CN102586613A - Method for recycling vanadium from vanadium-containing steel slag - Google Patents
Method for recycling vanadium from vanadium-containing steel slag Download PDFInfo
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Abstract
The invention discloses a method for recycling vanadium from vanadium-containing steel slag, which comprises the following steps, (1) reaction: the vanadium-containing steel slag is reacted in NaOH solution with the mass concentration being 10%-50%, and reaction slurry is obtained; the mass ratio of the NaOH solution to the steel slag is (3:1)-(10:1), the reaction temperature is 180 DEG C to 350 DEG C, the reaction time is 0.5-10h, and the reaction pressure is 0.3-12MPa; (2) dilution: the reaction slurry is diluted through a diluent so as to enable the concentration of sodium hydroxide in the slurry to be 100-400g/L, and mixed slurry is obtained; (3) solid-liquid separation: solid-liquid separation is carried out to the mixed slurry, and calcium-rich tailings and dissolved-out liquid are obtained; (4) impurity removal: a desiliconization agent is added into the dissolved-out liquid to perform impurity removal, then solid-liquid separation is performed, and impurity-removed liquid and silicon-containing slag are obtained; and (5) crystallizing: the impurity-removed liquid is cooled and crystallized, and a sodium vanadate product is obtained. The method effectively reduces production cost of vanadium, and the vanadium leaching rate can be 99%.
Description
Technical field
The invention belongs to belong to and contain the metallurgical and vanadium chemical field of vanadium chromic slag wet method, especially a kind of method that from v-bearing steel slag, reclaims vanadium.
Background technology
V-bearing steel slag then is a sub product of smelting vanadium titano-magnetite, is the formed V of containing of vanadium-bearing hot metal steel-making
2O
5Slag 2%～10% (compare its calcium contents with vanadium slag big), its production process has 2 kinds of approach, and a kind of is that vanadium remaining in the half steel gets in the slag through the steel-making rear oxidation, and another kind is that the molten iron direct steelmaking without the blowing vanadium slag obtains v-bearing steel slag.V-bearing steel slag has following characteristics: (1) CaO and iron level are high, and crystallization is perfect, and quality is closely knit, and liberation degree is poor; (2) complicated component, and fluctuation is bigger; (3) content of vanadium is lower, the vanadium disperse be distributed in multiple ore deposit mutually in, occurrence status is complicated.Based on above characteristics, the v-bearing steel slag vanadium extraction remains a science difficult problem.
Nearly 1,000,000 tons of the v-bearing steel slag of the annual discharging of China, contaminate environment not only, and cause the loss of valuable element vanadium.At present, the v-bearing steel slag vanadium extraction mainly contains 2 kinds of approach, and the one, v-bearing steel slag returns ironmaking enrichment vanadium; Produce height and contain vanadium slag; Further vanadium extraction again, soon v-bearing steel slag is added on as flux and gets into blast-furnace smelting in the agglomerate, and vanadium is fused in the molten iron; Obtain the higher-grade vanadium slag through blowing vanadium, as vanadium extraction or smelting ferrovanadium alloy materials.This technology can not only reclaim valuable elements such as iron, manganese, and reduces the energy consumption of iron steel ratio, but is prone to cause the phosphorus enrichment that in molten iron, circulates, and increases the weight of slag dephosphorization task; And slag impurity is many, and effective CaO content is less relatively, can reduce grade of sinter, increases the iron manufacturing process energy consumption, so this method fails to obtain to promote.The treatment process of another kind of v-bearing steel slag is direct vanadium extracting method, sodium roasting, calcification baking is arranged, fall technologies such as calcium roasting and direct acidleach.Sodium roasting is to be additive with salt or soda, through roasting at a low price vanadium be oxidized to the soluble sodium salt of 5 valency vanadium, adopt water or carbonating to leach.The commentaries on classics of this technology vanadium soaks that rate is lower, and the sodium salt consumption is big, the roasting process polluted air, be difficult to administer, and this technology is not suitable for V
2O
5The bessemer furnace slag that content is low, CaO content is high.Calcification baking is to make roasting flux with lime etc., adopts carbonating leaching etc. to leach vanadium.This method has certain selectivity to material, and there are problems such as transformation efficiency is on the low side, cost is higher in general slag, is inappropriate for large-scale production.To fall the calcium roasting and propose, to its objective is that CaO content height causes the difficult problem that leaches of vanadium in the v-bearing steel slag in order solving by Amiri.Falling the calcium roasting is with slag and Na
3PO
4, Na
2CO
3Baking mixed, Na
3PO
4Combine to form Ca with CaO
3(PO
4)
2, vanadium and sodium generate water miscible vanadic acid sodium, and water logging is leachable vanadium then.But this method only rests on the laboratory study stage, and phosphatic proportioning is big, and cost is high, does not also have industrialization promotion at present.Directly acidleach is meant without calcining process, wet method vanadium extraction fully. but owing to CaO content in the slag is high, the acid consumption is bigger, and cost is higher; The acidleach process needs in strong acid solution, to carry out, and the leach liquor impurity that obtains is more, is difficult to carry out later separation.
