CN104017999A - Vanadium extraction method for converter vanadium slag - Google Patents
Vanadium extraction method for converter vanadium slag Download PDFInfo
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- CN104017999A CN104017999A CN201410290331.3A CN201410290331A CN104017999A CN 104017999 A CN104017999 A CN 104017999A CN 201410290331 A CN201410290331 A CN 201410290331A CN 104017999 A CN104017999 A CN 104017999A
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Abstract
The invention relates to a vanadium extraction method for converter vanadium slag, belonging to the field of resource recycling. The vanadium extraction method for converter vanadium slag comprises the following steps: a. acid pickling: adding sulfuric acid into the converter vanadium slag, agitating and filtering to obtain a filtrate, namely vanadium-containing acid pickling liquid; b. reduction: adding a reductant into the vanadium-containing acid pickling liquid for conducting reduction treatment to reduce VO2<+> and Fe<3+> in the vanadium-containing acid pickling liquid into VO<2+> and FE<2+> so as to obtain a reduced acid pickling liquid; c. synergistic extraction-back extraction: extracting the reduced acid pickling liquid, and then conducting back extraction to the obtained organic phase, wherein subnatant is a vanadium-containing solution. Further, the invention discloses a preparation method of vanadium pentoxide. The method is simple in extraction technology compared with the traditional technology, lower in requirement on equipment due to low temperature and low acidity, and free from the use of a rotary kiln or multi-hearth furnace and other high-temperature roasting equipment; the extraction and purification of vanadium in the acid pickling liquid is facilitated by conducting reduction pretreatment to the acid pickling liquid and extraction and back extraction to low-valent vanadium.
Description
Technical field
The present invention relates to the extraction vanadium method of From Converter Vanadium-bearing Slag, belong to resource and reclaim field.
Background technology
In the process for extracting vanadium taking From Converter Vanadium-bearing Slag as raw material of report, mainly adopt alkali salt roasting-extract technology at present, destroy the vanadium iron spinel structure in raw material, make valuable element in slag be easy to leach.How raw material after roasting, be combined with alkali salt and generate water miscible vanadic acid sodium or acid soluble vanadic acid calcium.But roasting process easily produces Cl
2, the obnoxious flavour such as HCl and a large amount of CO
2greenhouse gases, major polluting atmosphere environment; Roasting process need to use the equipment such as fluidizing furnace or rotary kiln simultaneously, and technical process is long, and supplies consumption amount is large.Along with the attention of the whole world to environment protection and raising utilization of resources, and the fast development of hydrometallurgy strengthening leaching-out technique, the inferior position of roasting-extract technology manifests gradually.
For the extraction of the vanadium containing vanadic acid immersion liquid, because acidleach process ion selectivity is not strong, most of valuable metal all enters into pickling liquor, and it is high that these traditional technologys of the precipitator method and recrystallization method are not suitable for processing foreign matter content, the Leaching Systems that kind is many.Conventional pickling liquor extraction vanadium method mainly contains ion exchange method and solvent extration at present, wherein common with solvent extration.Solvent extraction can make lower concentration vanadium obtain enrichment on the one hand, makes on the other hand vanadium in pickling liquor separate with impurity.Existing extraction process, normally using sulfonated kerosene as organic solvent, according to the selective extraction of extraction agent and extracting power, adds one or two kinds of extraction agents and extracts promotor.Can from acidic solution, there be amine extractant and acidic phosphorus extractant by the extraction agent of extracting vanadium.Wherein amine extractant is used for extracting V (V), acidic phosphorus extractant both can extract V (IV), can extract again V (V), and under acidic conditions, the extracting power of V (IV) is better than to V (V).
At present in process for extracting vanadium, mainly can be divided into four classes according to raw material and composition difference: a class is for vanadium titano-magnetite From Converter Vanadium-bearing Slag, adopt traditional sodium roasting-leaching, calcification baking-leaching, saltless roasting-leaching and without the vanadium extraction of roasting direct leaching process.Sodium roasting-extract technology is most widely used, and technology is the most ripe, is applicable to the extraction vanadium method taking From Converter Vanadium-bearing Slag as raw material; Calcification baking-extract technology is higher mainly for calcic in raw material, and roasting material is not easy to water logging and adopts roasting to generate the method for vanadic acid calcium acidleach; Without roasting-extract technology mainly for the extraction vanadium method taking bone coal as raw material.
