CN109970368A - A kind of method that the melting and reducing dealkalize of iron red mud vortex mentions the direct cement of iron - Google Patents

A kind of method that the melting and reducing dealkalize of iron red mud vortex mentions the direct cement of iron Download PDF

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Publication number
CN109970368A
CN109970368A CN201910290643.7A CN201910290643A CN109970368A CN 109970368 A CN109970368 A CN 109970368A CN 201910290643 A CN201910290643 A CN 201910290643A CN 109970368 A CN109970368 A CN 109970368A
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iron
red mud
raw material
vortex
mixture
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Inventor
张廷安
王艳秀
豆志河
王坤
刘燕
吕国志
张子木
赵秋月
傅大学
张伟光
韩继标
郭军华
晁曦
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Northeastern University China
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Northeastern University China
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Priority to CN201910290643.7A priority Critical patent/CN109970368A/en
Priority to PCT/CN2019/090842 priority patent/WO2020206833A1/en
Publication of CN109970368A publication Critical patent/CN109970368A/en
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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
    • 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
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/48—Clinker treatment
    • C04B7/52—Grinding ; After-treatment of ground cement
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B11/00—Making pig-iron other than in blast furnaces
    • 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
    • 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
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/08—Making cast-iron alloys
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Manufacture Of Iron (AREA)

Abstract

A kind of method that the melting and reducing dealkalize of iron red mud vortex mentions the direct cement of iron, sequentially includes the following steps: (1) and prepares raw material iron red mud；(2) raw material drying obtains dehydrated raw material；Mixture is made in dehydrated raw material and solid carbonaceous reducer and slag former mixing, and the swirl center of vortex stirring high temperature furnace is arrived in blowing, carries out vortex stirring reduction；(3) molten iron and liquid slag formed after restoring is layered, continuous overflow separation；Ferrochrome is added into molten iron and wear resistant cast iron product is made in manganese iron；(4) liquid slag adjusts component in smelting furnace and complies with clinker requirement, is crushed after air-cooled and clinker is made in grinding.The extraction of sodium and iron in red mud can be achieved at the same time in method of the invention, and processing step is simple, and the recovery rate of soda and iron is higher, and red mud utilization rate is up to 100%.

