WO2022267190A1 - 一种高磷鲕状铁矿的处理方法 - Google Patents

一种高磷鲕状铁矿的处理方法 Download PDF

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WO2022267190A1
WO2022267190A1 PCT/CN2021/111725 CN2021111725W WO2022267190A1 WO 2022267190 A1 WO2022267190 A1 WO 2022267190A1 CN 2021111725 W CN2021111725 W CN 2021111725W WO 2022267190 A1 WO2022267190 A1 WO 2022267190A1
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pellets
phosphorus
iron
reduced
magnetic separation
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PCT/CN2021/111725
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English (en)
French (fr)
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黄武胜
江共养
延黎
孙体昌
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中钢设备有限公司
北京科技大学
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Publication of WO2022267190A1 publication Critical patent/WO2022267190A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/2406—Binding; Briquetting ; Granulating pelletizing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0073—Selection or treatment of the reducing gases
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/008—Use of special additives or fluxing agents
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0086—Conditioning, transformation of reduced iron ores
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/143—Reduction of greenhouse gas [GHG] emissions of methane [CH4]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • the invention belongs to the technical field of mineral processing, and in particular relates to a processing method for high-phosphorus oolitic iron ore.
  • High phosphorus iron ore is one of the typical representatives of this kind of refractory iron ore.
  • high-phosphorus iron ore is mainly distributed in the United States, France, the United Kingdom, Canada, Norway, Nigeria, Ukraine and China, with a total reserve of more than 2 ⁇ 1010t. Due to the complex structure and high phosphorus content of this type of ore, only iron concentrates with high phosphorus content can be obtained by physical beneficiation.
  • the object of the present invention is to provide a kind of treatment method of high-phosphorus oolitic iron ore, the removal rate of phosphorus of the method in the present invention is high, the iron grade and recovery rate of the powder reduced iron of gained are all higher, and raw ore iron grade and phosphorus content Changes within a certain range do not affect the restoration effect.
  • the invention provides a kind of processing method of high-phosphorus oolitic iron ore, comprising the following steps:
  • the dephosphorization agent includes calcium carbonate and calcium fluoride, and the mass ratio of calcium carbonate and calcium fluoride is 1: (0.15-0.30);
  • the high-phosphorus oolitic iron ore is one or more of high-phosphorus oolitic hematite, high-phosphorus oolitic magnetite and high-phosphorus oolitic hematite/magnetite.
  • the particle size of the high-phosphorus oolitic iron ore is ⁇ 1mm, the iron grade is 43-60%, and the mass fraction of phosphorus is ⁇ 1.5%.
  • the mass ratio of the high-phosphorus oolitic iron ore, dephosphorization agent and water is 1:(0.2-0.4):(0.05-0.15).
  • the temperature of the oxidation roasting is 1000-1500° C.; the time of the oxidation roasting is 50-100 min.
  • the reducing atmosphere is natural gas cracked gas and/or water gas.
  • the temperature of the reduction calcination is 1100-1300° C.; the time of the reduction calcination is 150-200 min.
  • the reduced pellets are cooled to room temperature in isolation from air, crushed to -2 mm, and then subjected to two-stage grinding-magnetic separation to obtain reduced iron products.
  • the particle content of the first-stage grinding to -0.074mm is not less than 65%, and the magnetic field strength of the first-stage magnetic separation is 1600-1800 Oersted; the second-stage grinding to -0.074mm The particle content is not less than 85%, and the magnetic field strength of the second-stage magnetic separation is 1300-1400 Oersted.
  • the invention provides a method for processing high-phosphorus oolitic iron ore, comprising the following steps: A) mixing high-phosphorus oolitic iron ore, a dephosphorization agent and water, pressing into pellets to obtain mixed pellets; the dephosphorization The agent includes calcium carbonate and calcium fluoride, and the mass ratio of the calcium carbonate and calcium fluoride is 1: (0.15-0.30); B) drying the mixed pellets and performing oxidative roasting to obtain oxidative roasted pellets C) reducing and roasting the oxidized and roasted pellets in a reducing atmosphere to obtain reduced pellets; D) cooling the reduced pellets to room temperature in isolation from air, and then performing grinding-magnetic separation to obtain reduced iron product.
