CN106367607A - Method for stepwise recovering valuable metal in converter slag - Google Patents

Method for stepwise recovering valuable metal in converter slag Download PDF

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Publication number
CN106367607A
CN106367607A CN201610823205.9A CN201610823205A CN106367607A CN 106367607 A CN106367607 A CN 106367607A CN 201610823205 A CN201610823205 A CN 201610823205A CN 106367607 A CN106367607 A CN 106367607A
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China
Prior art keywords
slag
filtrate
ball milling
stage nitration
leaching
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CN201610823205.9A
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Chinese (zh)
Inventor
向俊
向俊一
黄青云
吕学伟
白晨光
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Chongqing University
Chongqing University of Science and Technology
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Chongqing University
Chongqing University of Science and Technology
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Priority to CN201610823205.9A priority Critical patent/CN106367607A/en
Publication of CN106367607A publication Critical patent/CN106367607A/en
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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
    • C22B7/04—Working-up slag
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C21/00—Disintegrating plant with or without drying of the material
    • 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
    • B03C1/30—Combinations with other devices, not otherwise provided for
    • 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
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
    • C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
    • C22B34/1245—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a halogen ion as active agent
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • 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
    • C22B7/007—Wet processes by acid leaching
    • 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

Abstract

The invention discloses a method for stepwise recovering valuable metal in converter slag. According to the method, the converter slag is crushed through mechanical treatment, and magnetic substances and non-magnetic substances are separated by combining screening with magnetic separation; the magnetic substances are mainly metallic iron and can serve as steelmaking raw materials, and the non-magnetic substances are subjected to ball-milling activation, calcium roasting and weak acid two-stage leaching for selective recovery of vanadium; and vanadium-extracted tailings are subjected to carbon reduction, ball milling and magnetic separation for secondary recovery of metallic iron, and magnetic separation tailings are subjected to hydrochloric acid leaching and high-temperature hydrolysis for recovery of titanium, and titanium-extracted tailings are subjected to resourceful treatment. By adoption of the method, comprehensive recovery and utilization of iron, vanadium and titanium in the converter slag are achieved; the method has the characteristics of being simple in procedure, high in comprehensive recovery rate, clean and efficient; and industrial production is facilitated, and the method has high application and popularization value.

Description

A kind of method that step reclaims valuable metal in vessel slag
Technical field
The invention belongs to metallurgical technology field and in particular to a kind of step reclaim vessel slag in valuable metal method.
Background technology
Vanadium is important strategic materials, is that development modern industry, modern national defense and modern science and technology are indispensable heavy Want material.Wherein about 87% vanadium is applied in steel and iron industry.At present, the vanadium metal of China more than 90% or vanadium iron Producing is all with vanadium titano-magnetite as raw material production.Domestic main with vanadium titano-magnetite as raw material, double using blast furnace-converter Connection technique productions general steel and vessel slag.
In vanadium extraction steelmaking process, slag sluicing system is not exclusively so that be mingled with a certain amount of ferrum oxide and metal in vessel slag Ferrum.Metallic iron mostly is block and granular, and granularity is larger, is not only difficult to crush, and easily causes the follow-up vanadium extracting process of vessel slag Middle dysoxidation, furnace charge seriously bonds.Therefore, must be by most Magnetic Materials in the pretreatment process of follow-up process for extracting vanadium Separate.Separate the Magnetic Materials in vessel slag at present typically through slightly broken, ball milling, magnetic separation separation or to sieve, but low separation efficiency, energy Consumption is higher.
Extracting vanadic anhydride technique the most ripe from vanadium containing slag is sodium roasting-water logging vanadium extraction and calcification roasting Burn-acid-leaching vanadium-extracted two kinds.Sodium vanadium extracting method requires calcium content in vanadium slag low, and produces hcl, cl during roasting2、so2、so3Etc. invading Corrosion gas, sodium salt additive also can make residue containing sodium be difficult to continue with.Calcification extraction vanadium method avoids harmful gass Produce, be a kind of process for cleanly preparing of alternative tradition sodium extraction vanadium method, but basic research and industrial practice are pointed out: calcium Change process for extracting vanadium vanadium turn leaching rate low have become as it and limit it replace the fatal defects of sodium process for extracting vanadium completely.