Chinese patent CN102071321A has proposed to extract from v-bearing steel slag with the Pottasium Hydroxide medium of high basicity the method for vanadium, chromium, and this method does not need high-temperature roasting, and temperature of reaction is reduced to 160～240 ℃, and wet method vanadium extraction chromium has effectively been stopped C in the process
12, HCl, SO
2, atmospheric polluting material such as dust, and reduced waste water generation and quantity discharged; Shortcoming is that the KOH medium costs an arm and a leg, and the mass ratio of KOH and slag be 3:1 is 60%～90% to 5:1, reaction base concentration, and then the KOH medium of loss is more, causes production cost higher, and the product benefit reduces.
Chinese patent CN102094123A has proposed a kind ofly from v-bearing steel slag, to extract the method for vanadium with the sodium hydroxide medium of high density, and this method temperature of reaction is 180～240 ℃, and the wet method vanadium extraction does not have waste gas, dust pollution in the process; Shortcoming is that alkali concn is higher, and basicity is 65%～90%, and the heat of the evaporation concentration needs when then causing medium circulation to be utilized is higher, and then production cost is higher, and the V amount of remnants is higher in the finishing slag, and leaching yield is not high, and V content is 0.3%～0.5% in the finishing slag.
Summary of the invention
The technical problem that the present invention will solve provides high, the lower-cost method that from v-bearing steel slag, reclaims vanadium of a kind of leaching yield.
For solving the problems of the technologies described above, the technical scheme that the present invention taked is: this method adopts following process step: (1) reaction: v-bearing steel slag reacts in mass concentration is 10%～50% NaOH solution, obtains reaction paste; The mass ratio of said NaOH solution and slag is 3:1～10:1, and temperature of reaction is 180 ℃～350 ℃, and the reaction times is 0.5～10h, and reaction pressure is 0.3～12MPa;
(2) dilution: using thinner is 100～400g/L with the naoh concentration that reaction paste is diluted to slurry, obtains containing the mixed slurry of rich iron tailings and sodium hydroxide, vanadic acid sodium;
(3) solid-liquid separation: mixed slurry is carried out solid-liquid separation, obtain rich calcium tailings and the dissolution fluid that contains sodium hydroxide, vanadic acid sodium and water-soluble impurity component;
(4) removal of impurities: dissolution fluid is added desiliconization agent carry out removal of impurities; Solid-liquid separation then obtains after the removal of impurities liquid and contains white residue;
(5) crystallization:, promptly obtain the vanadic acid sodium product with but crystallization of liquid cooling after the removal of impurities.
Preferably, the mass ratio of NaOH solution in the said step (1) and v-bearing steel slag is that 4:1 is to 6:1; Described temperature of reaction is that 200～300 ℃, reaction times are for being 1～4h.
Thinner in the step according to the invention (2) is a clear water, or the rich calcium tailings water in the said step (3) carries out the washings that obtains after the multi-stage countercurrent washing.
Mixed slurry carries out solid-liquid separation at 80～130 ℃ in the step according to the invention (3).
Desiliconization agent in the step according to the invention (4) is Al
2O
3, Al (OH)
3, NaAlO
2, among CaO and the MgO one or more; The add-on of said desiliconization agent is SiO in the dissolution fluid
21～3 times of weight.
Preferred desiliconization agent is CaO and/or NaAlO
2The add-on of preferred desiliconization agent is SiO in the dissolution fluid
21.5 times of weight.
