CN101182600A - Combined technology for separating and extracting vanadium from high calcium and high ferro steel scoria - Google Patents
Combined technology for separating and extracting vanadium from high calcium and high ferro steel scoria Download PDFInfo
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- CN101182600A CN101182600A CNA2007100659752A CN200710065975A CN101182600A CN 101182600 A CN101182600 A CN 101182600A CN A2007100659752 A CNA2007100659752 A CN A2007100659752A CN 200710065975 A CN200710065975 A CN 200710065975A CN 101182600 A CN101182600 A CN 101182600A
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 54
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000011575 calcium Substances 0.000 title claims abstract description 30
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 30
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 15
- 239000010959 steel Substances 0.000 title claims abstract description 15
- 238000005516 engineering process Methods 0.000 title claims description 15
- 241000876852 Scorias Species 0.000 title 1
- 238000000605 extraction Methods 0.000 claims abstract description 80
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- 238000002386 leaching Methods 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 238000001556 precipitation Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000002893 slag Substances 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 17
- 239000012074 organic phase Substances 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 239000012141 concentrate Substances 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 230000001627 detrimental effect Effects 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000003637 basic solution Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- 229910001655 manganese mineral Inorganic materials 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 28
- 239000000284 extract Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 5
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 239000003599 detergent Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 230000005484 gravity Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- -1 iron ion Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000002308 calcification Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
A metallurgic combination process for extracting vanadium from high-calcium high-iron steel residues relates to a method for extracting vanadium, in particular to a method for extracting vanadium from the waste steel residues with the metallurgic combination process. The steps of the process are as follows that the high-calcium high-iron steel residues are crushed and the reelection pattern is adopted for stripping down light calcium and other nocuous impurities; the refined ore is directly extracted with 95 to 98 percent concentrated sulphurinc acid and then the process of solid-liquid separation is implemented; the extracted liquid is oxidated and the acidity of the liquid is regulated to make the pH value be 1.4 to 2.5; the redox potential is -900mv to -300mv; by adopting the extraction of more than three grades, the extraction phase ratio of O/A is 1/8 to 1/1 and the water phase is unloaded; the load is organically washed and iron is stripped down to effectively realize iron-vanadium separation; the detergent is sulfate; the alkaline solution of 0.25 M to 1.5M is used for the reverse extraction agent for reverse extraction and the phase ratio O/A is 1/1 to 8/1; the process of acidic precipitation of vanadate-leaching Solution is implemented on the reverse extraction solution. The invention has simple process and can effectively extract vanadium from the high-calcium high iron steel residues; in this way, the invention is characterized by low cost, little pollution and high recovery rate.
Description
Technical field
The present invention relates to a kind of metallurgical method that extracts vanadium, particularly from the depleted slag, use selecting smelting combination technology extraction vanadium method.
Background technology
V-bearing steel slag results from the steelmaking process of vanadium-bearing hot metal, is characterized in calcium oxide, iron level height, and content of vanadium is low.Add vanadium occurrence patterns complexity in the v-bearing steel slag, the whole disperses of vanadium be distributed in multi mineral mutually in, is difficult to direct choosing, smelting and separates, thereby the vanadium extraction of high calcium high ferro v-bearing steel slag is difficult unusually.
The annual total flow rate of China slag reaches millions of tons, and is not only significant to resources effective utilization as vanadium that will be wherein extraction and application economically and reasonably because the v-bearing steel slag source is wide, total amount is big, and can bring remarkable economical, environment and social benefit.
A large amount of existence of calcium influence greatly the roasting transformation efficiency in the slag, because calcium easy and V in roasting process
2O
5Generate water-fast vanadic acid calcium (CaOV
2O
5) or calcareous vanadium bronze.Studies show that: the every increase by 1% of the massfraction of CaO, will bring 4.7%～9.0%V
2O
5Loss.And iron level height in the slag, not only influence roasting process (metallic iron is oxidation heat liberation in roasting process, can make the material bonding), be unfavorable for the oxidation of vanadium, and a large amount of existence of iron make it easily enter leach liquor with vanadium, bring severe bad influence for follow-up extraction, back extraction precipitation.Therefore, decalcification, deironing have become the key point and the difficult point of the efficient vanadium extraction of v-bearing steel slag.
