WO2020206831A1 - Calcified-carbonized high-iron red mud recycling iron and tailings cementation method - Google Patents

Calcified-carbonized high-iron red mud recycling iron and tailings cementation method Download PDF

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WO2020206831A1
WO2020206831A1 PCT/CN2019/090839 CN2019090839W WO2020206831A1 WO 2020206831 A1 WO2020206831 A1 WO 2020206831A1 CN 2019090839 W CN2019090839 W CN 2019090839W WO 2020206831 A1 WO2020206831 A1 WO 2020206831A1
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iron
red mud
calcified
molten
speed
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PCT/CN2019/090839
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French (fr)
Chinese (zh)
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张廷安
刘燕
牛丽萍
豆志河
吕国志
赵秋月
傅大学
张伟光
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东北大学
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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
    • C21B13/0006—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
    • 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
    • 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
    • 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 belongs to the technical field of environmental protection, and specifically relates to a method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings.
  • 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 utilization rate of red mud 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%.
  • the non-magnetic products are dissolved in ammonia water to dissolve alumina, and the washing slag is mixed with water to form a slurry, which acts as an absorbent to absorb SO 2 in coal-fired flue gas ,
  • Add high concentrated acid to the washing residue for acid hydrolysis dissolve scandium and titanium in the acid hydrolysis solution, filter out the acid hydrolysis residue, add metatitanic acid seed crystals to the acid hydrolysis solution, and the titanium is passed through water in the form of metatitanic acid
  • the acid hydrolysate after extraction of titanium used 13% P204, 7% TBP and 80% kerosene as the extractant, the scandium in the solution was extracted, and the solution after the extraction of scandium was added to ammonia water to neutralize it with 19% P204, 8% TBP and 73% kerosene are used as extractants to extract vanadium.
  • 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 separately have long treatment processes, large amounts of waste water, and unavailable tailings Utilization and other issues.
  • the purpose of the present invention is to better realize the comprehensive utilization of red mud and provide a method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings.
  • the method uses calcified-carbonized high-speed iron red mud as a raw material and uses gaseous
  • the reducing agent completely calcifies and carbonizes the iron in the red mud.
  • the molten slag is cooled, crushed, and ground at a high temperature to adjust the composition to directly become cement clinker to realize the recovery of iron in the calcification-carbonized high-speed iron red mud and realize the slag-free treatment of the red mud .
  • a method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings includes the following steps:
  • the slag agent is a mixture of CaO and CaF 2 , CaO is added according to the basicity of the mixture at 1.0-1.4, and the mass of CaF 2 is added at 10-30% of the mass of CaO;
  • Vortex stirring is carried out in the molten pool at a temperature of 1300 to 1600 °C, while gaseous reducing agent is introduced for reduction for 10 to 60 minutes; reduced molten iron and molten slag are obtained, wherein the stirring speed is 120 to 150 r/min, The added mass of the gaseous reducing agent is 1.2 to 1.5 times the theoretical mass required to completely reduce the iron in the mixture;
  • the components and mass percentages of the calcified-carbonized high-iron red mud are TFe 20-40%, Al 2 O 3 8-12%, SiO 2 5-20%, A/S 0.2 ⁇ 0.9, Na 2 O 0.1 ⁇ 1.0%, H 2 O 5 ⁇ 20%.
  • the calcified-carbonized high-speed iron red mud is dried and dehydrated in advance to form dried red mud, and then mixed with a slagging agent, wherein the drying temperature is 150-200°C, and the moisture content of the dried red mud It is 1% or less.
  • the mixture of the calcified-carbonized high-speed iron red mud and the slagging agent is ground to a 0.2mm sieve residue of 1 to 4%.
  • the alkalinity is calculated by the following formula (1):
  • mCaO is the mass of calcium oxide in the mixture
  • mAl 2 O 3 is the mass of alumina in the mixture
  • mSiO 2 is the mass of silicon oxide in the mixture.
  • the stirring blade used for stirring is provided with a pipeline, and the gaseous reducing agent is blown in from the bottom of the molten pool or along the stirring blade pipeline.
  • the gaseous reducing agent is a mixture of one or more of water gas, hydrogen, or natural gas.
  • the mixing ratio is any ratio.
  • the extraction rate of iron reaches more than 95%, and the utilization rate of red mud reaches 100%.
  • the calcified-carbonized high-iron red mud used as the raw material in the method of the present invention belongs to low-alkali and low-aluminum red mud, which eliminates the limitation of alkali in the red mud on cement production, and can increase the amount of cement clinker burned by the red mud.
  • the monomer dissociation degree of the iron-containing phase in the calcified-carbonized high-iron red mud of the present invention is high, which is beneficial to the extraction of iron in the reduction process, and the iron extraction rate can reach more than 95%.
  • the method of the present invention adopts vortex stirring smelting reduction, and the raw material does not need to be sintered, and can be directly fed into the furnace for reduction.
  • the reduction process in the molten pool uses stirring and gaseous reducing agent to promote the mass transfer process, and the reduction kinetics conditions are sufficient.
  • the method of the present invention is used for reduction to obtain molten iron, which is directly smelted into wear-resistant cast iron products by adding ferrochrome and ferromanganese to increase the added value;
  • tailings obtained by the method of the present invention are directly added to the powder composition control under vortex stirring at high temperature, and are completely used for producing cement clinker, and the red mud utilization rate reaches 100%.
  • Figure 1 is a schematic diagram of the process flow diagram of the method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings of the present invention.
  • FIG. 1 The process flow diagram of the method for recovering iron from calcification-carbonized high-speed iron red mud and cementing tailings in the following embodiments is shown in FIG. 1.
  • the calcified-carbonized high-speed iron red mud described in the following examples refers to the method disclosed by the invention patent "a method for absorbing red mud (application number: CN201110275030.X)", which changes the red mud through calcification transformation and carbonization transformation
  • the structure and composition can obtain calcified-carbonized red mud with calcium silicate and calcium carbonate as the main phases.
  • the vortex stirring reduction in the following examples refers to the method disclosed in the invention of "a method for vortex stirring smelting reduction ironmaking (CN106435080A)".