The waste residue that vessel slag containing vanadium produces after vanadium extraction is tailings in vanadium extraction.The annual tailings in vanadium extraction discharged of Chan Fan enterprise of China About 300,000 t, volume of cargo in storage greatly, does not only take up the land resource of preciousness, but also pollutes local environment.At present, tailings in vanadium extraction one As be used for producing cement, wall body brick, ceramic tile, devitrified glass, build black porcelain, far ultrared paint etc..But utilization rate is not high, disappear Consumption less it is impossible to consume substantial amounts of tailings in vanadium extraction.And ferrotitanium content is higher in tailings in vanadium extraction, there is higher value, But all do not obtain effective recycling at present.
Content of the invention
For deficiencies of the prior art, the present invention provides a kind of step to reclaim the side of valuable metal in vessel slag Method, it is intended to improve vessel slag Mineral separation efficiency, improves vanadium slag calcification baking efficiency and vanadium turns leaching rate, efficient recovery tailings in vanadium extraction Middle ferrotitanium resource, improves valuable metal utilization rate in vessel slag.
To achieve these goals, the technical solution used in the present invention is as follows:
A kind of method that step reclaims valuable metal in vessel slag, comprises the following steps:
1) using vessel slag as raw material crush and ball milling after, obtain crushed material, then crushed material sieved, obtain thick Slag, middle slag and fine slag；Thick slag is reclaimed as iron resource；Described middle slag is carried out secondary ball milling, obtains secondary ball milling slag；Again will This secondary ball milling slag and fine slag mix and carry out magnetic separation, obtain Magnetic Materials slag charge and non magnetic slag charge；Using Magnetic Materials slag charge as Iron resource reclaims.
2) by step 1) the nonmagnetics slag charge that obtains mixed homogeneously with the calcium containing compound of powder and ball milling activation, obtains To activation slag；By oxidizing roasting 1h in described activation slag oxidizing roasting stove at 800 DEG C, be then air cooled to room temperature, more broken i.e. Obtain roasting grog.
3) by step 2) the roasting grog that obtains soaks 10～20min to carry out first paragraph in 50 DEG C of one section of leachate Leach, then carry out filtration separation, obtain one section and leach filtrate and one section of leached mud；By described one section of leached mud in 50 DEG C of two-stage nitration Soak 10～20min in leachate carrying out second segment leaching, then carry out filtration separation, obtain two-stage nitration and leach filtrate and two-stage nitration leaching Slag tap.
One section of described leaching filtrate and two-stage nitration are leached filtrate as the raw materials recovery purifying process for extracting vanadium.
4) by step 3) the two-stage nitration leached mud that obtains carries out washing, is dried, then with addition of coal dust in 1200-1450 DEG C of reduction Carry out reduction reaction 0.5-2h in stove, obtain after cooling reducing slag iron, reduction slag iron is carried out ball milling, then carry out magnetic separation separating, Obtain metal abrasive grit and remove ferrum tailings；Metal abrasive grit is reclaimed as iron resource.
5) by step 4) leaching except ferrum tailings is placed in 60-90 DEG C of hydrochloric acid solution of obtaining, work as tio2Leaching rate reaches Carry out filtration separation when 90%, obtain titaniferous filtrate and titanium extraction tailings；Scrubbed for described titanium extraction tailings, neutralisation treatment are built Material recovery.
Described titaniferous filtrate is placed in hydrolysis 2h in 108 DEG C of hydrolytic decomposition pot, and is stirred with the rotating speed of 400rpm, filter Separate and obtain hydrolyzing filter cake and hydrolysis filtrate；
Cake Wash, drying, calcining will be hydrolyzed, that is, obtain solid tio2Powder.
