CN107326182B - High-value comprehensive utilization method for red mud - Google Patents

High-value comprehensive utilization method for red mud Download PDF

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CN107326182B
CN107326182B CN201710433412.8A CN201710433412A CN107326182B CN 107326182 B CN107326182 B CN 107326182B CN 201710433412 A CN201710433412 A CN 201710433412A CN 107326182 B CN107326182 B CN 107326182B
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red mud
sulfuric acid
leaching
scandium
iron
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CN107326182A (en
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范艳青
蒋训雄
张登高
冯林永
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Beijing General Research Institute of Mining and Metallurgy
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/02—Magnetic separation acting directly on the substance being separated
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation
    • 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
    • C22B1/02—Roasting processes
    • C22B1/06—Sulfating roasting
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/0015—Obtaining aluminium by wet processes
    • C22B21/0023—Obtaining aluminium by wet processes from waste materials
    • 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
    • C22B59/00—Obtaining rare earth 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
    • C22B7/006—Wet processes
    • 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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Abstract

The invention discloses a method for extracting aluminum, iron, rare earth and scandium from red mud, belonging to the field of high-valued comprehensive utilization of red mud.The red mud is evenly mixed with a proper amount of concentrated sulfuric acid, cured and rapidly reduced, roasted and desulfurized with a reducing agent at a certain temperature, and the sulfur-containing agent contains SO2The flue gas is recycled by sulfuric acid regeneration through acid preparation. Leaching rare earth and scandium by adopting water for reducing calcine, and enriching, separating and purifying a water leaching solution by adopting hydrometallurgy to obtain Sc2O3Products and rare earth concentrates. And carrying out magnetic separation on the water leaching residues to obtain iron ore concentrate and magnetic separation tailings, and carrying out alkaline leaching on the magnetic separation tailings to prepare aluminum oxide. The invention realizes that the components in the red mud are separated according to a principle of one step, can be effectively separated, has a ready industrial production process in each step, and is easy to realize industrial production.

Description

A kind of method of the high-valued comprehensive utilization of red mud
Technical field
The invention belongs to the high-valued field of comprehensive utilization of red mud, it is specifically related to one kind and extracts aluminium, iron, dilute from red mud The method of soil, scandium.
Background technique
Red mud is generated residue when bauxite is leached through highly basic in aluminum oxide production process, 1 ton of aluminium oxide of every production Just there is 1~1.6 ton of red mud to generate.According to incompletely statistics, about 70,000,000 tons of the red mud that the whole world generates every year, China are only five big Alumina producer, the red mud generated every year is just up to 6,000,000 tons.The discharge amount of whole world red mud is big, but utilization rate is low, and a large amount of red muds are still So using stockpiling or sea row by the way of handle, flood tide red mud be not utilized effectively cause many socio-ecological environment's problems with Economical efficiency.
A large amount of soils need to be occupied by storing useless red mud, and red mud dump dam break leakage accident happens occasionally, and tremendous economic is caused to damage It loses.Such as red mud dam-break accident occurs every year for Guizhou Aluminum Factory and the red mud dump of Zhengzhou Aluminium Plant 1986 and 1988.What red mud carried Soiling solution containing alkali leaks into nearby river, lake and farmland, causes the serious pollution of body of groundwater and surface water, endangers fishery and work Agricultural production, the red mud after drying is dusty, destroys ecological environment, makes Air seriously polluted.
Red mud is in addition to main component iron, aluminium, calcium, silicon, sodium, also containing rare elements such as rare earth, scandiums.Thus red mud is regarded as Secondary resource, research are the work with strategic importance and realistic meaning, especially from each valuable constituent of wherein synthetical recovery In the case where metallic mineral resources are increasingly reduced and tend to exhausted, this work just seems even more important.
It is reported that 1,930,000 tons of scandium reserves there are about 75%~80% are associations in bauxite in the earth's crust.In production aluminium oxide When, 98% or more scandium is enriched in red mud in bauxite, Sc in red mud2O3Content some up to 0.02%, than common scandium mine Middle scandium content is higher by an order of magnitude, the solid waste red mud of each aluminium manufacturer's discharge in China, the alumina orefield difference because using and The production method of aluminium oxide is different, and scandium, content of rare earth also differ widely.Sc in Guizhou Aluminum Factory Bayer process red mud2O3For 107 μ g/g, RE2O3(rare earth element total amount) is up to 1400 μ g/g；Red mud from sintering process Sc2O3For 92.5 μ g/g, RE2O3For 1320 μ g/g；Zhengzhou aluminium Sc in factory's red mud2O3For 70.5 μ g/g, RE2O3For 66 μ g/g；Sc in the red mud of Shanxi Aluminium Plant2O3For 41.2 μ g/g, RE2O3It is 355 μg/g；Sc in the red mud of Shandong Aluminum Plant2O3For 44.9 μ g/g, RE2O3For 664 μ g/g.So a large amount of red mud is scandium, rare earth Important potential source recycles scandium from red mud, rare earth has very important industrial value.
Recycling to valuable metal in red mud, main or elemental iron, aluminium comprehensive utilization, some processes have also investigated scandium Recycling.Currently, there are mainly five types of the techniques studied.
The direct magnetic separation recovery iron process of red mud: Li Chaoxiang reports half industrialness from China Pingguo aluminium recovering iron from red mud Test, technique directly adopt SLON type pulsating high gradient magnetic separator without reduction and make sorting equipment, using a full magnetic separation of a thick essence Process.Main problem existing for the technique is that the rate of recovery of iron is low.