  • the vortex stirring smelting reduction high-temperature furnace involved is the equipment used in the method, and the resulting vortex stirring melting
  • the high-temperature furnace vortex height-diameter ratio is 0.5-2.5.
  • the drying temperature of the calcified-carbonized high iron red is 150-200°C.
  • the molten slag adjusting component is adding calcareous raw materials, siliceous raw materials and/or iron raw materials.
  • 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.
  • kind is
  • a method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings includes the following steps:
  • the raw material calcified-carbonized high-iron red mud includes components and mass percentages: TFe content is 30%, Al 2 O 3 content is 12%, SiO 2 content is 20%, Na 2 O content is 0.5%, H 2 O content 10%;
  • (1) Dehydrate and dry the calcified-carbonized high-speed iron red mud to a moisture content of less than 1% to obtain dried red mud. Grind the dried red mud and the slagging agent mixture to a 0.2mm sieve remaining 4% to form a mixture. The mixture is directly sprayed into the vortex center of the vortex stirring smelting reduction high temperature furnace without sintering and is drawn into the molten pool.
  • the slagging agent is a mixture of CaO and CaF 2 , and CaO is added according to the alkalinity of the mixture at 1.4. The quality of CaF 2 Add 20% of the mass of CaO;
  • Vortex stirring is carried out in the molten pool at a temperature of 1600°C, while water gas is blown from the bottom of the molten pool, and the vortex stirring reduction is carried out for 10 minutes.
  • the added mass of water gas is 1.2 times the theoretical value required for complete reduction of iron in the raw material. Speed 120r/min to obtain reduced molten iron and molten slag;
  • the molten slag is added to the smelting furnace by adding calcium, siliceous, and iron materials to adjust the composition to meet the requirements of cement, then air-cooled to room temperature, crushed, and ground directly into cement clinker.
  • the clinker contains CaO, SiO 2 , and Al
  • the contents of 2 O 3 and Fe 2 O 3 are 64%, 20%, 6%, and 2.5%, respectively, which meet the composition requirements of cement clinker.
  • a method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings includes the following steps:
  • the raw material calcified-carbonized high-iron red mud includes components and mass percentages: TFe content is 30%, Al 2 O 3 content is 12%, SiO 2 content is 20%, Na 2 O content is 0.5%, H 2 O content 10%;
  • (1) Dehydrate and dry the calcified-carbonized high-speed iron red mud to a moisture content of less than 1% to obtain dried red mud. Grind the dried red mud and the slagging agent mixture to a 0.2mm sieve remaining 1% to form a mixture. The mixture is directly sprayed to the vortex center of the vortex stirring smelting reduction high temperature furnace without sintering and is drawn into the molten pool.
  • the slagging agent is a mixture of CaO and CaF 2 , and CaO is added according to the basicity of the mixture at 1.0. The quality of CaF 2 Add 30% of the mass of CaO;
  • Vortex stirring is carried out in the molten pool at a temperature of 1300°C, and hydrogen is blown from the bottom of the molten pool to reduce for 60 minutes.
  • the hydrogen is added at 1.5 times the mass of the theoretical value required for complete reduction of iron in the raw material, and the stirring speed is 150r/min to obtain reduction Molten iron and molten slag;
  • the molten slag is added to the vortex stirring high temperature furnace by adding calcium, siliceous, and iron raw materials to adjust the composition to meet the requirements of cement, then air-cooled to room temperature, crushed, and ground directly into cement clinker.
  • the clinker contains CaO and SiO 2
  • the contents of Al 2 O 3 , Fe 2 O 3 are 62%, 24%, 6%, and 3%, respectively, which meet the composition requirements of cement clinker.
  • a method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings includes the following steps:
  • the raw material calcified-carbonized high iron red mud includes components and mass percentages: TFe content is 20%, Al 2 O 3 content is 8%, SiO 2 content is 12%, Na 2 O content is 0.4%, H 2 O content is 13%;
  • (1) Dehydrate and dry the calcified-carbonized high-speed iron red mud to a moisture content of less than 1% to obtain dried red mud. Grind the dried red mud and the slagging agent mixture to a 0.2mm sieve remaining 2% to form a mixture. The mixture is directly sprayed to the center of the vortex of the vortex stirring smelting reduction high temperature furnace without sintering and is drawn into the molten pool.
  • the slagging agent is a mixture of CaO and CaF 2 , and CaO is added according to the alkalinity of the mixture at 1.2. The quality of CaF 2 Add 10% of the mass of CaO;
  • Vortex stirring is carried out in the molten pool at a temperature of 1600°C, and at the same time, natural gas is blown from the bottom of the molten pool to reduce for 10 minutes, and the stirring speed is 150r/min.
  • Molten iron and molten slag
  • the molten slag is added to the vortex stirring high temperature furnace by adding calcium, siliceous, and iron raw materials to adjust the composition to meet the requirements of cement, then air-cooled to room temperature, crushed, and ground directly into cement clinker.
  • the clinker contains CaO and SiO 2
  • the contents of Al 2 O 3 , Fe 2 O 3 are 63%, 23%, 4.8%, and 3.2%, respectively, which meet the composition requirements of cement clinker.
  • a method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings includes the following steps:
  • the raw material calcified-carbonized high-iron red mud includes components and mass percentages: TFe content is 30%, Al 2 O 3 content is 12%, SiO 2 content is 20%, Na 2 O content is 0.5%, H 2 O content 10%;
  • (1) Dehydrate and dry the calcified-carbonized high-speed iron red mud to a moisture content below 1% to obtain dried red mud. Grind the dried red mud and the slagging agent mixture to a 0.2mm sieve with 3% remaining to form a mixture. The mixture is directly sprayed to the center of the vortex of the vortex stirring smelting reduction high temperature furnace without sintering and is drawn into the molten pool.
  • the slagging agent is a mixture of CaO and CaF 2 , and CaO is added according to the alkalinity of the mixture at 1.2. The quality of CaF 2 Add 30% of the mass of CaO;
  • the molten slag is added to the vortex stirring high temperature furnace by adding calcium, siliceous, and iron raw materials to adjust the composition to meet the requirements of cement, then air-cooled to room temperature, crushed, and ground directly into cement clinker.