Further, step 1) in, when fragmentation procedure is carried out to vessel slag using jaw crusher or autogenous tumbling mill；Described thick The granularity of slag>4mm, the granularity of middle slag is 0.25～4mm, the granularity<0.25mm of fine slag.
Further, step 1) in, the granularity ＜ 4mm of described secondary ball milling slag, wherein < quality of 0.25mm accounts for secondary ball The 60% of mill slag amount.
Further, step 2) in, the time of ball milling activation is 20～80min；Described powdered calcareous compound is carbon Sour calcium or calcium oxide, its addition according to nonmagnetics slag charge with the calcium containing compound of powder mixed calcium vanadium mol ratio is 1:1 calculates；The granularity of described activation slag is 1～5 μm；Described oxidizing roasting stove is rotary kiln or wedge furnance, described roasting < 125 μm of the granularity of grog.
Further, step 3) in, described one section of leachate is the sulfuric acid solution for 2.5 for the ph value, and described two-stage nitration leachate is Mass concentration is 1～5% sulfuric acid solution.
Further, step 4) in, described coal dust is that ferrum oxide in two-stage nitration leached mud is reduced to metallic iron with addition of amount The 100～120% of theoretical amount；Described reduction furnace is rotary hearth furnace or shaft furnace.
Further, step 5) in, the mass concentration of described hydrochloric acid solution is 15～20%；Described hydrochloric acid solution with except ferrum tailings Volume ratio > 10；Described tio2The computing formula of leaching rate is:
Further, using step 3) described in two-stage nitration leach filtrate and mix with two-stage nitration leachate and make as new two-stage nitration leachate With to improve the concentration of wherein vanadium ion.
Further, by step 5) in the hydrolysis filtrate that obtains process through regeneration of hydrochloric acid system and obtain regenerating hydrochloric acid, with again For step 5) leaching operation in.
Compared with prior art, the invention has the following beneficial effects:
1st, compare traditional slightly break, ball milling, magnetic separation separates or sieve method is compared, the present invention is using screening magnetic separation joint means To improve the efficiency of separation.
2nd, compare in traditional calcification baking technique to improve oxidizing roasting efficiency using improving sintering temperature, the present invention adopts Mechanical activation means are improving oxidizing roasting efficiency, and improve the leaching rate of vanadium.
3rd, the method using joining carbon reduction-ball milling magnetic separation for the present invention, the iron resource in efficient recovery tailings in vanadium extraction.
4th, the present invention has reclaimed the titanium resource in tailings in vanadium extraction using salt Ore Leaching-pyrohydrolytic method, improves vessel slag Middle valuable metal utilization rate.
Brief description
Fig. 1 is the process chart of the present invention.
Specific embodiment
Following examples are intended to further illustrate present invention, rather than the protection model limiting the claims in the present invention Enclose.
First, a kind of method that step reclaims valuable metal in vessel slag, its technological process is shown in Fig. 1, comprises the following steps:
1) using vessel slag as raw material crush and ball milling after, obtain crushed material, then crushed material sieved, obtain thick Slag, middle slag and fine slag；Thick slag is reclaimed as iron resource.
Described middle slag is carried out secondary ball milling, obtains secondary ball milling slag；Again this secondary ball milling slag and fine slag mixing are gone forward side by side Row magnetic separation, obtains Magnetic Materials slag charge and non magnetic slag charge；Magnetic Materials slag charge is reclaimed as iron resource.
Through inspection, the main component of described magnetic slag charge is mfe；The main chemical compositions of non magnetic slag charge are feo, v2o3、 sio2、tio2、mno、cao、mgo.