Description

A kind of method that the melting and reducing dealkalize of iron red mud vortex mentions the direct cement of iron
Technical field
The present invention relates to environmental protection technical fields, and in particular to it is straight that a kind of vortex melting and reducing dealkalize of iron red mud mentions iron The method of water receiving argillization.
Technical background
Red mud be using bauxite as waste aluminium oxide or aluminium hydroxide after generated strong basicity solid waste.Mesh Before, global red mud reserves estimation alreadys exceed 3,000,000,000 tons, and is about increased every year with 1.2 hundred million tons of speed, and world's red mud is flat Equal utilization rate is 15%.Chinese red mud adds up volume of cargo in storage and has risen to 600,000,000 tons, and is about increased every year with 100,000,000 tons of speed, Chinese red mud utilization rate is only 4%.The method disposition that most of red mud still takes land to store up.Red mud pilling not only wastes Secondary resource occupies a large amount of soils, and destroys the surrounding enviroment of red mud dump, brings serious environmental problem, causes The environmental protection pressure of aluminum i ndustry increases severely.The environmental risk of red mud pilling causes the weight of government, each alumina producing state and enterprise already Depending on solving the problems, such as that the key of red mud is research and development red mud comprehensive utilization technique.
To realize that efficient utilization and the valuable element of red mud extract, China's aluminum i ndustry has carried out a large amount of R&D work, Existing red mud generally can be divided into two kinds using technology: one is as general raw material of industry whole utilization, Ru Zhaoguang is bright etc. (application number: being to dealkalize red mud 201210031710.1) to human hair bright " a method of utilize red mud produce clinker " Three of the above material is uniformly mixed in agitator tank, while water being added to adjust its concentration by middle addition dealkalize gypsum and flyash To 30%.It is lower than 25% using plate and frame high-pressure pressure filter filters pressing to solid mixture water content, is then fed into calcining in rotary kiln At clinker；Wang Wenju et al. invention " a kind of aluminum i ndustry technique waste residue be all transformed into the technique of ecological architectural material with Method " (application number: CN200710105971), using aluminum i ndustry in process of production institute's output solid waste red mud (sintering Method, Bayer process), boiler slag, milltailings, ashing slag, gas generator slag, six kinds of waste residues itself of sludge material property, By drying, crushing, rational proportion, machine-shaping (roll, squeeze) consolidation or sintering process, it is converted into novel Load materials And construction material.
Also there is the technology extracted from red mud and have the valuable metals element such as Na, Al, Fe, rare metal；The invention such as Lou Dongmin " a kind of dealkalization method of Bayer process red mud " (application number: 201810572642.7) first grinding red mud, makes red mud Surface Renewal, it is anti-by dealkalize then again to carrying out de-alkali reaction after the red mud that Surface Renewal is handled is mixed with milk of lime Red mud slurry after answering washed, solid-liquor separation, can obtain the solution containing alkali, returning alumina production procedure, after separation The red mud of Lower alrali content send red mud dam to store up；
The inventions such as Chen Huanyue " a method of sorting mentions iron except sodium, the Shen of publication number CN108686828A from red mud The fine red mud material based on subparticle please is made by crushing or ball milling in red mud, fine red mud material is classified, it will 10~98% separating in subparticle of the partial size less than 5 microns in fine red mud material, the partial size separated is micro- less than 5 The subparticle product of rice is the product based on Sodium-silica slag and calcium-silicon slag, and wherein sodium oxide content is greater than 10%, is remained after classification Remaining red mud material is iron ore product, and wherein iron oxide content is greater than 30%.
There are red mud alkalinity to restrict when red mud is as general raw material of industry whole utilization, product price is low, income is poor etc. Problem；The method for extracting valuable element respectively has that recovery rate is low, product purity is low directly to utilize for enrichment of element mostly again The problems such as.Although the research that therefore aluminum oxide industry is utilized about red mud is numerous, the stockpiling problem of red mud is still failed at present To properly settling.
Summary of the invention
In order to preferably realize the comprehensive utilization of red mud, the present invention provides a kind of iron red mud vortex melting and reducing dealkalize and mentions The method of the direct cement of iron by the iron red mud of dehydration and drying and solid carbonaceous reducer and is made using iron red mud as raw material The blowing of slag agent mixing mentions iron to reduction high temperature furnace swirl center reduction, and sodium enters off-gas recovery in reduction process, and liquid slag is in height Temperature lowers whole group and is directly becoming clinker at through cooling, broken, grinding.
Method of the invention sequentially includes the following steps:
(1) prepare raw material iron red mud, iron red mud 20~40% TFe by mass percentage, Na2O 2~15%, Al2O315~25%, SiO215~25%, CaO 5~25%, H2O 5~20%；
(2) by mass percent≤1% of raw material drying to water, dehydrated raw material is obtained；By dehydrated raw material with it is solid carbonaceous Mixture is made in reducing agent and slag former mixing, and the directly swirl center of blowing to vortex stirring high temperature furnace, mixture is involved in In molten bath, 10~60min is restored in 1300~1600 DEG C of progress vortex stirrings；The solid carbonaceous reducer is coking coal, Gu The molar ratio of Fe is 1.2~1.5 in the amount and raw material of state carbonaceous reducing agent, and slag former is CaO and CaF2Mixture, wherein CaO is 1.0~1.4 additions, CaF by the basicity of mixture2Account for the 10~30% of CaO gross mass:
(3) molten iron and liquid slag formed after restoring is layered, and carries out continuous overflow separation；Add into the molten iron isolated Enter ferrochrome and manganese iron is directly smelted and cast and wear resistant cast iron product is made；
(4) liquid slag isolated adjusts component in smelting furnace and complies with clinker requirement, then through being air-cooled to Room temperature, then clinker is made through broken and grinding.
In the above method, the calculating formula of basicity is pressed:
In formula, mCaO is the quality of calcium oxide in mixture, mAl2O3For the quality of aluminium oxide in mixture, mSiO2It is mixed Close the quality of silica in material.
In the above method, sodium enters flue gas in vortex stirring reduction process, recycles through flue gas dust collection system.
In the above method, the main reaction formula that reduction process is related to is as follows:
