CN107385197B - A kind of resource utilization method of red mud - Google Patents
A kind of resource utilization method of red mud Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
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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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/0409—Waste from the purification of bauxite, e.g. red mud
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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
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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
- C04B7/32—Aluminous cements
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- 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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
A kind of resource utilization method of red mud, the following steps are included: (1) slurry reproducibility converts: by red mud, restore transforming agent, slurry is made in lime and water, in temperature 60 C~350 DEG C, reproducibility heat chemistry causticization reduction reaction is carried out under the conditions of pressure 0.1013MPa~4.5MPa, it displaces the alkali combined in the mineral such as alumino-silicate in red mud and forms strong basicity slurry, and ferroso-ferric oxide is converted by the Iron Oxide Minerals reduction in red mud in strong basicity slurry, and/or by iron contained in red mud and chromium, titanium, vanadium, gallium, the synchronous reduction such as scandium circulates the isomorphous Ferrite that the elements such as chromium titanium vanadium gallium scandium are formed in ferrite lattice；(2) magnetic separation mentions iron；(3) separation mentions alkali；(4) aluminosilicate mineral utilizes.The present invention have many advantages, such as low energy consumption, economy, it is without secondary pollution, can three big main components in effective recycling red mud.
Description
Technical field
The present invention relates to environmental protection and waste utilization technical fields, and in particular to a kind of resource utilization method of red mud.
Background technique
Currently, China has been alumina producing big country, the world, and China's aluminium oxide production capacity has accounted for global aggregated capacity within 2015
51.98% up to 7160.27 ten thousand tons, China's aluminium oxide yield has accounted for the 51.18% up to 5898.90 ten thousand tons of global aluminium oxide total output,
In addition 2017 newly 6,000,000 tons of operation production capacity, aggregated capacity will be expected to reach 80,000,000 tons, 2017 annual outputs are expected to reach 65,600,000
Ton.Industrial oxidation aluminium production process almost all is alkaline process at present, mainly there is Bayer process, sintering process and Bayer-sintering combination method
Technique is with alkali (NaOH or NaCO3) processing bauxite, so that the alumina leaching in bauxite is switched to sodium aluminate solution, alumina
The impurity such as iron, silicon, calcium, magnesium, titanium, scandium, gallium, chromium, vanadium, strontium, fluorine in mine raw material enter in insoluble matter residue, separate the residual of discharge
Slag (waste) because take on a red color containing a large amount of iron oxide thus referred to as red mud.General one ton of aluminium oxide of every production is about discharged 1.0~
1.3t red mud, part are even up to 2~3t.Additive in the bauxite and production process of different process, heterogeneity
Material composition it is different, the red mud component difference of discharge is larger, and in general, the main chemical compositions of red mud from sintering process are CaO
And SiO2, secondary chemical Al2O3And Fe2O3, alkali content is lower, highest among calcium oxide content three, mixed combining method and burning
The ingredient of the arranged red mud of connection is roughly the same, and the content of iron oxide and aluminium oxide is lower, and mixed combining method alkali content is up to more than ten for most
Height, as Shanxi, Shandong, Guizhou and Central Region, Zhengzhou use sintering process He wave the chemical component of aluminium manufacturer's red mud of ∕ or mixed combining method
It moves in Fe2O35~9.5%, Al2O36.4~9.5%, SiO220~26%, CaO 36~47%, TiO22.5~7.5%, K2O
0.2~0.8%, Na2O 3~12%, MgO 1.5~2.5%, Loss 8~16.5%, average out to Fe2O3 8.0%、Al2O3 8.1%、
SiO2 20.4%、CaO 45%、TiO2 5.%、K2O 0.4%、Na2O 4.8%,MgO2.1%,Loss 8.3%；Bayer process red mud oxygen
It is high to change iron and alumina content, for iron oxide up to the 28%~34% of total amount, aluminium oxide is 17% or so of total amount, alkali content is lower,
Calcium oxide content is low, as the chemical component of the Bayer process red mud of Pingguo aluminium manufacturer is generally Fe2O328~34%, Al2O316~
19%、SiO27~9%, CaO 18~21%, TiO2 6.5~7.5%, K2O0.04~0.1%, Na2O 2.2~8.6%, MgO 0.3
~0.8%, Loss 11~14%.