  • the clinker contains CaO and SiO 2
  • the contents of Al 2 O 3 , Fe 2 O 3 are 63%, 23%, 5%, and 3%, respectively, which meet the composition requirements of cement clinker.

Abstract

Provided is a calcified-carbonized high-iron red mud recycling iron and tailings cementation method, the process steps are: (1) drying the high-iron red mud which is treated through the calcification-carbonization method; (2) grinding the slagging agent and red mud mixture, directly spraying and blowing to the vortex center of the vortex stirring smelting reduction high-temperature furnace; (3) carrying out vortex stirring in the molten pool at 1300-1600℃, meanwhile, feeding the gaseous reducing agent; (4) obtaining the reduced molten iron and the melted slag which are separated; (5) smelting the molten iron into wear-resistant cast iron; (6) treating the molten slag into cement clinker. The utilization rate of the red mud is 100％, and the extraction rate of the iron is more than 90％.

Description

一种钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法Method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings 技术领域：Technical field:
本发明属于环境保护技术领域，具体涉及一种钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法。The invention belongs to the technical field of environmental protection, and specifically relates to a method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings.
背景技术：Background technique:
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。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 utilization rate of red mud 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.
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。In order to realize the efficient use of red mud and the extraction of valuable elements, China's aluminum industry has carried out a large amount of research and development. The existing 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%. Use a plate and frame high-pressure filter press to filter the solid mixture until the water content of the solid mixture is less than 25%, and then send it to the rotary kiln for calcination into cement clinker; Wang Wenju and others invented "a kind of aluminum industrial process waste residue is transformed into an ecological building material "Techniques and Methods" (application number: CN200710105971), using solid waste red mud (sintering method, Bayer method), boiler slag, beneficiation tailings, ashing slag, gas generator slag, The six kinds of sludge waste residues have their own material properties, which are transformed into new road materials and building wall materials through drying, crushing, reasonable proportioning, processing and molding (rolling, extrusion) consolidation or sintering processes.
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；There are also technologies for extracting valuable metal elements such as Na, Al, Fe, and rare metals from red mud; Lou Dongmin and others invented "a Bayer process red mud dealkalization method" (application number: CN201810572642.7). The mud is ground to renew the surface of the red mud, and then the red mud that has undergone surface renewal treatment is mixed with the lime milk and then subjected to dealkalization reaction. After the dealkalization reaction, the red mud slurry is washed and separated from liquid to solid. The alkali-containing solution is returned to the alumina production process, and the separated red mud with low alkali content is sent to the red mud dam for storage;
董红军等发明的“从赤泥中综合回收铁、铝、钪、钛、钒等有价金属的方法，申请号CN201410121083.X”将赤泥与还原剂混合进行还原焙烧，使Fe 2O 3转化成Fe 3O 4，通过磁选得到磁性铁精矿和非磁性产品，非磁性产品经过氨水溶出氧化铝，洗涤渣与水配成矿浆，作为 吸收剂，吸收燃煤烟气中的SO 2，向洗涤渣中加入高浓酸进行酸解，溶出钪、钛于酸解液中，过滤出酸解渣后，向酸解液加入偏钛酸晶种,钛以偏钛酸的形式通过水解析出，提取了钛以后的酸解液用13％P204、7％TBP和80％煤油作为萃取剂，萃取溶液中的钪，萃取钪后的溶液加入氨水中和，用19％P204、8％TBP和73％煤油做萃取剂萃取得到钒。 The method for comprehensive recovery of iron, aluminum, scandium, titanium, vanadium and other valuable metals from red mud, invented by Dong Hongjun, application number CN201410121083.X, combines red mud with a reducing agent for reduction roasting to make Fe 2 O 3 It is converted into Fe 3 O 4 , and magnetic iron concentrate and non-magnetic products are obtained through magnetic separation. The non-magnetic products are dissolved in ammonia water to dissolve alumina, and the washing slag is mixed with water to form a slurry, which acts as an absorbent to absorb SO 2 in coal-fired flue gas , Add high concentrated acid to the washing residue for acid hydrolysis, dissolve scandium and titanium in the acid hydrolysis solution, filter out the acid hydrolysis residue, add metatitanic acid seed crystals to the acid hydrolysis solution, and the titanium is passed through water in the form of metatitanic acid It was analyzed that the acid hydrolysate after extraction of titanium used 13% P204, 7% TBP and 80% kerosene as the extractant, the scandium in the solution was extracted, and the solution after the extraction of scandium was added to ammonia water to neutralize it with 19% P204, 8% TBP and 73% kerosene are used as extractants to extract vanadium.
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处理工艺流程过长、废水量大、尾渣无法得到利用等问题。张廷安等发明的“一种消纳赤泥的方法”(申请号：CN201110275030.X)将拜耳法赤泥与熟石灰混合，进行钙化脱碱后，向容器内通入CO 2得到主要成分为硅酸钙、碳酸钙以及氢氧化铝的碳化渣，最后使用氢氧化钠溶液或铝酸钠溶液提取氢氧化铝，通过钙化转型和碳化转型改变赤泥的结构和组成，从而得到以硅酸钙和碳酸钙为主要物相的钙化-碳化赤泥。 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 separately have long treatment processes, large amounts of waste water, and unavailable tailings Utilization and other issues. Invented by Zhang Ting’an and others, “A method for dissipating red mud” (application number: CN201110275030.X), Bayer process red mud is mixed with slaked lime, and after calcification and dealkalization, CO 2 is introduced into the container to obtain the main component of silicic acid Carbonization residue of calcium, calcium carbonate and aluminum hydroxide, and finally use sodium hydroxide solution or sodium aluminate solution to extract aluminum hydroxide, and change the structure and composition of red mud through calcification transformation and carbonization transformation, thereby obtaining calcium silicate and carbonate Calcium is the main phase of calcified-carbonized red mud.