(1) in Chinese patent 92108960.0 " a kind of method of processing vanadium slag extraction Vanadium Pentoxide in FLAKES ", high temperature vanadium slag is carried out to an alkali metal salt roasting+oxygen-rich oxide-water logging technique, according to liquid-solid ratio≤1,100 DEG C～250 DEG C of temperature, the leaching condition of buck mass ratio 0.5～0.6, and to carrying out precipitation containing vanadium leachate, the refining Vanadium Pentoxide in FLAKES that obtains;
(2) Chinese patent 200510032012.3 " a kind of method of extracting Vanadium Pentoxide in FLAKES from navajoite stone " provides a kind of technique of producing Vanadium Pentoxide in FLAKES containing navajoite stone calcification baking-dilute sulfuric acid-vanadium liquid purification-ion-exchange-pyrolysis deamination.This technique has good leaching effect for the higher raw material of calcic, but roasting process complexity, and technical process is long, produces a large amount of obnoxious flavoures, contaminate environment in production process;
(3) in Chinese patent 200510031722.4 " a kind of baking composite additive with sodium for extracting vanadium ", account for containing 10%～15% of vanadium slag gross weight at composite additive, under 750 DEG C～800 DEG C conditions of maturing temperature, roasting just can reach roasting effect for 2 hours.Although improved roasting efficiency in this patent, the control difficulty of composite additive consumption, has relatively high expectations to production technology and operation water product;
(4) Chinese patent 99115427.4 " a kind of from the turnover method containing vanadium extraction navajoite stone roasting material and in coal calcination-directly the leach application in process for extracting vanadium ", its principal feature is that next step completes oxidation and decarbonization process 800 DEG C～1000 DEG C conditions, one group of quiet soaking of acid adding after pulverizing, one group adds that alkali is quiet to be soaked, then soda acid leach liquor is mixed to pH value 6～9, add flocculation agent purification and impurity removal, this technique has reduced supplies consumption, but the leaching yield of roasting material is not satisfactory;
(5) Chinese patent 200610011042.0 method of bone coal oxidative conversion of leached vanadium " under the pressure field from " is by joining bone coal, oxygenant, sulfuric acid autoclave, control suitable invert point, pressure and reaction times, the vanadium that direct oxidation transforms in bone coal enters solution.
Therefore, find a kind of low pollution, the high efficiency extraction vanadium method without roasting-extract technology From Converter Vanadium-bearing Slag, seem particularly important.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of extraction vanadium method of From Converter Vanadium-bearing Slag.
The extraction vanadium method of From Converter Vanadium-bearing Slag of the present invention, comprises the steps:
A, acidleach: by adding sulfuric acid, stirring, filtration in From Converter Vanadium-bearing Slag, obtain filtrate, obtain containing vanadic acid immersion liquid;
B, reduction: containing adding reductive agent in vanadic acid immersion liquid, reduce processing, will be containing VO in vanadic acid immersion liquid
2 +be reduced to VO
2+, Fe
3+be reduced to Fe
2+, obtain reductinic acid immersion liquid;
C, synergistic extraction-reextraction: to reductinic acid, immersion liquid extracts, then strip the organic phase obtaining, and subnatant is containing vanadium solution;
Wherein, extraction conditions is:
Extraction agent is the mixture of two (2-ethylhexyl phosphoric acids), tributyl phosphate, sulfonated kerosene composition, by volume, and two (2-ethylhexyl phosphoric acids): tributyl phosphate: sulfonated kerosene=5～25:5:70～90; Extraction phase is than (O/A)=0.6～1.2:1;
Reextraction condition is:
Wherein, the sulfuric acid that reverse-extraction agent is 50～300g/L, (O/A)=(2～10) are compared in back extraction: 1.
Wherein, in a step, the pH value containing vanadic acid immersion liquid is preferably 0.5～3.0.