Crystallisation by cooling in the step according to the invention (5) is: liquid is cooled to 30～50 ℃, growing the grain 0.5～3h by 80～130 ℃ after the removal of impurities; Stirring velocity in the said process of cooling is 100～400 rev/mins.
Preferably, the crystallisation by cooling in the said step (5) is: liquid is cooled to 40 ℃, growing the grain 1h by 80～100 ℃ after the removal of impurities; Stirring velocity in the said process of cooling is 150～250 rev/mins.
The crystalline mother solution that obtains after step according to the invention (5) crystallization joins in the said reaction of step (1) as circulation fluid.
Adopt the beneficial effect that technique scheme produced to be: (1) the present invention see from reaction system; NaOH solution with lower concentration is leach liquor; The leach liquor composition is simple, does not introduce the difficult phase of separating in the system, and the water-soluble by product that in reaction and leaching process, generates is water glass, sodium phosphate; Can remove together through adding desiliconization agent, realize product separation, dense-medium purification; Has easily separated, technology characteristic of simple.
(2) temperature of reaction of the present invention is 180～350 ℃, compares with existing technology, greatly reduces temperature of reaction, and then energy consumption is little in the process; Leaching process NaOH strength of solution is 10%～50%, and basicity reduces greatly, and then raw materials cost reduces; Therefore the present invention effectively reduces the production cost of vanadium.
(3) vanadium leaching yield of the present invention is high, can reach 99%, and content of vanadium is low in the tailings that obtains, Ca (OH)
2Content is higher, realizes easily comprehensive utilization having realized cleaner production.
(4) but the recycle of the present invention's realization response medium, NaOH, damage by water consumption are little, therefore cleaning, environmental protection more.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is done further detailed explanation.
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Embodiment 1: shown in Figure 1, this method that from v-bearing steel slag, reclaims vanadium adopts following process step.
(1) reaction (be among Fig. 1 band pressure solution go out): in autoclave, add the NaOH solution of v-bearing steel slag and 30wt%; Wherein, sodium hydroxide solution: v-bearing steel slag=4:1 (quality), v-bearing steel slag contains V
2O
53.6wt%; Be heated to 250 ℃, the still internal pressure is 2.4MPa, and reaction 4h obtains containing NaOH, Na
3VO
4, Na
2SiO
4Deng solution and rich calcium tailings blended reaction paste;
(2) dilution: reaction paste uses diluent to naoh concentration to be 200g/L, obtains containing the mixed slurry of rich iron tailings and sodium hydroxide, vanadic acid sodium; Thinner adopts technological process step last time (3) to obtain washings;
(3) solid-liquid separation: mixed slurry 90 ℃ of filtering separation, is obtained containing the dissolution fluid and the rich calcium tailings of sodium hydroxide, vanadic acid sodium and water-soluble impurity component; Described rich calcium tailings water carries out the multi-stage countercurrent washing, and the washings that obtains is used for the dilution technique of technological process next time;
(4) dissolution fluid removal of impurities: in dissolution fluid, add the CaO removal of impurities, obtain after the removal of impurities liquid after the solid-liquid separation and contain white residue; The add-on of CaO is SiO in the dissolution fluid
21.5 times of weight;
(5) vanadic acid sodium crystallization: liquid after the removal of impurities is cooled to 40 ℃ naturally by 90 ℃, and the stirring velocity in the process of cooling is 200 rev/mins; Crystallization 1.5h separates obtaining the vanadic acid sodium crystal product then; Through detecting, the leaching yield of slag vanadium is 99.1%, V in the finishing slag
2O
5Content is reduced to 0.085wt%;
(6) remaining crystalline mother solution gets in the autoclave of step (1) through evaporation concentration after the crystallization, gets into circulating reaction next time, and rich calcium tailings can be used as the ferrous metallurgy raw material after advancing the washing of three stage countercurrents.
Embodiment 2: this method that from v-bearing steel slag, reclaims vanadium adopts following process step.