Traditional sodium-salt calcination-water logging process for extracting vanadium, the leaching yield of vanadium is low, has only 45%-75%.Though the calcification baking that Recent study goes out-carbonating extract technology has solved the harm of calcium oxide, but no matter be sodium roasting or calcification baking, not only serious environment pollution is difficult to by environmental protection inspection and acceptance, and follow-up water logging or carbonating leach and also all have the very low problem of the rate of recovery.Adopt high-concentration sulfuric acid solution, though can improve the leaching yield of vanadium, but other component in the leaching process material is also dissolved, resulting leach liquor impurity is more, concentration is higher, especially a large amount of iron ion enters, not only serious disturbance follow-up extraction, back extraction precipitation process, and influenced V
2O
5Quality.
The purification of iron ion mainly contains the heavy iron processes of routine hydrolysis and with solvent extraction or ion exchange method vanadium is separated with iron ion in the leach liquor.And the outstanding feature of trivalent Fe is its intensive hydrolysis tendency and the ability that forms title complex in the aqueous solution, and therefore, in the time of the heavy iron of hydrolysis, the loss of vanadium is bigger.As seen, conventional method uses yellow soda ash or sodium hydrate regulator solution pH value to make Fe
2+, Fe
3+Generate precipitation of hydroxide and the thinking limitation of impurity and purification is too big Deng positively charged ion, and solution needs to consume a large amount of alkaline matters when being adjusted to neutrality, alkalescence, solution must concentrate after the removal of impurities, so its production cost height, production process are difficult to control.
Though existing useless admittedly process for extracting vanadium is many, ubiquity cost height, pollute big, the rate of recovery is low and the shortcoming of argument processing greatly, applies being restricted, and is and less to high calcium, high ferro slag suitability.So, seek short flow process, extensive, low-cost, comprehensive reutilization that oligosaprobic universality novel process is used for high calcium, the vanadium extraction of high ferro v-bearing steel slag and residue, be to contain vanadium one of the vanadium extraction new technology development in future important directions of giving up admittedly.
Summary of the invention
Technical problem to be solved by this invention provides a kind of selecting smelting combination technology of vanadium extraction from high calcium, high ferro slag, and its technology is lacked flow process, scale is big, low-cost, pollution is little, rate of recovery height.
Solve the scheme that technical problem of the present invention adopts following steps arranged:
(1) pulverizes high calcium high ferro slag, adopt reselection modes to slough light weight calcium and other parts detrimental impurity;
(2) directly leach with 95～98% the vitriol oil sorting concentrate, again solid-liquid separation;
(3) leach liquor is carried out the adjusting of oxidation and acidity, making pH is 1.4～2.5, redox potential is-and 900mv～-300mv;
(4) adopt extraction more than 3 grades, extraction phase is 1/8～1/1 than O/A, the unloading water;
(5) to the organic washing of load, remove iron, realize that effectively iron-vanadium separates, washing composition is a vitriol;
(6) carry out back extraction with 0.25M～1.5M basic solution as reverse-extraction agent, comparing O/A is 1/1～8/1, to containing the vanadium solution precipitation.
The present invention has also adopted following technical scheme:
When (1) pulverizing v-bearing steel slag, grinding fineness reaches more than the 55%-200 order; (2) the concentrate vitriolic acid consumption that sorts per ton is 1.0t/t ore deposit～2.0t/t ore deposit; Liquid-solid ratio is controlled at 1.5～8: 1, and extraction time 0.5h～5h; When (3) carrying out the adjusting of oxidation and acidity, oxygenant adopts any of hydrogen peroxide, sodium chlorate, manganese mineral, and acidity adjustment adopts any of ammoniacal liquor, sodium hydroxide, yellow soda ash, lime; When (4) extracting, the agent of main collection adopts amine, synergist to adopt phosphoric acid (one, two, three) butyl ester or 8～12 carbochain alcohols, thinner employing sulfonated kerosene solution or alkane; (5) to the organic washing of load, remove iron, realize that effectively iron-vanadium separates, washing composition is a vitriol; (6) adopt back extraction more than 1 grade during back extraction, reverse-extraction agent is any or a composite solution of yellow soda ash, sodium hydroxide, ammoniacal liquor, and organic phase is returned extraction process and recycled.Again strip liquor is carried out the acid ammonium salt precipitation
When V concentration in the acid leaching liquor of slag＞2%, the hydrogen peroxide consumption is 1%～6% of a leach liquor volume; The collection extraction is carried out under suitable agitation condition or oscillating condition, and two-phase is controlled in the 3min duration of contact; Consisting of of organic phase: the volume ratio of main collection agent is 5%～35%, and synergist is 2.5%～20%, and surplus is a thinner; To sorting the leaching agent that has also added its quality 1%～2% when concentrate leaches; Use the acid ammonium salt precipitation after the back extraction.