  • a dephosphorizing agent is added to the pellets, and the dephosphorizing agent reacts with the components in the ore under an oxidizing atmosphere to change its mineral composition and at the same time make the phosphorus originally present in the iron minerals generate a separate phosphorus-containing mineral , will also change the structure of the ore and create conditions for iron reduction and dephosphorization.
  • the technological process in the present invention is simple, and the removal rate of phosphorus in high-phosphorus oolitic iron ore is high, and the iron grade and recovery rate of the obtained powder reduced iron are high, and changes in the iron grade and phosphorus content of the raw ore within a certain range do not affect Restoration effect.
  • Fig. 1 is the flow chart of the processing method of high phosphorus oolitic iron ore of the present invention.
  • the invention provides a kind of processing method of high-phosphorus oolitic iron ore, comprising the following steps:
  • the dephosphorization agent includes calcium carbonate and calcium fluoride, and the mass ratio of calcium carbonate and calcium fluoride is 1: (0.15-0.30);
  • the raw materials are raw ore, dephosphorization agent and water.
  • the present invention mixes the above raw materials and presses them into balls to obtain mixed pellets.
  • the raw ore is preferably high phosphorus oolitic hematite, high phosphorus oolitic magnetite and high phosphorus oolitic red/magnetite, etc., wherein the high phosphorus oolitic red/magnetite It means that the ore contains both high-phosphorus oolitic hematite and high-phosphorus oolitic magnetite; the particle size of the high-phosphorus oolitic iron ore raw ore is less than 1mm, and the iron grade in the raw ore is preferably 43-60%. Content ⁇ 1.5%.
  • the dephosphorization agent is preferably a mixture of calcium carbonate and calcium fluoride, wherein the mass ratio of calcium carbonate and calcium fluoride is preferably 1: (0.15-0.30), specifically, in an embodiment of the present invention, it may be 1 :0.15 or 1:0.30.
  • the mass ratio of the raw ore, dephosphorization agent and water is preferably 1:(0.2-0.4):(0.05-0.15), more preferably 1:(0.25-0.30):(0.08-0.09), Specifically, in the embodiment of the present invention, it may be 1:0.25:0.09, or 1:0.30:0.09.
  • the mixed pellets are dried first, and then oxidized and roasted in an oxidizing atmosphere to obtain oxidized and roasted pellets.
  • the drying temperature is preferably 150-180°C, more preferably 160-170°C, specifically, in an embodiment of the present invention, it may be 150°C or 180°C; the drying The time is preferably 100-120 min, more preferably 110-120 min, specifically, in the embodiment of the present invention, it may be 120 min.
  • the dried pellets are oxidized and roasted in an oxidizing atmosphere, and in the present invention, the oxidizing atmosphere is preferably air;
  • the oxidation roasting temperature is preferably 1000-1500°C, more preferably 1100-1400°C, most preferably 1200-1300°C; specifically, in an embodiment of the present invention, it may be 1200°C or 1300°C;
  • the oxidation roasting time is preferably 50-100 min, more preferably 60-90 min, most preferably 70-80 min, specifically, in the embodiment of the present invention, it may be 60 min or 80 min.
  • a dephosphorization agent consisting of calcium carbonate and calcium fluoride is added in the oxidation roasting process, and the above-mentioned dephosphorization agent reacts with the components in the iron ore under an oxidizing atmosphere to change its mineral composition and at the same time make the original iron ore Phosphorus in minerals generates independent phosphorus-containing minerals, and also changes the structure of ore, creating conditions for the reduction and dephosphorization of iron.
  • This special technique in the present invention makes the treatment effect among the present invention (such as reduction Phosphorus content, iron grade and recovery rate) in iron products are significantly better than other processes.
  • the oxidized and roasted pellets are subjected to reduction roasting under a reducing atmosphere to obtain reduction roasted pellets.