The partial size of red mud particle substantially>0.075mm 3~6%, 0.075~0.005mm 87~92%,<0.005mm 4
~7%；And the essential mineral of red mud be aragonite and calcite, opal, gibbsite, goethite, there are also a small amount of titanium mineral,
Siderite, waterglass, sodium aluminate, trona and caustic soda.Wherein aragonite and calcite content are often up to 50~65%, aragonite, calcite
Cementation is played with composition skeleton, needle magnesium mine, gibbsite, opal, waterglass etc. such as siderites, there is red mud cementing
The hole rack-like structure that structure-condensate, structure-collection plastochondria, 3 level structure of structure-aggregate are constituted；Keep the specific surface area of red mud total
Higher fluctuation is in 186.9m on body2/ g~64.09m2/ g, and amplitude of variation is big；2840~2870g/m of specific gravity3.Due to red mud
Mineral dispersion degree and lattice structure otherness are significant, and not only water content is big for red mud, and water-holding capacity is up to 79.03~93.2%, vibration
When condensate rate up to 5~14.93%.The red mud newly stacked is in liquid-plastic state, soft, easily-deformable, easy liquefaction.High water-holding capacity can cause
Red mud piling up is still in soft modeling-plastic flow mud matter state for many years.But after stacking a period of time under certain conditions, by de-
Water, bleed, recrystallization continuous cropping are with can dry hardening.
The generation process and its ingredient of red mud determine that the pollutant in red mud and its attached liquid mainly has alkali, heavy metal, fluorine
Compound, chloride, sulfate etc., and the pH value of red mud is up to 10.3~12,4.89~8.6mg/l of content of fluoride, leachate
PH value up to 12.1~14,11.5~26.7mg/l of content of fluoride.Therefore, it is useless to belong to strong basicity nocuousness for red mud (containing attached liquid)
Slag need to carry out harmlessness disposing.
Foreign countries, the red mud of alumina producing enterprise originally mainly filled out extra large stockpiling, and red mud is filled out sea stockpiling and prohibited by explicit order now
Only, stockpiling of building a dam has become main processing mode.The country, red mud is largely discharged into culvert undderground river and simple earthing is filled out
It buries.In recent years, with the reinforcing of environmental protection, red mud is largely built a dam stockpiling, the accumulation super several hundred million tons of volume of cargo in storage.Red mud dump construction
It is high with maintenance cost, and the red mud waste liquid leakage of strong basicity, high salinity will cause alkalization of soils, polluted underground water source is also broken
Surrounding enviroment are broken, serious environmental problem is brought, the environmental protection pressure of aluminum i ndustry is caused to increase severely, it has also become influence China's aluminum i ndustry
The thorny problem of sustainable development.
Currently, the environmental risk of red mud pilling causes the attention of government, each alumina producing state already, and reaches common understanding:
The key for solving the problems, such as red mud is research and development red mud comprehensive utilization technique.It is big around the resource utilization of red mud and harmless treatment two
Theme, lot of domestic and foreign scientific research institutions and technical staff expand multi-field, multi-disciplinary red mud comprehensive utilization technique research.Greatly
Cause can summarize are as follows:
1) cement technology is produced using red mud
It is always as the great support items of the national science and technology in China, from the sixties in last century using red mud production cement
Huge manpower, fund are persistently put into.
It is specifically that SiO necessary to portland cement is contained with red mud from sintering process using red mud production cement technology2、
Fe2O3、Al2O3, the components such as CaO and the lower feature of alkali content, replace clay etc. as the original of manufacture of cement using red mud from sintering process
Material.Domestic Shandong Aluminum Plant begins the sixties in last century, replaces raw clay using red mud from sintering process, is successfully given birth to using wet processing
Ordinary portland cement is produced.But because alkali content is high and kiln condition, product quality is relatively low the problems such as, fail to promote and apply, after more because
Limitation of the national new standard to cement-stabilized soil, causes the doping level of red mud from sintering process in manufacture of cement little.
China Aluminum Co., Ltd in 2008 assumes responsibility for Eleventh Five-Year Plan national science and technology supporting plan project " at red mud harmless again
Reason and application technology as the second resource research " and " red mud dealkalization is tested and studied using dealkalize red mud production ordinary portland cement " item
Mesh is used for manufacture of cement using the dealkalize of two-phase method lime to red mud from sintering process, but because of technology and sake of economy, the red mud is harmless
Change and still has uncertainty so far from effective industrial application using technology and two-phase method lime dealkalize technology.
2) novel wall material technology is produced using red mud
In terms of using red mud production new wall material, the manpower and fund of China's investment are also very huge, have carried out a large amount of
Technological development, as China Aluminum Corporation began both to have carried out with great project verification with part red mud and powdered silica material in 2000
A kind of microporous calcium silicate thermal insulating material is made in material, lime, fibre reinforced materials etc., agitated, gelation, molding, steam pressure and drying
Expect heat insulating material, but energy consumption is higher, and the consumption of red mud is limited.Other as national major scientific and technological projects also
" red-mud coal ash fired brick " was unfolded as national " 95 " tackling of key scientific and technical problems major project in 1997, " red-mud coal ash is unburned
Brick " is in the baking-free brick of red mud novel wall material of 2004 Nian Youzhong aluminium postdoctoral workstations and domestic well-known university's cooperation development
Technology and " red mud from sintering process and Bayer process red mud fired brick " were corrected by capital construction commission's wall the THE INDUSTRIAL TRIAL skill under supporting in 2008
Art research etc., but these national scientific and technological result projects are not all because the problems such as less economical and product cracking, scum, is able to achieve
Industrialization.