The invention has the beneficial effects as follows: can be in slag under the lower situation of calcium and iron level height, vanadium grade, remove light weight calcium and the part detrimental impurity has been avoided the disadvantageous effect of high calcium to leaching yield by ore dressing, better solved the harm of high calcium, increased substantially the leaching yield of vanadium, than being 8%～9% without the direct acidleach leaching yield of raw material under reselection conditions increase rate. And sort concentrate without roasting, directly acidleach, and eliminated of the pollution of conventional roasting process for extracting vanadium again to environment, reduced production cost significantly.
During the pickling liquor vanadium extraction, by the optimization of extraction system and the control of selection and extraction process condition, obtained and extracted index preferably, the percentage extraction of vanadium reaches more than 98.5%, and has suppressed the extraction of iron to a certain extent.The optimization of the setting of laundry operation and washing composition and composition thereof and concentration and selection have realized the selective separation of iron and vanadium preferably, have reached the purpose of deironing, have avoided the influence of high ferro to back extraction precipitation and pure vanadium quality product.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment 1
At first, river, Sichuan prestige group particle slag is pulverized, equipment adopts wet-type ball mill, and the milling product grinding fineness is to reach-200 orders more than 65%;
Ore milling product carries out gravity treatment, and equipment adopts cloud tin formula shaking table, and the vanadium major part has entered gravity concentrate, the rate of recovery of vanadium can reach more than 80%, light weight calcium and other detrimental impurity of part have then entered mine tailing, can abandon processing, thereby eliminate the disadvantageous effect of calcium to leaching yield.Leaching yield during the direct acidleach of gravity concentrate leaching yield raw material under similarity condition, the leaching yield increase rate is 8%～9%.
95～98% vitriol oil consumption is 1.3t/ (t ore deposit), liquid-solid ratio 4: 1, extraction time 1.5h during leaching, and the leaching agent consumption is 1% of an ore deposit amount, and leaching yield reaches more than 94%.
Leach liquor adopts industrial hydrogen peroxide as oxidant to carry out oxidation, and its consumption is 1.5% of a leach liquor volume, then, use ammoniacal liquor regulate extracting mother liquid acidity to pH=1.60 ± 0.05, Eh (redox potential) is approximately-710mv;
During extraction, organic phase and water volume ratio O/A=1: 3, two-phase should be controlled in the 3min duration of contact during extraction, and the extracted organic phase system is a 10%N235+5%TBP+85% sulfonated kerosene solution, and by the extraction of 6 stage countercurrents, percentage extraction has reached 98.50%.
After the extraction, load organic phases is washed, washing composition is the 0.3M metabisulfite solution, O/A=3: 1, the washing rate of iron reaches more than 98%, and vanadium only minute quantity enter washings, under the situation of Fe/V (concentration ratio)＞20, realize separating of iron and vanadium preferably, avoided in the solution high content iron to the disadvantageous effect of back extraction and precipitation, thereby reached the purpose of efficient deironing.
Reverse-extraction agent adopts 0.5MNa2CO3 solution reverse-extraction agent, O/A=3: 1, and back extraction ratio is more than 99%.Carrying out the acid ammonium salt precipitation then handles.
Embodiment 2
Research object v-bearing steel slag degree of oxidation is darker, need not carry out roasting and get final product.
Ore dressing pretreatment adopts dual mode:
(1) pulverize the employing wet-type ball mill, the milling product grinding fineness is the 70%-200 order; The ore grinding ore pulp carries out gravity treatment, and equipment adopts cloud tin formula shaking table, and gravity concentrate has reclaimed 80% vanadium, and has deviate from most of light weight calcium and other detrimental impurity of part, for follow-up extract technology provides comparatively qualified raw material.
(2) pulverize the employing dry ball, the milling product grinding fineness is the 70%-200 order; The directly acidleach of pulverizing back, but the leaching yield ratio is through hanging down 4%～9% with acidleach leaching yield under the condition after the re-selection process.
95～98% vitriol oil consumption is 1.3t/t ore deposit～1.8t/t ore deposit, liquid-solid ratio 3.5: 1, extraction time 1.5h～4h during leaching, and the leaching agent consumption is 1%～2% of an ore deposit amount, and leaching yield reaches more than 93%.
