CN1006642B - Iion-smelting process of comprehensive using leach slag with v, cr - Google Patents
Iion-smelting process of comprehensive using leach slag with v, crInfo
- Publication number
- CN1006642B CN1006642B CN 88101431 CN88101431A CN1006642B CN 1006642 B CN1006642 B CN 1006642B CN 88101431 CN88101431 CN 88101431 CN 88101431 A CN88101431 A CN 88101431A CN 1006642 B CN1006642 B CN 1006642B
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- tailings
- chromium
- blast
- iron
- agglomerate
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Abstract
The present invention relates to solid waste treatment which is mainly suitable for treating tailings leached from discharged chromium and vanadium at the time of producing chromium salts, chrome salts and V2O5 in enterprises of metallurgy and chemical industry. The process is mainly characterized in that a low temperature reduction sintering process is adopted, the tailings leached from the chromium and the vanadium are sintered into a self-fluxing sintering ore, and the sintering ore is smelted into foundry iron. The process thoroughly eliminates the pollution of sexavalent chrome to environment, reclaims valuable elements, including Fe, V, Cr, Mn, and the like in the tailings, and has important social and economic benefit.
Description
The invention belongs to solid waste disposal.Be applicable to that mainly metallurgy and chemical enterprise are at production chromium metal, chromic salts product and V
2O
5The time, the chromic chromium that contains of being discharged is leached tailings and contains the processing that alkali-metal vanadium leaches tailings.
Metallurgical Factory is in the process of producing chromium metal, and the chromium of being discharged leaches the sexavalent chrome (Cr that contains in the tailings about 1%
6+).The sexavalent chrome of this solubility is carcinogenic highly toxic substance, serious environment pollution.Vanadium leaches tailings and has alkaline matter, and environment is also had pollution.The at present domestic chromium of storing up leaches about 3,000,000 tons of tailings, and vanadium leaches more than 100 ten thousand tons of tailings, is a serious threat to personnel safety and environment.
In early days, abroad the processing to chromium leaching tailings is to be placed on cement to make in the sealed vessel, drops into the sea.In recent years, occurred fully utilizing this slag, added silicate material and reductive agent in the tailings, made ball, used (special public clear 52-10094) as building light weight aggregate after the high-temperature roasting as leaching at chromium; Also have in chromium leaching tailings and add prussiate, powdery converter slag, gypsum, FeSO
4Or FeS, make mixture, as the solidifying agent use (J57 184498) of construction materials; Also have in chromium leaching tailings to add coke powder, silica, unslaked lime, add pulping liquor after the mixing, make ball, after 150 ℃ of oven dry, add in the electrosmelting (J580025455) as flux.
There is following shortcoming in above-mentioned treatment process: (1) can not thoroughly eliminate chromic pollution; (2) can not reclaim valuable element in the slag; (3) power consumption is high, and benefit is low.
The objective of the invention is to leach by vanadium, chromium the ironmaking comprehensive utilization of tailings, solubility sexavalent chrome and the vanadium slag thoroughly eliminated in the chromium leaching tailings leach the pollution of tailings neutral and alkali material to environment, make it to reach national specified discharge standard; Reclaim simultaneously elements such as iron in two slags, chromium, vanadium, manganese effectively, make the specific alloy iron that contains vanadium, chromium, obtain good social benefit and economic benefit.
In order to achieve the above object, the present invention has adopted following main technical schemes:
After chromium leached tailings, vanadium and leach tailings, iron powder, coke powder and mix, sinter into from the dissolubility agglomerate; Should can be made into fine and contain V, Cr specific alloy iron from the dissolubility agglomerate by blast-furnace smelting.
In sintering process, chromium leaches the most Cr in the tailings
6+C in the mixed material, Fe, FeO and CO reduce, and generate Cr
2O
3, promptly be reduced into trivalent chromium, Cr
6+Elimination factor reach more than 97%; In addition, by blast-furnace smelting, remaining sexavalent chrome is thoroughly reduced, and sexavalent chrome finally drops to the value that is lower than the national specified discharge standard defined, has thoroughly eliminated the pollution of sexavalent chrome to environment.Simultaneously, by blast-furnace smelting, elements such as Fe, V, Cr, Mn, Ti have been reclaimed from the dissolubility agglomerate effectively.
Major technique feature of the present invention is as follows:
(1) on the batching of agglomerate, the overwhelming majority adopts waste material.Its raw material leaches tailings except chromium and vanadium leaches the tailings, also needs iron powder and coke powder, and wherein iron powder can adopt the screen underflow (being tankage), iron scale, iron filings, converter dust of magnetic concentration etc.; Useless coke powder after coke powder can adopt metallurgical coke to sieve.