(1) reaction: in autoclave, add the NaOH solution of v-bearing steel slag and 40wt%; Wherein, sodium hydroxide solution: v-bearing steel slag=5:1 (quality), v-bearing steel slag contains V
2O
54.6wt%; Be heated to 230 ℃, the still internal pressure is 1.6MPa, and reaction 3h obtains reaction paste;
(2) dilution: reaction paste uses diluent to naoh concentration to be 250g/L, obtains mixed slurry; Thinner adopts technological process step last time (3) to obtain washings;
(3) solid-liquid separation: mixed slurry 100 ℃ of filtering separation, is obtained dissolution fluid and rich calcium tailings; Described rich calcium tailings water carries out multi-stage countercurrent washing, and the washings that obtains is used for the dilution technique of next technological process;
(4) dissolution fluid removal of impurities: in dissolution fluid, add NaAlO
2Removal of impurities obtains after the removal of impurities liquid and contains white residue after the solid-liquid separation; NaAlO
2Add-on be SiO in the dissolution fluid
21.5 times of weight;
(5) vanadic acid sodium crystallization: liquid after the removal of impurities is cooled to 35 ℃ naturally by 100 ℃, and the stirring velocity in the process of cooling is 150 rev/mins; Crystallization 1.0h separates obtaining the vanadic acid sodium crystal product then; Through detecting, the leaching yield of slag vanadium is 98.4%, V in the finishing slag
2O
5Content is reduced to 0.12wt%;
(6) remaining crystalline mother solution gets in the autoclave of step (1) through evaporation concentration after the crystallization, gets into circulating reaction next time, and rich calcium tailings can be used as the ferrous metallurgy raw material after advancing the washing of three stage countercurrents.
Embodiment 3: this method that from v-bearing steel slag, reclaims vanadium adopts following process step.
(1) reaction: in autoclave, add the NaOH solution of v-bearing steel slag and 50wt%; Wherein, sodium hydroxide solution: v-bearing steel slag=4:1 (quality), v-bearing steel slag contains V
2O
54.5wt%; Be heated to 200 ℃, the still internal pressure is 0.4MPa, and reaction 2h finally obtains reaction paste;
(2) dilution: reaction paste uses diluent to naoh concentration to be 350g/L, obtains mixed slurry; Thinner adopts technological process step last time (3) to obtain washings;
(3) solid-liquid separation: mixed slurry 110 ℃ of filtering separation, is obtained dissolution fluid and rich calcium tailings; Described rich calcium tailings carries out multi-stage countercurrent washing with clear water, and the washings that obtains is used for the dilution technique of next technological process;
(4) dissolution fluid removal of impurities: in dissolution fluid, add NaAlO
2And CaO (weight ratio 1:1) removal of impurities, obtain after the removal of impurities liquid after the solid-liquid separation and contain white residue; NaAlO
2With the add-on of CaO be SiO in the dissolution fluid
21.0 times of weight;
(5) vanadic acid sodium crystallization: vanadic acid sodium crystallization: liquid after the removal of impurities is cooled to 45 ℃ naturally by 110 ℃, and the stirring velocity in the process of cooling is 250 rev/mins; Crystallization 2.0h separates obtaining the vanadic acid sodium crystal product then; Through detecting, the leaching yield of slag vanadium is 99.4%, V in the finishing slag
2O
5Content is reduced to 0.10wt%;
(6) crystalline mother solution returns circulating reaction next time through evaporation concentration, and rich calcium tailings both can be used as ferrous metallurgy raw material or desiliconization raw material after advancing the washing of three stage countercurrents.
Embodiment 4: this method that from v-bearing steel slag, reclaims vanadium adopts following process step.
(1) reaction: in autoclave, add the NaOH solution of v-bearing steel slag and 10wt%; Wherein, sodium hydroxide solution: v-bearing steel slag=10:1 (quality), v-bearing steel slag contains V
2O
52.0wt%; Be heated to 300 ℃, the still internal pressure is 7.5MPa, and reaction 1.0h finally obtains reaction paste;
(2) dilution: reaction paste uses clear water to be diluted to naoh concentration to be 100g/L, to obtain mixed slurry.
(3) solid-liquid separation: mixed slurry 130 ℃ of filtering separation, is obtained dissolution fluid and rich calcium tailings.
(4) dissolution fluid removal of impurities: in dissolution fluid, add Al (OH)
3Removal of impurities obtains after the removal of impurities liquid and contains white residue after the solid-liquid separation; Al (OH)
3Add-on be SiO in the dissolution fluid
22.0 times of weight;
(5) vanadic acid sodium crystallization: vanadic acid sodium crystallization: liquid after the removal of impurities is cooled to 50 ℃ naturally by 130 ℃, and the stirring velocity in the process of cooling is 100 rev/mins; Crystallization 3.0h separates obtaining the vanadic acid sodium crystal product then.Through detecting, the leaching yield of slag vanadium is 96.1%, V in the finishing slag
2O
5Content is reduced to 0.14wt%.