Roasting reduction-magnetic separation-extract technology: U.S. mineral office, which has studied, mixes red mud, lime stone, sodium carbonate with coal, Carried out under the conditions of 800~1000 DEG C after grinding it is reductive sintered, agglomerate crush after with it is water-soluble out, aluminium has 89% to be dissolved, Filtrate returns to Bayer process system and recycles aluminium after filtering, and molten slag carries out high-intensitive magnetic separator sorting, and magnetic part is carried out at 1480 DEG C The reduction melting output pig iron, nonmagnetic portion sulfuric acid dissolution titanium therein, filtered titanyl sulfate hydrolyzed, the system of calcining Obtain TiO2, which can be made the pig iron containing Fe 93~94%, C 4~4.5%, press through laboratory's lab scale, pilot-plant test Magnetic part iron content calculates, and iron recovery reaches 95%, and TiO2 purity generated is 87%~89%, and titanium is in non magnetic portion The rate of recovery in point is 73%~79%, and main problem existing for the technique is that the efficiency of magnetic separation of iron is low.
Luo Daocheng of Xiangtan Polytechnical College of China etc. has studied similar U.S.'s reduction-magnetic separation process recently, but by restoring Additive is added in the process makes the degree of metalization of iron reach 92.12%, iron concentrate grade 92.58%, iron recovery after magnetic separation Up to 94.7%.
Xiang Qinfang, Schiesinger Mark E. etc. also reports a kind of low-temperature reduction-magnetic separation from red mud Iron process is separated, research is thought: in reduction process, making solid phase reduction medium, reduction temperature with coal, charcoal, wood sawdust, bagasse 350 DEG C can be reduced to, the red mud after reduction has equally well recycled iron through magnetic separation.
Wu Qiongzhen etc. has carried out " pingguo bauxite Bayer process red mud comprehensive utilizating research ", by red mud with magnetic after reduction roasting Choosing, reaches the rate of recovery 86.96% of iron, sponge iron iron content 84.17%, the technical indicator of degree of metalization 91.49%.Tailing is through acid It roasts, leach after processing, then the extracting scandium from leachate, the extraction yield of scandium is 90.13%.Raffinate is obtained through alkali and acid processing The rate of recovery of aluminium oxide and sodium sulphate product, aluminium oxide and alkali is respectively 84.95% and 82.72%.Acid leaching residue is for producing water The target of mud realization zero-emission.
Red mud reduction melting-clinker extract technology: the principle that reduction melting-clinker leaches is in red mud plus carbon restores Ferrous metalization in red mud is precipitated, so that scandium be made to separate with iron, scandium enters clinker.The purpose of reduction melting mainly restores recycling Iron in red mud, and the interference of the extraction reduction impurity iron for subsequent scandium.To the processing of clinker, there are mainly two types of methods: first is that through Lye (NaOH or Na2CO3) scandium enters leached mud (white clay) after leaching, the change that scandium is formed after acidleach or chlorination is carried out to white clay Object is closed, then is recycled scandium；Second is that recycling scandium from leachate after to the direct acidleach of clinker.
The former Soviet Union has studied in alumina production process flow, the distribution situation of scandium oxide and oxygen is recycled from red mud Change the method for scandium.A kind of processing method is CaO to be added first in red mud and coke causes ball block, then by ball block in electric arc furnaces Middle carry out reduction melting separates the rare elements such as Sc, Ti with iron and enters clinker, then obtains one from the clinker with soda solution Kind white slag, this white slag use H containing 1.65 times that scandium is the amount containing scandium in red mud2SO4This white slag is subjected to sulphation at 200 DEG C, then It leaches, about 90% scandium and lanthanum enters solution, then with hydrometallurgy enrichment, separation and purification, obtains Sc2O3Product；It is another Processing method is will to contain the red mud of scandium to be used as blast furnace ironmaking raw material, and the iron oxide in red mud is reduced into Fe, Sc be not reduced and It is enriched in clinker.With this clinker of alkaline leaching, Sc is stayed in leached mud, filters to isolate the residue containing Sc, and then again 700 DEG C This residue of chlorination, makes Sc become ScCl3, with hydrometallurgy separation, purification, obtain pure Sc2O3。
Hungary's aluminium Trust engineering and centre of development and the E.Ercagt of Turkey etc. carried out electric arc melting red mud and Clinker hydrometallurgy experimental study, technical process include that red mud roasting pretreatment, arc melting obtain conversion pig and clinker, Wherein the pig iron average assay of Hungary's output is (%): Si 0.3~0.6；Ti 0.2~0.7；Mn 0.3~5.0；V 0.3 ~0.4；C 4.2~5.0；P<0.3；S < 0.01 is a kind of special iron between foundry iron and the steel pig iron processed, can use In production steel alloy and chill casting.Clinker is after water quenching with the Na of 60~80g/L2CO3It is leached, due to the CaO in clinker With the further causticization of the alkali in solution is made, the alkali and aluminium in red mud are more conducive to enter solution, and solution returning alumina is raw Production system makes alkali and aluminium obtain larger recycling.Alkali in molten slag can drop to 0.3%~0.4%, can be used for manufacture of cement.The work Skill major defect is not carry out synthetical recovery to other valuable metals.