  • the reducing atmosphere is preferably natural gas cracked gas and/or water gas;
  • the temperature of the reducing roasting is preferably 1100-1300°C, more preferably 1150-1200°C, specifically, in the embodiments of the present invention , can be 1150°C or 1200°C;
  • the reduction roasting time is preferably 150-200min, more preferably 160-180min, specifically, in the embodiment of the present invention, it can be 150min or 180min.
  • the reduced-calcined pellets it is preferred to cool the reduced-calcined pellets to room temperature under air-isolated conditions, more preferably to cool to room temperature in air-isolated graphite box to obtain reduced balls.
  • the reduction ball needs to be cooled to room temperature under the condition of isolation of air, which can be cooled by water or nitrogen as the medium.
  • the present invention crushes the reduced balls to a particle size below 2mm (-2mm), and then performs two-stage grinding-magnetic separation;
  • the ore grinding and magnetic separation is divided into (illustration: the two-stage ore grinding and magnetic separation just includes one stage and two stages) two-stage ore grinding-magnetic separation;
  • One-stage grinding Grinding the crushed reduction balls until the particle content of -0.074mm is no less than 65%, such as 65% or 70%; then performing one-stage magnetic separation, the magnetic field strength of the one-stage magnetic separation is preferably 1600-1800 aerse Oersted, more preferably 1700-1800 Oersted;
  • the second-stage grinding grinds the magnetic part of the material after the first-stage magnetic separation until the particle content of -0.074mm is not less than 85%, such as 85% or 95%; then carry out the second-stage magnetic separation, and the second-stage magnetic separation
  • the magnetic field strength is preferably 1300-1400 Oe, more preferably 1400 Oe.
  • the iron grade is >93%
  • the iron recovery rate is >92%
  • the phosphorus content is ⁇ 0.08%.
  • the invention provides a method for processing high-phosphorus oolitic iron ore, comprising the following steps: A) mixing high-phosphorus oolitic iron ore, a dephosphorization agent and water, pressing into pellets to obtain mixed pellets; the dephosphorization The agent includes calcium carbonate and calcium fluoride, and the mass ratio of the calcium carbonate and calcium fluoride is 1: (0.15-0.30); B) drying the mixed pellets and performing oxidative roasting to obtain oxidative roasted pellets C) reducing and roasting the oxidized and roasted pellets in a reducing atmosphere to obtain reduced pellets; D) cooling the reduced pellets to room temperature in isolation from air, and then performing grinding-magnetic separation to obtain reduced iron product.
  • a dephosphorizing agent is added to the pellets, and the dephosphorizing agent reacts with the components in the ore under an oxidizing atmosphere to change its mineral composition and at the same time make the phosphorus originally present in the iron minerals generate a separate phosphorus-containing mineral , will also change the structure of the ore and create conditions for iron reduction and dephosphorization.
  • the technological process in the present invention is simple, and the removal rate of phosphorus in high-phosphorus oolitic iron ore is high, and the iron grade and recovery rate of the obtained powder reduced iron are high, and changes in the iron grade and phosphorus content of the raw ore within a certain range do not affect Restoration effect.
  • the finally obtained powdered reduced iron has an iron grade of 96.55%, an iron recovery rate of 94.99%, and a phosphorus content of 0.08%.
  • the finally obtained powdered reduced iron has an iron grade of 93.28%, an iron recovery rate of 92.30%, and a phosphorus content of 0.07%.
  • the finally obtained powdered reduced iron has an iron grade of 92.35%, an iron recovery rate of 91.48%, and a phosphorus content of 0.27%. It can be seen that powdered reduced iron with a phosphorus content lower than 0.1% cannot be obtained by using this process without adding a dephosphorization agent.
  • the same high-phosphorus oolitic hematite with a particle size of less than 1mm, an iron grade of 43.65%, and a phosphorus content of 0.83% is used as the raw ore.
  • the finally obtained powdered reduced iron has an iron grade of 91.15%, an iron recovery rate of 89.24%, and a phosphorus content of 0.17%. It can be seen that powdered reduced iron with a phosphorus content less than 0.1% can not be obtained only by adding calcium carbonate as a dephosphorization agent.
