过程调控产物形貌与粒度，烘干后得到粒径为20～30nm的球形Fe5(PO4)4(OH)3成品，工艺过程如图1所示，产物的XRD如图2所示。反应方程式如下所示：
10Fe1.5P+2H3PO4+47.5H2O2→3Fe5(PO4)4(OH)3+46H2O
该反应中，以磷酸为补充磷源，双氧水为氧化剂，不超过300℃反应，产物为磷酸铁Fe5(PO4)4(OH)3和水H2O，没有其他有害副产物生成，水可以蒸发冷凝循环利用，实现了绿色环保清洁生产。
实施例2
采用外加磁场强化传递过程和反应过程，由磷铁Fe2P制备磷酸铁FePO4，将磷铁Fe2P粉碎至粒度在1000目以上，然后与补充磷源P2O5粉体在干燥气氛下按比例混合均匀后转移入带减压阀的密闭加热容器中，通入一定量的空气使粉体达到沸腾状态，用1T～10T的外磁场强化磷铁粉在反应容器中的传递过程和反应，在100℃～500℃反应10～35h，得到FePO4成品。反应方程式如下所示：
4Fe2P+2p2O5+11O2→8FePO4
该反应中，以P2O5为补充磷源，空气中的O2为氧化剂，产物只有磷酸铁FePO4，没有其他副产物形成，实现了绿色环保清洁生产，产物和原料通过他们的密度差异进行分离。另外，氧气O2可以用臭氧O3替代。
实施例3
采用等离子体法由磷铁FeP制备磷酸铁FePO4，以镀铝不锈钢为阳极、不锈钢槽壁为阴极、蒸馏水配置的溶液为电解液组成等离子体发生装置，将磷铁FeP放入钛篮中，置于产生等离子体的阳极区氧化0.5～5h，调控等离体子电源的电压和电流调控氧化产物的组成，调整溶液组成调控磷酸盐氧化产物的溶解性，利用磷酸盐的溶解性对产物进行提纯，通过浓缩调 整粒度和形貌，烘干后得到FePO4成品。另外，可以通过调整电解液对磷铁进行原位掺杂改性。
实施例4
利用产物溶解性促进气固反应，由磷铁Fe2P制备磷酸铁FePO4，首先将磷铁Fe2P粉碎至粒度在800目以上，然后将磷铁粉体转移入一定浓度的磷酸水溶液中，通入臭氧氧化1～3h，用磷酸调控溶液pH在1.5以下，得到FePO4溶液，通过溶液pH调控产物在溶液中的溶解度以促使反应朝着生成FePO4的方向移动，反应完成后加氨水调整溶液pH在2.5～4.0之间，将FePO4沉淀析出，经过滤、洗涤、烘干后得到FePO4成品。
该反应中，前期用原料磷酸调节pH，后期添加氨水调节pH，整个反应副产物为磷酸铵水溶液，可以用为化肥，利用反应过程除杂，实现了绿色环保清洁生产。
实施例5
采用气固氧化法由磷铁FeP制备磷酸铁FePO4，首先将磷铁FeP粉碎至粒度在2000目以上，然后将磷铁粉体转移入沸腾炉中，通入空气达到沸腾状态，再通入臭氧在300℃～500℃氧化1～3h，通过通入的臭氧含量和沸腾炉温度调控反应过程，使其安全稳定运行，利用原料与产物的密度差异分离出产物，得到FePO4成品。反应方程式如下所示：
3FeP+4O3→3FePO4
该反应中，以臭氧为氧化剂，没有其他副产物形成，产物仅为磷酸铁FePO4。
实施例6
以磷铁Fe3P为铁源和部分磷源制备Fe3(PO4)2，将磷铁和补充磷源P2O5粉体按比例混合均匀，移入气氛炉中并通入CO2，利用1～10T外加磁场强化反应过程，在200℃～400℃反应1～10h，往产生的热尾气中通入空气，然后将处理的尾气重新通入反应体系中循环利用，降温后得到磷酸亚铁成品。反应方程式如下所示：
2Fe3P+P2O5+11CO2→2Fe3(PO4)2+11CO
2CO+O2→2CO2
实施例7
以磷铁FeP为铁源和部分磷源制备Fe3(PO4)2，将磷铁和补充磷源(NH4)2HPO4粉体按比例混合均匀，再与一定量生物质厚朴粉混合均匀后转移入气氛炉中，在200℃～550℃惰性气氛下反应1～5h，将产生的热尾气经空气氧化后重新通入反应体系中，降温后得到磷酸亚铁 成品。
实施例8
以磷铁Fe2P为铁源和部分磷源制备Fe3(PO4)2，将磷铁和补充磷源(NH4)2HPO4粉体按比例混合均匀，再与一定量甘蔗渣混合均匀后球磨1～10h，转移入气氛炉中，经300～600W微波炉处理0.5～5h，降温后得到磷酸亚铁成品。

Claims (8)

  1. 一种由磷铁低温制备含FexPO4物质的方法，以磷铁为原料，x为不同化学组成所确定的系数，其特征在于工艺步骤如下：将磷铁与氧化性物质混合，根据磷铁组成补充磷源或铁源，在低温下反应，得到含FexPO4物质。
  2. 根据权利要求1所述的由磷铁低温制备含FexPO4物质的方法，其特征在于：所述的氧化性物质指含氧的物质。
  3. 根据权利要求1所述的由磷铁低温制备含FexPO4物质的方法，其特征在于：所述的低温指外界提供给反应体系的温度不超过600℃。
  4. 根据权利要求1所述的由磷铁低温制备含FexPO4物质的方法，其特征在于：所述的补充磷源指含磷的物质。
  5. 根据权利要求1所述的由磷铁低温制备含FexPO4物质的方法，其特征在于：所述的补充铁源指含铁的物质。
  6. 根据权利要求1所述的由磷铁低温制备含FexPO4物质的方法，其特征在于：所述的含FexPO4物质指组成中含有FexPO4的物质。
  7. 根据权利要求1所述的由磷铁低温制备含FexPO4物质的方法，其特征在于：所述的含FexPO4物质中，0<x≤2，尤其指磷酸铁、磷酸亚铁、羟基磷酸铁、羟基磷酸亚铁、碳酸磷酸铁、碳酸磷酸亚铁。
  8. 根据权利要求1或3所述的由磷铁低温制备含FexPO4物质的方法，其特征在于：所述的低温指80℃～400℃。
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