Embodiment 5: this method that from v-bearing steel slag, reclaims vanadium adopts following process step.
(1) reaction: in autoclave, add the NaOH solution of v-bearing steel slag and 45wt%; Wherein, sodium hydroxide solution: v-bearing steel slag=3:1 (quality), v-bearing steel slag contains V
2O
510wt%; Be heated to 350 ℃, the still internal pressure is 12MPa, and reaction 0.5h finally obtains reaction paste;
(2) dilution: reaction paste uses clear water to be diluted to naoh concentration to be 400g/L, to obtain mixed slurry;
(3) solid-liquid separation: mixed slurry 80 ℃ of filtering separation, is obtained dissolution fluid and rich calcium tailings;
(4) dissolution fluid removal of impurities: in dissolution fluid, add Al
2O
3Removal of impurities obtains after the removal of impurities liquid and contains white residue after the solid-liquid separation; Al
2O
3Add-on be SiO in the dissolution fluid
21.5 times of weight;
(5) vanadic acid sodium crystallization: vanadic acid sodium crystallization: liquid after the removal of impurities is cooled to 30 ℃ naturally by 80 ℃, and the stirring velocity in the process of cooling is 400 rev/mins; Crystallization 0.5h separates obtaining the vanadic acid sodium crystal product then.Through detecting, the leaching yield of slag vanadium is 98.8%, V in the finishing slag
2O
5Content is reduced to 0.94wt%.
Embodiment 6: this method that from v-bearing steel slag, reclaims vanadium adopts following process step.
(1) reaction: in autoclave, add the NaOH solution of v-bearing steel slag and 35wt%; Wherein, sodium hydroxide solution: v-bearing steel slag=6:1 (quality), v-bearing steel slag contains V
2O
56.5wt%; Be heated to 180 ℃, the still internal pressure is 0.3MPa, and reaction 10h obtains reaction paste;
(2) dilution: reaction paste uses diluent to naoh concentration to be 300g/L, obtains mixed slurry; Thinner adopts technological process step last time (3) to obtain washings;
(3) solid-liquid separation: mixed slurry 120 ℃ of filtering separation, is obtained dissolution fluid and rich calcium tailings; Described rich calcium tailings water carries out multi-stage countercurrent washing, and the washings that obtains is used for the dilution technique of next technological process;
(4) dissolution fluid removal of impurities: in dissolution fluid, add NaAlO
2And Al (OH)
3(weight ratio 2:1) removal of impurities obtains after the removal of impurities liquid and contains white residue after the solid-liquid separation; NaAlO
2And Al (OH)
3Add-on be SiO in the dissolution fluid
21.0 times of weight;
(5) vanadic acid sodium crystallization: liquid after the removal of impurities is cooled to 40 ℃ naturally by 120 ℃, and the stirring velocity in the process of cooling is 300 rev/mins; Crystallization 2.5h separates obtaining the vanadic acid sodium crystal product then; Through detecting, the leaching yield of slag vanadium is 98.6%, V in the finishing slag
2O
5Content is reduced to 0.11wt%;
(6) remaining crystalline mother solution gets in the autoclave of step (1) through evaporation concentration after the crystallization, gets into circulating reaction next time, and rich calcium tailings can be used as the ferrous metallurgy raw material after advancing the washing of three stage countercurrents.
Claims (9)
1. method that from v-bearing steel slag, reclaims vanadium is characterized in that this method adopts following process step: (1) reaction: v-bearing steel slag reacts in mass concentration is 10%～50% NaOH solution, obtains reaction paste; The mass ratio of said NaOH solution and slag is 3:1～10:1, and temperature of reaction is 180 ℃～350 ℃, and the reaction times is 0.5～10h, and reaction pressure is 0.3～12MPa;
(2) dilution: using thinner is 100～400g/L with the naoh concentration that reaction paste is diluted to slurry, obtains containing the mixed slurry of rich iron tailings and sodium hydroxide, vanadic acid sodium;
(3) solid-liquid separation: mixed slurry is carried out solid-liquid separation, obtain rich calcium tailings and the dissolution fluid that contains sodium hydroxide, vanadic acid sodium and water-soluble impurity component;
(4) removal of impurities: dissolution fluid is added desiliconization agent carry out removal of impurities; Solid-liquid separation then obtains after the removal of impurities liquid and contains white residue;
(5) crystallization:, promptly obtain the vanadic acid sodium product with but crystallization of liquid cooling after the removal of impurities.
