CN1089374C - Process for separating titanium component from titanium-contained slags - Google Patents

Process for separating titanium component from titanium-contained slags Download PDF

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CN1089374C
CN1089374C CN98114444A CN98114444A CN1089374C CN 1089374 C CN1089374 C CN 1089374C CN 98114444 A CN98114444 A CN 98114444A CN 98114444 A CN98114444 A CN 98114444A CN 1089374 C CN1089374 C CN 1089374C
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slag
titanium
contained
separating
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CN1253185A (en
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隋智通
娄太平
傅念新
李光强
陈丙辰
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Northeastern University China
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Abstract

The present invention relates to a method for separating titanium component from slag containing titanium, which comprises selective enrichment, selective growth and selective separation. Firstly, the slag is modified, the components of molten slag are regulated, and the oxygen level of the slag is controlled to lead titanium in the slag to selectively enrich in a perovskite phase. Subsequently, the cooling speed and temperature range are controlled during cooling process, and a small amount of additive agent is added in the slag, so the perovskite phase precipitated is prompted to grow up and thicken. Finally, coagulate slag is crushed and milled, and a phase rich in titanium and enrich in perovskite is selectively separated by a mineral processing method. The present invention has the advantages of less investment, large treating capacity, low energy consumption, high efficiency, easy industrialization, etc., the integrated utilization of resources is realized, and environmental pollution is avoided.

