WO2020206830A1 - 一种赤泥回收钠、铁和钛同时熔融渣直接水泥化的方法 - Google Patents

一种赤泥回收钠、铁和钛同时熔融渣直接水泥化的方法 Download PDF

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WO2020206830A1
WO2020206830A1 PCT/CN2019/090838 CN2019090838W WO2020206830A1 WO 2020206830 A1 WO2020206830 A1 WO 2020206830A1 CN 2019090838 W CN2019090838 W CN 2019090838W WO 2020206830 A1 WO2020206830 A1 WO 2020206830A1
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titanium
iron
red mud
slag
sodium
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French (fr)
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张廷安
刘燕
豆志河
吕国志
赵秋月
傅大学
张伟光
张子木
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/14—Cements containing slag
    • C04B7/147—Metallurgical slag
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • 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
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • 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
    • 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
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Definitions

  • the invention relates to the technical field of environmental protection, and in particular to a method for recovering sodium, iron and titanium from red mud while directly cementing molten slag.
  • Red mud is a strong alkaline solid waste produced by preparing alumina or aluminum hydroxide from bauxite. At present, the global red mud reserve is estimated to exceed 3 billion tons, and it is growing at a rate of about 120 million tons per year. The average utilization rate of red mud in the world is 15%. The cumulative stock of red mud in China has grown to 600 million tons, and is growing at a rate of about 100 million tons per year. The red mud utilization rate in China is only 4%. Most of the red mud is still disposed of on land.
  • Red mud storage not only wastes secondary resources and occupies a large amount of land, but also destroys the surrounding environment of the red mud storage yard, causing serious environmental problems, resulting in a sharp increase in environmental protection pressure on the aluminum industry.
  • the environmental risks of red mud storage have long attracted the attention of the governments and enterprises of various alumina producing countries.
  • the key to solving the red mud problem is to develop red mud comprehensive utilization technology.
  • red mud utilization technologies can generally be divided into two types: one is the overall utilization as a general industrial raw material, such as Zhao Guangming “A method for producing cement clinker using red mud” (application number: CN201210031710.1) invented by others is to add dealkalized gypsum and fly ash to dealkalized red mud, and put the above three materials in a mixing tank Mix it evenly, and add water to adjust its concentration to 30%.
  • Zhao Guangming A method for producing cement clinker using red mud” (application number: CN201210031710.1) invented by others is to add dealkalized gypsum and fly ash to dealkalized red mud, and put the above three materials in a mixing tank Mix it evenly, and add water to adjust its concentration to 30%.
  • Chen Huanyue et al. invented "a method for separating, extracting iron and removing sodium from red mud, application number CN108686828A".
  • the red mud is crushed or ball milled into a fine red mud material mainly composed of fine particles.
  • the material is classified to separate 10 to 98% of the fine particles with a particle size of less than 5 microns in the fine red mud.
  • the separated products with a particle size of less than 5 microns are mainly sodium silica slag and calcium silica slag.
  • the sodium oxide content is greater than 10%
  • the remaining red mud material after classification is an iron ore product, and the iron oxide content is greater than 30%.
  • red mud When red mud is used as a general industrial raw material, there are problems such as red mud alkalinity restriction, low product price, poor profitability, etc.; most of the methods for extracting valuable elements have low extraction rate and low purity of element-enriched products, which cannot be used directly. problem. Therefore, despite the numerous studies on the utilization of red mud in the alumina industry, the problem of red mud storage has not been properly resolved.
  • the present invention provides a method for recovering sodium, iron and titanium from red mud while molten slag is directly cemented.
  • the high-iron and high-titanium red mud is used as a raw material and mixed with a reducing agent and a slag-forming agent. Then it is sprayed to the vortex center of the high-temperature reduction furnace to reduce iron, sodium enters the flue gas for recovery, the molten slag is slowly cooled to enrich and separate the titanium-containing phase, and the remaining slag adjusts the components to be ground directly into cement clinker.