发明内容：Summary of the invention:
本发明的目的为了更好的实现赤泥的综合利用，提供一种钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法，该方法以钙化-碳化处理的高铁赤泥为原料，利用气态还原剂完全钙化-碳化赤泥中的铁，熔融渣在高温下调整组成经冷却、破碎、研磨直接成为水泥熟料，实现钙化-碳化高铁赤泥中铁的回收，实现赤泥的无渣化处理。The purpose of the present invention is to better realize the comprehensive utilization of red mud and provide a method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings. The method uses calcified-carbonized high-speed iron red mud as a raw material and uses gaseous The reducing agent completely calcifies and carbonizes the iron in the red mud. The molten slag is cooled, crushed, and ground at a high temperature to adjust the composition to directly become cement clinker to realize the recovery of iron in the calcification-carbonized high-speed iron red mud and realize the slag-free treatment of the red mud .
为实现上述目的，本发明采用以下技术方案：In order to achieve the above objectives, the present invention adopts the following technical solutions:
一种钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法，包括以下步骤：A method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings includes the following steps:
(1)将钙化-碳化高铁赤泥与造渣剂混料研磨，形成混合料，直接喷吹到涡流搅拌熔融还原高温炉漩涡中心，并被卷入到熔池中，其中：所述的造渣剂为CaO和CaF 2的混合物，CaO按混合料碱度为1.0～1.4添加，CaF 2质量按CaO质量的10～30％添加； (1) Grind the mixture of calcified-carbonized high-speed iron red mud and slagging agent to form a mixture, which is directly sprayed into the center of the vortex of the vortex stirring smelting reduction high-temperature furnace, and is drawn into the molten pool, where: The slag agent is a mixture of CaO and CaF 2 , CaO is added according to the basicity of the mixture at 1.0-1.4, and the mass of CaF 2 is added at 10-30% of the mass of CaO;
(2)在1300～1600℃温度的熔池中进行涡流搅拌，同时通入气态还原剂，还原10～60min；获得还原铁水和熔融渣，其中，所述的搅拌速度为120～150r/min，所述的气态还原剂添加质量按将混合料中铁完全还原所需理论值质量的1.2～1.5倍添加；(2) Vortex stirring is carried out in the molten pool at a temperature of 1300 to 1600 ℃, while gaseous reducing agent is introduced for reduction for 10 to 60 minutes; reduced molten iron and molten slag are obtained, wherein the stirring speed is 120 to 150 r/min, The added mass of the gaseous reducing agent is 1.2 to 1.5 times the theoretical mass required to completely reduce the iron in the mixture;
(3)得到的还原铁水和熔融渣分层，并进行连续溢流分离，获得铁水和熔融渣；(3) The obtained reduced molten iron and molten slag are separated into layers and subjected to continuous overflow separation to obtain molten iron and molten slag;
(4)铁水中加入铬铁、锰铁直接冶炼成耐磨铸铁产品；(4) Add ferrochrome and ferromanganese to molten iron to directly smelt into wear-resistant cast iron products;
(5)熔融渣在熔炼炉中调整组成使其符合水泥要求；(5) Adjust the composition of molten slag in the smelting furnace to meet the requirements of cement;
(6)熔融渣经冷却、破碎、研磨直接成为水泥熟料，冷却方式采用空气冷却或随炉冷却。(6) The molten slag is cooled, crushed, and ground directly into cement clinker, and the cooling method adopts air cooling or furnace cooling.
所述的步骤(1)中，钙化-碳化高铁赤泥中包括组分及质量百分含量为TFe 20～40％，Al 2O 38～12％，SiO 2 5～20％，A/S 0.2～0.9，Na 2O 0.1～1.0％，H 2O 5～20％。 In the step (1), the components and mass percentages of the calcified-carbonized high-iron red mud are TFe 20-40%, Al 2 O 3 8-12%, SiO 2 5-20%, A/S 0.2～0.9, Na 2 O 0.1～1.0%, H 2 O 5～20%.
所述的步骤(1)中，钙化-碳化高铁赤泥预先经过干燥脱水处理，形成干燥赤泥后，再与造渣剂混料，其中，干燥温度为150～200℃，干燥赤泥含水率为1％以下。In the step (1), the calcified-carbonized high-speed iron red mud is dried and dehydrated in advance to form dried red mud, and then mixed with a slagging agent, wherein the drying temperature is 150-200°C, and the moisture content of the dried red mud It is 1% or less.
所述的步骤(1)中，钙化-碳化高铁赤泥与造渣剂混料研磨至0.2mm筛余1～4％。In the step (1), the mixture of the calcified-carbonized high-speed iron red mud and the slagging agent is ground to a 0.2mm sieve residue of 1 to 4%.
所述的步骤(1)中，碱度按下式(1)方法计算：In the step (1), the alkalinity is calculated by the following formula (1):
Figure PCTCN2019090839-appb-000001
Figure PCTCN2019090839-appb-000001
式(1)中，mCaO为混合料中氧化钙的质量，mAl 2O 3为混合料中氧化铝的质量，mSiO 2为混合料中氧化硅的质量。 In formula (1), mCaO is the mass of calcium oxide in the mixture, mAl 2 O 3 is the mass of alumina in the mixture, and mSiO 2 is the mass of silicon oxide in the mixture.
所述的步骤(2)中，搅拌采用的搅拌桨设有管道，所述的气态还原剂从熔池底部吹入或沿搅拌桨管道吹入。In the step (2), the stirring blade used for stirring is provided with a pipeline, and the gaseous reducing agent is blown in from the bottom of the molten pool or along the stirring blade pipeline.
所述的步骤(3)中，气态还原剂为水煤气、氢气或天然气中的一种或几种混合，当为多种混合时，混合比为任意比。In the step (3), the gaseous reducing agent is a mixture of one or more of water gas, hydrogen, or natural gas. When multiple types are mixed, the mixing ratio is any ratio.
所述的方法中，铁的提取率达95％以上，赤泥利用率达100％。In the method, the extraction rate of iron reaches more than 95%, and the utilization rate of red mud reaches 100%.