Former Yugoslavia has carried out system research to each element synthetical recovery aspect in red mud, the synthetical recovery work proposed Skill process includes 1. red mud agglomeration: the red mud after dry is mixed with coke and lime stone in batch mixer again after sintering, briquetting Or agglomeration again after raw material mixing；2. reduction melting: being carried out in electric arc Shanghai or coreless induction furnace, react fusing point to reduce, restoring Dolomite or lime stone is added in the process to obtain the clinker of proper viscosity, Al2O3, TiO2, ZrO2, ThO2 in red mud enter Clinker, Ni, Mo, Nb, V and Cr are then largely reduced into the pig iron, and a small amount of TiO2 is also reduced.Gained slag composition is substantially For (%): FeO1.57~3.47, TiO2 8.07~10.30, Al2O3 31.2~34.7, SiO2 8.5~16.77, CaO 31.27~40.10, MgO7.94~11.19, pig iron impurity content are then suitable with hungarian method；3. clinker leaches: clinker warp It is dissolved out under the conditions of liquid-solid ratio is 1: 6, temperature is 80~90 DEG C, the reaction time is 30~60min with sulfuric acid after crushing, acid consumption 900-1285kg/t clinker, Al2O3, TiO2, ZrO2, ThO2 and part rare earth, which are dissolved, enters solution；4. extraction and separation: leaching Liquid is separated with 5% two (2- ethylhexyl) phosphoric acid extractions out, and 100%Zr, 99.5%Ti and 100%Th, Sc and rare earth enter Organic phase and other element sepatations, then by being stripped with 10%Na2CO3, strip liquor through hydrolysis isolates titanium hydroxide, and (calcination obtains ), TiO2 solution is dried by evaporation and can get the rare mine of rich zirconium after hydrolysis, ingredient following (%): Zr 85.5, Hf 1.05, U 0.925,Sc 0.0015,Th 0.078,Y 0.295,Ce 0.175.The technique is than hungarian method in valuable metal recovery side Further work has been done in face, but does not make further to extract recycling to dissipated metals such as scandium and rare earths.
Extraction integrated treatment red mud or low-grade bauxite, the clinker through reduction melting red mud output are once studied by Canada It is 10-3% containing about Sc amount, uses 30%H2SO4It leaches, 5% 2-(2- ethylhexyl) of the filtrate 2-Ethylhexyl Alcohol of addition 2% The extraction of phosphoric acid kerosin, then use 10%Na2CO3Solution back extraction, hydrolysis are followed except after titanium, strip liquor returns to stripping section through 2-3 times After ring improves concentration, then extract scandium and other rare metals.In addition, also useful HCl is directly dissolved out containing Sc2O3's about 0.002% The scandium of bauxite, about 10-15% enters solution, with two-(2- ethylhexyl) phosphoric acid extracting scandiums from acid solution, last scandium Overall recovery be 70-80%.
Although red mud reduction iron production-clinker extract technology has effectively recycled iron etc., it requires iron content in red mud Height, can only handle Bayer process red mud, and red mud from sintering process is difficult to restore to recycle with above-mentioned technique to obtain the pig iron.
Red mud directly leaches extraction process: India reports with acid processing red mud recycling aluminium, iron and titanium technique.It first will be red Mud salt Ore Leaching does not dissolve titanium since hydrochloric acid can dissolve Al, Fe etc., so that Al, Fe etc. is entered solution, roast through evaporation Al2O3、Fe2O3Mixture, roasting gas HCl return to salt Ore Leaching and recycle；TiO2It is then enriched in leached mud, content can It is increased to 58% from 31%, leached mud is dissolved out at 270 DEG C with sulfuric acid, makes TiO2Titanyl sulfate is generated, hydrolyzed, roast system Obtain 96%TiO2, it is used as pigment or production TiCl4.Pankj Kasliwal etc. is it has recently been reported that the side that salt acid leaching slag roasts Method is further enriched with titanium: leached mud and Na2CO3SiO after roasting, in slag2Generate soluble Na2O·SiO2, secondary through hydrochloric acid It leaches, TiO2It can further be enriched with, enrichment degree can increase to 76% by the 36% of former leached mud.In addition there are by salt Ore Leaching Slag and aluminium powder, CaO, CaF2、NaNO3Uniformly mixing carries out aluminothermic reduction and produces the ferro-titanium for being similar to industrial alloy ingredient Report.
Luige Piga etc., which is reported, to be produced ice crystal with HCl treatment and recycle aluminium, iron, titanium technique: red mud hydrochloric acid exists It is leached under the conditions of 60~80 DEG C, through filtering, hydrofluoric acid, which is added, in filtrate precipitates silicon with silicic acid, silicic acid is filtered out, to filtrate Middle addition NaCl, the additional amount of NaCl are subject to sodium amount needed for generating ice crystal, and crystallization generates ice crystal after evaporating, and crystallization is female Liquid is that this evaporation mother liquor is added to front salt acid leaching slag together with the silicic acid of pre-separation containing silicofluoric acid and hydrochloric acid solution In, dissolve Fe, Al further, to recycle the iron in solution, aluminium, insoluble Ti-enriched slag carries out chlorination recovery Pd.In addition, Akash deep etc. has studied with thiophosphorous acid from hydrochloric acid leachate extraction and separation titanium, and Cengloglu Y. etc. studies red mud warp Recycled with amberplex after dissolving with hydrochloric acid and be enriched with aluminium, titanium, iron etc..
Grecian M.Ochesenk ǖ hn ǖ Petropulu etc. has studied hydrochloric acid, sulfuric acid, the nitric acid for using various concentration respectively And SO2Leaching condition (such as extraction time, temperature, liquid-solid ratio) and corresponding leaching effect when gas pressure leaches study table It is bright, leaching agent concentration be 0.5M, temperature 298K, extraction time for 24 hours, liquid-solid ratio 1:50 under the conditions of, leaching rate is followed successively by Nitric acid > hydrochloric acid > sulfuric acid, but difference is not that too greatly, when wherein nitric acid leaches, the leaching rate of recovery of scandium is 80%, the recycling of yttrium For rate up to 90%, it is more than 70% that heavy rare earth (Dy, Er, Yb), which leaches the rate of recovery, and middle rare earth (Nd, Sm, Eu, Gd) leaches the rate of recovery and is more than 50%, it is more than 30% that light rare earth (La, Ce, Pr), which leaches the rate of recovery,.Since nitric acid has stronger corrosivity, and extraction therewith Processing medium cannot mutually be connected therewith, therefore, mostly use hydrochloric acid, sulfuric acid leaching greatly.