Leach liquor adopts industrial hydrogen peroxide as oxidant to carry out oxidation, and its consumption is 2.0%～2.5% of a leach liquor volume, then, uses ammoniacal liquor to regulate extracting mother liquid acidity to pH=1.50～1.60, and Eh (redox potential) is approximately-800mv;
During extraction, organic phase and water volume ratio O/A=1: 3, two-phase duration of contact is 3min during extraction.The organic phase system is a 6%N235+3%TBP+91% sulfonated kerosene solution during extraction, and by the extraction of 6 stage countercurrents, percentage extraction has reached more than 98%.
After the extraction, load organic phases is washed, washing composition is 0.3M～0.5M metabisulfite solution, O/A=2: 1～3: 1, the washing rate of iron reaches more than 98%, and vanadium only minute quantity enter washings, under the situation of Fe/V＞20, realize separating of iron and vanadium preferably, avoided in the solution high content iron to the disadvantageous effect of back extraction and precipitation, thereby reached the purpose of efficient deironing.
Reverse-extraction agent adopts 0.5MNa2CO3+0.25MNaCl solution reverse-extraction agent, O/A=3: 1, and back extraction ratio is more than 99%.Carrying out the acid ammonium salt precipitation then handles.
Embodiment 3
Certain v-bearing steel slag degree of oxidation is darker, but iron, calcium contents are higher, and calcium oxide content is up to 42%.Pulverize and adopt wet-type ball mill, the milling product grinding fineness is the 55%-200 order;
The ore grinding ore pulp carries out gravity treatment, and for saving equipment takes up an area of, equipment adopts spiral chute, and gravity concentrate has reclaimed 82% vanadium, and has deviate from most of light weight calcium and other detrimental impurity of part, for follow-up extract technology provides comparatively qualified raw material.
95～98% vitriol oil consumption is 1.5t/t ore deposit raw material, liquid-solid ratio 3.5: 1, extraction time 2.5h during leaching, does not add leaching agent, and leaching yield reaches more than 93%.
Leach liquor adopts industrial hydrogen peroxide as oxidant to carry out oxidation, and its consumption is 2.5% of a leach liquor volume, then, uses ammoniacal liquor to regulate extracting mother liquid acidity to pH=1.50; Eh (redox potential) is approximately-400mv;
During extraction, organic phase and water volume ratio O/A=1: 4, two-phase duration of contact is 3min during extraction, and the extracted organic phase system is a 20%N235+10%TBP+70% sulfonated kerosene solution, and by the extraction of 5 stage countercurrents, percentage extraction has reached more than 98%.
After the extraction, load organic phases is washed, washing composition is the 0.3M metabisulfite solution, O/A=2: 1, the washing rate of iron reaches more than 98%, and vanadium only minute quantity enter washings, under the situation of Fe/V＞20, realize separating of iron and vanadium preferably, avoided in the solution high content iron to the disadvantageous effect of back extraction and precipitation, thereby reached the purpose of efficient deironing.
Reverse-extraction agent adopts 0.5MNaCl+0.5MNaOH solution reverse-extraction agent, O/A=3: 1, and back extraction ratio is more than 99%.Carrying out the precipitation of acid ammonium salt then handles.
This vanadium extraction novel process combines the advantage of ore dressing and hydrometallurgy, realized perfect adaptation interdisciplinary, solved the technology and the economic headache of high calcium, high ferro slag vanadium extraction preferably, and this technology have the characteristics of environmental friendliness, short flow process, low cost, pollution-free, universality.The invention of this novel process, it is significant that China is contained efficiently utilizing of vanadium resource, and can bring remarkable economical, environment and social benefit.
Claims (3)
1. the selecting smelting combination technology of a vanadium extraction from high calcium, high ferro slag is characterized in that processing step is as follows:
(1) pulverizes high calcium high ferro slag, adopt reselection modes to slough light weight calcium and other parts detrimental impurity;
(2) directly leach with 95～98% the vitriol oil sorting concentrate, again solid-liquid separation;
(3) leach liquor is carried out the adjusting of oxidation and acidity, making pH is 1.4～2.5, redox potential is-and 900mv～-300mv;
(4) adopt extraction more than 3 grades, extraction phase is 1/8～1/1 than O/A, the unloading water;
(5) to the load organic phases washing, remove iron, washing composition is a vitriol;
(6) carry out back extraction with 0.25M～1.5M basic solution as reverse-extraction agent, comparing O/A is 1/1～8/1, to containing the vanadium solution precipitation.