与现有技术相比，本发明的特点和有益效果是：Compared with the prior art, the features and beneficial effects of the present invention are:
(1)本发明方法中原料采用的钙化-碳化高铁赤泥属于低碱低铝赤泥，消除了赤泥中碱对水泥生产的限制，可增加赤泥烧制水泥熟料的添配量。(1) The calcified-carbonized high-iron red mud used as the raw material in the method of the present invention belongs to low-alkali and low-aluminum red mud, which eliminates the limitation of alkali in the red mud on cement production, and can increase the amount of cement clinker burned by the red mud.
(2)本发明的钙化-碳化高铁赤泥中含铁相的单体解离度高，有利于还原过程铁的提取，铁的提取率可达95％以上。(2) The monomer dissociation degree of the iron-containing phase in the calcified-carbonized high-iron red mud of the present invention is high, which is beneficial to the extraction of iron in the reduction process, and the iron extraction rate can reach more than 95%.
(3)本发明的方法采用涡流搅拌熔融还原，原料不用烧结，可直接入炉还原。熔池中还原过程采用搅拌和气态还原剂促进传质过程，还原动力学条件充分。(3) The method of the present invention adopts vortex stirring smelting reduction, and the raw material does not need to be sintered, and can be directly fed into the furnace for reduction. The reduction process in the molten pool uses stirring and gaseous reducing agent to promote the mass transfer process, and the reduction kinetics conditions are sufficient.
(4)采用本发明的方法进行还原得到铁水加入铬铁、锰铁直接冶炼成耐磨铸铁产品，提高附加值；(4) The method of the present invention is used for reduction to obtain molten iron, which is directly smelted into wear-resistant cast iron products by adding ferrochrome and ferromanganese to increase the added value;
(5)本发明方法获得的尾渣在高温下涡流搅拌直接加入粉料组成调控，完全用于生产水泥熟料，赤泥利用率达100％。(5) The tailings obtained by the method of the present invention are directly added to the powder composition control under vortex stirring at high temperature, and are completely used for producing cement clinker, and the red mud utilization rate reaches 100%.
附图说明：Description of the drawings:
图1为本发明的钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法工艺流程示意图。Figure 1 is a schematic diagram of the process flow diagram of the method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings of the present invention.
具体实施方式：detailed description:
下面结合实施例对本发明作进一步的详细说明。The present invention will be further described in detail below in conjunction with the embodiments.
以下实施例的钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法工艺流程示意图如图1所示。The process flow diagram of the method for recovering iron from calcification-carbonized high-speed iron red mud and cementing tailings in the following embodiments is shown in FIG. 1.
以下实施例中所述的钙化-碳化高铁赤泥是指由发明专利“一种消纳赤泥的方法(申请号：CN201110275030.X)”公开的方法，经钙化转型和碳化转型改变赤泥的结构和组成，得到以硅酸钙和碳酸钙为主要物相的钙化-碳化赤泥。The calcified-carbonized high-speed iron red mud described in the following examples refers to the method disclosed by the invention patent "a method for absorbing red mud (application number: CN201110275030.X)", which changes the red mud through calcification transformation and carbonization transformation The structure and composition can obtain calcified-carbonized red mud with calcium silicate and calcium carbonate as the main phases.
以下实施例中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(CN106435080A)”公开的方法，所涉及的涡流搅拌熔融还原高温炉为该方法使用的设备，形成的涡流搅拌熔融高温炉漩涡高径比为0.5-2.5。The vortex stirring reduction in the following examples refers to the method disclosed in the invention of "a method for vortex stirring smelting reduction ironmaking (CN106435080A)". The vortex stirring smelting reduction high-temperature furnace involved is the equipment used in the method, and the resulting vortex stirring melting The high-temperature furnace vortex height-diameter ratio is 0.5-2.5.
以下实施例中钙化-碳化高铁赤干燥时的温度为150～200℃。In the following examples, the drying temperature of the calcified-carbonized high iron red is 150-200°C.
以下实施例中熔融渣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。In the following embodiments, the molten slag adjusting component is adding calcareous raw materials, siliceous raw materials and/or iron raw materials. 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. Kind.
实施例1Example 1
一种钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法，包括以下步骤：A method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings includes the following steps:
原料钙化-碳化高铁赤泥中包括组分及质量百分含量为：TFe含量在30％，Al 2O 3含量在12％，SiO 2含量在20％，Na 2O含量在0.5％，H 2O含量10％； The raw material calcified-carbonized high-iron red mud includes components and mass percentages: TFe content is 30%, Al 2 O 3 content is 12%, SiO 2 content is 20%, Na 2 O content is 0.5%, H 2 O content 10%;
(1)将钙化-碳化高铁赤泥脱水干燥至含水率1％以下，获得干燥后赤泥，将干燥后赤泥与造渣剂混料研磨至0.2mm筛余4％，形成混合料，将混合料不经烧结直接喷吹到涡流搅拌熔融还原高温炉漩涡中心并被卷入到熔池中，造渣剂为CaO和CaF 2的混合物，CaO按混合料碱度为1.4添加，CaF 2质量按CaO质量的20％添加； (1) Dehydrate and dry the calcified-carbonized high-speed iron red mud to a moisture content of less than 1% to obtain dried red mud. Grind the dried red mud and the slagging agent mixture to a 0.2mm sieve remaining 4% to form a mixture. The mixture is directly sprayed into the vortex center of the vortex stirring smelting reduction high temperature furnace without sintering and is drawn into the molten pool. The slagging agent is a mixture of CaO and CaF 2 , and CaO is added according to the alkalinity of the mixture at 1.4. The quality of CaF 2 Add 20% of the mass of CaO;
(2)在1600℃温度的熔池中进行涡流搅拌，同时从熔池底部吹入水煤气，进行涡流搅拌还原还原10min，水煤气添加质量按原料中铁完全还原所需理论值质量的1.2倍添加，搅拌速度120r/min，获得还原铁水和熔融渣；(2) Vortex stirring is carried out in the molten pool at a temperature of 1600℃, while water gas is blown from the bottom of the molten pool, and the vortex stirring reduction is carried out for 10 minutes. The added mass of water gas is 1.2 times the theoretical value required for complete reduction of iron in the raw material. Speed 120r/min to obtain reduced molten iron and molten slag;
(3)得到的还原铁水和熔融渣分层并进行连续溢流分离，得到铁水加入铬铁、锰铁直接冶炼成耐磨铸铁产品，铁的回收率为95％；铁水加入铬铁、锰铁直接冶炼成ISO21988/JN/HBW555Cr13牌号耐磨铸铁，耐磨铸铁中Cr含量为13％，Mn含量为1.2％；(3) The obtained reduced molten iron and molten slag are layered and separated by continuous overflow, and the molten iron is added to ferrochrome and ferromanganese to directly smelt into wear-resistant cast iron products. The iron recovery rate is 95%; the molten iron is added to ferrochrome and ferromanganese Directly smelted into ISO21988/JN/HBW555Cr13 wear-resistant cast iron, the content of Cr in the wear-resistant cast iron is 13%, and the content of Mn is 1.2%;
(4)熔融渣在熔炼炉中加入钙质、硅质、铁质原料调整组成使其符合水泥要求后，空冷至室温、破碎、研磨直接成为水泥熟料，熟料中CaO、SiO 2、Al 2O 3、Fe 2O 3的含量分别为64％、20％、6％、2.5％，满足水泥熟料的成分要求。 (4) The molten slag is added to the smelting furnace by adding calcium, siliceous, and iron materials to adjust the composition to meet the requirements of cement, then air-cooled to room temperature, crushed, and ground directly into cement clinker. The clinker contains CaO, SiO 2 , and Al The contents of 2 O 3 and Fe 2 O 3 are 64%, 20%, 6%, and 2.5%, respectively, which meet the composition requirements of cement clinker.