3) red mud is as roadbed material technology
Red mud is with red mud from sintering process and flyash, lime, cement etc. for primary raw material as pavement material, in 2004
Aluminium implements Demonstration Application engineering by cooperation by production, study and research.It is low in cost that red mud makees roadbed material, can also save a large amount of Huang
Soil resource, but objectively still only displaced pollution.
4) the agricultural fertilizer technology of red mud system
The agricultural fertilizer technology of red mud system include red mud drying is made to powder or be made graininess as soil conditioner it is (also known as red
Mud siliceous fertilizer or silico-calcium compound fertilizer) or to add part phosphorus nitrogen potassium and/or organic waste that graininess multielement is made the red mud compound
Fertilizer is for ploughing.Though red mud agricultural fertilizer can dissolve the environmental protection pressure problem of alumina producing enterprise really, essence is will to concentrate
Pollution transportation diffusion.
5) valuable metal technology is extracted from red mud
Containing the yttriums such as titanium, scandium, gallium, niobium, tantalum, zirconium, thorium and uranium in red mud, therefore, extracted from red mud titanium,
The valuable metals element such as scandium, gallium, niobium, tantalum is always the project of domestic and international scientific research personnel's research.Currently, the main method taken is
High temperature reduction melting and acid leaching extraction method, but complex process, energy consumption are high, and secondary pollution is serious, there is no so far can economy have
The method that the enrichment of effect ground is extracted without generating secondary pollution.
6) Bayer process red mud selects iron technology
Fe in Bayer process red mud2O3 Content greatly up to 20%~40%, therefore, recycling iron from Bayer process red mud is always state
The target that inside and outside scientific and technical personnel make great efforts.The method for recycling iron in Bayer process red mud at present is broadly divided into metallurgical method and physics choosing
Mine method two major classes.
Reducing agent (predominantly C, CO, H is mainly added in metallurgical method2) in high temperature furnace reducing and smelting be separated into the pig iron or
The bloodstone of weak magnetic in red mud and goethite high temperature reduction are fired into magnetic iron ore, then magnetic separation separates again；
Physical upgrading method is mainly FLOTATION SEPARATION or use magnetic separation recovery ferriferous oxide.
Although the industrialization at present of metallurgical method and physical upgrading method, and Bayer process red mud magnetic selection method therein
Taken turns magnetic separation purification can be obtained some more high-grade iron ore concentrates more, but because the ferriferous oxide in red mud is mostly ultra-fine and height point
It dissipates and is covered by aluminosilicate mineral and wrapped up in, either current metallurgy method or physics magnetic method, actually technology and economy are all
It is not satisfactory, and still there are a large amount of waste residues to need to handle.
7) other application
There are also " research and development that red mud fills efficient cementing agent " using technical research for the harmless resource utilization of red mud
[" 95 " state key science and technology (tackling key problem) plans thematic project], " producing ceramic filter material using red mud " (aluminium is developed in 2003
Utilize red mud 27%~35%, flyash 35%, gangue 5%~6%, tailing about 30% produce novel environment friendly ceramic filter material), " red mud
Compound flame redundant " (Eleventh Five-Year Plan national science and technology supporting plan project), " red mud prepares ecological restoration material " (" 11
Five " national science and technology supporting plan projects), " red mud devitrified glass " (with red mud and chrome ore slag, quartz sand, calcined soda for industry,
The sintering of the grindings such as feldspar), " red mud makees circulating fluid bed boiler desulfurization agent ", " red mud production steel-making covering slag " etc..These technologies
Or product is at present or in progress or because of product quality problem or because of economy and high energy consumption and secondary pollution problem, from work
The target of a large amount of consumption red muds of industryization application is still remote.