  • the finally obtained powdered reduced iron has an iron grade of 89.21%, an iron recovery rate of 92.14%, and a phosphorus content of 0.35%. It can be seen that when the gas reduction temperature is lower than 1100°C, the iron grade and phosphorus content of the reduced iron obtained cannot meet the required indicators.
  • the final iron grade obtained is 90.45%, the iron recovery rate is 90.12%, and the powdery reduced iron with a phosphorus content of 0.16%. It can be seen that if the temperature of oxidation and roasting is lowered to below 1200°C, the phosphorus content of powdered reduced iron will be higher than 0.1%, that is, qualified products cannot be obtained.

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Abstract

本发明提供了一种高磷鲕状铁矿的处理方法，包括以下步骤：A)将高磷鲕状铁矿、脱磷剂和水混合，压制成球，得到混合球团；所述脱磷剂包括碳酸钙和氟化钙，所述碳酸钙和氟化钙的质量比为1：(0.15～0.30)；B)将所述混合球团烘干后进行氧化焙烧，得到氧化焙烧的球团；C)将所述氧化焙烧的球团在还原性气氛下进行还原焙烧，得到还原球团；D)将所述还原球团隔绝空气冷却至室温，然后进行磨矿-磁选，得到还原铁产品。本发明中的工艺流程简单，对于高磷鲕状铁矿中磷的去除率高，所得的粉末还原铁的铁品位和回收率均较高，原矿铁品位和磷含量在一定范围内变化不影响还原效果。

Description

一种高磷鲕状铁矿的处理方法
本申请要求于2021年06月23日提交中国专利局、申请号为202110698735.6、发明名称为“一种高磷鲕状铁矿的处理方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于矿物加工技术领域，尤其涉及一种高磷鲕状铁矿的处理方法。
背景技术
随着世界钢铁工业的迅速发展，高品位铁矿资源逐渐减少，开发储量丰富的难处理铁矿石具有重要意义。高磷铁矿石就是这类难选铁矿石的典型代表之一。，高磷铁矿石主要分布在美国、法国、英国、加拿大、阿尔及利亚、尼日利亚、哈萨克斯坦以及中国，总储量超过2×1010t。由于该类矿石的结构复杂，磷含量高，因此，采用物理选矿工艺方法只能得到磷含量较高的铁精矿，如果将该产品作为高炉炼铁的原料，在冶炼的过程中，几乎所有的磷会富集至铁水中，这种高磷铁水不能满足炼钢对原料磷含量的要求，因此，在炼钢工艺之前进行脱磷是实现高磷铁矿石有效利用的合理方式。
目前，对于高磷铁矿石利用的研究较多，对于其提铁降磷相关工艺的研究也颇为深入，但目前的研究多采用浮选、浮选-磁选联合、化学浸出、生物浸出等方法，这些方法有的操作简单，但得到的铁精矿铁品位和回收率等都较低，去磷效果不佳，因此，研究一种高效、便捷、环境友好、工业上能应用的处理高磷铁矿石的方法极其重要。