Further, as preferred version, in a step, sulfuric acid concentration is 100～250g/L, the solid-liquid ratio of From Converter Vanadium-bearing Slag and sulphuric acid soln is 1:(5～20) g/ml, acidleach temperature is 90～160 DEG C, and leaching time is 30～150min, and stir speed (S.S.) is 100～600rpm.
Preferably, the particle diameter≤0.075mm of described From Converter Vanadium-bearing Slag.
Further, in b step, reductive agent is preferably Na
2sO
3, Na
2s
2o
3, at least one in CuCl; More preferably Na
2sO
3.The consumption of reductive agent is preferably 1.1～1.5 times of theoretical consumption.
Further, as preferred version, in c step, by volume, two (2-ethylhexyl phosphoric acids): tributyl phosphate: sulfonated kerosene=20:5:75; Extraction phase is than (O/A)=1:1.
Preferably, in c step, extraction temperature is 20～60 DEG C, and when extraction, the concussion time is 2～15min, and optimum extraction progression is judged according to optimum extraction condition.
As preferred version, in described c step, (O/A)=5:1 is compared in back extraction.
Further, the invention also discloses the preparation method of Vanadium Pentoxide in FLAKES, comprise the steps:
A, be 100～250g/L sulfuric acid by adding concentration in the From Converter Vanadium-bearing Slag of particle diameter≤0.0075mm, be heated to 90～160 DEG C and stir 30～150min, filtration with 100～600rpm speed, obtain filtrate, obtain containing vanadic acid immersion liquid; Wherein, the solid-liquid ratio of From Converter Vanadium-bearing Slag and sulphuric acid soln is 1:(5～20) g/ml;
B, reduction: containing adding reductive agent in vanadic acid immersion liquid, reduce processing, will be containing VO in vanadic acid immersion liquid
2 +be reduced to VO
2+, Fe
3+be reduced to Fe
2+, obtain reductinic acid immersion liquid; Described reductive agent is Na
2sO
3, Na
2s
2o
3, at least one in CuCl; The consumption of reductive agent is 1.1～1.5 times of theoretical consumption;
C, synergistic extraction-reextraction: to reductinic acid, immersion liquid extracts, then strip the organic phase obtaining, and subnatant is containing vanadium solution;
Wherein, extraction conditions is:
Extraction agent is the mixture of two (2-ethylhexyl phosphoric acids), tributyl phosphate, sulfonated kerosene composition, by volume, and two (2-ethylhexyl phosphoric acids): tributyl phosphate: sulfonated kerosene=5～25:5:70～90; Extraction phase is than (O/A)=0.6～1.2:1; Extraction temperature is 20～60 DEG C, and when extraction, the concussion time is 2～15min, and optimum extraction progression is judged according to optimum extraction condition;
Reextraction condition is:
Wherein, the sulfuric acid that reverse-extraction agent is 50～300g/L, (O/A)=(2～10) are compared in back extraction: 1;
D, oxidation: to the oxygenant containing adding 1.3～1.5 times of theoretical consumptions in vanadium solution, by the VO containing in vanadium solution
2+be oxidized to VO
2 +; Described oxygenant is NaClO, KClO
3and Cl
2in at least one in;
E, ammonium salt precipitation, washing, calcining, obtain Vanadium Pentoxide in FLAKES.
Preferably, in c step, by volume, two (2-ethylhexyl phosphoric acids): tributyl phosphate: sulfonated kerosene=20:5:75; Extraction phase is than (O/A)=1:1, and (O/A)=5:1 is compared in back extraction.
Beneficial effect of the present invention:
(1) cancel roasting pretreatment process section, and directly adopted acidleach to destroy vanadium iron spinel structure, shortened technical process; Do not add an alkali metal salt, reduced material consumption;
(2) extract technology is simple compared with traditional technology, and the low acid of low temperature is lower to equipment requirements, without the high temperature such as rotary kiln or multiple hearth furnace roasting apparatus;
(3) pickling liquor is carried out to reduction pretreatment, Low Valent Vanadium is extracted and back extraction, be conducive to the extraction and cleanup of vanadium in pickling liquor.