(2) on the agglomerate proportion of raw materials, the one, the reductibility in the time of considering to improve sintering guarantees fixed carbon more than 4.6%, usually, and the agglomerate batching, its fixed carbon only is 3～4%; The 2nd, consider ternary basicity (CaO+MgO/SiO
2) should be controlled at 0.9～1.4 scope, dual alkalinity (CaO/SiO
2) be controlled at 0.5～0.8 scope.It is higher than the ternary basicity in normal sintering ore deposit, and is lower than the dual alkalinity in normal sintering ore deposit.
(3) on agglomerate technology, adopt the low-temperature reduction sintering process, can fully reduce Cr
6+, can improve the intensity of agglomerate again.CO that produces in reductive sintered process and FeO can further reduce Cr
6+, make Cr
6+Decreasing ratio reach more than 97%, eliminated pollution.
(4) aspect blast furnace ironmaking, broken through three technological difficulties: 1. traditional concept is thought, in the raw material if contain TiO
2, then by the high temperature reduction district of blast furnace, Ti is reduced, and generates TiO, TiN, TiCN compound, forms foam thickness slag, makes the difficult branch of scum; 2. contain basic metal in the raw material, basic metal is volatile, forms shoddye simultaneously, in the easy dross in blast furnace top, and the easy etch refractory lining brick in bottom; 3. in blast-furnace smelting, Fe, V are reclaimed in requirement simultaneously, three elements of Cr are inconvenient.
The present invention regulates, improves the temperature of tuyere angle and control high-temperature zone by the blast furnace upper and lower part, suppresses TiO
2A large amount of reduction, avoid forming a large amount of foamy slags; By adopting the acid slag and the big quantity of slag, get rid of basic metal effectively.But in blast furnace hearth, also exist a part of thickness slag (being materials such as TiC, TiN) and a part of shoddye simultaneously (promptly by Na
2Basic metal such as O form).It is considered herein that, in same closed system, produce simultaneously and have dry slag and shoddye, have acidic substance and alkaline matter simultaneously, also favourable factor because of when slag liquid stirs, can reach rare thick neutralization, acid-base neutralisation makes modest viscosity, is fit to blast-furnace smelting.Facts have proved that above-mentioned argument is correct.
In addition, by the comprehensive judgement working of a furnace, adopt big air quantity, blast furnace air-supply coefficient reaches 7.6, is generally 2～5; Simultaneously, suitably control furnace temperature and basicity of slag, the rate of recovery of Fe is reached more than 95%, the rate of recovery of V reaches more than 80%, the rate of recovery of Cr＞70%.
Technical process of the present invention is: batching-batch mixing-sintering-agglomerate fragmentation-blast-furnace smelting.
Now each operation is described below:
One, batching
The raw material of agglomerate of the present invention leaches tailings, vanadium leaching tailings (or fine iron breeze), iron powder, coke powder by chromium.Wherein iron powder can adopt screen underflow, iron scale, iron filings, converter dust of magnetic concentration etc., the useless coke powder after coke powder can adopt metallurgical coke to sieve.The granularity of chromium, vanadium leaching tailings can be less than 0.5mm, and iron particle size requires less than 4mm, and useless coke fines size requires less than 5mm.
(weight %) is as follows for the proportioning raw materials of agglomerate: chromium leaches tailings 20～40%, and vanadium leaches one or both sums 50～70% in tailings, the fine iron breeze, iron powder 6～10%, coke powder 5～8%.
The chemical ingredients of each component (weight %) is shown in table 1, table 2 in the batching.
＜2〉batch mixing
Chromium, the vanadium for preparing according to the above ratio leached in tailings, iron powder, the coke powder adding mixer, add 5～10% water simultaneously, mix then, carry out sintering for agglumeration after mixing.
＜3〉sintering
Compound spread into agglomerating plant carry out sintering, sintering temperature is 800～1250 ℃, and blast volume is 1000～1300 meters
3/ ton agglomerate.