China Yin starts to have delivered middle forest nineteen ninety-five " extracts the preliminary examination of scandium oxide from the Bayer process red mud of Pingguo aluminium ore Test research ".The research directly dissolves red mud using hydrochloric acid, and technique includes primary leaching, extracts twice, and extraction is equal twice For synergistic system.Red mud is leached with the pure concentrated hydrochloric acid of 12mol/L first, under certain condition, the leaching rate of scandium is reachable 92.48%.Synergic reagent is P204+ sec-octyl alcohol when pickle liquor extracts for the first time, and synergic reagent is that TBP+ is secondary at second Octanol, extracting diluent twice is kerosene.The extracted species precipitation method, by further Refining, obtaining purity is about 95.25% Sc2O3.
Wang Keqin etc. takes hydrochloric acid directly to leach Shanxi aluminium manufacturer red mud, and extracts scandium in hydrochloric acid leachate and carried out in detail Research, the results showed that leaching liquid-solid ratio largely influences the leaching rate of scandium, while having an effect on the slag of salt Ore Leaching red mud Amount, the concentration of hydrochloric acid determine the content of iron in leachate.In the case where red mud leaching proposes the optimal conditions of scandium, the leaching rate of scandium is greater than 85%.
Shao Mingwang makes red mud under the conditions of 3,150 DEG C of liquid-solid ratio in such a way that direct 50% sulfuric acid directly leaches red mud With sulfuric acid reaction 1h.Then liquid-solid ratio 15, room temperature, water logging 5h are used.Infusion is extracted with P204+15% sec-octyl alcohol+sulfonated kerosene, The metallic elements such as scandium, iron and aluminium enter extraction phase, are then stripped using the sulfuric acid of 7mol/L in room temperature, then with the hydrogen-oxygen of 4mol/L Change sodium back extraction, be finally acidified with hydrochloric acid, oxalic acid precipitation, ignition of precipitate obtains Sc2O3 powder, and the rate of recovery of scandium is greater than 80%.
Red mud pretreatment-acid leaching process: red mud pretreatment is primarily referred to as roasting, dealkalize, the original of roasting-leaching with sulfuric acid technique Reason is to destroy the cementing status of red mud by the moisture of roasting removal red mud, then keep Sc, Fe, Ti, RE etc. valuable by leaching Metal enters solution and most of impurity etc. stays in leached mud, to realize the separation of valuable metal and impurity.
The red mud that Xue An of Guizhou University etc. is generated with Guangxi alumina producer Bayer process, using roasting-leaching with sulfuric acid work Skill achieves preferable effect when recycling scandium.Its result of study show when 65-80 μm of red mud average grain diameter, 90 DEG C of extraction temperature, Under conditions of extraction time 3h, liquid-solid ratio 3, the rate of recovery of scandium is up to 80% or more.
Sun Daoxing, using lime method dealkalize, utilizes the sodium salt of different shape in red mud using the red mud of Shandong Aluminum Plant as raw material It is directly or indirectly reacted with calcium ion, is largely changed into water soluble alkali and insoluble calcium phosphate.Wherein typical reaction is calcium sodium Displacement reaction, i.e., aqueous sodium silicoaluminate are reacted with calcium oxide, generate the lower ca aluminosilicate of solubility.Red mud extraction Titanium, Scandium uses sulphuric leaching technique, is first leached with the HCl of 6mol/l, then with the sulfuric acid leaching of 17.1mol/l.Hydrochloric acid leachate matter Measure the P507 solution extraction of score 1%, the sodium hydroxide solution back extraction of 2mol/l, the recovery rate of scandium is up to 91% or more.Salt acidleach The sulfuric acid to leach of red mud residue 17.1mol/l after out, acid sludge mass ratio are 3:1, and leaching temperature is 200 DEG C, leaching practice For 2h, the rate of recovery of titanium is up to 95%.
Carbonate or borate smelting process: the technique is will to dry red mud and a certain amount of Na2CO3、Na2B4O7Mixing, Using the absorption of Dowex 50W X8 ion exchange resin after roasting 20min at 1100 DEG C, being leached with the HCl of 1.5M, 1.75M is used HCl desorption, Fe, Al, Ca, Si, Ti, Na etc. be desorbed first, and Sc, Y, REE are then stayed in resin, then the desorption of the HCl through 6M Afterwards, extraction and separation are carried out with the DEHPA of 0.05M under conditions of PH=0, being comparably 5-10:1, the scandium 2M in organic phase NaOH back extraction, pure Sc can be made by further being purified2O3。
Sulfating roasting: Jiang Pingguo is discussed in " recycling rare metal in red mud " text sulfating roasting.I.e. red mud+ The concentrated sulfuric acid (200 DEG C, 1h) -2.5N sulfuric acid leaching (s/1=1:10) leachate (contains scandium).
Application number 201610615704.9 is a kind of from Bayer red mud in the patent of the method for Selectively leaching scandium and sodium, root It according to the occurrence patterns of scandium in red mud, is mixed using the concentrated sulfuric acid, after low temperature sulfation, then carries out medium temperature roast, in salinization in Sulfur trioxide, sulfur dioxide or the sulfuric acid of recycling evolution while temperature roasting, after impurity sulfate object phase decomposition, water logging is obtained The low iron washing lotion of rich scandium sodium.The exchange of immersion liquid subsequent ion, flux extraction and back extraction recycling scandium, leached mud can be used as building materials or blast furnace refining Iron material.
This patent uses medium temperature roast, reduces just for Bayer process red mud by being mainly Leaching of Scandium and sodium described in patent The leaching of aluminium, iron.Iron content is low and since calcium sulfate can make sulfur content exceeded in leached mud, can not refine directly as blast furnace Iron material is not able to achieve the synthetical recovery of aluminium in red mud, iron.