  • the method of the present invention is carried out in the following steps:
  • the high-iron and high-titanium red mud is 20-40% by mass percentage TFe, containing TiO 2 3-10%, Na 2 O 2-15%, Al 2 O 3 15-25%, SiO 2 15-25%, CaO 5-25%, H 2 O 5-20%;
  • the titanium-containing components are gradually enriched to form a titanium-containing phase, which is separated from the residual slag; the titanium-containing phase is taken out, and the composition of the residual slag is adjusted to meet the requirements of cement clinker. It is crushed and ground to make cement clinker.
  • mCaO mixed powder mass percent of calcium oxide mAl 2 O 3 as the weight percentage of alumina in the mixed powder
  • mSiO 2 mixed oxide powder mass percent of silicon mTiO 2 mixed powder The mass percentage of titanium oxide.
  • sodium enters the flue gas during the vortex stirring reduction process, and is recovered by the flue gas dust collection system.
  • the iron recovery rate is ⁇ 90%.
  • the recovery rate of sodium is ⁇ 95%.
  • the main component of the titanium-rich phase is titanium oxide, and the recovery rate of titanium is ⁇ 60%.
  • the high-speed iron and high-titanium red mud is reduced by vortex smelting. After the red mud is mixed with the reducing agent and the slagging agent, it is directly sprayed into the vortex area of the vortex smelting reduction furnace without any request. Sodium enters the flue gas recovery during the reduction process to obtain The molten iron is directly smelted into wear-resistant cast iron products by adding ferrochrome and ferromanganese, which can simultaneously extract sodium and iron in the red mud;
  • the extraction rate of sodium and iron is higher, above 90% and 95%, respectively.
  • the molten slag is cooled to enrich and separate the titanium-containing phase.
  • the extraction rate of titanium can reach more than 60%, and the tailings after extraction are completely Used in the production of cement clinker, the utilization rate of red mud reaches 100%.
  • Fig. 1 is a schematic flow diagram of a method for recovering sodium, iron and titanium from red mud while directly cementing molten slag.
  • Examples cement clinker composition embodiment of the present invention containing mass percent CaO 62 ⁇ 64%, SiO 2 20 ⁇ 23%, Al 2 O 3 4 ⁇ 6%, Fe 2 O 3 3 ⁇ 5%.
  • the Na 2 O mass percentage of the molten slag is less than 0.5%.
  • the wear-resistant cast iron product in the embodiment of the present invention is wear-resistant cast iron of the brand HBW555Cr13 (ISO 21988/JN/HB).
  • the temperature when the raw material is dried is 150-200°C.
  • the vortex stirring reduction of the present invention refers to the method disclosed in the invention of "a method for vortex stirring smelting reduction ironmaking", and the involved vortex stirring reduction high-temperature furnace is the equipment used for this method.
  • a vortex stirring smelting reduction ironmaking method of the present invention is a patent application with publication number CN106435080A.
  • the adjusting component is adding calcium raw material, siliceous raw material and/or iron raw material.
  • the calcareous raw material is at least one of limestone and calcium carbide slag;
  • the siliceous raw material is at least one of kaolin, clay, fly ash, and tailings slag;
  • the iron raw material is at least one of high-speed iron red mud, iron slag, and steel slag.
  • the calcareous raw material is at least one of limestone and calcium carbide slag;
  • the siliceous raw material is at least one of kaolin, clay, fly ash, and tailings slag;
  • the iron raw material is at least one of high-speed iron red mud, iron slag, and steel slag.
  • the recovery rate of sodium is ⁇ 95%, and the recovery rate of iron is ⁇ 90%.
  • the main component of the titanium-rich phase is titanium oxide, and the recovery rate of titanium is ⁇ 60%.
  • the high-iron and high-titanium red mud is TFe 40% by mass, containing 10% TiO 2 and 12% Na 2 O;
  • the titanium-containing components are gradually enriched to form a titanium-containing phase, which is separated from the residual slag; the titanium-containing phase is taken out, and the composition of the residual slag is adjusted to meet the requirements of cement clinker.
  • the mass percentages of CaO, SiO 2 , Al 2 O 3 and Fe 2 O 3 in the cement clinker are 62%, 23%, 5% and 4% respectively, which meet the requirements of cement clinker The composition requirements.
  • the titanium-containing components are gradually enriched to form a titanium-containing phase, which is separated from the residual slag; the titanium-containing phase is taken out, and the composition of the residual slag is adjusted to meet the requirements of cement clinker.