发明内容
本发明的目的在于提供一种高磷鲕状铁矿的处理方法，本发明中的方法磷的去除率高，所得的粉末还原铁的铁品位和回收率均较高，原矿铁品位和磷含量在一定范围内变化不影响还原效果。
本发明提供一种高磷鲕状铁矿的处理方法，包括以下步骤：
A)将高磷鲕状铁矿、脱磷剂和水混合，压制成球，得到混合球团；
所述脱磷剂包括碳酸钙和氟化钙，所述碳酸钙和氟化钙的质量比为1：(0.15～0.30)；
B)将所述混合球团烘干后进行氧化焙烧，得到氧化焙烧的球团；
C)将所述氧化焙烧的球团在还原性气氛下进行还原焙烧，得到还原球团；
D)将所述还原球团隔绝空气冷却至室温，然后进行磨矿-磁选，得到还原铁产品。
优选的，所述高磷鲕状铁矿为高磷鲕状赤铁矿、高磷鲕状磁铁矿和高磷鲕状赤/磁铁矿中的一种或几种。
优选的，所述高磷鲕状铁矿的粒度＜1mm，铁品位为43～60％，磷的质量分数＜1.5％。
优选的，所述高磷鲕状铁矿、脱磷剂和水的质量比为1：(0.2～0.4)：(0.05～0.15)。
优选的，所述氧化焙烧的温度为1000～1500℃；所述氧化焙烧的时间为50～100min。
优选的，所述还原性气氛为天然气裂解气和/或水煤气。
优选的，所述还原焙烧的温度为1100～1300℃；所述还原焙烧的时间为150～200min。
优选的，将所述还原球团隔绝空气冷却至室温，破碎至-2mm，然后进行两段磨矿-磁选，得到还原铁产品。
优选的，所述两段磨矿-磁选中，一段磨矿至-0.074mm的颗粒含量不低于65％，一段磁选磁场强度为1600～1800奥斯特；二段磨矿至-0.074mm的颗粒含量不低于85％，二段磁选磁场强度为1300～1400奥斯特。
本发明提供了一种高磷鲕状铁矿的处理方法，包括以下步骤：A)将高磷鲕状铁矿、脱磷剂和水混合，压制成球，得到混合球团；所述脱磷剂包括碳酸钙和氟化钙，所述碳酸钙和氟化钙的质量比为1：(0.15～0.30)；B)将所述混合球团烘干后进行氧化焙烧，得到氧化焙烧的球团；C)将所述氧化焙烧的球团在还原性气氛下进行还原焙烧，得到还原球团；D)将所述还原球团隔绝空气冷却至室温，然后进行磨矿-磁选，得到还原铁产品。本发明在球团中加入脱磷剂，脱磷剂在氧化气氛下通过与矿石中的成分发生反应，改变其矿物成分，同时使原来存在于铁矿物中的磷生成单独的含磷矿物，也会改变矿石的结构构造，为铁的还原和脱磷创造条件。本发明中的工艺流程简单，对于高磷鲕状铁矿中磷的去除率高，所得的粉末还原铁的铁品位和回收率均较高，原矿铁品位 和磷含量在一定范围内变化不影响还原效果。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。
图1为本发明高磷鲕状铁矿的处理方法的流程图。
具体实施方式
本发明提供一种高磷鲕状铁矿的处理方法，包括以下步骤：
A)将高磷鲕状铁矿、脱磷剂和水混合，压制成球，得到混合球团；
所述脱磷剂包括碳酸钙和氟化钙，所述碳酸钙和氟化钙的质量比为1：(0.15～0.30)；
B)将所述混合球团烘干后进行氧化焙烧，得到氧化焙烧的球团；
C)将所述氧化焙烧的球团在还原性气氛下进行还原焙烧，得到还原球团；
D)将所述还原球团隔绝空气冷却至室温，然后进行磨矿-磁选，得到还原铁产品。
本发明首先进行配料和压球，所述原料为原矿、脱磷剂和水，本发明将上述原料混合后压制成球，得到混合球团。
在本发明中，所述原矿优选为高磷鲕状赤铁矿、高磷鲕状磁铁矿和高磷鲕状赤/磁铁矿等，其中，所述高磷鲕状赤/磁铁矿指的是矿石中既含有高磷鲕状赤铁矿同时也含有高磷鲕状磁铁矿；所述高磷鲕状铁矿原矿的粒度＜1mm，原矿中铁品位优选为43～60％，磷含量＜1.5％。
所述脱磷剂优选为碳酸钙和氟化钙的混合物，其中碳酸钙和氟化钙的质量比优选为1：(0.15～0.30)，具体的，在本发明的实施例中，可以是1:0.15或1:0.30。