实施例2Example 2
一种钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法，包括以下步骤：A method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings includes the following steps:
原料钙化-碳化高铁赤泥中包括组分及质量百分含量为：TFe含量在30％，Al 2O 3含量在12％，SiO 2含量在20％，Na 2O含量在0.5％，H 2O含量10％； The raw material calcified-carbonized high-iron red mud includes components and mass percentages: TFe content is 30%, Al 2 O 3 content is 12%, SiO 2 content is 20%, Na 2 O content is 0.5%, H 2 O content 10%;
(1)将钙化-碳化高铁赤泥脱水干燥至含水率1％以下，获得干燥后赤泥，将干燥后赤泥与造渣剂混料研磨至0.2mm筛余1％，形成混合料，将混合料不经烧结直接喷吹到涡流搅拌熔 融还原高温炉漩涡中心并被卷入到熔池中，造渣剂为CaO和CaF 2的混合物，CaO按混合料碱度为1.0添加，CaF 2质量按CaO质量的30％添加； (1) Dehydrate and dry the calcified-carbonized high-speed iron red mud to a moisture content of less than 1% to obtain dried red mud. Grind the dried red mud and the slagging agent mixture to a 0.2mm sieve remaining 1% to form a mixture. The mixture is directly sprayed to the vortex center of the vortex stirring smelting reduction high temperature furnace without sintering and is drawn into the molten pool. The slagging agent is a mixture of CaO and CaF 2 , and CaO is added according to the basicity of the mixture at 1.0. The quality of CaF 2 Add 30% of the mass of CaO;
(2)在1300℃温度的熔池中进行涡流搅拌，同时从熔池底部吹入氢气还原60min，氢气按原料中铁完全还原所需理论值质量的1.5倍添加，搅拌速度150r/min，获得还原铁水和熔融渣；(2) Vortex stirring is carried out in the molten pool at a temperature of 1300℃, and hydrogen is blown from the bottom of the molten pool to reduce for 60 minutes. The hydrogen is added at 1.5 times the mass of the theoretical value required for complete reduction of iron in the raw material, and the stirring speed is 150r/min to obtain reduction Molten iron and molten slag;
(3)得到的还原铁水和熔融渣分层并进行连续溢流分离，得到铁水加入铬铁、锰铁直接冶炼成耐磨铸铁产品，铁的回收率为90％；铁水加入铬铁、锰铁直接冶炼成ISO21988/JN/HBW555Cr13牌号耐磨铸铁，耐磨铸铁中Cr含量为11％，Mn含量为1.4％；(3) The obtained reduced molten iron and molten slag are layered and separated by continuous overflow, and the molten iron is added to ferrochrome and ferromanganese to be directly smelted into wear-resistant cast iron products. The iron recovery rate is 90%; the molten iron is added to ferrochrome and ferromanganese Directly smelted into ISO21988/JN/HBW555Cr13 grade wear-resistant cast iron, the content of Cr in the wear-resistant cast iron is 11%, and the content of Mn is 1.4%;
(4)熔融渣在涡流搅拌高温炉中加入钙质、硅质、铁质原料调整组成使其符合水泥要求后，空冷至室温、破碎、研磨直接成为水泥熟料，熟料中CaO、SiO 2、Al 2O 3、Fe 2O 3的含量分别为62％、24％、6％、3％，满足水泥熟料的成分要求。 (4) The molten slag is added to the vortex stirring high temperature furnace by adding calcium, siliceous, and iron raw materials to adjust the composition to meet the requirements of cement, then air-cooled to room temperature, crushed, and ground directly into cement clinker. The clinker contains CaO and SiO 2 The contents of Al 2 O 3 , Fe 2 O 3 are 62%, 24%, 6%, and 3%, respectively, which meet the composition requirements of cement clinker.