  • the mass percentages of CaO, SiO 2 , Al 2 O 3 and Fe 2 O 3 in the cement clinker are 64%, 20%, 6%, and 5% respectively, which meet the requirements of cement clinker The composition requirements.
  • the titanium-containing components are gradually enriched to form a titanium-containing phase, which is separated from the residual slag; the titanium-containing phase is taken out, and the composition of the residual slag is adjusted to meet the requirements of cement clinker.
  • the mass percentages of CaO, SiO 2 , Al 2 O 3 and Fe 2 O 3 in the cement clinker are respectively 63%, 21%, 4% and 3%, which meet the requirements of cement clinker The composition requirements.

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Abstract

一种赤泥回收钠、铁和钛同时熔融渣直接水泥化的方法，按以下步骤进行：(1)准备原料高铁高钛赤泥；(2)脱水原料与固态碳质还原剂和造渣剂混料制成混合料，喷吹到涡流搅拌高温炉的漩涡中心，进行涡流搅拌还原；(3)还原后形成的铁水与含钛熔融渣分离；铁水制成耐磨铸铁产品；(4)含钛熔融渣在冷却过程中，含钛成分富集形成含钛相，与余渣分离；余渣调整组分，再经破碎和研磨制成水泥熟料；钠经烟气收尘系统回收。该方法可同时实现赤泥中钠、铁和钛的提取，钠、铁和钛的提取率较高。

Description

一种赤泥回收钠、铁和钛同时熔融渣直接水泥化的方法 技术领域
本发明涉及环境保护技术领域，具体涉及一种赤泥回收钠、铁和钛同时熔融渣直接水泥化的方法。
技术背景
赤泥是以铝土矿为原料制取氧化铝或氢氧化铝后所产生的强碱性固体废物。目前，全球赤泥储量估测已经超过30亿吨，并且每年大约以1.2亿吨的速度增长，世界赤泥平均利用率为15％。中国赤泥累计堆存量已增长至6亿吨，并且每年大约以1亿吨的速度增长，中国赤泥利用率仅为4％。大部分赤泥仍然采取陆地堆存的方法处置。赤泥堆存不仅浪费了二次资源、占用大量土地，而且破坏了赤泥堆场的周边环境，带来了严重的环境问题，致使铝工业的环保压力剧增。赤泥堆存的环境风险早已引起了各氧化铝生产国政府及企业的重视，解决赤泥问题的关键是研发赤泥综合利用技术。
为实现赤泥的高效利用以及有价元素提取，我国铝工业进行了大量的研发工作，现有的赤泥利用技术一般可分为两种：一种是作为一般性工业原料整体利用，如赵广明等人发明的“一种利用赤泥生产水泥熟料的方法”(申请号：CN201210031710.1)，是向脱碱赤泥中添加脱碱石膏和粉煤灰，将以上三种材料在搅拌罐中混合均匀，同时加水将其浓度调整至30％。使用板框式高压压滤机压滤至固体混合物含水量低于25％，然后送入转窑内煅烧成水泥熟料；王文举等人发明的“一种铝工业工艺废渣全部转型为生态建筑材料的工艺与方法”(申请号：CN200710105971)，利用铝工业在生产过程中所产出的固体废物赤泥(烧结法、拜耳法)、锅炉炉渣、选矿尾矿、化灰渣、煤气发生炉渣、污泥六种废渣自身的物质属性，通过干燥、粉碎、合理配比、加工成型(碾压、挤压)固结或烧结工艺，转化为新型的路用材料和建筑墙体材料。