在本发明中，所述原矿、脱磷剂和水的质量比优选为1：(0.2～0.4)：(0.05～0.15)，更优选为1：(0.25～0.30)：(0.08～0.09)，具体的，在本发明的实施例中，可以是1:0.25:0.09，或者1:0.30:0.09。
得到混合球团之后，本发明将所述混合球团先进行烘干，然后在氧化气氛下进行氧化焙烧，得到氧化焙烧的球团。
在本发明中，所述烘干的温度优选为150～180℃，更优选为160～170℃，具体的，在本发明的实施例中，可以是150℃或180℃；所述烘干的时间优选为100～120min，更优选为110～120min，具体的，在本发明的实施例中，可以是120min。
烘干后的球团在氧化气氛下进行氧化焙烧，在本发明中，所述氧化气氛优选为空气；
在本发明中，所述氧化焙烧的温度优选为1000～1500℃，更优选为1100～1400℃，最优选为1200～1300℃；具体的，在本发明的实施例中，可以是1200℃或1300℃；所述氧化焙烧的时间优选为50～100min，更优选为60～90min，最优选为70～80min，具体的，在本发明的实施例中，可以是60min或80min。
本发明在氧化焙烧过程中加入成分为碳酸钙和氟化钙的脱磷剂，上述脱磷剂在氧化气氛下与铁矿石中的成分发生反应，改变其矿物成分，同时使原来存在于铁矿物中的磷生成单独的含磷矿物，也会改变矿石的结构构造，为铁的还原和脱磷创造条件，本发明中的这种特殊的工艺使得本发明中的处理效果(如还原铁产品中的磷含量、铁品位和回收率)明显优于其他工艺。
氧化焙烧后的球团在还原气氛下进行还原焙烧，得到还原焙烧的球团。
在本发明中，所述还原气氛优选为天然气裂解气和/或水煤气；所述还原焙烧的温度优选为1100～1300℃，更优选为1150～1200℃，具体的，在本发明的实施例中，可以是1150℃或1200℃；所述还原焙烧的时间优选为150～200min，更优选为160～180min，具体的，在本发明的实施例中，可以是150min或180min。
本发明优选将还原焙烧后的球团在隔绝空气的条件下进行冷却至室温，更优选在石墨盒中隔绝空气冷却至室温，得到还原球。还原球需要在隔绝空气的条件下冷却至室温，可以采用水冷却，也可用氮气为介质冷却。
得到还原球之后，本发明将所述还原球破碎至粒径为2mm以下(-2mm)，然后进行两段磨矿-磁选；
在本发明中，所述磨矿磁选分为(说明：两段磨矿磁选就包括一段和二段)两段磨矿-磁选；
一段磨矿将所述破碎的还原球磨至-0.074mm的颗粒含量不低于65％，如65％或70％；然后进行一段磁选，所述一段磁选的磁场强度优选为1600～1800奥斯特，更优选为1700～1800奥斯特；
二段磨矿将所述一段磁选后的磁性部分物料磨至-0.074mm的颗粒含量不低于85％，如85％或95％；然后进行二段磁选，所述二段磁选的磁场强度优选为1300～1400奥斯特，更优选为1400奥斯特。
按照上述工艺得到的还原铁产品中，铁品位＞93％，铁回收率＞92％，磷含量＜0.08％。
本发明提供了一种高磷鲕状铁矿的处理方法，包括以下步骤：A)将高磷鲕状铁矿、脱磷剂和水混合，压制成球，得到混合球团；所述脱磷剂包括碳酸钙和氟化钙，所述碳酸钙和氟化钙的质量比为1：(0.15～0.30)；B)将所述混合球团烘干后进行氧化焙烧，得到氧化焙烧的球团；C)将所述氧化焙烧的球团在还原性气氛下进行还原焙烧，得到还原球团；D)将所述还原球团隔绝空气冷却至室温，然后进行磨矿-磁选，得到还原铁产品。本发明在球团中加入脱磷剂，脱磷剂在氧化气氛下通过与矿石中的成分发生反应，改变其矿物成分，同时使原来存在于铁矿物中的磷生成单独的含磷矿物，也会改变矿石的结构构造，为铁的还原和脱磷创造条件。本发明中的工艺流程简单，对于高磷鲕状铁矿中磷的去除率高，所得的粉末还原铁的铁品位和回收率均较高，原矿铁品位和磷含量在一定范围内变化不影响还原效果。