Embodiment
The extraction vanadium method of From Converter Vanadium-bearing Slag of the present invention, comprises the following steps:
A, acidleach: by adding sulfuric acid, stirring, filtration in From Converter Vanadium-bearing Slag, obtain filtrate, obtain containing vanadic acid immersion liquid;
B, reduction: containing adding reductive agent in vanadic acid immersion liquid, reduce processing, will be containing VO in vanadic acid immersion liquid
2 +be reduced to VO
2+, Fe
3+be reduced to Fe
2+, obtain reductinic acid immersion liquid;
C, synergistic extraction-reextraction: to reductinic acid, immersion liquid extracts, then strip the organic phase obtaining, and subnatant is containing vanadium solution;
Wherein, extraction conditions is:
Extraction agent is the mixture of two (2-ethylhexyl phosphoric acids), tributyl phosphate, sulfonated kerosene composition, by volume, and two (2-ethylhexyl phosphoric acids): tributyl phosphate: sulfonated kerosene=5～25:5:70～90; Extraction phase is than (O/A)=0.6～1.2:1;
Reextraction condition is:
Wherein, the sulfuric acid that reverse-extraction agent is 50～300g/L, (O/A)=(2～10) are compared in back extraction: 1.
Wherein, in a step, the pH value containing vanadic acid immersion liquid is preferably 0.5～3.0.
Wherein, two (2-ethylhexyl phosphoric acids) also referred to as TBP, all can adopt commercially available prod also referred to as P204 extraction agent, tributyl phosphate, and sulfonated kerosene is that commercially available technical grade kerosene is through sulfuric acid sulfonation gained.
Further, From Converter Vanadium-bearing Slag described in a step is the vanadium slag obtaining after the blowing of finger blast furnace vanadium-bearing hot metal.In order to accelerate the preparation containing vanadic acid immersion liquid, improve leaching process thermodynamic condition, in a step, also need heating, stir simultaneously, then to carry out acidleach, then obtain through solid-liquid separation, liquid phase is containing vanadic acid immersion liquid, and solid phase is for leaching rich titanium slag.PH value containing vanadic acid immersion liquid is preferably 0.5～3.0.
Further, in order to improve the leaching yield of vanadium, ensure under the condition of enough raw material ratio, preparation is preferably 100～250g/L containing the sulfuric acid concentration of vanadic acid immersion liquid, the solid-liquid ratio of From Converter Vanadium-bearing Slag and sulphuric acid soln is preferably 1:(5～20) g/ml, acidleach temperature is preferably 90～160 DEG C, and leaching time is preferably 30～150min, and stir speed (S.S.) is preferably 100～600rpm.
Further, in order to promote vanadium slag and sulfuric acid contact area, accelerate the preparation containing vanadic acid immersion liquid, described From Converter Vanadium-bearing Slag preferably carries out ball milling, ball milling granularity≤0.075mm before being that sulfuric acid mixes.
Further, in the extraction system of c step, two (2-ethylhexyl phosphoric acids), as acidic phosphorus extractant, have high selectivity to V (IV), but simultaneously to Fe
3+also there is certain extracting power and to Fe
2+without extracting power, in order better to separate vanadium, iron, before extraction, reduce processing, make to contain the Fe in vanadic acid immersion liquid
3+be reduced to Fe
2+, avoid iron to enter organic phase; A step reductive agent is preferably Na
2sO
3, Na
2s
2o
3with at least one in CuCl, more preferably Na
2sO
3, in order to make containing all Fe in vanadic acid immersion liquid
3+thoroughly be reduced to Fe
2+, simultaneously for fear of waste, the consumption of reductive agent can be a little more than theoretical consumption, Na
2sO
3consumption be preferably 1.1～1.5 times of theoretical consumption.Meanwhile, extraction system almost without extracting power, can reach the object of thorough purification vanadium extraction to impurity elements such as metal ion and phosphorus such as chromium, titanium, manganese, the reaction that extraction process occurs:
VO
2 2++(HR
2PO
4)
2(O)＝VO
2[R
2PO
4]H
2(O)+2H
+
Further, extraction conditions is preferably, by volume, and two (2-ethylhexyl phosphoric acids): tributyl phosphate: sulfonated kerosene=20:5:75; Extraction phase is than (O/A)=1:1.