也有从赤泥中提取有Na、Al、Fe、稀有金属等有价金属元素的技术；娄东民等发明的“一种拜耳法赤泥的脱碱方法”(申请号：CN201810572642.7)先对赤泥进行磨制，使赤泥的表面更新，然后再对经过表面更新处理的赤泥与石灰乳混合后进行脱碱反应，经过脱碱反应后的赤泥浆液进行洗涤、液固分离，可以获得含碱的溶液，返回氧化铝生产流程，分离后低碱含量的赤泥送赤泥大坝堆存；
陈环月等发明的“一种从赤泥中分选提铁除钠的方法，申请号CN108686828A”将赤泥通过粉碎或球磨制成以微细颗粒为主的微细赤泥料，对微细赤泥料进行分级，将微细赤泥料中粒径小于5微米的微细颗粒中的10～98％分离出来，分离出来的粒径小于5微米的微细颗粒产品为以钠硅渣和钙硅渣为主的产品，其中氧化钠含量大于10％，分级后剩余的赤泥料为铁 矿产品，其中氧化铁含量大于30％。
赤泥作为一般性工业原料整体利用时存在赤泥碱性制约、产品价格低、收益差等问题；分别提取有价元素的方法又大多存在提取率低、元素富集产品纯度低无法直接利用等问题。因此尽管氧化铝工业关于赤泥利用的研究众多，目前赤泥的堆存问题仍然未能得到妥善解决。
发明内容
为了更好的实现赤泥的综合利用，本发明提供一种赤泥回收钠、铁和钛同时熔融渣直接水泥化的方法，以高铁高钛赤泥为原料，与还原剂和造渣剂混料，再喷吹到还原高温炉漩涡中心还原提铁，钠进入烟气回收，熔融渣经缓冷使含钛相富集分离，余渣调整组分研磨直接成为水泥熟料。
本发明的方法按以下步骤进行：
(1)准备原料高铁高钛赤泥，高铁高钛赤泥按质量百分比TFe 20～40％，含TiO 2 3～10％，Na 2O 2～15％，Al 2O 3 15～25％，SiO 2 15～25％，CaO 5～25％，H 2O 5～20％；
(2)将原料干燥至水的质量百分比≤1％，获得脱水原料；将脱水原料与固态碳质还原剂和造渣剂混料制成混合料，直接喷吹到涡流搅拌高温炉的漩涡中心，混合料被卷入熔池中，在1300～1450℃进行涡流搅拌还原10～60min；所述的固态碳质还原剂为焦煤，固态碳质还原剂的量与原料中Fe的摩尔比为1.2～1.5，造渣剂为CaO和CaF 2的混合物，其中CaO按混合料的碱度为1.0～1.4添加，CaF 2占CaO总质量的10～30％：
(3)还原后形成的铁水与含钛熔融渣分层，并进行连续溢流分离；向分离出的铁水中加入铬铁和锰铁直接冶炼并浇铸制成耐磨铸铁产品；
(4)分离出的含钛熔融渣在冷却过程中，含钛成分逐渐富集形成含钛相，与余渣分离；将含钛相取出，余渣调整组分使其符合水泥熟料要求，再经破碎和研磨制成水泥熟料。
上述的碱度的计算公式按
Figure PCTCN2019090838-appb-000001
式中，mCaO为混合粉体中氧化钙的质量百分数，mAl 2O 3为混合粉体中氧化铝的质量百分数，mSiO 2为混合粉体中氧化硅的质量百分数，mTiO 2为混合粉体中氧化钛的质量百分数。
上述方法中，氧化铁还原的主要反应为：
Fe xO y+yC＝yCO+xFe   (2)、
Fe xO y+yCO＝yCO 2+xFe   (3)
和
Fe xO y+y/2C＝y/2CO 2+xFe   (4)。
上述方法中，钠在涡流搅拌还原过程进入烟气，经烟气收尘系统回收。
上述方法中，铁的回收率≥90％。
上述方法中，钠的回收率≥95％。
上述方法中，富钛相主要成分为氧化钛，钛的回收率≥60％。
与现有技术相比，本发明的特点和有益效果是：