FexOy+ yC=yCO+xFe (2),
FexOy+ yCO=yCO2+xFe (3)
With
FexOy+ y/2C=y/2CO2+xFe (4)。
In the above method, the rate of recovery >=90% of iron.
In the above method, the rate of recovery >=95% of sodium.
Compared with prior art, the features of the present invention and beneficial effect are:
(1) iron red mud is directly vortexed melting and reducing at high temperature, and soda enters off-gas recovery, reduced iron in reduction process Ferrochrome is added in water, manganese iron directly smelts the extraction that sodium and iron in red mud can be achieved at the same time at wear resistant cast iron；
(2) processing step is simple, the liquid slag Na after dealkalize2O content meets clinker to alkalinity less than 0.5% Component requirements, can increase red mud calcining cement clinker adds dosage；
(3) vortex stirring melting and reducing is used, raw material does not have to sintering, can directly enter furnace reduction, and reduction kinetics condition is filled Point.
(4) recovery rate of soda and iron is higher, and the tailings after 95% or more and 90% or more, extraction is entirely used for respectively Aluminous cement clinker is produced, red mud utilization rate is up to 100%.
Detailed description of the invention
Fig. 1 is the method flow signal that a kind of iron red mud of the invention is vortexed that melting and reducing dealkalize mentions the direct cement of iron Figure.
Specific embodiment
The ingredient of clinker contains CaO 63~66%, SiO by mass percentage in the embodiment of the present invention220~22%, Al2O34~6%, Fe2O32.5~5%.
The Na of liquid slag in the embodiment of the present invention2O mass percent is less than 0.5%.
Wear resistant cast iron product in the embodiment of the present invention is the wear-resisting casting of trade mark HBW555Cr13 (ISO 21988/JN/HB) Iron.
Temperature in the embodiment of the present invention when raw material drying is 150~200 DEG C.
Vortex stirring reduction of the invention refers to a kind of method disclosed in invention " vortex stirring method for melting reduction iron making ", Related vortex stirring reduction high temperature furnace is the equipment that this method is.
A kind of vortex stirring method for melting reduction iron making of the invention is the patent application of publication number CN106435080A.
It is that calcareous raw material, siliceous raw material and/or ferriferous raw material is added that component is adjusted in the embodiment of the present invention.Calcareous raw material choosing With at least one of lime stone, carbide slag；Siliceous raw material selects kaolin, clay, flyash, at least one in mine tailings Kind；Ferriferous raw material selects at least one of iron red mud, scum, steel slag.
The rate of recovery >=95% of sodium in the embodiment of the present invention, the rate of recovery >=90% of iron.
The present invention will be further described in detail below with reference to the embodiments.
Embodiment 1
(1) prepare raw material iron red mud, red TFe 40% by mass percentage of high-speed rail, Na2O 2%；
(2) by mass percent≤1% of raw material drying to water, dehydrated raw material is obtained；By dehydrated raw material with it is solid carbonaceous Mixture is made in reducing agent and slag former mixing, and the directly swirl center of blowing to vortex stirring high temperature furnace, mixture is involved in In molten bath, 60min is restored in 1300 DEG C of progress vortex stirrings；The solid carbonaceous reducer is coking coal, solid carbonaceous reduction The molar ratio of Fe is 1.2 in the amount and raw material of agent, and slag former is CaO and CaF2Mixture, wherein CaO press mixture basicity For 1.0 additions, CaF2Account for the 30% of CaO gross mass: sodium enters flue gas in vortex stirring reduction process, returns through flue gas dust collection system It receives；
(3) molten iron and liquid slag formed after restoring is layered, and carries out continuous overflow separation；Add into the molten iron isolated Enter ferrochrome and manganese iron is directly smelted and cast and wear resistant cast iron product is made；
(4) liquid slag isolated adjusts component in smelting furnace and complies with clinker requirement, then through being air-cooled to Room temperature, then clinker is made through broken and grinding；CaO, SiO in clinker2、Al2O3And Fe2O3Content be respectively 63%, 20%, 6% and 5%, meet the component requirements of clinker.
Embodiment 2
(1) prepare raw material iron red mud, red TFe 20% by mass percentage of high-speed rail, Na2O 15%；
(2) by mass percent≤1% of raw material drying to water, dehydrated raw material is obtained；By dehydrated raw material with it is solid carbonaceous Mixture is made in reducing agent and slag former mixing, and the directly swirl center of blowing to vortex stirring high temperature furnace, mixture is involved in In molten bath, 10min is restored in 1600 DEG C of progress vortex stirrings；The solid carbonaceous reducer is coking coal, solid carbonaceous reduction The molar ratio of Fe is 1.4 in the amount and raw material of agent, and slag former is CaO and CaF2Mixture, wherein CaO press mixture basicity For 11 additions, CaF2Account for the 20% of CaO gross mass: sodium enters flue gas in vortex stirring reduction process, returns through flue gas dust collection system It receives；
(3) molten iron and liquid slag formed after restoring is layered, and carries out continuous overflow separation；Add into the molten iron isolated Enter ferrochrome and manganese iron is directly smelted and cast and wear resistant cast iron product is made；
(4) liquid slag isolated adjusts component in smelting furnace and complies with clinker requirement, then through being air-cooled to Room temperature, then clinker is made through broken and grinding；CaO, SiO in clinker2、Al2O3And Fe2O3Content be respectively 65%, 21%, 5% and 2.5%, meet the component requirements of clinker.
Embodiment 3
(1) prepare raw material iron red mud, red TFe 30% by mass percentage of high-speed rail, Na2O 10%；
(2) by mass percent≤1% of raw material drying to water, dehydrated raw material is obtained；By dehydrated raw material with it is solid carbonaceous Mixture is made in reducing agent and slag former mixing, and the directly swirl center of blowing to vortex stirring high temperature furnace, mixture is involved in In molten bath, 40min is restored in 1400 DEG C of progress vortex stirrings；The solid carbonaceous reducer is coking coal, solid carbonaceous reduction The molar ratio of Fe is 1.5 in the amount and raw material of agent, and slag former is CaO and CaF2Mixture, wherein CaO press mixture basicity For 1.4 additions, CaF2Account for the 10% of CaO gross mass: sodium enters flue gas in vortex stirring reduction process, returns through flue gas dust collection system It receives；
(3) molten iron and liquid slag formed after restoring is layered, and carries out continuous overflow separation；Add into the molten iron isolated Enter ferrochrome and manganese iron is directly smelted and cast and wear resistant cast iron product is made；
(4) liquid slag isolated adjusts component in smelting furnace and complies with clinker requirement, then through being air-cooled to Room temperature, then clinker is made through broken and grinding；CaO, SiO in clinker2、Al2O3And Fe2O3Content be respectively 66%, 22%, 4%, 4%, meet the component requirements of clinker.