Description

The method of separating titanium component from titanium-contained slag
The invention belongs to a kind of mining and metallurgy processing method, particularly a kind of from titanium-contained slag the method for separating titanium component.
Vanadium titano-magnetite is that China contains one of abundant many metals mineral intergrowth, iron content 30-45% wherein, TiO 26-15%.This ore deposit is formed complicated, and disseminated grain size is thin, direct ore dressing separation of iron and titanium, poor effect.Adopt pyrometallurgy, can realize that slag-iron separates after in metallurgical furnace, finishing smelting, but most of titaniferous oxide compound is deposited slag mutually with very tiny and dispersion state tax, becomes titaniferous metallurgical slag.Adopt the method for technology separating titaniums from titanium-contained slag such as pyrometallurgy, hydrometallurgy or ore dressing separation in the prior art in addition, but, reason such as treatment capacity few, contaminate environment, long flow path, investment big or benefit low low because of separation efficiency, finally all can not on technical scale, use, so far bulk deposition, both wasted resource, again contaminate environment.
The object of the present invention is to provide a kind of less energy-consumption, high benefit, less investment, treatment capacity big, the method that can from the titaniferous waste residue, titanium component be separated effectively.
Substance of the present invention is at first titanium-contained slag to be carried out modification, adjusts slag and forms, and the oxygen position of control slag makes and disperses to be present in the titanium of various titaniferous in mutually in the slag and optionally be enriched to a kind of rich titanium mineral phase---uhligite (CaTiO 3) mutually in, and in process of cooling subsequently optimization of treatment conditions, controlled chilling speed and temperature range, add a small amount of additive, impel the uhligite of separating out to grow up mutually and alligatoring, reach more than the median size 50 μ m,, adopt mineral working method selective separation to go out the rich titanium phase of enrichment uhligite then with the crust block pulverizing and jevigating.Method of the present invention is mainly by selective enrichment, and selectivity is grown up and three links of selective separation constitute.
Selective enrichment: the distribution of titanium disperses very much in the titanium-contained slag, has titaniferous ore phase more than five kinds in the slag at least, as table 1.
The distribution of titaniferous ore phase in table 1. titanium-containing blast furnace slag
Mineral Uhligite Titanaugite Rich titandiopside Magnesium-aluminium spinel Ti (C, N) sosoloid
TiO in the slag 2Distribution % 14.30 62.87 14.20 0.1 0.33
TiO in the mineral facies 2Content % 53.94 13.96 19.49 2.23 93.45
For solving " dispersion " problem, it is very crucial to adjust slag composition and character.Selective enrichment is exactly by add oxycompound CaO, SiO in the slag of slag ladle or slag runner 2, Al 2O 3, MgO, FeO x, MnO 2Deng another or several metallurgical waste (as dust, mine tailing, waste residue etc.), can adjust slag basicity R (R=CaO/SiO 2) between 1-2, add-on is the 5-15% of total quantity of slag.For keeping the oxygen position, make oxygen partial pressure maintain 10 by winding-up air or oxygen in slag -6-1atm scope.In the selective enrichment process, control basicity and oxygen position all the time and be promote in the slag dispersive titanium be enriched to uhligite mutually in, increase the uhligite prerequisite of the amount of separating out mutually.Selectivity is grown up: mutually very tiny ((10 μ m) can not satisfy the isolating granularity requirements of mineral to uhligite in the undressed titanium-contained slag.For solving " tiny " problem, need optimization of treatment conditions, promote that uhligite is grown up and alligatoring mutually in the slag.The control slag when the cooling of 1500 ℃ of-1200 ℃ of temperature ranges, speed of cooling O.5-5 ℃/min between, add the additive of 1-3% simultaneously, adjust slag structure, change uhligite and separate out pattern mutually.Contain one or more following compound: Cr in the additive 2O 3, MnO 2, CaF 2, P 2O 5, si 3N 4, SiC, TiC, FeS, MnS, NiS, TiN etc.For guaranteeing that slag reaches above-mentioned speed of cooling, slag ladle need add loam cake, the sidewall filled heat insulating material.Selective separation: the physical parameter of test calcium neodymium ore deposit phase: proportion is 4.1g/cm 3, specific susceptibility 38.94 * 10 -6BGSMcm 3/ g.Uhligite is mineral facies heavier in the slag mutually, has weak magnetic, adopts gravity treatment or the gravity treatment method in conjunction with magnetic separation and flotation or gravity treatment-flotation-electric separation associating, and the uhligite in the crust block is separated out.Can realize rich titanium component (＞35%TiO 2) and poor titanium component (＜10%TiO 2) isolating purpose.
Further narrate content of the present invention with drawings and Examples below:
Fig. 1 is the technical process block diagram of the present invention's separating titanium component from titanium-contained slag,
Fig. 2 is the uhligite graph of a relation of the amount of separating out and basicity mutually,
Fig. 3 is Chinese Panzhihua Iron blast furnace slag microstructure figure,
Fig. 4 changes contrast figure for the microstructure that adds the forward and backward uhligite phase of additive;
Fig. 5 separating calcium titanium ore from crust block sorts principle flow chart mutually.
Embodiment 1, and the composition of original blast furnace slag is as shown in table 2.
The original composition of table 2. titanium-containing blast furnace slag
Composition TiO 2 SiO 2 Al 2O 3 CaO MgO TFe
％ 24.38 17.60 14.59 20.34 8.20 8.48
At first carry out selective enrichment: for adjusting the composition and the character of slag, add slag, it is formed as table 3.
The composition of table 3. slag
Composition TiO 2 SiO 2 Al 2O 3 CaO MgO TFe
％ 1.38 8.54 0.41 53.30 7.66 15.25
Purpose is to impel to generate uhligite phase (CaTiO in the slag 3) reaction (1) carry out to the right
(1) for promoting uhligite phase (CaTiO 3) separate out, improve a in the slag (CaO)And Activity is necessary.But also there be (MgO) in the slag, (Al 2O 3) and (SiO 2) etc. component, other pair reaction can also take place, as generating diopside (CaOMgO2SiO 2)