(1)高铁高钛赤泥采用涡流熔融还原，赤泥与还原剂和造渣剂混合后，不经造求直接喷吹到涡流熔融还原炉涡流区域，钠在还原过程进入烟气回收，得到铁水加入铬铁、锰铁直接冶炼成耐磨铸铁产品，可同时实现赤泥中钠和铁的提取；
(2)工艺步骤简单，脱碱后的熔融渣Na 2O含量小于0.5％，更能符合水泥熟料的成分要求，可增加赤泥烧制水泥熟料的添配量；
(3)钠和铁的提取率较高，分别在90％以上和95％以上，熔融渣经冷却使含钛相富集分离，钛的提取率可达60％以上，提取后的尾渣完全用于生产水泥熟料，赤泥利用率达100％。
附图说明
图1为本发明的一种赤泥回收钠、铁和钛同时熔融渣直接水泥化的方法流程示意图。
具体的实施方式
本发明实施例中水泥熟料的成分按质量百分比含CaO 62～64％，SiO 2 20～23％，Al 2O 34～6％，Fe 2O 3 3～5％。
本发明实施例中熔融渣的Na 2O质量百分比小于0.5％。
本发明实施例中的耐磨铸铁产品为牌号HBW555Cr13(ISO 21988/JN/HB)的耐磨铸铁。
本发明实施例中原料干燥时的温度为150～200℃。
本发明的涡流搅拌还原是指发明“一种涡流搅拌熔融还原炼铁方法”公开的方法，所涉及的涡流搅拌还原高温炉为该方法是用的设备。
本发明的一种涡流搅拌熔融还原炼铁方法为公开号CN106435080A的专利申请。
本发明实施例中调整组分是加入钙质原料、硅质原料和/或铁质原料。钙质原料选用石灰石、电石渣中的至少一种；硅质原料选用高岭土、黏土、粉煤灰、尾矿渣中的至少一种；铁质原料选用高铁赤泥、铁渣、钢渣中的至少一种。
本发明实施例中钠的回收率≥95％，铁的回收率≥90％。
本发明实施例中富钛相主要成分为氧化钛，钛的回收率≥60％。
下面结合实施例对本发明做进一步的详细说明。
实施例1
(1)准备原料高铁高钛赤泥，高铁高钛赤泥按质量百分比TFe 40％，含TiO 2 10％，Na 2O12％；
(2)将原料干燥至水的质量百分比≤1％，获得脱水原料；将脱水原料与固态碳质还原剂和造渣剂混料制成混合料，直接喷吹到涡流搅拌高温炉的漩涡中心，混合料被卷入熔池中，在1300℃进行涡流搅拌还原60min；所述的固态碳质还原剂为焦煤，固态碳质还原剂的量与原料中Fe的摩尔比为1.2，造渣剂为CaO和CaF 2的混合物，其中CaO按混合料的碱度为1.4添加，CaF 2占CaO总质量的10％：钠在涡流搅拌还原过程进入烟气，经烟气收尘系统回收；
(3)还原后形成的铁水与含钛熔融渣分层，并进行连续溢流分离；向分离出的铁水中加入铬铁和锰铁直接冶炼并浇铸制成耐磨铸铁产品；
(4)分离出的含钛熔融渣在冷却过程中，含钛成分逐渐富集形成含钛相，与余渣分离；将含钛相取出，余渣调整组分使其符合水泥熟料要求，再经破碎和研磨制成水泥熟料，水泥熟料中CaO、SiO 2、Al 2O 3和Fe 2O 3的质量百分比分别为62％、23％、5％和4％，满足水泥熟料的成分要求。
实施例2
(1)准备原料高铁高钛赤泥，高铁高钛赤泥按质量百分比TFe 20％，TiO 2 4％，Na 2O 3％；
(2)将原料干燥至水的质量百分比≤1％，获得脱水原料；将脱水原料与固态碳质还原剂和造渣剂混料制成混合料，直接喷吹到涡流搅拌高温炉的漩涡中心，混合料被卷入熔池中，在1450℃进行涡流搅拌还原10min；所述的固态碳质还原剂为焦煤，固态碳质还原剂的量与原料中Fe的摩尔比为1.5，造渣剂为CaO和CaF 2的混合物，其中CaO按混合料的碱度为1.2添加，CaF 2占CaO总质量的20％：钠在涡流搅拌还原过程进入烟气，经烟气收尘系统回收；
(3)还原后形成的铁水与含钛熔融渣分层，并进行连续溢流分离；向分离出的铁水中加入铬铁和锰铁直接冶炼并浇铸制成耐磨铸铁产品；