2. the method that from v-bearing steel slag, reclaims vanadium according to claim 1, it is characterized in that: the NaOH solution in the said step (1) and the mass ratio of v-bearing steel slag are that 4:1 is to 6:1; Described temperature of reaction is that 200～300 ℃, reaction times are for being 1～4h.
3. the method that from v-bearing steel slag, reclaims vanadium according to claim 1, it is characterized in that: the thinner in the said step (2) is a clear water, or the rich calcium tailings in the said step (3) carries out the washings that obtains after the multi-stage countercurrent washing with clear water.
4. the method that from v-bearing steel slag, reclaims vanadium according to claim 1 is characterized in that: mixed slurry carries out solid-liquid separation at 80～130 ℃ in the said step (3).
5. the method that from v-bearing steel slag, reclaims vanadium according to claim 1, it is characterized in that: the desiliconization agent in the said step (4) is Al
2O
3, Al (OH)
3, NaAlO
2, among CaO and the MgO one or more; The add-on of said desiliconization agent is SiO in the dissolution fluid
21～3 times of weight.
6. the method that from v-bearing steel slag, reclaims vanadium according to claim 6, it is characterized in that: said desiliconization agent is CaO and/or NaAlO
2The add-on of said desiliconization agent is SiO in the dissolution fluid
21.5 times of weight.
7. from v-bearing steel slag, reclaim the method for vanadium according to described any one of claim 1-6, it is characterized in that the crystallisation by cooling in the said step (5) is: liquid is cooled to 30～50 ℃, growing the grain 0.5～3h by 80～130 ℃ after the removal of impurities; Stirring velocity in the said process of cooling is 100～400 rev/mins.
8. the method that from v-bearing steel slag, reclaims vanadium according to claim 7, it is characterized in that described crystallisation by cooling is: liquid is cooled to 40 ℃, growing the grain 1h by 80～100 ℃ after the removal of impurities; Stirring velocity in the said process of cooling is 150～250 rev/mins.
9. from v-bearing steel slag, reclaim the method for vanadium according to described any one of claim 1-6, it is characterized in that: the crystalline mother solution that obtains after said step (5) crystallization joins in the said reaction of step (1) as circulation fluid.
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Cited By (9)
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| CN103276227A (en) * | 2013-05-17 | 2013-09-04 | 中国科学院过程工程研究所 | Method for extracting vanadium from vanadium-titanium magnetite concentrates |
| CN103725892A (en) * | 2013-12-13 | 2014-04-16 | 金川集团股份有限公司 | Method for recycling valuable metals from precious smelting slag |
| CN105132676A (en) * | 2015-09-11 | 2015-12-09 | 吕志芳 | Hydrometallurgy matched equipment capable of cyclically using water |
| CN106756117A (en) * | 2016-12-14 | 2017-05-31 | 安徽工业大学 | A kind of method that Rock coal containing alum and v-bearing steel slag combine vanadium enrichment |
| CN107236870A (en) * | 2017-06-22 | 2017-10-10 | 中国科学院过程工程研究所 | A kind of method of v-bearing steel slag carbonization vanadium extraction |
| CN107287453A (en) * | 2017-06-22 | 2017-10-24 | 河钢股份有限公司承德分公司 | A kind of method of v-bearing steel slag ion exchange method vanadium extraction |
| CN107892317A (en) * | 2017-11-14 | 2018-04-10 | 河钢股份有限公司承德分公司 | A kind of vanadium reclaimed in calcification precipitation tailings and the method for preparing nano-calcium carbonate |
| CN108658126A (en) * | 2018-06-29 | 2018-10-16 | 河钢股份有限公司承德分公司 | A method of extracting vanadium from calcium phosphorus slag |
| CN110396611A (en) * | 2019-07-25 | 2019-11-01 | 河钢股份有限公司承德分公司 | A method of recycling vanadium iron dedusting ash prepares sodium vanadate solution |
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