WO2020206831A1 - Procédé de cimentation de résidus et de fer de recyclage de boue rouge à haute teneur en fer carbonisé calcifié - Google Patents

Procédé de cimentation de résidus et de fer de recyclage de boue rouge à haute teneur en fer carbonisé calcifié 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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English (en)
Chinese (zh)
Inventor
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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Publication of WO2020206831A1 publication Critical patent/WO2020206831A1/fr

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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.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Structural Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé de cimentation de résidus et de fer de recyclage de boue rouge à haute teneur en fer carbonisé calcifié, les étapes de procédé consistant à : (1) sécher de la boue rouge à haute teneur en fer qui est traitée par le procédé de calcification-carbonisation ; (2) broyer l'agent de scorification et le mélange de boue rouge, pulvériser directement et le souffler vers le centre de tourbillon du four à haute température de réduction de fusion à agitation tourbillonnaire ; (3) effectuer une agitation de tourbillon dans le bain de fusion à une température comprise entre 1300 et 1600 °C, pendant ce temps, alimenter l'agent de réduction gazeux ; (4) obtenir le fer fondu réduit et le laitier fondu qui sont séparés ; (5) faire fondre le fer fondu en fonte résistant à l'usure ; (6) traiter le laitier fondu en clinker de ciment. Le taux d'utilisation de la boue rouge est de 100 %, et le taux d'extraction du fer est supérieur à 90 %.
PCT/CN2019/090839 2019-04-11 2019-06-12 Procédé de cimentation de résidus et de fer de recyclage de boue rouge à haute teneur en fer carbonisé calcifié WO2020206831A1 (fr)

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CN113174457B (zh) * 2021-04-28 2022-10-04 东北大学 一种处理高铁赤泥的侧顶复合喷吹熔炼还原炉的使用方法
CN113174455B (zh) * 2021-04-28 2022-10-04 东北大学 一种侧顶复合吹熔融还原高铁赤泥的综合利用方法
CN113174456B (zh) * 2021-04-28 2022-10-04 东北大学 一种底顶复合吹熔融还原高铁赤泥的综合利用方法
CN113562770B (zh) * 2021-07-26 2023-04-14 中钢集团马鞍山矿山研究总院股份有限公司 一种梯级回收赤泥中铁钠资源及尾渣全量化利用的方法

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