为了进一步说明本发明，以下结合实施例对本发明提供的一种高磷鲕状铁矿的处理方法进行详细描述，但不能将其理解为对本发明保护范围的限定。
实施例1
取粒度小于1mm，铁品位55.81％，磷含量0.72％的高磷鲕状赤铁矿为原矿，加入25％的脱磷剂(CaCO 3与CaF 2氟化钙的质量为比1:0.15)和9％的水，混合均匀后，在压球机上压制成球，得到混合球团；将混合球团在150℃下烘干120min，然后在1200℃下氧化焙烧60min；再在1150℃下通入水煤气进行还原，还原150min，之后置于石墨盒中隔绝空气冷却至室温，得到还原球；最后将还原球破碎至-1mm，经过两段磨矿-磁选后，得到粉末还原铁，其中，一段磨矿至-200目占65％，一段磁选磁场强度为1800奥斯特；二段磨矿至-200 目占85％，二段磁选磁场强度为1400奥斯特。
最终所得到铁品位96.55％，铁回收率94.99％，磷含量0.08％的粉状还原铁。
实施例2
取粒度小于1mm，铁品位43.65％，磷含量0.83％的高磷鲕状赤铁矿为原矿，加入30％的脱磷剂(CaCO 3与CaF 2氟化钙的质量为比1:0.30)和9％的水，混合均匀后，在压球机上压制成球，得到混合球团；将混合球团在180℃下烘干120min，然后在1300℃下氧化焙烧80min；再在1200℃下通入水煤气进行还原，还原180min，之后置于石墨盒中隔绝空气冷却至室温，得到还原球；最后将还原球破碎至-1mm，经过两段磨矿-磁选后，得到粉末还原铁，其中，一段磨矿至-200目占70％，一段磁选磁场强度为1800奥斯特；二段磨矿至-200目占95％，二段磁选磁场强度为1400奥斯特。
最终所得到铁品位93.28％，铁回收率92.30％，磷含量0.07％的粉状还原铁。
比较例1
取粒度小于1mm，铁品位43.65％，磷含量0.83％的高磷鲕状赤铁矿为原矿，不添加脱磷剂，只加入9％水，混合均匀后，在压球机上压制成球，得到混合球团；将混合球团在180℃下烘干120min，然后在1300℃下氧化焙烧80min；再在1200℃下通入水煤气进行还原，还原时间180min，之后置于石墨盒中隔绝空气冷却至室温，得到还原球；最后将还原球破碎至-1mm，经过两段磨矿-磁选后，得到粉末还原铁，其中，一段磨矿至-200目占75％，一段磁选磁场强度为1800奥斯特；二段磨矿至-200目占90％，二段磁选磁场强度为1400奥斯特。
最终所得到铁品位92.35％，铁回收率91.48％，磷含量0.27％的粉状还原铁。可见，不添加脱磷剂用此工艺无法得到磷含量低于0.1％的粉末还原铁。
比较例2
同样是粒度小于1mm，铁品位43.65％，磷含量0.83％的高磷鲕状赤铁矿为原矿，加入20％的CaCO 3和9％的水，混合均匀后，在压球机上压制成球，得到混合球团；将混合球团在180℃下烘干120min，然后在1300℃下氧化焙 烧80min；再在1200℃下通入水煤气进行还原，还原180min，之后置于石墨盒中隔绝空气冷却至室温，得到还原球；最后将还原球破碎至-1mm，经过两段磨矿-磁选后，得到粉末还原铁，其中，一段磨矿至-200目占70％，一段磁选磁场强度为1800奥斯特；二段磨矿至-200目占95％，二段磁选磁场强度为1400奥斯特。
最终所得到铁品位91.15％，铁回收率89.24％，磷含量0.17％的粉状还原铁。可见，只添加碳酸钙为脱磷剂也不能得到磷含量小于0.1％的粉末还原铁。
比较例3