2) by step 1) the nonmagnetics slag charge that obtains mixed homogeneously with the calcium containing compound of powder and ball milling activation, obtains To activation slag；By oxidizing roasting 1h in described activation slag oxidizing roasting stove at 800 DEG C, be then air cooled to room temperature, more broken i.e. Obtain roasting grog.
3) by step 2) the roasting grog that obtains soaks 10～20min to carry out first paragraph in 50 DEG C of one section of leachate Leach, then carry out filtration separation, obtain one section and leach filtrate and one section of leached mud；By described one section of leached mud in 50 DEG C of two-stage nitration Soak 10～20min in leachate carrying out second segment leaching, then carry out filtration separation, obtain two-stage nitration and leach filtrate and two-stage nitration leaching Slag tap.
Through inspection, the main chemical compositions of described two-stage nitration leached mud are fe2o3、sio2、tio2、mno、cao、mgo.
One section of described leaching filtrate and two-stage nitration are leached filtrate as the raw materials recovery purifying process for extracting vanadium；By at present relatively One section can be leached filtrate and the two-stage nitration leaching purified remove impurity of filtrate, precipitation, drying calcining are consolidated by ripe Technology Body vanadic anhydride.
4) by step 3) the two-stage nitration leached mud that obtains carries out washing, is dried, then with addition of coal dust in 1200-1450 DEG C of reduction Carry out reduction reaction 0.5-2h in stove, obtain after cooling reducing slag iron, reduction slag iron is carried out ball milling, then carry out magnetic separation separating, Obtain metal abrasive grit and remove ferrum tailings；Metal abrasive grit is reclaimed as iron resource.
In reduction process, metal abrasive grit president is big, can use water-cooled during cooling, so can be obtained by reducing slag iron.
5) by step 4) obtain carry out leaching operation except ferrum tailings is placed in 60-90 DEG C of hydrochloric acid solution, then carry out Filtration separation, obtains titaniferous filtrate and titanium extraction tailings；Scrubbed for described titanium extraction tailings, neutralisation treatment are made construction material reclaim, Other recycling treatment can also be carried out.
Described titaniferous filtrate is placed in hydrolysis 2h in 108 DEG C of hydrolytic decomposition pot, and is stirred with the rotating speed of 400rpm, filter Separate and obtain hydrolyzing filter cake and hydrolysis filtrate；Cake Wash, drying, calcining will be hydrolyzed again, that is, obtain solid tio2Powder.Wherein Washing, the technique being dried, calcining are ripe, are operated using existing process.
Wherein, the tio that described titaniferous filtrate mainly contains2+、fe2+、fe3+、ca2+、mg2+、mn4+；Described hydrolysis filter cake becomes Divide predominantly tio2；Described hydrolysis filtrate mainly contains free acid, fecl2、fecl3、cacl2、mgcl2Deng.
For improving tio2Purity, can carry out multiple pickling to described hydrolysis filter cake, to go the removal of impurity.
As optimization, in step 1) in, broken using jaw crusher or autogenous tumbling mill when fragmentation procedure is carried out to vessel slag Broken, granularity Detection can be carried out to discharging, when discharging-material size tends towards stability, then be sieved with screening machine；Wherein, screening is thick The granularity of slag>4mm, the granularity of middle slag is 0.25～4mm, the granularity<0.25mm of fine slag.
As optimization, in step 1) in, the granularity ＜ 4mm of described secondary ball milling slag, wherein < quality of 0.25mm accounts for two The 60% of secondary ball milling slag amount.
As optimization, step 1) in,
As optimization, step 2) in, the time of ball milling activation is 20～80min；Described powdered calcareous compound is Calcium Carbonate or calcium oxide, its addition is according to the calcium containing compound mixed calcium vanadium mol ratio of nonmagnetics slag charge and powder Calculate for 1:1；The granularity of described activation slag is 1～5 μm；Described oxidizing roasting stove is rotary kiln or wedge furnance, described roasting < 125 μm of the granularity of overburnt material.