The chromium slag produces following main reduction reaction and free energy thereof in the sintering process:
In sintering process,, make CrO owing in the compound carbon, metallic iron and ferrous existence are arranged
3, CrO
2Be reduced, produce CO and FeO simultaneously, they are CrO equally
3And CrO
2Reductive agent.CrO
3And CrO
2Generate Cr with C, CO, Fe and FeO reaction
2O
3△ F ° value be bigger negative value all the time, and all at Fe
2O
3Under the △ F ° negative value that is reduced, therefore CrO in sintering
3And CrO
2Be reduced into Cr the most at last
2O
3In sintering process, will not have more CrO
3And CrO
2Existing, can only be micro-.And the Cr that generates
2O
3Be extremely stable, also can not generate CrO and Cr
3O
4Or metal simple-substance chromium.Carbon containing and metallic iron are high more in the agglomerating compound, and then sexavalent chrome is reduced thoroughly more.Because the increase of carbon content certainly will strengthen its reductibility, thereby cause FeO content increase in the agglomerate, this is favourable for the intensity that raising contains the low vanadium of Fe amount, chromium leaching tailings agglomerate.FeO existence simultaneously also can further improve the hexavalent chrome reduction decreasing ratio.
In sintering process, ternary basicity should be controlled at 0.9～1.4, and dual alkalinity should be controlled at 0.5～0.8.
After sintering circuit is finished, sexavalent chrome (Cr in the metallurgical performance index of the chemical ingredients of agglomerate, agglomerate and the sintering process
6+) the degree that removes be described below respectively:
The main chemical compositions of agglomerate (weight %) is: TFe34～60%, (wherein FeO5～20%), CaO5～10%, MgO5～10%, SiO27～14%, Cr
6+0.01～0.001%, Na
2O2～4.5%, MnO1～6%, Al
2O
32～5%, V
2O
50.5～1.3%, TiO
24～8%, Cr0.2～2%, S0.2～0.01%, P0.007～0.1%.
The metallurgical physicals of agglomerate is: dropping strength (＞5mm)＞97%, tumbler index (＞5mm)＞85%, basicity (CaO+MgO/SiO
2)＞1.0,1040 ℃ of softening beginning temperature, 1137 ℃ of end softening temperatures between the softened zone are 97.5 ℃, reduction and pulverization ratio (＞5m/m)＜5%, 800 reduction ratio＞21% under ℃ hydrogen shield, void content＜35%.
Chromic average residual storage＜0.0075% in the agglomerate.The yield rate of agglomerate＞60%, having surpassed with the iron ore primary ore is the yield rate level of feedstock production self-fluxed sinter.
Every technical indicator of the chemical constitution of gained agglomerate and metallurgical physicals all meets the requirement of blast furnace ironmaking.
＜4〉blast furnace ironmaking
1. raw material
Utilize above-mentioned chromium to leach tailings and vanadium and leach self-fluxed sinter that tailings etc. sinters into raw material as blast-furnace smelting.The chemical ingredients of this agglomerate and metallurgical physicals are as previously mentioned.Sintering nugget granularity is 6～35 millimeters.Fuel adopts coke.The fixed carbon of coke＞80%, ash content＜14%, volatile matter＜2%, the coke granularity is 6～40 millimeters.
In the blast-furnace smelting, use a small amount of flux Wingdale and micro-fluorite.
2. prepare burden
The ratio of components of blast-furnace smelting (weight ratio) is; Self-fluxed sinter: coke: Wingdale: fluorite=(100～220): (100～115): (10～22): (0～4).Coke ratio is 1.15～1.8.
3. charging system
Blow-on begins and early stage, employing 3PNK ↓, 7KPN ↓, adopt 6PNK ↓ 4KPN ↓ (P represents ore, and N represents Wingdale, and K represents coke, and ↓ expression great bell puts down once, promptly adds a batch of material) in the ordinary production stage.
4. blast-furnace technique operation
For effective control temperature of the furnace hearth, take two measure: a, the air port is changed into to 5 °～20 ° of cupola well lower tilt, b, spray into air by cinder notch.
In order effectively to arrange alkali, take the big quantity of slag operation of low basicity policy.Ternary basicity is controlled at 0.9～1.2, and dual alkalinity is controlled at about 0.6, and slag iron ratio is 1.2～1.3.
Metallurgical characteristics (fusing point is low, porosity is big) in order to adapt to two slag agglomerate adopts big air quantity, and blast furnace air-supply coefficient is about in the of 7.6.(promptly 60～70 meters
3/ minute)
Blast furnace uses hot blast temperature generally between 720～770 ℃.Blast 180～220 mercury column millimeters, throat temperature is 200～250 ℃.