In the production process of bauxite aluminium oxide, rare earth ion is made quantitatively to be transformed into rare earth hydrogen-oxygen under highly basic state Compound just generates rare earth oxide gel and becomes oxide after dry and be dispersed in red mud after dehydration.Domestic expert is to red Scandium in mud has mutually carried out a large amount of research with the object of RE, the results showed that, scandium and RE in red mud are not ion types, It is not present in the aluminium silicate mineral phase newly formed, bauxite and its accessory mineral such as gold is mainly scattered in class matter in-phase version Red stone, ilmenite, rutile titania stone, zircon, in monazite.
In view of rare earth, the main preservation of scandium in titanium mineral phase, using the industrial practice of method for producing gtitanium dioxide with sulphuric acid, using sulphur Acid curing destroys mineral facies, forms soluble rare earth, scandium sulfate is more satisfactory processing method.
Existing research has certain limitation, cannot generally be applicable in both for a certain red mud.As reduction melting is raw Iron content in the technical requirements red mud of iron in the pretreatments such as iron, reduction roasting-magnetic separation, direct ore dressing recycling red mud wants high. It is handled using the direct acid-hatching of young eggs, since the impurity such as a large amount of iron, aluminium, calcium, magnesium not only consume a large amount of acid, and a large amount of impurity enter The problems such as solution also results in METAL EXTRACTION difficulty, the purity of product scandium oxide is not high.
Summary of the invention
The present invention is directed to the red mud of various processes, comprehensively considers the factors such as technology, economy, cost, proposes new red The high-valued comprehensive utilization technique of mud, i.e., with " red mud sulfuric acid curing activation --- iron/aluminium sulfate reduction decomposition and acid regeneration --- Process flow based on the rare elements such as water logging rare earth, scandium --- magnetic separation of iron ore concentrate --- alkali leaching alum recovery ".The present invention realizes red Ingredient in mud is separated a kind of principle by a step, can be efficiently separated, each step process has ready-made industrial manufacture process, work Industry metaplasia, which produces, easily to be realized.
For achieving the above object, a kind of method of the high-valued comprehensive utilization of red mud of the invention includes the following steps:
(1) sulfuric acid cures: curing after red mud is mixed in a certain ratio uniformly with the concentrated sulfuric acid, obtains sulfuric acid curing Material；
(2) reduction roasting: the sulfuric acid Curing material that above-mentioned steps (1) are obtained together with appropriate reducing agent at a certain temperature Quick reduction roasting is carried out, guarantees the activity and the generation of Armco magnetic iron of aluminium oxide.Obtain calcining and containing SO2Flue gas contains SO2Flue gas Relieving haperacidity return step (1) is recycled after collection；
(3) flooding rare earth, scandium: the calcining that above-mentioned steps (2) obtain is leached with water, liquid divides admittedly after the completion of leaching From obtaining containing rare earth, scandium solution and water logging slag.Infusion hydrometallurgy is enriched with, separated and purified, Sc is obtained2O3Product and Rareearth enriching material.
(4) water logging slag magnetic separation iron: the water logging slag that above-mentioned steps (3) are obtained carries out magnetic separation, obtains iron ore concentrate and magnetic separation tail Mine；
(5) alkali extracts aluminium: the magnetic tailing that above-mentioned steps (4) obtain being carried out alkali leaching with the solution containing sodium hydroxide, is soaked Solid-liquor separation obtains sodium aluminate solution and Silicon-rich slag after out.Sodium aluminate solution prepares aluminium hydroxide through kind point, is then separated by solid-liquid separation Aluminium hydroxide and mother liquor are obtained, mother liquor, which returns, to be recycled, and aluminium hydroxide produces aluminium oxide through calcining.
Further, the concentration of the sulfuric acid used in sulfuric acid curing in step (1) is greater than 80% (mass fraction), by 98% The additional amount of concentrated sulfuric acid meter is 0.5-3.0 times of the red mud quality.
Further, sulfuric acid cures in step (1), and 150-500 DEG C of curing temperature, curing time 1-48h.
Further, the reducing agent in step (2) is coal dust, coal gangue powder, coal gas, natural gas, sulphur or petroleum coke etc. One of low value carbon-containing fuel is one kind of multiple.
Further, the reducing agent in step (2) is coal dust, and the supplying of coal dust is than the 3- for the sulfuric acid Curing material quality 30%, it is incorporated than suitably being adjusted according to the content of aluminium, iron in red mud.
Further, 500-900 DEG C of reduction roasting maturing temperature, preferably 650-800 DEG C in step (2), quickly reduction roasting Burn time 1-30min.
Further, reduction roasting described in step (2) is fluosolids roasting, and roaster is circulating fluidization roasting One of furnace, gaseous pollutant control or fluidised form flash roaster guarantee the activity of aluminium oxide to realize quick reduction roasting With the generation of Armco magnetic iron.
Further, flooding rare earth described in step (3), calcining is at 20-90 DEG C of extraction temperature in scandium, time 0.5- 2h, liquid-solid ratio 2: 1-5: 1 make scandium, rare earth enter infusion.Infusion hydrometallurgy is enriched with, separated and purified, is obtained Sc2O3Product and rareearth enriching material.
Further, water logging slag magnetic separation of iron ore concentrate described in step (4), carries out magnetic below magnetic field strength 800kA/m Choosing, magnetic concentration prepare iron ore concentrate, the leaching of magnetic tailing alkali.
Further, the leaching of alkali described in step (5) is one of the leaching of normal pressure alkali, alkaline pressure of oxygen leaching or Bayer Process digestion.Its Alkali soaks condition are as follows: and 80-250 DEG C of leaching temperature, alkali concentration 30-220g/L, extraction time 20-80min, ingredients molecular ratio αk0.8- 2.0, when leaching, adds lime, and lime-crushed stone pile is the 0-15% of magnetic tailing quality.Kind point is carried out to dissolution fluid, obtains hydrogen-oxygen Change aluminium product, metallurgical-grade aluminum oxide product is prepared after calcining, seed precipitation solution returns to ingredient and dissolves out magnetic tailing.