(2) and generate calcium aluminosilicate (CaOAl 2O 3SiO 2)
(3) above-mentioned respectively being reflected in the slag all can be taken place.There is competition each other.For guaranteeing that reacting (1) fully carries out, and needs to improve calcium oxide activity a on the one hand (CaO), also to reduce silicon oxide activity simultaneously Carrying out in the hope of inhibited reaction (2) and (3).Improve slag basicity R (R=CaO/SiO for this reason 2) be very necessary, but basicity is too high.The viscosity of slag also increases as the index, is unfavorable for the carrying out of mass transfer in the slag." selectivity is grown up " of continuing played inhibition, so basicity to be controlled certain limit, the definite R=1-2 the best of experiment.Present embodiment control R=1.2.On the other hand, blast furnace slag belongs to the reductibility slag, and titanium can exist by several valence states in slag: Ti 2+, Ti 3+, Ti 4+, this also is that titanium disperses to be present in one of several titaniferous reason in mutually in the slag.Make for reaching that titanium is enriched to CaTiO as much as possible in the molten slag 3Mutually, must make slag titanium Ti at a middle or low price 2+And Ti 3+, be oxidized to Ti as much as possible 4+Enter CaTiO 3Phase, control slag oxygen position then is the condition of another one necessity for this reason.
It below then is the principle foundation of present embodiment selective enrichment.The method of implementing is to adjust slag to form, and improves basicity, and by add CaO in slag, CaO activity realizes in the increase slag.The material that contains calcium oxide is a lot, considers that copper smelter slag is a high basicity slag, common R＞5, and CaO intelligence amount is more than 50%, and slag is again the oxidisability slag simultaneously, helps making titanylization at a low price.Moreover slag is metallurgical refuse, adjusts slag with slag and forms, and cost is low.Slag adds mode: both its broken back can be joined in the slag runner when the tap cinder, also can join in the slag ladle, improve the mode of slag oxygen position: the oxygen of both can in slag, the having jetted air of also can jetting, time 1-10 minute, the slag of fragmentation and gas can also be mixed and jet in slag.Whole selective enrichment link was finished (slag ladle volume heal big time longer) in 10-30 minute.Finish and then enter selectivity behind the selective enrichment and grow up.The purpose of growing up is to make the CaTiO that separates out in the slag 3Solid phase is grown up as best one can and alligatoring is bigger crystal grain, for follow-up selective separation link creates conditions.Because during crystal grain too little (＜40 μ m), the expense of ore grinding increases substantially, so determine uhligite phase CaTiO 3The lower limit of grain-size is 50 μ m, the certainly crystal grain favourable separation of healing more greatly.Temperature range when the processing method that realization is grown up is controlled chilling is between 1500-1200 ℃, and when temperature was lower than 1200 ℃, coarsening rate was too low, no practical significance.Say that in principle speed of cooling more helps growing up, but the suitable difficulty of the speed of cooling that realizes being lower than 0.5 ℃/min in technical scale.For guaranteeing O.5-5 ℃/speed of cooling of min scope that slag ladle need add loam cake, sidewall needs fill insulant material to be incubated.Speed of cooling greater than 5 ℃/be unfavorable for CaTiO when min is above 3Grow up mutually.It is 0.5 ℃/min that present embodiment is selected speed of cooling, and soaking time continues about about 10 hours.For improving CaTiO 3The pattern of precipitated phase.Help mineral and separate, also need add additive, several additives of listing all produce effect.Add-on gets final product at 1-3%.Add 1%Cr in the present embodiment 2O 3The adding method be to add when slag is formed adjusting.The selective separation link is that crust block is poured out by slag ladle, and pulverizing and jevigating is after gravity treatment separates, and the test of crust block washability shows, the uhligite particle is bordering on and is evenly distributed in each grade, make the gravity treatment separating device with shaking table, sort principle process such as Fig. 5, sort result such as table 4.
Table 4. table concentration separating resulting
Name of product Productive rate % TiO 2Grade % Rate of recovery %
Concentrate 21.12 42.73 49.65
Chats 17.20 20.89 19.77
Mine tailing 61.68 9.01 30.58
Raw ore 100.00 18.18 * 100.00
*Make head grade reduce in the product that finally obtains rich its TiO of titanium phase concentrate because of adding slag 2Grade 〉=42.13%, poor its TiO of titanium phase tailings 2Grade≤9.01%.
Embodiment 2, the composition such as the table 5 of original slag.
The original composition of table 5. titanium-containing blast furnace slag
Composition TiO 2 SiO 2 Al 2O 3 CaO MgO TFe
％ 24.44 23.60 14.51 27.45 7.53 6.88
Add dust and the lime formed as table 6.
The composition of table 6. dust and lime
Composition TiO 2 SiO 2 Al 2O 3 CuO MgO TFe
Dust % 0.43 1.05 0.32 5.04 2.42 59.75
Lime % 0 2.42 1.01 81.0 2.66 1.37
The adjustment slag is formed, and reaches R=1.35, oxygen partial pressure
Figure C9811444400061
=10 -6Atm, in 1500-1200 ℃ of temperature range, speed of cooling=2.0 ℃ min, addition of C aF 2, addition 3%.The selective separation method of crust block sorts result such as table 7 with embodiment 1.
Table 7. table concentration separating resulting
Name of product Productive rate % TiO 2Grade % Rate of recovery %
Concentrate 23.77 38.24 38.33
Chats 36.36 25.28 38.76
Mine tailing 39.87 10.63 22.91
Raw ore 100.00 23.60 100.00
Crust block obtains isolating rich titanium phase, TiO after gravity treatment separates 2Grade 〉=38.24%, the TiO of remaining poor titanium phase 2Grade about 10%.
Use the rich titanium of method gained of the present invention and can do the furnace retaining material, titanium white raw material etc. mutually; Remaining poor titanium tailings can be done cement admixture. The present invention has small investment, and treating capacity is large, and energy consumption is low, high efficiency, easily industrialization, can realize comprehensive utilization of resources, stops the advantages such as environmental pollution.