Claims (5)

1. the method that a kind of vortex melting and reducing dealkalize of iron red mud mentions the direct cement of iron, it is characterised in that according to the following steps into Row:
(1) prepare raw material iron red mud, red 20~40% TFe by mass percentage of high-speed rail, Na2O 2~15%, Al2O315~ 25%, SiO215~25%, CaO 5~25%, H2O 5~20%；
(2) by mass percent≤1% of raw material drying to water, dehydrated raw material is obtained；By dehydrated raw material and solid carbonaceous reduction Mixture is made in agent and slag former mixing, and the directly swirl center of blowing to vortex stirring high temperature furnace, mixture is involved in molten bath In, 10~60min is restored in 1300~1600 DEG C of progress vortex stirrings；The solid carbonaceous reducer is coking coal, solid carbon The molar ratio of Fe is 1.2~1.5 in the amount and raw material of matter reducing agent, and slag former is CaO and CaF2Mixture, wherein CaO is pressed The basicity of mixture is 1.0~1.4 additions, CaF2Account for the 10~30% of CaO gross mass:
(3) molten iron and liquid slag formed after restoring is layered, and carries out continuous overflow separation；Chromium is added into the molten iron isolated Iron and manganese iron, which are directly smelted and cast, is made wear resistant cast iron product；
(4) liquid slag isolated adjusts component in smelting furnace and complies with clinker requirement, then through being air-cooled to room temperature, Clinker is made through broken and grinding again.
2. the method that a kind of iron red mud vortex melting and reducing dealkalize according to claim 1 mentions the direct cement of iron, Be characterized in that the calculating formula of the basicity by:
In formula, mCaO is the quality of calcium oxide in mixture, mAl2O3For the quality of aluminium oxide in mixture, mSiO2For mixture The quality of middle silica.
3. the method that a kind of iron red mud vortex melting and reducing dealkalize according to claim 1 mentions the direct cement of iron, It is characterized in that the rate of recovery >=90% of iron.
4. the method that a kind of iron red mud vortex melting and reducing dealkalize according to claim 1 mentions the direct cement of iron, It is characterized in that the rate of recovery >=95% of sodium.
5. the method that a kind of iron red mud vortex melting and reducing dealkalize according to claim 1 mentions the direct cement of iron, It is characterized in that in step (2), sodium enters flue gas in vortex stirring reduction process, recycles through flue gas dust collection system.
CN201910290643.7A 2019-04-11 2019-04-11 A kind of method that the melting and reducing dealkalize of iron red mud vortex mentions the direct cement of iron Pending CN109970368A (en)

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PCT/CN2019/090842 WO2020206833A1 (en) 2019-04-11 2019-06-12 Method of vortex melting, reducing, dealkalization, iron extraction and direct cement production of high-iron red mud

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CN113087328A (en) * 2021-04-26 2021-07-09 中国科学院地球化学研究所 Method for removing sodium and potassium in red mud by using manganese slag leachate
CN113174455A (en) * 2021-04-28 2021-07-27 东北大学 Comprehensive utilization method for smelting reduction of high-iron red mud by side-top combined blowing
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CN113087328A (en) * 2021-04-26 2021-07-09 中国科学院地球化学研究所 Method for removing sodium and potassium in red mud by using manganese slag leachate
CN113174455A (en) * 2021-04-28 2021-07-27 东北大学 Comprehensive utilization method for smelting reduction of high-iron red mud by side-top combined blowing
CN113174456A (en) * 2021-04-28 2021-07-27 东北大学 Comprehensive utilization method for smelting reduction of high-iron red mud by bottom-top combined blowing

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Application publication date: 20190705