Sulphation curing of the present invention is mutually to be sent out using the pyroreaction activity of the concentrated sulfuric acid with the main object of red mud Raw reaction, the Gibbs free energy of major metal iron, aluminium and sulfuric acid reaction is both less than zero in red mud, is all easy to and sulfuric acid reaction, Corresponding sulfate is generated, and the reaction of aluminium is easier to occur than iron reaction.
Al2O3+3H2SO4(l)=Al2(SO4)3+3H2O(g)
Fe2O3+3H2SO4(l)=Fe2(SO4)3+3H2O(g)
Reduction roasting of the present invention is that the sulfuric acid Curing material of red mud is directly carried out reduction roasting with reducing agent.Cause For the decomposition temperature of corresponding sulfate can be reduced under the reducing atmosphere known to thermodynamic data analysis relative to direct medium temperature roast Degree, and also essence is different for the decomposition product generated.
Temperature range in 1000 DEG C, three decomposition reactions of aluminum sulfate and ferric sulfate are all easily sent out under reducing agent effect It is raw, and react trend from easy to difficult are as follows: Fe3O4-FeO-Fe2O3.From this analysis, passing through the control of reduction and desulfurization condition, reach It is decomposed to aluminium, iron, while quick reduction roasting, makes to decompose the generation active γ-Al of aluminium oxide2O3, iron is converted into easily generated Fe 3 O 4 magnetic iron.Simultaneously under reducing agent effect, the sulfurous gas that sulphate decomposition generates is SO2, it is easy to towerman Industry black sulfuric acid.
Serial number Chemical reaction
1 Fe2(SO4)3+ 2C=2FeO+2CO2(g)+3SO2(g)
2 1.5Fe2(SO4)3+ 2.5C=Fe3O4+2.5CO2(g)+4.5SO2(g)
3 Fe2(SO4)3+ 1.5C=Fe2O3+1.5CO2(g)+3SO2(g)
4 Al2(SO4)3+ 1.5C=Al2O3+1.5CO2(g)+3SO2(g)
Calcining water logging of the present invention, rare earth, the sulfate water logging of scandium are straight in the calcining obtained by the reduction roasting It taps into solution.With hydrometallurgy enrichment, separation and purification, Sc is obtained2O3Product and rareearth enriching material.Water logging slag carries out magnetic separation Enrichment prepares iron ore concentrate and magnetic tailing.
Alkali leaching is carried out to magnetic tailing, Leach reaction such as following formula:
Al2O3+3H2O+2NaOH=2NaAl (OH)4
A kind of method of the high-valued comprehensive utilization of red mud provided by the invention, enhances red mud using concentrated sulfuric acid pyroreaction In main object phase decomposition, realize that the desulfurization of sulfuric acid Curing material is decomposed using reducing agent, and guarantee the magnetic of the activity of aluminium oxide, iron Property, the flue gas that desulfurization generates realizes the regeneration of main agents sulfuric acid by relieving haperacidity.The flooding rare earth of desulfurization calcining progress simultaneously, Scandium prepares rare earth, scandium Related product, and water logging slag carries out magnetic concentration and prepares iron ore concentrate, because aluminium oxide has work in magnetic tailing Property, alkaline process dissolution may be implemented, carry out the preparation of conventional alumina product.
Detailed description of the invention
Fig. 1 is principle process flow chart of the invention.
Specific embodiment
Further explanation is made to the present invention below in conjunction with attached drawing.
Red mud and the concentrated sulfuric acid are mixed in a certain ratio, the concentration of the concentrated sulfuric acid of use is greater than 80%, by 98% concentrated sulfuric acid The additional amount of meter is 0.5-3.0 times of the red mud quality, 150-500 DEG C of curing temperature, curing time 1-48h.
The sulfuric acid Curing material of red mud is subjected to reduction roasting together with reducing agent, the supplying of reducing agent coal dust is than for the sulphur The 3-30% of sour Curing material quality, 500-900 DEG C of reduction roasting maturing temperature, calcining time 1-30min.Reduction roasting output Containing SO2Fume collection extracting sulfuric acid realizes the recycling utilization of sulfuric acid.
By 20-90 DEG C of reduced calcine extraction temperature, time 0.5-2h, liquid-solid ratio 2: 1-5: 1 makes rare earth and scandium enter water logging Liquid is enriched with, separates and purifies to infusion hydrometallurgy, obtains Sc2O3Product and rareearth enriching material.
Water logging slag carries out magnetic separation below magnetic field strength 800kA/m, and enrichment prepares iron ore concentrate, the leaching of magnetic tailing alkali.
Magnetic tailing is leached with the solution containing sodium hydroxide, alkali soaks 80-250 DEG C of temperature, alkali concentration 30-220g/ L, extraction time 20-80min, ingredients molecular ratio α k0.8-2.0, lime-crushed stone pile 0-15%.Alkali obtains after soaking solid-liquid separation on ore pulp To sodium aluminate solution point prepare aluminium hydroxide through kind, be recycled after seed precipitation solution processing.Alkali phase analysis can be directly as building Build the siliceous raw material of product.
Method of the invention is further described with nonlimiting examples below, it is of the invention to help to understand Content and its advantage, and not as limiting the scope of the present invention, protection scope of the present invention is determined by claims.
Embodiment 1
Red mud is mixed with 90% concentrated sulfuric acid, additional amount is 1.6 times of the red mud quality, mixing based on 98% concentrated sulfuric acid After uniformly, sulfuric acid Curing material is obtained under the conditions of 200 DEG C of curing temperature, curing time 8h.Sulfuric acid Curing material is by coal than 8% mixing Uniformly, quick reduction roasting, calcining time 5min are carried out at 750 DEG C of temperature.