The harmless resource utilization comprehensive utilization of today, red mud have become the whole world is paid close attention to jointly one big problem.Although state
It is inside and outside to have done a large amount of research work in this respect, a large amount of achievement is achieved, also develops many red mud products, but more
The experience and lessons that red mud comprehensively utilizes over year show: containing in red mud largely includes heavy in conjunction with alkali and the metal oxide of complexity
Metal either makees inorganic filler even using red mud containing alkali as raw material, or is the building such as to produce cement, brick material and build the road
Material, alkali are all harmful constituents, directly affect the quality and use scope of product, seriously restrict red mud comprehensive utilization ratio
It improves.And can this industrial residue of red mud utilize the effective solution for involving these problems to greatest extent.How effectively
Using the ingredient and physical characteristic of red mud, using the Bayer process red mud of red mud especially high-speed rail as a kind of raw material, low energy consumption, economy
And it is without secondary pollution, it is reasonable and sufficiently effective recycle red mud in major main component implement resource utilization,
Have become an extremely urgent task at this stage.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of physical characteristic using red mud and main mineral constituent are special
Point, low energy consumption, economic and without secondary pollution, reasonable and sufficiently effective three big main components recycled in red mud
Implement the method for resource utilization.
The technical solution adopted by the present invention to solve the technical problems is: a kind of resource utilization method of red mud, including
Following steps:
(1) slurry reproducibility converts: slurry is made in red mud, reduction transforming agent, lime and water, in temperature 60 C~350
DEG C, reproducibility heat chemistry causticization reduction reaction is carried out under the conditions of pressure 0.1013MPa~4.5MPa, displace aluminosilicate in red mud
The alkali combined in the mineral such as salt forms strong basicity slurry, and the Iron Oxide Minerals in red mud are restored conversion in strong basicity slurry
It is circulated in ferrite lattice for ferroso-ferric oxide, and/or by the reduction synchronous with chromium, titanium, vanadium, gallium, scandium etc. of iron contained in red mud
Form the isomorphous Ferrite of the elements such as chromium titanium vanadium gallium scandium；
(2) magnetic separation mentions iron: four oxidations three in a manner of magnetic separation in the resulting reproducibility conversion slurry of separation and Extraction step (1)
Iron and Ferrite, water washing cleaning obtain the iron ore concentrate containing ferroso-ferric oxide and Ferrite, and iron ore concentrate is used as iron-smelting raw material or work
The raw material of the valuable metal and iron that wherein melt admittedly for separation and Extraction, remaining slurry are sent to subsequent processing；
(3) separation mentions alkali: the remaining slurry of step (2) is separated by filtration, obtains filter residue and aqueous slkali, filter residue water washing cleaning,
Ca aluminosilicate mineral slag is obtained, aqueous slkali is by well known method concentrated base or soda ash；
(4) aluminosilicate mineral using: using the resulting ca aluminosilicate mineral slag of step (3) as relevant production with former
Material: material raw material 1. is blended as production activity；2. as low-grade silicate cementing material or anhydrite cementitious material is produced
Use raw material；3. directly supplying cement plant or brickmaking factory as raw material；4. as production aluminium oxide and/or titanium dioxide and/or white
The raw material of carbon black.
Further, in step (1), the red mud is the waste residue in alkaline process alumina producing, and preferably Bayer process high-speed rail is red
Mud.
Further, in step (1), the described reduction transforming agent be hydrazine with efficient strong reducing property and/or hydrazine hydrate and/
Or methyl hydrazine and/or uns-dimethylhydrazine, preferably hydrazine and/or hydrazine hydrate.
Further, in step (1), the dosage of the reduction transforming agent works as meter with mole (mol), contained by red mud
The equivalent proportion of the di-iron trioxide molal quantity (mol) of ferro element conversion is 0.1~1.0:1.0(preferably 0.15~0.45:1.0).
Further, in step (1), the dosage of the lime is the 6~65% of red mud dry weight.
Further, in step (1), in the slurry, red mud, reduction transforming agent, the gross mass of lime and the quality of water
Than for 1:1~15.
Further, in step (1), the reaction time is 0.5h~12h.
Further, in step (1), other hydrazines that quality is the reduction transforming agent dosage 30~300% can be also added and spread out
Biological (such as hydrazine amine, benzyl hydrazine), alcohol ethers compound (such as ethylene glycol, glycerol), ammoniac compounds (such as ammonia, methylamine),
One or more of ferrous salt (such as ferrous sulfate) is used as assisted Reduction transforming agent.
Further, in step (4), the heat treatment kiln be well known fluidized bed furnace or fluid bed furnace or vertical heater or
Rotary kiln or cyclone furnace or tube furnace.
Further, if needing vented gasses or steam to use by well known oxidizing decontamination process during red mud resource utilization
Oxidant (such as ferrate, hypochlorite, chlorine dioxide) solution may wherein contain micro- as cleanser atomization purification
Measure hydrazine；Resulting three categories raw material (smart iron ore, alkali, ca aluminosilicate mineral) depending on the circumstances or the needs of the situation whether, using 0.01~2.00%
Decontaminant solutions purify wherein remaining Determination of Trace Hydrazine.
Further, in step (2) and step (3), water lotion Returning utilization is in step (1).