2. by the selecting smelting combination technology of the described vanadium extraction from high calcium, high ferro slag of claim 1, it is characterized in that: when (1) pulverized v-bearing steel slag, grinding fineness reached more than the 55%-200 order; (2) the concentrate vitriolic acid consumption that sorts per ton is 1.0t/t ore deposit～2.0t/t ore deposit; Liquid-solid ratio is controlled at 1.5～8: 1, and extraction time 0.5h～5h; When (3) carrying out oxidation and acidity pre-treatment and regulate, oxygenant adopts any of hydrogen peroxide, sodium chlorate, manganese mineral, and acidity adjustment adopts any of ammoniacal liquor, sodium hydroxide, yellow soda ash, lime; When (4) extracting, the agent of main collection adopts amine, synergist to adopt butyl phosphate or 8～12 carbochain alcohols, thinner employing sulfonated kerosene solution or alkane; Washing composition is a vitriol when (5) load organic phases being washed; (6) the used reverse-extraction agent of back extraction is any or a composite solution of yellow soda ash, sodium hydroxide, ammoniacal liquor, and organic phase is returned extraction process and recycled.
3. according to the selecting smelting combination technology of claim 1 and 2 described vanadium extractions from high calcium, high ferro slag, it is characterized in that: when V concentration in the acid leaching liquor of slag＞2%, the hydrogen peroxide consumption is 1%～6% of a leach liquor volume; Extraction is carried out under agitation condition or oscillating condition, and two-phase is controlled in the 3min duration of contact; Consisting of of organic phase: the volume ratio of main collection agent is 5%～35%, and synergist is 2.5%～20%, and surplus is a thinner.To sorting the leaching agent that has also added its quality 1%～2% when concentrate leaches; Use the acid ammonium salt precipitation after the back extraction.
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Cited By (8)
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| CN102560116A (en) * | 2011-10-11 | 2012-07-11 | 虹京环保有限公司 | Method for recovering manganese and vanadium from titanium white waste acid, manganese slag and vanadium-containing steel slag |
| CN106048261A (en) * | 2016-08-22 | 2016-10-26 | 东北大学 | Method for extracting vanadium from acidic solution by using ionic liquid [OMIM]BF4 |
| CN107058753A (en) * | 2016-12-05 | 2017-08-18 | 张俊宝 | A kind of stainless steel slag recovery and reusing and recycling method |
| CN109609775A (en) * | 2018-12-31 | 2019-04-12 | 南京格洛特环境工程股份有限公司 | A kind of Resource comprehensive utilization method of steel slag |
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| CN114686698A (en) * | 2020-12-30 | 2022-07-01 | 北京博萃循环科技有限公司 | Treatment method of laterite-nickel ore |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102560116A (en) * | 2011-10-11 | 2012-07-11 | 虹京环保有限公司 | Method for recovering manganese and vanadium from titanium white waste acid, manganese slag and vanadium-containing steel slag |
| CN102560116B (en) * | 2011-10-11 | 2013-08-14 | 虹京环保有限公司 | Method for recovering manganese and vanadium from titanium white waste acid, manganese slag and vanadium-containing steel slag |
| CN106048261A (en) * | 2016-08-22 | 2016-10-26 | 东北大学 | Method for extracting vanadium from acidic solution by using ionic liquid [OMIM]BF4 |
| CN107058753A (en) * | 2016-12-05 | 2017-08-18 | 张俊宝 | A kind of stainless steel slag recovery and reusing and recycling method |
| CN109609775A (en) * | 2018-12-31 | 2019-04-12 | 南京格洛特环境工程股份有限公司 | A kind of Resource comprehensive utilization method of steel slag |
| CN109609775B (en) * | 2018-12-31 | 2020-08-07 | 南京格洛特环境工程股份有限公司 | Resource comprehensive utilization method of steel slag |
| CN109777964A (en) * | 2019-03-04 | 2019-05-21 | 昆明理工大学 | A method of strengthening the calcining vanadium extraction of acidleach v-bearing steel slag using hydrogen peroxide |
| CN111560523A (en) * | 2020-06-05 | 2020-08-21 | 昆明理工大学 | New process for purifying and recovering calcium components in vanadium-containing steel slag |
| CN114686698A (en) * | 2020-12-30 | 2022-07-01 | 北京博萃循环科技有限公司 | Treatment method of laterite-nickel ore |
| CN114686698B (en) * | 2020-12-30 | 2023-10-13 | 北京博萃循环科技有限公司 | Treatment method of laterite nickel ore |
| CN117758068A (en) * | 2024-02-22 | 2024-03-26 | 中国恩菲工程技术有限公司 | method for preparing vanadyl sulfate from stone coal |
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