Every technical indicator of blast furnace is: slag iron ratio is 1.2～1.3 kilograms/ton, utilization coefficient≤2.0, combustion intensity＞2.2, actual coke ratio 1.15～1.8, coke load 2.1～2.3, the V rate of recovery＞75%, the Cr rate of recovery＞70%.
The ferriferous chemical ingredients of blast furnace is: C3～4%, Si3.26～0.46%, Mn1.4～1.7%, P＜0.2%, S≤0.03%, Cr＞3%, Ti＞0.5%, Fe＞87%.
The chemical ingredients of slag is: Al
2O
38～10%, CaO18～25%, MgO 10～15%, TiO
27～10%, V＞0.2%, Cr＞0.8%, Fe1.0～1.6%, Mn3.5～5.5%, Na3.0～5.0%, Cr
6+Be 0.
5. eliminated Cr
6+Pollution
By the drastic reduction of blast-furnace smelting, Cr
6+In the competent system of the airtight reductive agent of high temperature, at the liquid slag that seethes, liquid metal iron with under a large amount of red-hot cokes fully contact, Cr
6+Substantially reduced.Through chemical analysis, Cr in the slag
6+Be 0; Cr in the blast furnace flue gas
6+Concentration be 0.0000412～0.0000784 kilogram/hour, national regulation Cr
6+Secondary discharge standard is 0.05 kilogram/hour, so be lower than national specified discharge standard; BF Area atmospheric surveillance data, in 20～100 meters scopes of distance blast furnace, Cr
6+Concentration be respectively 0.00084,0.00047,0.000093 milligram/meter
3, and national regulation (TJ36-79) Cr
6+Emission standard is 0.0015 milligram/meter
3, also be lower than discharging standards.
In sum, distinguishing feature of the present invention: the one, make full use of four kinds of waste materials and make high duty alloy iron, reclaim valuable elements such as Fe, V, Cr, Mn, Ti effectively; The 2nd, thoroughly eliminate Cr
6+Source of pollution.Have important social benefit and economic benefit.
Embodiment
1. chromium, vanadium leach the sintering of tailings
According to the chemical ingredients scope of agglomerate raw material each component of the present invention, the proportioning of each component and the sintering process parameter that sets, carried out the agglomerate sintering of three lot numbers.Table 3, table 4, table 5, table 6 are respectively the main chemical compositions that chromium leaches tailings, vanadium leaching tailings, iron powder and coke powder.
The chemical ingredients (weight %) of the used coke of table 6 embodiment agglomerate
Chemical ingredients by above-mentioned each component is prepared burden in three batches, and the proportioning of three batches of batching each components is as shown in table 7.After three batch of materials prepare, enter mixer, add certain water (water be ingredients by weight 5～10%), mix then, after mixing, enter the agglomerating plant sintering in three batches.The sintering process significant parameter is as shown in table 8.
The proportioning (weight %) of table 7 embodiment agglomerate raw material each component
The sintering process significant parameter of table 8 embodiment
According to the chemical ingredients of the resulting three batches of agglomerate of above-mentioned sintering process and metallurgical physicals respectively shown in table 9, table 10.
The chemical ingredients (weight %) of table 9 embodiment gained agglomerate
Continuous table 9
MnO Al
2O
3V
2O
5TiO
2Cr S P
5.12????3.52????1.13????5.81????1.61????0.15????0.064
4.82????3.52????1.20????5.71????1.51????0.17????0.060
4.11????4.0????1.10????6.10????1.1????0.18????0.068
The metallurgical physicals of table 10 embodiment gained agglomerate
2. blast-furnace smelting
Above-mentioned 3 batches of agglomerate that sinter are mixed, and as raw material, are fuel with the coke, and Wingdale is a flux, carries out blast furnace ironmaking.Agglomerating lump ore granularity is in 8～35 millimeters scopes, and the coke granularity is in 8～40 millimeters scopes, and limestone granularity is 10～40 millimeters.
Adopt 6PNK ↓ 4KPN ↓ charging system.In the blast furnace ironmaking process, measured technico-economical comparison, blase furnace cast iron composition and the blast furnace slag composition of three phases.The composition that adds three batch of materials corresponding to three stages is as shown in table 11.Table 12 is the every technico-economical comparison of testing in three stages of blast furnace, and table 13, table 14 be the chemical ingredients of the blast furnace ironmaking pig iron that three phases goes out and slag respectively.