Further, in step (4), material raw material 1. is blended as production activity: ca aluminosilicate mineral slag is sent at heat
In 650 DEG C~1200 DEG C roastings in reason kiln, activity is made and blends material, after directly admixture or grinding are made in supply cement plant
Supply cement plant, concrete mixing plant make admixture；2. as low-grade silicate cementing material or anhydrite gelling material is produced
Material raw material: the waste gypsum that ca aluminosilicate mineral slag adds quality to be equivalent to ca aluminosilicate mineral slag 8~90% is sent into together at heat
In reason kiln in 700 DEG C~1200 DEG C oxidizing atmospheres calcination for activation, be made with gelation activity matured slag, matured slag grinding
Building material is used for directly as cementitious material afterwards.
Beneficial effects of the present invention:
1) method is simple, and treating capacity is big and without secondary pollution.
2) the three categories component based on smart iron ore, alkali and ca aluminosilicate is directly decomposed into after converting red mud, respectively as
Raw material is rationally applied to different enterprises and produces different products as alternative raw material, conducive to resource-effective and circular economy
Development.
Specific embodiment
The invention will be further described with reference to embodiments.
Embodiment 1
The Bayer process red mud for selecting certain factory fresh, butt chemical component are Fe2O3 32.72%、Al2O3 17.04%、
SiO27.26%、CaO 18.89%、TiO2 6.45%、K2O 0.09%、Na2O 5.29%,MgO 0.33%,Loss 10.97%；Also
Former transforming agent selects commercially available hydrazine (content 98.5%)；Lime selects commercially available white lime (product after block ash aquation impurity elimination)；Only
Agent selects commercially available ClO 2 solution to be diluted to concentration 0.10% for purification gas and steam and resulting raw material；By such as
Lower step carries out the resource utilization of red mud:
(1) slurry reproducibility converts: slurry (red mud, hydrazine, the gross mass of lime and water is made in red mud, hydrazine, lime and water
Mass ratio be 1:8), the dosage of hydrazine works as meter with mole (mol), with ferro element contained in red mud conversion di-iron trioxide rub
Your number (mol) equivalent proportion is 0.4:1.0, and the dosage of lime is 240 DEG C of 60%, the Yu Wendu of red mud butt quality, pressure
Reproducibility heat chemistry causticization reduction reaction is carried out under the conditions of 3.35MPa, reaction time 2h, after conversion terminates, slurry color switchs to
Brownish black, sedimentation are fast；
(2) magnetic separation mentions iron: magnetic separation separation and Extraction reproducibility converts the ferroso-ferric oxide and Ferrite in slurry, and water is cleaned
Change, obtains iron ore concentrate, water lotion Returning utilization, remaining slurry is sent to subsequent processing；
Detection: the iron ore concentrate iron-content 69.38% of extraction, iron recovery 94.73% in red mud are recycled as iron-smelting raw material；
(3) separation mentions alkali: remaining slurry being separated by filtration, filter residue and aqueous slkali are obtained, filter residue water washing cleaning obtains ca aluminosilicate
Mineral slag, water lotion Returning utilization, aqueous slkali are passed through CO2Soda ash is made in concentration；
Detection；Ca aluminosilicate slag contains alkali (R2O) 0.89%, alkali recovery 95.38%；
(4) aluminosilicate mineral using: using ca aluminosilicate mineral slag as production activity blend material raw material: by aluminosilicate
Calcium mineral slag is sent into heat treatment kiln and is roasted 45 minutes in 900 DEG C, and activity is made and blends material, blends material with this activity and replaces
The slag (quality proportioning 35%) of cement is ground, it is suitable with the physical and mechanical property of cement ground with slag.