As optimization, step 3) in, described one section of leachate is the sulfuric acid solution for 2.5 for the ph value, described two-stage nitration leachate It is the sulfuric acid solution that mass concentration is 1～5%.
As optimization, step 4) in, described coal dust is that ferrum oxide in two-stage nitration leached mud is reduced to metallic iron with addition of amount Theoretical amount 100～120%；Described reduction furnace is rotary hearth furnace or shaft furnace.
As optimization, step 5) in, the mass concentration of described hydrochloric acid solution is 15～20%；Described hydrochloric acid solution with except ferrum tailings Volume ratio > 10；Described tio2The computing formula of leaching rate is:
As optimization, using step 3) described in two-stage nitration leach filtrate mix as new two-stage nitration leachate with two-stage nitration leachate Use, to improve the concentration of wherein vanadium ion, so can improve the yield of solid vanadic anhydride in follow-up process.
As optimization, by step 5) in the hydrolysis filtrate that obtains process through regeneration of hydrochloric acid system and obtain regenerating hydrochloric acid, with again Secondary for step 5) leaching operation in.Described regeneration of hydrochloric acid system can adopt the ripe Technology such as spray roasting.
Hydrolysis filtrate is passed through heating, dehydration, the oxidation of ferrous salt and decomposition and is generated chlorine and hydrogen chloride gas, through absorbing Generate hydrochloric acid.The method disposal ability is big, resource recovery is high, regeneration concentration is high.The dominant response occurring is as follows:
2fecl2+2h2o+0.5o2→fe2o3+4hcl
cl2+h2o→2hcl+0.5o2
2nd, embodiment
Using industrial vessel slag as raw material, multistage echelon is carried out using the process of the present invention and adds valuable metal.Warp Assay, in industrial vessel slag, the weight/mass percentage composition of each component is: v2o5: 12.42%, tfe (full ferrum): 38.65%, tio2: 11.42%.Specifically comprise the following steps that
1) adopt jaw crusher and ball mill comminuting matter, and grain size analyses are carried out to ball milling discharging, work as discharging-material size When tending towards stability, carry out screening in entrance screening machine and obtain thick slag, middle slag and fine slag；Wherein thick slag particle degree > 4mm, middle slag particle degree 0.25～4mm, fine slag granularity < 0.25mm.
Wherein, thick slag accounts for the 5.8% of vessel slag gross mass, and middle slag accounts for 21.1%, and fine slag accounts for 73.1%.Thick slag is essentially Metal iron block, can directly store up as steelmaking feed；Fine slag has a small amount of metal abrasive grit, v2o5Content is 14.79%；In middle slag Most of metallic iron and slag is still had to bond together, v2o5Content is only 13.32%.
Middle slag is carried out secondary ball milling, obtains secondary ball milling slag.Secondary ball milling slag is divided by magnetic separator magnetic separation with fine slag From, obtain magnetic slag charge and and non magnetic slag charge.Tfe content about 30% in non magnetic slag charge, but metal Ferrum content is reduced to 0.7% about, vanadium and titanium are also enriched in nonmagnetic portion, wherein v2o5Content about 15.3%, tio2Content about 14.4%.
2) calcium containing compound of above-mentioned nonmagnetics part and powder is sufficiently mixed in batch mixer, then through high energy Ball mill ball milling 80min, obtains activating slag.The particle mean size of activation slag is 1～5 μm.
Slag 800 DEG C of constant temperature oxidation roasting 1h in high-temperature roasting furnace will be activated, discharging is air cooled to room temperature ball mill crushing extremely Granularity is less than 125 μm, obtains roasting grog.
3) sulfuric acid solution being 2.5 using ph leaches roasting grog in retort, leaches liquid-solid ratio 5:1, extraction temperature 50 DEG C, extraction time 20min.Adding concentrated sulphuric acid in leaching process maintains solution ph constant.Leach slurry through filtering, washing Leach filtrate and one section of leached mud to one section.