By 90 DEG C of reduced calcine extraction temperature, time 60min, liquid-solid ratio 4: 1 makes rare earth and scandium enter infusion, rare earth Leaching rate is 70%, scandium leaching rate is 85%, and infusion hydrometallurgy is enriched with, separates and is purified, obtains Sc2O3Product and Rareearth enriching material.
Water logging slag carries out magnetic separation at magnetic field strength 500kA/m, and enrichment prepares 80% iron ore concentrate of iron content.
Alkali soluble, leaching condition are carried out to magnetic tailing are as follows: 100 DEG C of leaching temperature, alkali concentration 150g/L, ingredients molecular ratio αk1.5, time 60min, lime-crushed stone pile 0%.At this point, the practical dissolution rate 80% of aluminium, carries out kind point to dissolution fluid, obtains hydrogen Alumina product, prepares metallurgical-grade aluminum oxide product after calcining, seed precipitation solution returns to calcining dissolution.
Embodiment 2
Red mud after washing to be adhered to alkali is mixed with 93% concentrated sulfuric acid, and additional amount is the red mud matter based on 98% concentrated sulfuric acid 2.2 times of amount, after mixing, obtain sulfuric acid Curing material under the conditions of 320 DEG C of curing temperature, curing time 8h.Sulfuric acid curing Material is uniformly mixed than 15% with coal dust by coal, carries out quick reduction roasting, calcining time 10min at 800 DEG C of temperature.
By 70 DEG C of reduced calcine extraction temperature, time 30min, liquid-solid ratio 3: 1 makes rare earth and scandium enter infusion, rare earth Leaching rate is 80%, scandium leaching rate is 92%, and infusion hydrometallurgy is enriched with, separates and is purified, obtains Sc2O3Product and Rareearth enriching material.
Water logging slag carries out magnetic separation at magnetic field strength 300kA/m, and enrichment prepares 90% iron ore concentrate of iron content.
Alkali soluble, leaching condition are carried out to magnetic tailing are as follows: 90 DEG C of leaching temperature, alkali concentration 70g/L, ingredients molecular ratio αk1.2, time 40min, lime-crushed stone pile 2%.At this point, the practical dissolution rate of aluminium carries out kind point 91%, to dissolution fluid, obtain Aluminum hydroxide product, prepares metallurgical-grade aluminum oxide product after calcining, seed precipitation solution returns to ingredient and dissolves out new mine.
Embodiment 3
Red mud is mixed with 95% concentrated sulfuric acid, additional amount is 1.8 times of the red mud quality, mixing based on 98% concentrated sulfuric acid After uniformly, sulfuric acid Curing material is obtained under the conditions of 380 DEG C of curing temperature, curing time 4h.Sulfuric acid Curing material is in fluosolids roasting It is passed through coal gas in furnace, carries out quick reduction roasting, calcining time 1min at 750 DEG C of temperature.
By 90 DEG C of reduced calcine extraction temperature, time 30min, liquid-solid ratio 5: 1 makes rare earth and scandium enter infusion, rare earth Leaching rate is 82%, scandium leaching rate is 90%, and infusion hydrometallurgy is enriched with, separates and is purified, obtains Sc2O3Product and Rareearth enriching material.
Water logging slag carries out magnetic separation at magnetic field strength 600kA/m, and enrichment prepares 75% iron ore concentrate of iron content.
Alkali soluble, leaching condition are carried out to magnetic tailing are as follows: 150 DEG C of leaching temperature, alkali concentration 50g/L, ingredients molecular ratio αk1.6, time 60min, lime-crushed stone pile 0%.At this point, the practical dissolution rate of aluminium carries out kind point 88%, to dissolution fluid, obtain Aluminum hydroxide product, prepares metallurgical-grade aluminum oxide product after calcining, seed precipitation solution returns to ingredient and dissolves out new mine.
Embodiment 4
Red mud is mixed with 98% concentrated sulfuric acid, additional amount is 2.0 times of the flyash quality based on 98% concentrated sulfuric acid, is mixed After closing uniformly, at 250 DEG C of curing temperature, the curing time obtains sulfuric acid Curing material under the conditions of for 24 hours.Sulfuric acid Curing material is roasted in fluidization It burns in furnace and is passed through natural gas, carry out quick reduction roasting, calcining time 2min at 850 DEG C of temperature.
By 50 DEG C of reduced calcine extraction temperature, time 20min, liquid-solid ratio 4: 1 makes rare earth and scandium enter infusion, rare earth Leaching rate is 83%, scandium leaching rate is 92%, and infusion hydrometallurgy is enriched with, separates and is purified, obtains Sc2O3Product and Rareearth enriching material.
Water logging slag carries out magnetic separation at magnetic field strength 800kA/m, and enrichment prepares 60% iron ore concentrate of iron content.
Alkali soluble, leaching condition are carried out to magnetic tailing are as follows: 120 DEG C of leaching temperature, alkali concentration 160g/L, ingredients molecular ratio αk1.8, time 30min, lime-crushed stone pile 8%.At this point, the practical dissolution rate of aluminium carries out kind point 90%, to dissolution fluid, obtain Aluminum hydroxide product, prepares metallurgical-grade aluminum oxide product after calcining, seed precipitation solution returns to ingredient and dissolves out new mine.
Embodiment 5
Red mud is mixed with 90% concentrated sulfuric acid, additional amount is 1.2 times of the flyash quality based on 98% concentrated sulfuric acid, is mixed After closing uniformly, sulfuric acid Curing material is obtained under the conditions of 400 DEG C of curing temperature, curing time 2h.Sulfuric acid Curing material is by coal than 12% It is uniformly mixed, carries out quick reduction roasting, calcining time 15min at 600 DEG C of temperature.