Embodiment 2
The Bayer process red mud for selecting certain Ba Chang to store up, butt chemical component Fe2O3 29.76%、Al2O3 16.47%、
SiO27.16%、CaO 19.12%、TiO2 6.54%、K2O 0.11%、Na2O 7.06%,MgO 0.26%,Loss12.57%；Reduction
Transforming agent selects commercially available hydrazine hydrate (content 80%)；Assistant reducing agent selects ferrous sulfate (for the byproduct of titanium powder plant)；Stone
Ash selects commercially available quick lime；Cleanser select commercially available ClO 2 solution be diluted to concentration 0.10% for purification gas and
Steam and resulting raw material；The resource utilization of red mud is carried out as follows:
(1) slurry reproducibility convert: by red mud, hydrazine hydrate, lime and water be made slurry (red mud, hydrazine hydrate, lime it is total
The mass ratio of quality and water is 1:10), the dosage of hydrazine hydrate works as meter with mole (mol), converts with ferro element contained in red mud
Di-iron trioxide molal quantity (mol) equivalent proportion 0.23:1.0, the dosage of lime is the 43% of red mud butt quality, in slurry
Be additionally added assistant reducing agent, dosage be hydrazine hydrate quality 180 DEG C of 60%, Yu Wendu, pressure 1.003MPa under the conditions of restored
Property heat chemistry causticization reduction reaction, reaction time 4h, after conversion terminates, slurry color switchs to black, and sedimentation is fast；
(2) magnetic separation mentions iron: magnetic separation separation and Extraction reproducibility converts the ferroso-ferric oxide and Ferrite in slurry, and water is cleaned
Change, obtains iron ore concentrate, water lotion Returning utilization, remaining slurry is sent to subsequent processing；
Detection: the iron ore concentrate iron-content 68.75% of extraction, iron recovery 92.94% in red mud are recycled as iron-smelting raw material；
(3) separation mentions alkali: remaining slurry being separated by filtration, filter residue and aqueous slkali are obtained, filter residue water washing cleaning obtains ca aluminosilicate
35% concentrated base is made in mineral slag, water lotion Returning utilization, aqueous slkali concentration；
Detection；Ca aluminosilicate slag contains alkali (R2O) 0.94%, alkali recovery 92.78%；
(4) aluminosilicate mineral using: using ca aluminosilicate mineral slag as producing low-grade silicate cementing material original
Material: the fluorgypsum that ca aluminosilicate mineral slag adds quality to be equivalent to ca aluminosilicate mineral slag 10.2% is mixed, in 1100 DEG C of oxidisability
The matured slag with gelation activity is made in calcination for activation 30min in atmosphere, matured slag grinding to 80um tails over 5% powder, directly
It is pressed into shaped brick as cementitious material substitution low grade (27.5MPa) cement system, service performance and product performance index are suitable, nothing
Scum phenomenon.
Embodiment 3
The Bayer process red mud for selecting certain factory fresh, butt chemical component are Fe2O3 34.17%、Al2O3 16.31%、SiO2
7.46%、CaO 18.46%、TiO2 5.29%、K2O 0.08%、Na2O 6.09%,MgO 0.31%,Loss 10.21%；Reduction turns
Agent selects commercially available hydrazine hydrate (content 60%)；Lime selects commercially available white lime (product after block ash aquation impurity elimination)；Purification
Agent selects commercially available ClO 2 solution to be diluted to concentration 0.10% for purification gas and steam and resulting raw material；By as follows
The resource utilization of step progress red mud:
(1) slurry reproducibility convert: by red mud, hydrazine hydrate, lime and water be made slurry (red mud, hydrazine hydrate, lime it is total
The mass ratio of quality and water is 1:9), the dosage of hydrazine works as meter with mole (mol), three oxygen with ferro element contained in red mud conversion
Changing two iron molal quantity (mol) equivalent proportions is 0.6:1.0, and the dosage of lime is 85 DEG C of 60%, the Yu Wendu of red mud butt quality, presses
Power 0.101MPa(normal pressure) under the conditions of carry out reproducibility heat chemistry causticization reduction reaction, reaction time 8h, conversion terminate after, slurry
Color switchs to brownish black, and sedimentation is fast；
(2) magnetic separation mentions iron: magnetic separation separation and Extraction reproducibility converts the ferroso-ferric oxide and Ferrite in slurry, and water is cleaned
Change, obtains iron ore concentrate, water lotion Returning utilization, remaining slurry is sent to subsequent processing；
Detection: the iron ore concentrate iron-content 70.31% of extraction, iron recovery 91.87% in red mud are recycled as extracting valuable gold
Belong to the raw material with iron；
(3) separation mentions alkali: remaining slurry being separated by filtration, filter residue and aqueous slkali are obtained, filter residue water washing cleaning obtains ca aluminosilicate
Mineral residue, water lotion Returning utilization, aqueous slkali are passed through CO2Soda ash is made in concentration；
Detection；Ca aluminosilicate slag (R containing alkali2O) 0.83%, alkali recovery 94.78%；
(4) aluminosilicate mineral using: using ca aluminosilicate mineral slag as ordinary portland cement production raw material, for certain
The whole siliceous raw materials and part aluminum raw material of central laboratory, sulphate aluminium cement factory substitution production sulfoaluminate clinker ingredient,
Part calcareous raw material is handled by well known calcium sulphoaluminate clinker ingredient and grinding requirement according to feedback, is roasted 35 minutes through 1380 DEG C,
Sulfoaluminate clinker is made, performance indexes is normal, alkali content 0.03%.