Wherein, in order to improve extraction agent activity, improve effect of extracting, extraction temperature is preferably 20～60 DEG C, and when extraction, the concussion time is preferably 2～15min, and optimum extraction progression is judged according to optimum extraction condition.
Further, reextraction can, by the vanadium back extraction in extraction liquid in strip liquor, select suitable back extraction system can make vanadium further be purified simultaneously, therefore, after extracting, the organic phase that extraction is obtained is stripped, as preferred version, reverse-extraction agent is the sulfuric acid of 50～300g/L, back extraction is compared (O/A) for 5:1, through stripping, after two are separated, subnatant is strip liquor, also containing vanadium solution.
Wherein, what c step obtained contains in vanadium solution, and because this technique is taked the non-means of oxygen rich leaching of normal pressure, most of vanadium is with low price (VO
2+) form leaching, and have a small amount of part vanadium with high price (VO
2 +) form leaching.In order better the vanadium containing in vanadic acid immersion liquid to be extracted, and adopting under the prerequisite of extracting process, vanadium can all be leached, separate with other elements simultaneously, obtain pure, valence stability containing vanadium solution, the rational additive of this process choice carries out pre-treatment to it.
After measured, above-mentioned have significantly and improve containing vanadiumcontent in vanadium solution, and taking vanadiumcontent as 9.83% vanadium slag is as example, after above-mentioned steps is processed, vanadiumcontent can be up to more than 92.70%.
By aforesaid method to containing after vanadic acid immersion liquid processes, also can, by carrying out aftertreatment containing vanadium solution, obtain Vanadium Pentoxide in FLAKES product.Such as adding suitable oxygenant by the Low Valent Vanadium oxidation containing in vanadium solution, then add ammonium chloride to carry out conventional ammonium salt precipitation step, calcining step, obtains Vanadium Pentoxide in FLAKES product.
Further, above-mentioned oxygenant can be NaClO, KClO
3and Cl
2in at least one in, be preferably NaClO; In order to make Low Valent Vanadium oxidation completely, avoid unnecessary waste simultaneously, the consumption of oxygenant is theoretical consumption 1.3～1.5 times.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among described scope of embodiments.
Na used in the embodiment of the present invention
2sO
3, two (2-ethylhexyl phosphoric acid) (being P204) and tributyl phosphate (being TBP) are analytical pure, sulfonated kerosene be commercially available technical grade kerosene through sulfuric acid sulfonation gained, From Converter Vanadium-bearing Slag main component and content are as shown in table 1.
The chemical composition (wt%) of table 1 From Converter Vanadium-bearing Slag
Embodiment 1
By From Converter Vanadium-bearing Slag fragmentation, ball milling, get granularity-0.075～+ 0.055mm (200～+ 260 order) From Converter Vanadium-bearing Slag 100g, join in the sulphuric acid soln that just acid concentration is 200g/L, make vanadium enter into pickling liquor with vanadium sulfate acyl form, acid leaching process condition is: in ratio (liquid-solid ratio) 10:1 of sulfuric acid volume and From Converter Vanadium-bearing Slag quality, extraction time 90min, stir speed (S.S.) 500rpm, 130 DEG C of extraction temperatures.After leaching, carry out liquid-solid separation, obtain respectively containing vanadic acid immersion liquid and rich titanium slag.The leaching yield of vanadium is 96.63%, and the leaching yield of titanium is 15.95%, contains vanadium 0.76% in leached mud.
Containing main component in vanadic acid immersion liquid be: T[V]=9.83g/L, Ti=0.18g/L, Fe=28.19g/L, Mn=2.37g/L, Cr=1.38g/L, P=0.003g/L.In this solution, add 1.5 times to the Na of theoretical consumption
2sO
3after sufficient reacting, filter, and filtrate is extracted, extractant condition is: normal temperature (20 DEG C), pickling liquor (water) initial pH value 2.0, extraction agent composition: 20%P204+5%TBP+75% sulfonated kerosene, extraction phase, than (O/A) 1:1, shakes time 5min.In extraction gained raffinate, vanadium, iron level are respectively 2.51g/L and 27.65g/L, and one-level percentage extraction is respectively 74.49% and 1.92%, reaches 97.89% through the percentage extraction of level Four cross current solvent extraction vanadium.