By 40 DEG C of reduced calcine extraction temperature, time 40min, liquid-solid ratio 4: 1 makes rare earth and scandium enter infusion, rare earth Leaching rate is 78%, scandium leaching rate is 87%, and infusion hydrometallurgy is enriched with, separates and is purified, obtains Sc2O3Product and Rareearth enriching material.
Water logging slag carries out magnetic separation at magnetic field strength 200kA/m, and enrichment prepares 72% iron ore concentrate of iron content.
Alkali soluble, leaching condition are carried out to magnetic tailing are as follows: 100 DEG C of leaching temperature, alkali concentration 200g/L, ingredients molecular ratio αk1.9, time 60min, lime-crushed stone pile 3%.At this point, the practical dissolution rate of aluminium carries out kind point 77%, to dissolution fluid, obtain Aluminum hydroxide product, prepares metallurgical-grade aluminum oxide product after calcining, seed precipitation solution returns to ingredient and dissolves out new mine.
Embodiment 6
Red mud is mixed with 90% concentrated sulfuric acid, by 1.85 times that 98% concentrated sulfuric acid additional amount is the flyash quality, is mixed After closing uniformly, sulfuric acid Curing material is obtained under the conditions of 230 DEG C of curing temperature, curing time 12h.Sulfuric acid Curing material is by coal than 12% It is uniformly mixed, carries out quick reduction roasting, calcining time 7min at 650 DEG C of temperature.
By 30 DEG C of reduced calcine extraction temperature, time 50min, liquid-solid ratio 4: 1 makes rare earth and scandium enter infusion, rare earth Leaching rate is 78%, scandium leaching rate is 87%, and infusion hydrometallurgy is enriched with, separates and is purified, obtains Sc2O3Product and Rareearth enriching material.
Water logging slag carries out magnetic separation at magnetic field strength 200kA/m, and enrichment prepares 75% iron ore concentrate of iron content.
Alkali soluble, leaching condition are carried out to magnetic tailing are as follows: 90 DEG C of leaching temperature, alkali concentration 150g/L, ingredients molecular ratio α K1.4, time 120min, lime-crushed stone pile 0%.At this point, the practical dissolution rate of aluminium carries out kind point 82%, to dissolution fluid, obtain Aluminum hydroxide product, prepares metallurgical-grade aluminum oxide product after calcining, seed precipitation solution returns to ingredient and dissolves out new mine.

Claims (10)

1. a kind of method of the high-valued comprehensive utilization of red mud, which comprises the following steps:
(1) sulfuric acid cures: curing after red mud is mixed in a certain ratio uniformly with the concentrated sulfuric acid, obtains sulfuric acid Curing material；
(2) reduction roasting: the sulfuric acid Curing material that above-mentioned steps (1) obtain is carried out at a certain temperature together with appropriate reducing agent Quick reduction roasting obtains calcining and containing SO2Flue gas contains SO2Relieving haperacidity return step (1) is recycled after fume collection；
(3) flooding rare earth, scandium: the calcining that above-mentioned steps (2) obtain is leached with water, solid-liquor separation obtains after the completion of leaching To rare earth, scandium solution and water logging slag is contained, solution separating-purifying obtains rare earth and scandium product；
(4) water logging slag magnetic separation iron: the water logging slag that above-mentioned steps (3) are obtained carries out magnetic separation, obtains iron ore concentrate and magnetic tailing；
(5) alkali extracts aluminium: the magnetic tailing that above-mentioned steps (4) obtain being carried out alkali leaching with the solution containing sodium hydroxide, has been leached Sodium aluminate solution and Silicon-rich slag are obtained at rear solid-liquor separation；Sodium aluminate solution prepares aluminium hydroxide through kind point, is then separated by solid-liquid separation Aluminium hydroxide and mother liquor are obtained, mother liquor, which returns, to be recycled, and aluminium hydroxide produces aluminium oxide through calcining.
2. the method according to claim 1, wherein the concentrated sulfuric acid used in sulfuric acid curing in step (1) is dense Degree is greater than 80%, and the additional amount based on 98% concentrated sulfuric acid is 0.5-3.0 times of the red mud quality.
3. the method according to claim 1, wherein sulfuric acid curing, curing temperature 150-500 in step (1) DEG C, curing time 1-48h.
4. the method according to claim 1, wherein the reducing agent in step (2) is coal dust, coal gangue powder, coal One of gas, natural gas, sulphur or petroleum coke are a variety of.
5. the method according to claim 1, wherein the reducing agent in step (2) is coal dust, the supplying ratio of coal dust For the 3-30% of the sulfuric acid Curing material quality.
6. the method according to claim 1, wherein 500-900 DEG C of reduction roasting temperature in step (2), quickly Reduction roasting time 1-30min.
7. according to the method described in claim 6, it is characterized in that, 650-800 DEG C of reduction roasting temperature in step (2).
8. the method according to claim 1, wherein water logging condition described in step (3) are as follows: extraction temperature 20-90 DEG C, time 0.5-2h, liquid-solid ratio 2: 1-5: 1.
9. the method according to claim 1, wherein water logging slag magnetic separation of iron ore concentrate described in step (4), in magnetic Field intensity 800kA/m or less carries out magnetic separation.
10. the method according to claim 1, wherein alkali described in step (5) soaks condition are as follows: leaching temperature 80- 250 DEG C, alkali concentration 30-220g/L, extraction time 20-80min, ingredients molecular ratio αk0.8-2.0, when leaching, add lime, stone Grey additive amount is the 0-15% of magnetic tailing quality.
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CN109112293B (en) * 2018-10-26 2020-08-11 广西大学 Method for selectively enriching scandium from Bayer process red mud
CN109574052A (en) * 2019-01-28 2019-04-05 云南文山铝业有限公司 The recovery method of sodium aluminate solution filter residue
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