(4)分离出的含钛熔融渣在冷却过程中，含钛成分逐渐富集形成含钛相，与余渣分离；将含钛相取出，余渣调整组分使其符合水泥熟料要求，再经破碎和研磨制成水泥熟料，水泥熟料中CaO、SiO 2、Al 2O 3和Fe 2O 3的质量百分比分别为64％、20％、6％、5％，满足水泥熟料的成分要求。
实施例3
(1)准备原料高铁高钛赤泥，高铁高钛赤泥按质量百分比TFe 30％，TiO 2含量在3％，Na 2O 15％；
(2)将原料干燥至水的质量百分比≤1％，获得脱水原料；将脱水原料与固态碳质还原剂 和造渣剂混料制成混合料，直接喷吹到涡流搅拌高温炉的漩涡中心，混合料被卷入熔池中，在1400℃进行涡流搅拌还原30min；所述的固态碳质还原剂为焦煤，固态碳质还原剂的量与原料中Fe的摩尔比为1.4，造渣剂为CaO和CaF 2的混合物，其中CaO按混合料的碱度为1.0添加，CaF 2占CaO总质量的30％：钠在涡流搅拌还原过程进入烟气，经烟气收尘系统回收；
(3)还原后形成的铁水与含钛熔融渣分层，并进行连续溢流分离；向分离出的铁水中加入铬铁和锰铁直接冶炼并浇铸制成耐磨铸铁产品；
(4)分离出的含钛熔融渣在冷却过程中，含钛成分逐渐富集形成含钛相，与余渣分离；将含钛相取出，余渣调整组分使其符合水泥熟料要求，再经破碎和研磨制成水泥熟料，水泥熟料中CaO、SiO 2、Al 2O 3和Fe 2O 3的质量百分比分别为63％、21％、4％和3％，满足水泥熟料的成分要求。

Claims (6)

  1. 一种赤泥回收钠、铁和钛同时熔融渣直接水泥化的方法，其特征在于按以下步骤进行：
    (1)准备原料高铁高钛赤泥，高铁高钛赤泥按质量百分比TFe 20～40％，含TiO 2 3～10％，Na 2O 2～15％，Al 2O 3 15～25％，SiO 2 15～25％，CaO 5～25％，H 2O 5～20％；
    (2)将原料干燥至水的质量百分比≤1％，获得脱水原料；将脱水原料与固态碳质还原剂和造渣剂混料制成混合料，直接喷吹到涡流搅拌高温炉的漩涡中心，混合料被卷入熔池中，在1300～1450℃进行涡流搅拌还原10～60min；所述的固态碳质还原剂为焦煤，固态碳质还原剂的量与原料中Fe的摩尔比为1.2～1.5，造渣剂为CaO和CaF 2的混合物，其中CaO按混合料的碱度为1.0～1.4添加，CaF 2占CaO总质量的10～30％：
    (3)还原后形成的铁水与含钛熔融渣分层，并进行连续溢流分离；向分离出的铁水中加入铬铁和锰铁直接冶炼并浇铸制成耐磨铸铁产品；
    (4)分离出的含钛熔融渣在冷却过程中，含钛成分逐渐富集形成含钛相，与余渣分离；将含钛相取出，余渣调整组分使其符合水泥熟料要求，再经破碎和研磨制成水泥熟料。
  2. 根据权利要求1所述的一种赤泥回收钠、铁和钛同时熔融渣直接水泥化的方法，其特征在于所述的碱度的计算公式按
    Figure PCTCN2019090838-appb-100001
    式中，mCaO为混合粉体中氧化钙的质量百分数，mAl 2O 3为混合粉体中氧化铝的质量百分数，mSiO 2为混合粉体中氧化硅的质量百分数，mTiO 2为混合粉体中氧化钛的质量百分数。
  3. 根据权利要求1所述的一种赤泥回收钠、铁和钛同时熔融渣直接水泥化的方法，其特征在于步骤(2)中，钠在涡流搅拌还原过程进入烟气，经烟气收尘系统回收。
  4. 根据权利要求1所述的一种赤泥回收钠、铁和钛同时熔融渣直接水泥化的方法，其特征在于铁的回收率≥90％。
  5. 根据权利要求1所述的一种赤泥回收钠、铁和钛同时熔融渣直接水泥化的方法，其特征在于钠的回收率≥95％。
  6. 根据权利要求1所述的一种赤泥回收钠、铁和钛同时熔融渣直接水泥化的方法，其特征在于富钛相主要成分为氧化钛，钛的回收率≥60％。
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