In gained level Four cross current solvent extraction organic phase, vanadium, iron level are respectively 7.32g/L and 0.175g/L, extracted organic phase is carried out to back extraction with the dilute sulphuric acid of 200g/L, stripping process condition is: (O/A) 5:1 is compared in back extraction, concussion time 4min, under this condition, the back extraction ratio of vanadium reaches 98.57%, a small amount of iron, chromium plasma in organic phase do not enter containing vanadium solution, and vanadium extraction pickling liquor is purified.
After measured, after above-mentioned steps is processed, be 36.08g/L containing content of vanadium in vanadium solution.
Embodiment 2
By From Converter Vanadium-bearing Slag fragmentation, ball milling, gets granularity-0.075～+ 0.055mm (200～+ 260 order) From Converter Vanadium-bearing Slag 100g, joins in the sulphuric acid soln that just acid concentration is 200g/L, makes vanadium with vanadium sulfate acyl (VO
2+) form enters into pickling liquor, acid leaching process condition is: in sulfuric acid volume: the ratio (liquid-solid ratio) of From Converter Vanadium-bearing Slag quality is 20:1, extraction time 120min, stir speed (S.S.) 500rpm, 100 DEG C of extraction temperatures.After leaching, carry out liquid-solid separation, obtain the leached mud containing vanadic acid immersion liquid and enrichment titanium.Under this condition, the leaching yield of vanadium is 88.97%, and the leaching yield of titanium is 15.95%, contains vanadium 3.45% in leached mud.
The technique containing in vanadic acid immersion liquid employing embodiment 1 obtaining is carried out to extraction and back-extraction gets.
After measured, after treatment through above-mentioned steps is 32.10g/L containing content of vanadium in vanadium solution.
Embodiment 3
By From Converter Vanadium-bearing Slag fragmentation, ball milling, get granularity-0.075～+ 0.055mm (200～+ 260 order) From Converter Vanadium-bearing Slag 100g, join in the sulphuric acid soln that just acid concentration is 150g/L, make vanadium enter into pickling liquor with vanadium sulfate acyl form, acid leaching process condition is: in sulfuric acid volume: the ratio (liquid-solid ratio) of From Converter Vanadium-bearing Slag quality is 10:1, extraction time 90min, stir speed (S.S.) 500rpm, 130 DEG C of extraction temperatures.After leaching, carry out liquid-solid separation, obtain respectively containing vanadic acid immersion liquid and rich titanium slag.The leaching yield of vanadium is 91.97%, and the leaching yield of titanium is 10.78%, contains vanadium 1.81% in leached mud.
By obtain containing vanadic acid immersion liquid, adopt technique in embodiment 1 to carry out extraction and back-extraction and get.
After measured, after treatment through above-mentioned steps is 33.87g/L containing content of vanadium in vanadium solution.
Embodiment 4
By From Converter Vanadium-bearing Slag fragmentation, ball milling, get granularity-0.075～+ 0.055mm (200～+ 260 order) From Converter Vanadium-bearing Slag 100g, join in the sulphuric acid soln that just acid concentration is 200g/L, make vanadium enter into pickling liquor with vanadium sulfate acyl form, acid leaching process condition is: in ratio (liquid-solid ratio) 10:1 of sulfuric acid volume and From Converter Vanadium-bearing Slag quality, extraction time 90min, stir speed (S.S.) 500rpm, 130 DEG C of extraction temperatures.After leaching, carry out liquid-solid separation, obtain respectively containing vanadic acid immersion liquid and rich titanium slag.The leaching yield of vanadium is 96.63%, and the leaching yield of titanium is 15.95%, contains vanadium 0.76% in leached mud.