Composition (the weight: kg) of every batch of high furnace charge of table 11 embodiment
Claims (7)
1, a kind of pollution of eliminating Cr, chromium is leached tailings and vanadium to be leached tailings and smelts iron the novel process of comprehensive utilization, it is characterized in that: leaching tailings, vanadium leaching tailings, iron powder and coke powder with chromium is raw material, adopts the low-temperature reduction sintering process, makes from the fluidity agglomerate; Is raw material with chromium, vanadium slag from the dissolubility agglomerate, is fuel with the coke, is that flux carries out blast-furnace smelting with Wingdale, fluorite.
2, ironmaking comprehensive utilization novel process according to claim 1, the proportioning raw materials (weight %) that it is characterized in that agglomerate is: chromium leaches tailings 20～40%, vanadium leach tailings, fine iron breeze both one of or both sums 50～70%, iron powder 6～10%, coke powder 5～8%.
3, ironmaking according to claim 2 comprehensive utilization novel process is characterized in that iron powder can adopt the screen underflow, iron scale, iron filings, converter dust of magnetic concentration etc., the useless coke powder after coke powder can adopt metallurgical coke to sieve.
4, ironmaking comprehensive utilization novel process according to claim 1, it is characterized in that low-temperature reduction agglomerating main technologic parameters is as follows: sintering temperature is 800～1250 ℃, blast volume is 1000～1300 meters
3/ ton agglomerate, ternary basicity is 0.9～1.4, dual alkalinity is controlled at 0.5～0.8.
5, ironmaking comprehensive utilization novel process according to claim 1, the ratio of components (weight ratio) that it is characterized in that blast-furnace smelting is, chromium, vanadium slag are from the dissolubility agglomerate: coke: Wingdale: fluorite=(100～220): (100～115): (10～22): (0～4); Coke ratio is 1.15～1.8.
6, ironmaking comprehensive utilization novel process according to claim 1, main technologic parameters is during its feature blast-furnace smelting:
The blast furnace blast amount is 60～70 meters
3/ minute, the air-supply coefficient is 7.6, and wind-warm syndrome is 720～770 ℃, and blast is 180～220 mmhg;
Throat temperature is controlled at 200～250 ℃;
Carry out the big quantity of slag, slag iron ratio is 1.2～1.3 kilograms/ton;
Dual alkalinity should be controlled at about 0.6; Ternary basicity should be controlled at 0.9～1.2
7, according to claim 1 and 6 described ironmaking comprehensive utilization novel procesies, it is characterized in that downward-sloping 5～20 degree of tuyere angle of blast furnace, spray into air by cinder notch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88101431 CN1006642B (en) | 1988-03-21 | 1988-03-21 | Iion-smelting process of comprehensive using leach slag with v, cr |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88101431 CN1006642B (en) | 1988-03-21 | 1988-03-21 | Iion-smelting process of comprehensive using leach slag with v, cr |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1035848A CN1035848A (en) | 1989-09-27 |
| CN1006642B true CN1006642B (en) | 1990-01-31 |
Family
ID=4831744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88101431 Expired CN1006642B (en) | 1988-03-21 | 1988-03-21 | Iion-smelting process of comprehensive using leach slag with v, cr |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1006642B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875987B (en) * | 2009-12-02 | 2013-06-05 | 吐鲁番沈宏金属工业有限责任公司 | Method for smelting low chromium pig iron by utilizing chromium slag |
| CN102127656B (en) * | 2010-01-13 | 2013-07-10 | 中国科学院过程工程研究所 | Method for decomposing vanadium slag by liquid phase oxidation |
| CN104017927B (en) * | 2014-06-03 | 2015-11-25 | 中信锦州金属股份有限公司 | A kind of chromium slag melting that utilizes is containing the method for chromium pig iron |
| CN104674014B (en) * | 2015-02-09 | 2017-07-07 | 河北钢铁股份有限公司承德分公司 | A kind of method of chromium slag resource clean utilization |
| CN105238893B (en) * | 2015-11-02 | 2017-10-31 | 河北钢铁股份有限公司承德分公司 | A kind of method that solid waste containing vanadium sinters blast furnace ironmaking with ore deposit |
| CN105728435B (en) * | 2016-03-25 | 2018-08-28 | 无锡宇辰工业污泥处理技术研究院有限公司 | A kind of auxiliary agent of recycling treatment solid waste |
| CN111118282A (en) * | 2019-11-28 | 2020-05-08 | 攀钢集团攀枝花钢钒有限公司 | Method for improving metallurgical performance of vanadium-titanium sintered ore |
-
1988
- 1988-03-21 CN CN 88101431 patent/CN1006642B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN1035848A (en) | 1989-09-27 |
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