实施例3Example 3
一种钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法，包括以下步骤：A method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings includes the following steps:
原料钙化-碳化高铁赤泥中包括组分及质量百分含量为：TFe含量在20％，Al 2O 3含量在8％，SiO 2含量在12％，Na 2O含量在0.4％，H 2O含量13％； The raw material calcified-carbonized high iron red mud includes components and mass percentages: TFe content is 20%, Al 2 O 3 content is 8%, SiO 2 content is 12%, Na 2 O content is 0.4%, H 2 O content is 13%;
(1)将钙化-碳化高铁赤泥脱水干燥至含水率1％以下，获得干燥后赤泥，将干燥后赤泥与造渣剂混料研磨至0.2mm筛余2％，形成混合料，将混合料不经烧结直接喷吹到涡流搅拌熔融还原高温炉漩涡中心并被卷入到熔池中，造渣剂为CaO和CaF 2的混合物，CaO按混合料碱度为1.2添加，CaF 2质量按CaO质量的10％添加； (1) Dehydrate and dry the calcified-carbonized high-speed iron red mud to a moisture content of less than 1% to obtain dried red mud. Grind the dried red mud and the slagging agent mixture to a 0.2mm sieve remaining 2% to form a mixture. The mixture is directly sprayed to the center of the vortex of the vortex stirring smelting reduction high temperature furnace without sintering and is drawn into the molten pool. The slagging agent is a mixture of CaO and CaF 2 , and CaO is added according to the alkalinity of the mixture at 1.2. The quality of CaF 2 Add 10% of the mass of CaO;
(2)在1600℃温度的熔池中进行涡流搅拌，同时从熔池底部吹入天然气还原10min，搅拌速度150r/min，天然气按原料中铁完全还原所需理论值质量的1.5倍添加，获得还原铁水和熔融渣；(2) Vortex stirring is carried out in the molten pool at a temperature of 1600℃, and at the same time, natural gas is blown from the bottom of the molten pool to reduce for 10 minutes, and the stirring speed is 150r/min. Molten iron and molten slag;
(3)得到的还原铁水和熔融渣分层并进行连续溢流分离，得到铁水加入铬铁、锰铁直接冶炼成耐磨铸铁产品，铁的回收率为91％；铁水加入铬铁、锰铁直接冶炼成ISO21988/JN/HBW555Cr13牌号耐磨铸铁，耐磨铸铁中Cr含量为12％，Mn含量为1.1％；(3) The obtained reduced molten iron and molten slag are layered and separated by continuous overflow, and the molten iron is added to ferrochrome and ferromanganese to directly smelt into wear-resistant cast iron products. The iron recovery rate is 91%; the molten iron is added to ferrochrome and ferromanganese Directly smelted into ISO21988/JN/HBW555Cr13 grade wear-resistant cast iron, the content of Cr in the wear-resistant cast iron is 12%, and the content of Mn is 1.1%;
(4)熔融渣在涡流搅拌高温炉中加入钙质、硅质、铁质原料调整组成使其符合水泥要求后，空冷至室温、破碎、研磨直接成为水泥熟料，熟料中CaO、SiO 2、Al 2O 3、Fe 2O 3的含量分别为63％、23％、4.8％、3.2％，满足水泥熟料的成分要求。 (4) The molten slag is added to the vortex stirring high temperature furnace by adding calcium, siliceous, and iron raw materials to adjust the composition to meet the requirements of cement, then air-cooled to room temperature, crushed, and ground directly into cement clinker. The clinker contains CaO and SiO 2 The contents of Al 2 O 3 , Fe 2 O 3 are 63%, 23%, 4.8%, and 3.2%, respectively, which meet the composition requirements of cement clinker.
实施例4Example 4
一种钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法，包括以下步骤：A method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings includes the following steps:
原料钙化-碳化高铁赤泥中包括组分及质量百分含量为：TFe含量在30％，Al 2O 3含量在12％，SiO 2含量在20％，Na 2O含量在0.5％，H 2O含量10％； The raw material calcified-carbonized high-iron red mud includes components and mass percentages: TFe content is 30%, Al 2 O 3 content is 12%, SiO 2 content is 20%, Na 2 O content is 0.5%, H 2 O content 10%;
(1)将钙化-碳化高铁赤泥脱水干燥至含水率1％以下，获得干燥后赤泥，将干燥后赤泥与造渣剂混料研磨至0.2mm筛余3％，形成混合料，将混合料不经烧结直接喷吹到涡流搅拌熔融还原高温炉漩涡中心并被卷入到熔池中，造渣剂为CaO和CaF 2的混合物，CaO按混合料碱度为1.2添加，CaF 2质量按CaO质量的30％添加； (1) Dehydrate and dry the calcified-carbonized high-speed iron red mud to a moisture content below 1% to obtain dried red mud. Grind the dried red mud and the slagging agent mixture to a 0.2mm sieve with 3% remaining to form a mixture. The mixture is directly sprayed to the center of the vortex of the vortex stirring smelting reduction high temperature furnace without sintering and is drawn into the molten pool. The slagging agent is a mixture of CaO and CaF 2 , and CaO is added according to the alkalinity of the mixture at 1.2. The quality of CaF 2 Add 30% of the mass of CaO;
(2)在1500℃温度的熔池中进行涡流搅拌，同时沿搅拌桨管道吹入水煤气还原20min，水煤气按原料中铁完全还原所需理论值质量的1.5倍添加，搅拌速度150r/min，获得还原铁水和熔融渣；(2) Perform vortex stirring in a molten pool at a temperature of 1500℃, while blowing water gas along the stirring paddle pipe for 20min reduction. The water gas is added at 1.5 times the theoretical mass required for complete reduction of iron in the raw material. The stirring speed is 150r/min to obtain reduction. Molten iron and molten slag;
(3)得到的还原铁水和熔融渣分层并进行连续溢流分离，得到铁水加入铬铁、锰铁直接冶炼成耐磨铸铁产品，铁的回收率为94％；铁水加入铬铁、锰铁直接冶炼成ISO21988/JN/HBW555Cr13牌号耐磨铸铁，耐磨铸铁中Cr含量为12％，Mn含量为1.3％；(3) The obtained reduced molten iron and molten slag are layered and separated by continuous overflow, and the molten iron is added to ferrochrome and ferromanganese to be directly smelted into wear-resistant cast iron products. The iron recovery rate is 94%; the molten iron is added to ferrochrome and ferromanganese Directly smelted into ISO21988/JN/HBW555Cr13 wear-resistant cast iron, the content of Cr in the wear-resistant cast iron is 12%, and the content of Mn is 1.3%;
(4)熔融渣在涡流搅拌高温炉中加入钙质、硅质、铁质原料调整组成使其符合水泥要求后，空冷至室温、破碎、研磨直接成为水泥熟料，熟料中CaO、SiO 2、Al 2O 3、Fe 2O 3的含量分别为63％、23％、5％、3％，满足水泥熟料的成分要求。 (4) The molten slag is added to the vortex stirring high temperature furnace by adding calcium, siliceous, and iron raw materials to adjust the composition to meet the requirements of cement, then air-cooled to room temperature, crushed, and ground directly into cement clinker. The clinker contains CaO and SiO 2 The contents of Al 2 O 3 , Fe 2 O 3 are 63%, 23%, 5%, and 3%, respectively, which meet the composition requirements of cement clinker.

