CN114807632B - Short-process vanadium slag leaching method - Google Patents
Short-process vanadium slag leaching method Download PDFInfo
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- CN114807632B CN114807632B CN202210502146.0A CN202210502146A CN114807632B CN 114807632 B CN114807632 B CN 114807632B CN 202210502146 A CN202210502146 A CN 202210502146A CN 114807632 B CN114807632 B CN 114807632B
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 169
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 239000002893 slag Substances 0.000 title claims abstract description 164
- 238000000034 method Methods 0.000 title claims abstract description 79
- 238000002386 leaching Methods 0.000 title claims abstract description 74
- 238000005406 washing Methods 0.000 claims abstract description 77
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 74
- 239000001301 oxygen Substances 0.000 claims abstract description 74
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- 239000011734 sodium Substances 0.000 claims abstract description 46
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 41
- 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 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000605 extraction Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 9
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 51
- 238000011010 flushing procedure Methods 0.000 claims description 39
- 238000007664 blowing Methods 0.000 claims description 22
- 239000004744 fabric Substances 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 159000000000 sodium salts Chemical class 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 239000011324 bead Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000010791 quenching Methods 0.000 abstract description 6
- 230000000171 quenching effect Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 4
- 238000005299 abrasion Methods 0.000 abstract description 4
- 238000004176 ammonification Methods 0.000 abstract description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 150000003863 ammonium salts Chemical class 0.000 abstract description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 11
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 3
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000002308 calcification Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/36—Processes yielding slags of special composition
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a short-process vanadium slag leaching method, which comprises the following steps: pouring semisteel into a semisteel tank at the vanadium extraction end point of the converter, and optimizing an oxygen supply mode in the converter to convert low-valence vanadium in vanadium slag into pentavalent vanadium; pouring molten vanadium slag into a sodium treatment tank, adding sodium carbonate or sodium hydroxide for sodium treatment, granulating the high-temperature vanadium slag by adopting a water quenching method to obtain porous vanadium slag, and then performing the processes of cyclic leaching, step washing, filtering and separating to obtain sodium vanadate solution and tailings, wherein the sodium vanadate solution can be subjected to vanadium precipitation through acidic ammonium salt to obtain ammonium polyvanadate or calcified vanadium precipitation-ammonification to obtain ammonium metavanadate. The invention directly oxidizes the vanadium slag fully by using the converter, omits the normal-temperature sodium roasting process of the vanadium slag in the traditional vanadium extraction process, has simple process flow and greatly reduces the production energy consumption; porous vanadium slag is prepared by a water quenching method, vanadium is extracted by recycling leaching, tailings are washed by a multi-stage washing tank, fluid conveyed by each stage of pump is filtered solution, the slag amount is small, and the abrasion to the pump is small.
Description
Technical Field
The invention relates to the field of vanadium metallurgy and chemical industry, in particular to a short-process vanadium slag leaching method.
Background
Vanadium is an important strategic resource, has excellent strength, ductility and heat resistance, can obviously improve the performance of steel, is an indispensable important element for producing high-strength steel, and is widely used in important fields of steel, chemical industry, aerospace, military industry, electronic technology, vanadium battery energy storage, environmental protection and the like, and is called monosodium glutamate in modern industry.
The conventional vanadium titano-magnetite blast furnace iron-smelting-converter vanadium blowing-sodium (calcium) roasting vanadium extraction process has the problems that the converter vanadium blowing process and the sodium (calcium) roasting process are not generally in the same factory, the high Wen Fanzha of 1300-1400 ℃ obtained by converter vanadium blowing is cooled to normal temperature and then conveyed to the sodium (calcium) roasting factory, vanadium is extracted by crushing, ball milling, mixing and sodium (calcium) roasting (800-1000 ℃), the physical heat of high-temperature vanadium slag of the converter is not effectively utilized, and the sodium roasting process is also heated, so that the energy consumption is high.