Embodiment 4
The Bayer process red mud for selecting certain factory fresh, butt chemical component are Fe2O3 33.17%、Al2O3 18.67%、SiO2
5.97%、CaO 17.85%、TiO2 7.53%、K2O 0.10%、Na2O 5.73%,MgO 0.27%,Loss 9.76%；Reduction conversion
Commercially available hydrazine (content 98%) is selected in agent；Assistant reducing agent selects commercially available liquefied ammonia and ethylene glycol 1:1 in mass ratio；Lime is selected
Commercially available white lime；Cleanser select commercially available ClO 2 solution be diluted to concentration 0.10% for purification gas and steam and
Resulting raw material；The resource utilization of red mud is carried out as follows:
(1) slurry reproducibility converts: by (the total matter of red mud, hydrazine hydrate, lime of slurry made of red mud, hydrazine, lime and water
The mass ratio of amount and water is 1:9), the dosage of hydrazine works as meter with mole (mol), three oxidations with ferro element contained in red mud conversion
Two iron molal quantity (mol) equivalent proportions are 0.38:1.0, and the dosage of lime is the 9.3% of red mud butt quality, also added with auxiliary in slurry
Reducing agent is helped, dosage is progress reproducibility heat chemistry causticization under the conditions of 250 DEG C of 90%, Yu Wendu, the pressure 3.98MPa of hydrazine quality
Reduction reaction, reaction time 0.5h, after conversion terminates, slurry color switchs to black, and sedimentation is fast；
(2) magnetic separation mentions iron: magnetic separation separation and Extraction reproducibility converts the ferroso-ferric oxide and Ferrite in slurry, and water is cleaned
Change, obtains iron ore concentrate, water lotion Returning utilization, remaining slurry is sent to subsequent processing；
Detection: the iron ore concentrate iron-content 70.62% of extraction, iron recovery 91.86% in red mud are recycled as iron-smelting raw material；
(3) separation mentions alkali: remaining slurry being separated by filtration, filter residue and aqueous slkali are obtained, filter residue water washing cleaning obtains ca aluminosilicate
Mineral residue, water lotion Returning utilization, aqueous slkali are passed through CO2Soda ash is made in concentration；
Detection；Ca aluminosilicate slag (R containing alkali2O) 0.93%, alkali recovery 91.24%；
(4) aluminosilicate mineral utilizes: gained ca aluminosilicate mineral slag A/S 3.13, TiO211.23%, as extraction oxygen
Change the raw material of aluminium, titanium dioxide, white carbon black.
Embodiment 5
The combination method red mud that certain factory is fresh is selected, butt chemical component is Fe2O3 8.75%、Al2O3 7.26%、SiO2
23.28%、CaO 40.34%、TiO2 3.63%、K2O 0.41%、Na2O 5.26%,MgO 1.57%,Loss8.59%；Reduction conversion
Commercially available hydrazine (content 98%) is selected in agent；Lime selects commercially available quick lime；Cleanser selects commercially available ClO 2 solution dilution
To concentration 0.10% for purification gas and steam and resulting raw material；The resource utilization of red mud is carried out as follows:
(1) slurry reproducibility converts: slurry (red mud, hydrazine, the gross mass of lime and water is made in red mud, hydrazine, lime and water
Mass ratio be 1:8), the dosage of hydrazine works as meter with mole (mol), with di-iron trioxide molal quantity (mol) equivalent proportion in red mud
For 0.35:1.0, the dosage of quick lime be red mud butt quality 180 DEG C of 19%, Yu Wendu, pressure 1.00MPa under the conditions of carry out
Reproducibility heat chemistry causticization reduction reaction, reaction time 2h, after conversion terminates, slurry color switchs to brownish black, and sedimentation is fast；
(2) magnetic separation mentions iron: magnetic separation separation and Extraction reproducibility converts the ferroso-ferric oxide and Ferrite in slurry, and water is cleaned
Change, obtains iron ore concentrate, water lotion Returning utilization, remaining slurry is sent to subsequent processing；
Detection: the iron ore concentrate iron-content 68.43% of extraction, iron recovery 90.12% in red mud are recycled as extracting valuable gold
Category and iron material；
(3) separation mentions alkali: remaining slurry being separated by filtration, filter residue and aqueous slkali are obtained, filter residue water washing cleaning obtains siliceous aluminic acid
Calcium mineral residue, water lotion Returning utilization, aqueous slkali are passed through CO2Soda ash is made in concentration；
Detection；Ca aluminosilicate slag (R containing alkali2O) 0.88%, alkali recovery 91.77%；
(4) aluminosilicate mineral using: using ca aluminosilicate mineral slag as ordinary portland cement production raw material, for certain
The whole aluminum raw materials and part siliceous raw material, the calcareous original in part of cement plant central laboratory substitution production portland cement clinker ingredient
Material is handled by well known silicic acid calcium clinker ingredient and grinding requirement according to feedback, roasts 40 minutes through 1450 DEG C, it is ripe that silicate is made
Material, 28d compression strength average out to 67.33MPa, other performance index are normal, and alkali content 0.04% is less than national standard 0.06%.