Claims (6)

1, a kind of from titanium-contained slag the method for separating titanium component, it is characterized in that this method comprises three links:
A. selective enrichment: in the slag of slag ladle that titanium-contained slag is housed or slag runner, add and contain oxide compound CaO, SiO 2, Al 2O 3, MgO, FeO x, MnO 2Another or several metallurgical waste---dust, mine tailing, waste residue, addition is the 5-15% of titanium-contained slag total amount, control slag basicity R is between 1-2, the winding-up air or oxygen maintains between the 10-6-1atm oxygen partial pressure in slag;
B. selectivity is grown up: the control slag is at 1500 ℃ of-1200 ℃ of temperature range internal cooling, and speed of cooling is added the additive of 1-3% simultaneously at 0.5-5 ℃/min, requires to contain in the additive one or more Compound C r 2O 3, MnO 2, CaF 2, P 2O 5, Si 3N 4, SiC, TiC, FeS, NiS, MnS, TiN;
C. selective separation: adopt gravity treatment or gravity treatment the uhligite in the crust block to be separated out in conjunction with the method for magnetic separation and flotation or gravity treatment-flotation-electric separation associating.
2, as claimed in claim 1 from titanium-contained slag the method for separating titanium component, it is characterized in that said selective enrichment process adds oxidiferous metallurgical waste in titaniferous slag, its adding method joins in the slag runner in the time of the waste after the fragmentation can being emitted slag in by stove, or join in the slag ladle, can also mix with gas and jet in slag.
3, as claimed in claim 1 or 2 from titanium-contained slag the method for separating titanium component, it is characterized in that said selective enrichment process in slag, jet oxygen or air, the time of winding-up is 1-10 minute.
4, as claimed in claim 1 from titanium-contained slag the method for separating titanium component, it is characterized in that said selectivity growth process, determine uhligite phase CaTiO 3The lower limit of grain-size is 50 μ m.
5, as claim 1 or 4 described from titanium-contained slag the method for separating titanium component, it is characterized in that said selectivity growth process, be to guarantee speed of cooling, slag ladle need add loam cake, sidewall needs the fill insulant material insulation.
6, as claimed in claim 1 from titanium-contained slag the method for separating titanium component, it is characterized in that said selective separation, be from slag ladle, to pour out with the crust block that selectivity is grown up through selective enrichment, to separate with the mineral working method again behind the pulverizing and jevigating.
CN98114444A 1998-11-10 1998-11-10 Process for separating titanium component from titanium-contained slags Expired - Fee Related CN1089374C (en)

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CN101988158B (en) * 2010-12-07 2012-11-07 东北大学 Comprehensive utilization method of titanium-containing waste residues
CN102357398A (en) * 2011-06-17 2012-02-22 金华冠华水晶有限公司 Method for separating each component in waste residue in crystal industry
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CN103361451B (en) * 2013-06-21 2016-01-06 北京科技大学 A kind of hypergravity is separated the method for titanium resource in titanium slag
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CN108384962A (en) * 2018-04-20 2018-08-10 四川省川威集团有限公司 A kind of ferrotianium synthetic method and the method using titanium-containing blast furnace slag
CN108950226A (en) * 2018-08-07 2018-12-07 重庆大学 The device and method of titanium resource in a kind of high temperature concentration and separation titanium-containing blast furnace slag
CN108677026A (en) * 2018-08-07 2018-10-19 重庆大学 A kind of centrifugal granulation detaches the device and method of titanium resource in titanium-containing blast furnace slag
CN109338116A (en) * 2018-11-22 2019-02-15 王娜 A kind of method that short route processing titanium slag extraction prepares titanium and its alloy nanoparticle

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