Claims (8)

  1. 一种钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法，其特征在于，包括以下步骤：A method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings is characterized in that it comprises the following steps:
    (1)将钙化-碳化高铁赤泥与造渣剂混料研磨，形成混合料，直接喷吹到涡流搅拌熔融还原高温炉漩涡中心，并被卷入到熔池中，其中：所述的造渣剂为CaO和CaF 2的混合物，CaO按混合料碱度为1.0～1.4添加，CaF 2质量按CaO质量的10～30％添加； (1) Grind the mixture of calcified-carbonized high-speed iron red mud and slagging agent to form a mixture, which is directly sprayed into the center of the vortex of the vortex stirring smelting reduction high-temperature furnace, and is drawn into the molten pool, where: The slag agent is a mixture of CaO and CaF 2 , CaO is added according to the basicity of the mixture at 1.0-1.4, and the mass of CaF 2 is added at 10-30% of the mass of CaO;
    (2)在1300～1600℃温度的熔池中进行涡流搅拌，同时通入气态还原剂，还原10～60min；获得还原铁水和熔融渣，其中，所述的搅拌速度为120～150r/min，所述的气态还原剂添加质量按将混合料中铁完全还原所需理论值质量的1.2～1.5倍添加；(2) Vortex stirring is carried out in the molten pool at a temperature of 1300 to 1600 ℃, while gaseous reducing agent is introduced for reduction for 10 to 60 minutes; reduced molten iron and molten slag are obtained, wherein the stirring speed is 120 to 150 r/min, The added mass of the gaseous reducing agent is 1.2 to 1.5 times the theoretical mass required to completely reduce the iron in the mixture;
    (3)得到的还原铁水和熔融渣分层，并进行连续溢流分离，获得铁水和熔融渣；(3) The obtained reduced molten iron and molten slag are separated into layers and subjected to continuous overflow separation to obtain molten iron and molten slag;
    (4)铁水中加入铬铁、锰铁直接冶炼成耐磨铸铁产品；(4) Add ferrochrome and ferromanganese to molten iron to directly smelt into wear-resistant cast iron products;
    (5)熔融渣在熔炼炉中调整组成使其符合水泥要求；(5) Adjust the composition of molten slag in the smelting furnace to meet the requirements of cement;
    (6)熔融渣经冷却、破碎、研磨直接成为水泥熟料，冷却方式采用空气冷却或随炉冷却。(6) The molten slag is cooled, crushed, and ground directly into cement clinker, and the cooling method adopts air cooling or furnace cooling.
  2. 根据权利要求1所述的钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法，其特征在于，所述的步骤(1)中，钙化-碳化高铁赤泥中包括组分及质量百分含量为TFe 20～40％，Al 2O 3 8～12％，SiO 2 5～20％，A/S 0.2～0.9，Na 2O 0.1～1.0％，H 2O 5～20％。 The method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings according to claim 1, wherein in step (1), the calcified-carbonized high-speed iron red mud includes components and mass percentages The content is TFe 20-40%, Al 2 O 3 8-12%, SiO 2 5-20%, A/S 0.2-0.9, Na 2 O 0.1-1.0%, H 2 O 5-20%.
  3. 根据权利要求1所述的钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法，其特征在于，所述的步骤(1)中，钙化-碳化高铁赤泥预先经过干燥脱水处理，形成干燥赤泥后，再与造渣剂混料，其中，干燥温度为150～200℃，干燥赤泥含水率为1％以下。The method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings according to claim 1, wherein in the step (1), the calcified-carbonized high-speed iron red mud is dried and dehydrated in advance to form a dry After the red mud is mixed with a slag-making agent, the drying temperature is 150-200°C, and the moisture content of the dried red mud is below 1%.
  4. 根据权利要求1所述的钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法，其特征在于，所述的步骤(1)中，钙化-碳化高铁赤泥与造渣剂混料研磨至0.2mm筛余1～4％。The method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings according to claim 1, wherein in step (1), the mixture of calcified-carbonized high-speed iron red mud and slagging agent is ground to The 0.2mm sieve has a residue of 1-4%.
  5. 根据权利要求1所述的钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法，其特征在于，所述的步骤(1)中，所述的步骤(1)中，碱度按下式(1)方法计算：The method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings according to claim 1, wherein in said step (1), in said step (1), the alkalinity is as follows: (1) Method calculation:
    Figure PCTCN2019090839-appb-100001
    Figure PCTCN2019090839-appb-100001
  6. 根据权利要求1所述的钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法，其特征在于，所述的步骤(1)中，所述的步骤(2)中，搅拌采用的搅拌桨设有管道，所述的气态还原剂从熔池底部吹入或沿搅拌桨管道吹入。The method for recovering iron from calcification-carbonized high-speed iron red mud and cementing tailings according to claim 1, wherein in said step (1), in said step (2), a stirring blade is used for stirring A pipeline is provided, and the gaseous reducing agent is blown in from the bottom of the molten pool or along the stirring blade pipeline.
  7. 根据权利要求1所述的钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法，其特征在于，所述的步骤(1)中，所述的步骤(3)中，气态还原剂为水煤气、氢气或天然气中的一种或几种混合，当为多种混合时，混合比为任意比。The method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings according to claim 1, wherein in said step (1), in said step (3), the gaseous reducing agent is water gas , Hydrogen or natural gas one or more of them are mixed. When multiple types are mixed, the mixing ratio is any ratio.
  8. 根据权利要求1所述的钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法，其特征在于，所述的步骤(1)中，所述的方法中，铁的提取率达95％以上，赤泥利用率达100％。The method for recovering iron from calcified-carbonized high-speed iron red mud and cementing tailings according to claim 1, wherein in said step (1), in said method, the extraction rate of iron is more than 95% , The utilization rate of red mud reaches 100%.
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