Containing main component in vanadic acid immersion liquid be: T[V]=9.83g/L, Ti=0.18g/L, Fe=28.19g/L, Mn=2.37g/L, Cr=1.38g/L, P=0.003g/L.In this solution, add 1.1 times to the Na of theoretical consumption
2sO
3after sufficient reacting, filter, and filtrate is extracted, extractant condition is: normal temperature (20 DEG C), vanadium extraction pickling liquor (water) initial pH value 2.0, extraction agent composition: 5%P204+5%TBP+90% sulfonated kerosene, extraction phase, than (O/A) 1:1, shakes time 10min.In extraction gained raffinate, vanadium, iron level are respectively 4.11g/L and 26.69g/L, and one-level percentage extraction is respectively 58.17% and 5.32%.
According to the stripping process in embodiment 1, extracted organic phase is carried out to back extraction.
After measured, after treatment through above-mentioned steps is 22.96g/L containing content of vanadium in vanadium solution.
Claims (10)
1. the extraction vanadium method of From Converter Vanadium-bearing Slag, is characterized in that, comprises the steps:
A, acidleach: by adding sulfuric acid, stirring, filtration in From Converter Vanadium-bearing Slag, obtain filtrate, obtain containing vanadic acid immersion liquid;
B, reduction: containing adding reductive agent in vanadic acid immersion liquid, reduce processing, will be containing VO in vanadic acid immersion liquid
2 +be reduced to VO
2+, Fe
3+be reduced to Fe
2+, obtain reductinic acid immersion liquid;
C, synergistic extraction-reextraction: to reductinic acid, immersion liquid extracts, then strip the organic phase obtaining, and subnatant is containing vanadium solution;
Wherein, extraction conditions is:
Extraction agent is the mixture of two (2-ethylhexyl phosphoric acids), tributyl phosphate, sulfonated kerosene composition, by volume, and two (2-ethylhexyl phosphoric acids): tributyl phosphate: sulfonated kerosene=5～25:5:70～90; Extraction phase is than (O/A)=0.6～1.2:1;
Reextraction condition is:
Reverse-extraction agent is the sulfuric acid of 50～300g/L, and (O/A)=(2～10) are compared in back extraction: 1.
2. the extraction vanadium method of From Converter Vanadium-bearing Slag according to claim 1, is characterized in that: the pH value containing vanadic acid immersion liquid in a step is 0.5～3.0.
3. the extraction vanadium method of From Converter Vanadium-bearing Slag according to claim 1, it is characterized in that: in a step, sulfuric acid concentration is 100～250g/L, the solid-liquid ratio of From Converter Vanadium-bearing Slag and sulphuric acid soln is 1:(5～20) g/ml, acidleach temperature is 90～160 DEG C, leaching time is 30～150min, and stir speed (S.S.) is 100～600rpm.
4. the extraction vanadium method of From Converter Vanadium-bearing Slag according to claim 1, is characterized in that: the particle diameter≤0.075mm of described From Converter Vanadium-bearing Slag.
5. the extraction vanadium method of From Converter Vanadium-bearing Slag according to claim 1, is characterized in that: in b step, reductive agent is Na
2sO
3, Na
2s
2o
3, at least one in CuCl, be preferably Na
2sO
3; The consumption of reductive agent is 1.1～1.5 times of theoretical consumption.
6. the extraction vanadium method of From Converter Vanadium-bearing Slag according to claim 1, is characterized in that: in c step, by volume, two (2-ethylhexyl phosphoric acids): tributyl phosphate: sulfonated kerosene=20:5:75; Extraction phase is than (O/A)=1:1.
7. the extraction vanadium method of From Converter Vanadium-bearing Slag according to claim 1, is characterized in that: in c step, extraction temperature is 20～60 DEG C, and when extraction, the concussion time is 2～15min, and optimum extraction progression is judged according to optimum extraction condition.
8. the extraction vanadium method of From Converter Vanadium-bearing Slag according to claim 1, is characterized in that: in described c step, (O/A)=5:1 is compared in back extraction.