取粒度小于1mm，铁品位43.65％，磷含量0.83％的高磷鲕状赤铁矿为原矿，加入30％的脱磷剂(CaCO 3与CaF 2氟化钙的质量为比1:0.30)和9％的水，混合均匀后，在压球机上压制成球，得到混合球团；将混合球团在180℃下烘干120min，然后在1100℃下氧化焙烧80min；再在1050℃下通入水煤气进行还原，还原180min，之后置于石墨盒中隔绝空气冷却至室温，得到还原球；最后将还原球破碎至-1mm，经过两段磨矿-磁选后，得到粉末还原铁，其中，一段磨矿至-200目占70％，一段磁选磁场强度为1800奥斯特；二段磨矿至-200目占95％，二段磁选磁场强度为1400奥斯特。
最终所得到铁品位89.21％，铁回收率92.14％，磷含量0.35％的粉状还原铁。可见气体还原的温度低于1100℃时所得还原铁的铁品位和磷含量都达不到要求的指标。
比较例4
取粒度小于1mm，铁品位43.65％，磷含量0.83％的高磷鲕状赤铁矿为原矿，加入30％的脱磷剂(CaCO 3与CaF 2氟化钙的质量为比1:0.30)和9％的水，混合均匀后，在压球机上压制成球，得到混合球团；将混合球团在180℃下烘干120min，然后在1150℃下氧化焙烧80min；再在1200℃下通入水煤气进行还原，还原180min，之后置于石墨盒中隔绝空气冷却至室温，得到还原球；最后将还原球破碎至-1mm，经过两段磨矿-磁选后，得到粉末还原铁，其中，一段磨矿至-200目占70％，一段磁选磁场强度为1800奥斯特；二段磨矿至-200目占95％，二段磁选磁场强度为1400奥斯特。
最终所得到铁品位90.45％，铁回收率90.12％，磷含量0.16％的粉状还原 铁。可见降低氧化焙烧的温度到1200℃以下，粉末还原铁的磷含量就会高于0.1％，即得不到合格产品。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (9)

  1. 一种高磷鲕状铁矿的处理方法，包括以下步骤：
    A)将高磷鲕状铁矿、脱磷剂和水混合，压制成球，得到混合球团；
    所述脱磷剂包括碳酸钙和氟化钙，所述碳酸钙和氟化钙的质量比为1：(0.15～0.30)；
    B)将所述混合球团烘干后进行氧化焙烧，得到氧化焙烧的球团；
    C)将所述氧化焙烧的球团在还原性气氛下进行还原焙烧，得到还原球团；
    D)将所述还原球团隔绝空气冷却至室温，然后进行磨矿-磁选，得到还原铁产品。
  2. 根据权利要求1所述的处理方法，其特征在于，所述高磷鲕状铁矿为高磷鲕状赤铁矿、高磷鲕状磁铁矿和高磷鲕状赤/磁铁矿中的一种或几种。
  3. 根据权利要求1所述的处理方法，其特征在于，所述高磷鲕状铁矿的粒度＜1mm，铁品位为43～60％，磷的质量分数＜1.5％。
  4. 根据权利要求1所述的处理方法，其特征在于，所述高磷鲕状铁矿、脱磷剂和水的质量比为1：(0.2～0.4)：(0.05～0.15)。
  5. 根据权利要求1所述的处理方法，其特征在于，所述氧化焙烧的温度为1000～1500℃；所述氧化焙烧的时间为50～100min。
  6. 根据权利要求1所述的处理方法，其特征在于，所述还原性气氛为天然气裂解气和/或水煤气。
  7. 根据权利要求1所述的处理方法，其特征在于，所述还原焙烧的温度为1100～1300℃；所述还原焙烧的时间为150～200min。
  8. 根据权利要求1所述的处理方法，其特征在于，将所述还原球团隔绝空气冷却至室温，破碎至-2mm，然后进行两段磨矿-磁选，得到还原铁产品。
  9. 根据权利要求8所述的处理方法，其特征在于，所述两段磨矿-磁选中，一段磨矿至-0.074mm的颗粒含量不低于65％，一段磁选磁场强度为1600～1800奥斯特；二段磨矿至-0.074mm的颗粒含量不低于85％，二段磁选磁场强度为1300～1400奥斯特。
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