Claims (10)
1. a kind of resource utilization method of red mud, which comprises the following steps:
(1) slurry reproducibility converts: slurry is made in red mud, reduction transforming agent, lime and water, in temperature 60 C~350 DEG C, pressure
Reproducibility heat chemistry causticization reduction reaction is carried out under the conditions of power 0.1013MPa~4.5MPa, displaces aluminosilicate mineral in red mud
The alkali combined in object forms strong basicity slurry, and converts four oxygen for the Iron Oxide Minerals reduction in red mud in strong basicity slurry
Change three-iron, and/or the reduction synchronous with chromium, titanium, vanadium, gallium, scandium of iron contained in red mud is circulated into formation chromium titanium in ferrite lattice
The isomorphous Ferrite of vanadium gallium scandium element；
(2) magnetic separation mentions iron: ferroso-ferric oxide in a manner of magnetic separation in separation and Extraction step (1) resulting reproducibility conversion slurry and
Ferrite, water washing cleaning obtain the iron ore concentrate containing ferroso-ferric oxide and Ferrite, iron ore concentrate be used as iron-smelting raw material or as point
From the raw material for extracting the valuable metal and iron that wherein melt admittedly, remaining slurry is sent to subsequent processing；
(3) separation mentions alkali: the remaining slurry of step (2) being separated by filtration, filter residue and aqueous slkali are obtained, filter residue water washing cleaning obtains silicon
Calcium aluminate mineral slag, aqueous slkali is by well known method concentrated base or soda ash；
(4) aluminosilicate mineral using: using the resulting ca aluminosilicate mineral slag of step (3) as relevant production raw material: 1.
Material raw material is blended as production activity；2. as low-grade silicate cementing material or anhydrite cementitious material original is produced
Material；3. directly supplying cement plant or brickmaking factory as raw material；4. as production aluminium oxide and/or titanium dioxide and/or white carbon black
Raw material.
2. the resource utilization method of red mud according to claim 1, it is characterised in that: in step (1), the red mud
For the waste residue in alkaline process alumina producing.
3. the resource utilization method of red mud according to claim 1 or 2, it is characterised in that: described in step (1)
Transforming agent is restored as hydrazine and/or hydrazine hydrate and/or methyl hydrazine and/or uns-dimethylhydrazine with efficient strong reducing property.
4. the resource utilization method of red mud according to claim 3, it is characterised in that: in step (1), the reduction
In terms of molar equivalent, the equivalent proportion with the di-iron trioxide molal quantity of ferro element contained in red mud conversion is the dosage of transforming agent
0.1~1.0:1.0.
5. the resource utilization method of red mud according to claim 1 or 2, it is characterised in that: described in step (1)
The dosage of lime is the 6~65% of red mud dry weight.
6. the resource utilization method of red mud according to claim 1 or 2, it is characterised in that: described in step (1)
In slurry, red mud, the mass ratio for restoring transforming agent, the gross mass of lime and water are 1:1~15.
7. the resource utilization method of red mud according to claim 1 or 2, it is characterised in that: in step (1), when reaction
Between be 0.5h~12h.
8. the resource utilization method of red mud according to claim 1 or 2, it is characterised in that: in step (1), be additionally added
Quality is in the hydrazine derivate of the reduction transforming agent dosage 30~300%, alcohol ethers compound, ammoniac compounds, ferrous salt
One or more as assisted Reduction transforming agent.
9. the resource utilization method of red mud according to claim 1 or 2, it is characterised in that: step (2) and step (3)
In, water lotion Returning utilization is in step (1).
10. the resource utilization method of red mud according to claim 1 or 2, it is characterised in that: in step (4), 1. conduct
Production activity blends material raw material: ca aluminosilicate mineral slag is sent into heat treatment kiln and is roasted in 650 DEG C~1200 DEG C, system
Active blending material, directly supply that cement plant is made to supply cement plant after admixture or grinding, concrete mixing plant makees admixture；
2. as low-grade silicate cementing material or anhydrite cementitious material raw material is produced: ca aluminosilicate mineral slag is added quality phase
When the waste gypsum in ca aluminosilicate mineral slag 8~90% is sent into heat treatment kiln together in 700 DEG C~1200 DEG C oxidisability gas
The matured slag with gelation activity is made in calcination for activation in atmosphere, is used for building material directly as cementitious material after matured slag grinding.
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| CN103290207B (en) * | 2013-06-14 | 2015-08-12 | 中南大学 | A kind of method of red mud comprehensive reutilization iron and aluminium |
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