9. the preparation method of Vanadium Pentoxide in FLAKES, is characterized in that, comprises the steps:
A, be 100～250g/L sulfuric acid by adding concentration in the From Converter Vanadium-bearing Slag of particle diameter≤0.0075mm, be heated to 90～160 DEG C and stir 30～150min, filtration with 100～600rpm speed, obtain filtrate, obtain containing vanadic acid immersion liquid; Wherein, the solid-liquid ratio of From Converter Vanadium-bearing Slag and sulphuric acid soln is 1:(5～20) g/ml;
B, reduction: containing adding reductive agent in vanadic acid immersion liquid, reduce processing, will be containing VO in vanadic acid immersion liquid
2 +be reduced to VO
2+, Fe
3+be reduced to Fe
2+, obtain reductinic acid immersion liquid; Described reductive agent is Na
2sO
3, Na
2s
2o
3, at least one in CuCl; The consumption of reductive agent is 1.1～1.5 times of theoretical consumption;
C, synergistic extraction-reextraction: to reductinic acid, immersion liquid extracts, then strip the organic phase obtaining, and subnatant is containing vanadium solution;
Wherein, extraction conditions is:
Extraction agent is the mixture of two (2-ethylhexyl phosphoric acids), tributyl phosphate, sulfonated kerosene composition, by volume, and two (2-ethylhexyl phosphoric acids): tributyl phosphate: sulfonated kerosene=5～25:5:70～90; Extraction phase is than (O/A)=0.6～1.2:1; Extraction temperature is 20～60 DEG C, and when extraction, the concussion time is 2～15min, and optimum extraction progression is judged according to optimum extraction condition;
Reextraction condition is:
Wherein, the sulfuric acid that reverse-extraction agent is 50～300g/L, (O/A)=(2～10) are compared in back extraction: 1;
D, oxidation: to the oxygenant containing adding 1.3～1.5 times of theoretical consumptions in vanadium solution, by the VO containing in vanadium solution
2+be oxidized to VO
2 +; Described oxygenant is NaClO, KClO
3and Cl
2in at least one in;
E, ammonium salt precipitation, washing, calcining, obtain Vanadium Pentoxide in FLAKES.
10. the preparation method of Vanadium Pentoxide in FLAKES according to claim 9, is characterized in that: reductive agent is Na
2sO
3; By volume, two (2-ethylhexyl phosphoric acids): tributyl phosphate: sulfonated kerosene=20:5:75; Extraction phase is than (O/A)=1:1, and (O/A)=5:1 is compared in back extraction; Oxygenant is NaClO.
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| CN104357658A (en) * | 2014-11-05 | 2015-02-18 | 攀枝花兴辰钒钛有限公司 | Vanadium extraction process based on extraction-reverse extraction |
| CN106884089A (en) * | 2015-12-15 | 2017-06-23 | 北京矿冶研究总院 | Method for recovering vanadium from non-blast furnace titanium slag |
| CN107226484A (en) * | 2017-05-12 | 2017-10-03 | 重庆康普化学工业股份有限公司 | A kind of method that compound extracting prepares vanadic anhydride |
| CN107385265A (en) * | 2017-07-21 | 2017-11-24 | 湖南众鑫新材料科技股份有限公司 | A kind of high vanadium magnet prepares the production method of ferrovanadium nitride alloy |
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| CN115216649A (en) * | 2022-07-25 | 2022-10-21 | 中国石油大学(北京) | Method for preparing vanadium dioxide battery material by using waste vanadium titanium-based SCR catalyst |
| CN115247234A (en) * | 2020-10-17 | 2022-10-28 | 刘辉 | Method for preparing ammonium metavanadate by direct sulfuric acid oxidation and acidolysis of vanadium slag |
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| CN106884089A (en) * | 2015-12-15 | 2017-06-23 | 北京矿冶研究总院 | Method for recovering vanadium from non-blast furnace titanium slag |
| CN107226484A (en) * | 2017-05-12 | 2017-10-03 | 重庆康普化学工业股份有限公司 | A kind of method that compound extracting prepares vanadic anhydride |
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| CN110257647A (en) * | 2019-07-16 | 2019-09-20 | 昆明理工大学 | The method of vanadium is recycled from ferric vandate |
| CN115247234A (en) * | 2020-10-17 | 2022-10-28 | 刘辉 | Method for preparing ammonium metavanadate by direct sulfuric acid oxidation and acidolysis of vanadium slag |
| CN112281000A (en) * | 2020-10-29 | 2021-01-29 | 攀钢集团研究院有限公司 | Method for extracting vanadium from titanium tetrachloride refining tailings |
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