One section is leached v in filtrate2o5Concentration about 24.5g/l, can be used for subsequent purification vanadium extraction.
One section of leached mud continues to leach 20min, liquid-solid ratio 5:1 in 1% sulfuric acid solution, and 50 DEG C of extraction temperature, during leaching Between 20min.Leach slurry and obtain two-stage nitration leaching filtrate and two-stage nitration leached mud through filtering, washing.
Wherein, two-stage nitration leaches v in filtrate2o5Concentration about 4.6g/l.Two-stage nitration can be leached filtrate and supplement and repeatedly be used for after sulphuric acid Leach, be used further to subsequent purification vanadium extraction after vanadium ion concentration to improve.V in two-stage nitration leached mud2o5About 0.81% about, tfe is about 32%, tio2About 15%, there is the value continuing to extract.
4) will two-stage nitration leached mud wash, dry after, with addition of theoretical amount be 110% coal dust 1300 DEG C in shaft reduction stove After lower constant temperature 1h, water-cooled obtains reducing slag iron.Again reduction slag iron is entered magnetic separation in magnetic separator after ball mill crushing and separates and obtain Metal abrasive grit and reducing slag (removing ferrum tailings).
Metal abrasive grit can be used as steelmaking feed, and titanium is then enriched in reducing slag, its tio2Content reach 21% about, There is the value continuing to extract.
5) reducing slag is leached in retort using mass concentration 20% hydrochloric acid solution, 80 DEG C of extraction temperature, liquid-solid ratio 20: 1, extraction time 3h, mixing speed 400rpm.Leach slurry and obtain titaniferous filtrate and titanium extraction tailings through filtration washing.
Pyrohydrolysises titaniferous filtrate in a kettle., about 108 DEG C of hydrolysis temperature, hydrolysis time 2h, mixing speed 400rpm. It is then passed through filter and obtains hydrolyzing filter cake, scrubbed, dry, calcining obtains tio2Content is about 98.5% tio2Powder.
Wherein still contain higher concentration free acid, chloride in hydrolysis filtrate, salt can be reclaimed through HCl recovery device Acid, and return in salt Ore Leaching operation.
The above embodiment of the present invention only example to illustrate the invention, and it is not the enforcement to the present invention The restriction of mode.For those of ordinary skill in the field, can also be made other not on the basis of the above description Change and variation with form.Here all of embodiment cannot be exhaustive.Every belong to technical scheme The obvious change amplified out or change the row still in protection scope of the present invention.

Claims (9)

1. a kind of step reclaims the method for valuable metal in vessel slag it is characterised in that comprising the following steps:
1) using vessel slag as raw material crush and ball milling after, obtain crushed material, then crushed material sieved, obtain thick slag, in Slag and fine slag；Thick slag is reclaimed as iron resource；
Described middle slag is carried out secondary ball milling, obtains secondary ball milling slag；
Again this secondary ball milling slag and fine slag are mixed and carry out magnetic separation, obtain Magnetic Materials slag charge and non magnetic slag charge；By Magnetic Materials Slag charge reclaims as iron resource；
2) by step 1) the nonmagnetics slag charge that obtains mixed homogeneously with the calcium containing compound of powder and ball milling activation, lived Slugging；
By oxidizing roasting 1h in described activation slag oxidizing roasting stove at 800 DEG C, then it is air cooled to room temperature, more broken roasted Overburnt material；
3) by step 2) the roasting grog that obtains soaks 10～20min to carry out first paragraph leaching in 50 DEG C of one section of leachate Go out, then carry out filtration separation, obtain one section and leach filtrate and one section of leached mud；
Described one section of leached mud is soaked 10～20min carrying out second segment leaching in 50 DEG C of two-stage nitration leachate, then carries out Filtration separation, obtains two-stage nitration and leaches filtrate and two-stage nitration leached mud；
One section of described leaching filtrate and two-stage nitration are leached filtrate as the raw materials recovery purifying process for extracting vanadium；
4) by step 3) the two-stage nitration leached mud that obtains carries out washing, is dried, then with addition of coal dust in 1200-1450 DEG C of reduction furnace Carry out reduction reaction 0.5-2h, obtain after cooling reducing slag iron, reduction slag iron is carried out ball milling, then carry out magnetic separation separating, obtain Metal abrasive grit and remove ferrum tailings；Metal abrasive grit is reclaimed as iron resource；
5) by step 4) leaching except ferrum tailings is placed in 60-90 DEG C of hydrochloric acid solution of obtaining, work as tio2When leaching rate reaches 90% Carry out filtration separation, obtain titaniferous filtrate and titanium extraction tailings；Scrubbed for described titanium extraction tailings, neutralisation treatment are returned as construction material Receive；
Described titaniferous filtrate is placed in hydrolysis 2h in 108 DEG C of hydrolytic decomposition pot, and is stirred with the rotating speed of 400rpm, filtration separation Obtain hydrolyzing filter cake and hydrolysis filtrate；
Cake Wash, drying, calcining will be hydrolyzed, that is, obtain solid tio2Powder.
2. step according to claim 1 reclaims the method for valuable metal in vessel slag it is characterised in that step 1) in, When fragmentation procedure is carried out to vessel slag using jaw crusher or autogenous tumbling mill；The granularity of described thick slag > 4mm, the granularity of middle slag For 0.25～4mm, the granularity < 0.25mm of fine slag.
3. step according to claim 1 reclaims the method for valuable metal in vessel slag it is characterised in that step 1) in, The granularity ＜ 4mm of described secondary ball milling slag, wherein < quality of 0.25mm accounts for the 60% of secondary ball milling slag amount.
4. step according to claim 1 reclaims the method for valuable metal in vessel slag it is characterised in that step 2) in, The time of ball milling activation is 20～80min；Described powdered calcareous compound be Calcium Carbonate or calcium oxide, its addition according to Nonmagnetics slag charge is calculated for 1:1 with the calcium containing compound mixed calcium vanadium mol ratio of powder；The granularity of described activation slag For 1～5 μm；Described oxidizing roasting stove is rotary kiln or wedge furnance, < 125 μm of the granularity of described roasting grog.
5. step according to claim 1 reclaims the method for valuable metal in vessel slag it is characterised in that step 3) in, Described one section of leachate is the sulfuric acid solution for 2.5 for the ph value, and described two-stage nitration leachate is that the sulphuric acid that mass concentration is 1～5% is molten Liquid.
6. step according to claim 1 reclaims the method for valuable metal in vessel slag it is characterised in that step 4) in, Described coal dust is the 100～120% of the theoretical amount that ferrum oxide in two-stage nitration leached mud is reduced to metallic iron with addition of amount；Described also Former stove is rotary hearth furnace or shaft furnace.
7. step according to claim 1 reclaims the method for valuable metal in vessel slag it is characterised in that step 5) in, The mass concentration of described hydrochloric acid solution is 15～20%；Described hydrochloric acid solution with except the volume ratio of ferrum tailings > 10；Described tio2Leaching The computing formula going out rate is:
8. step according to claim 1 reclaims the method for valuable metal in vessel slag it is characterised in that by step 3) institute The two-stage nitration stated leaches filtrate and mixes with two-stage nitration leachate and uses as new two-stage nitration leachate, dense with raising wherein vanadium ion Degree.
9. step according to claim 1 reclaims the method for valuable metal in vessel slag it is characterised in that by step 5) in The hydrolysis filtrate obtaining through regeneration of hydrochloric acid system process obtain regenerate hydrochloric acid, to be re-used for step 5) leaching operation in.
CN201610823205.9A 2016-09-14 2016-09-14 Method for stepwise recovering valuable metal in converter slag Pending CN106367607A (en)

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