CN102086487B discloses a vanadium slag treatment method for energy saving and emission reduction, which comprises the following steps: separating from molten iron at 1200 deg.C or abovePlacing high-temperature liquid vanadium slag in a slag pot; then adding sodium compound into the slag pot according to the grade of vanadium slag, then using water-cooling supersonic speed or subsonic speed oxygen gun to supply oxygen into the slag pot to produce strong oxidizing atmosphere, at the same time, can play a role of stirring to promote quick production of water-soluble sodium vanadate in the vanadium slag, and processing the obtained slag containing water-soluble sodium vanadate to obtain V 2 O 5 . The method shortens the process flow and saves the energy consumption, but the method has the problems of difficult wastewater treatment or high treatment cost after vanadium precipitation of the sodium vanadate solution.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an energy-saving and green novel short-process vanadium slag leaching process, which directly oxidizes vanadium slag by using a converter, omits a normal-temperature sodium roasting process of vanadium slag in the traditional vanadium extraction process, has simple process flow and greatly reduces production energy consumption; the porous vanadium slag is prepared by a water quenching method, then the multi-stage reaction tank is used for extracting vanadium, the solutions conveyed by the pumps at each stage are all filtered solutions, the slag amount is very small, and the abrasion to the pumps is small; and returning the NaOH solution after sodium-treatment vanadium precipitation to a slag flushing system, and returning the crystallization separation mother liquor to an ammonium vanadium precipitation process without wastewater.
In order to achieve the purpose, the technical scheme adopted by the invention is shown in the figure 1, after the blast furnace ironmaking of vanadium titano-magnetite is completed, after semisteel is poured into a semisteel tank at the vanadium extraction end point of a converter, low-valence vanadium in vanadium slag is converted into pentavalent vanadium to the maximum extent through an optimized oxygen supply mode in the converter; pouring molten vanadium slag into a sodium treatment tank, adding sodium carbonate or sodium hydroxide for sodium treatment, gradually settling residual iron beads at the bottom of the tank, granulating high-temperature vanadium slag by adopting a water quenching method to obtain porous vanadium slag, circularly leaching, and carrying out fine filtration and separation on bottom slurry to obtain sodium vanadate filtrate and fine tailings; the sodium vanadate solution can be subjected to vanadium precipitation through an acidic ammonium salt to obtain ammonium polyvanadate or subjected to calcification vanadium precipitation-ammonification transformation to obtain ammonium metavanadate, the NaOH solution subjected to calcification vanadium precipitation is returned to a slag flushing system, vanadium oxide can be obtained through crystallization separation and drying calcination, and ammonia in the crystallization separation and drying calcination processes can be recycled and then converted into ammonium bicarbonate for recycling; filtering and separating the filtered matters in the hopper to obtain vanadium extraction tailings. The invention directly oxidizes the vanadium slag fully by using the converter, omits the normal-temperature sodium roasting process of the vanadium slag in the traditional vanadium extraction process, has simple process flow and greatly reduces the production energy consumption; the porous vanadium slag is prepared by a water quenching method, vanadium is extracted by recycling leaching, the tailings are washed by a multi-stage washing tank, the fluid conveyed by each stage of pump is a filtered solution, the slag amount is very small, and the abrasion to the pump is small; and returning the NaOH solution after calcified vanadium precipitation to a slag flushing system, and returning the crystallization separation mother liquor to an ammonification vanadium precipitation process without generating wastewater.
The method specifically comprises the following steps:
the method comprises the steps of (1) at the vanadium extraction end point of the converter, lifting an oxygen lance to stop oxygen blowing, pouring semisteel into a semisteel tank, and converting low-valence vanadium in vanadium slag into pentavalent vanadium to the greatest extent by optimizing the oxygen supply mode in the converter;
pouring the oxidized molten vanadium slag into a sodium treatment tank, and then adding Na into the molten vanadium slag 2 CO 3 Or NaOH is used for sodium treatment of vanadium slag, and an oxygen lance is arranged in a sodium treatment tank to blow oxygen so as to play roles in stirring and oxidization, and under the stirring effect, residual iron beads in the vanadium slag gradually settle at the bottom of the tank;
step (3), after the vanadium slag and the sodium salt are uniformly mixed, opening a right discharge port, discharging the vanadium slag, then impacting and granulating slag liquid to obtain porous vanadium slag, discharging the porous vanadium slag into a leaching tank, and stopping oxygen introduction after all the vanadium slag in the sodium treatment tank is discharged;
step (4), a hopper capable of moving up and down is arranged in the leaching tank, the outside of the hopper is of a basket-shaped structure, filter cloth is lined, slag flushing liquid flows to the bottom of the reaction tank through the filter cloth, and then the slag flushing liquid is pumped out by a slag flushing pump to be recycled as slag flushing liquid; after the vanadium concentration of the slurry at the bottom of the leaching tank reaches a certain value, carrying out fine filtration and separation on the slurry at the bottom to obtain sodium vanadate filtrate and fine tailings;
step (5), the hopper is placed into the washing tank step by step to carry out step washing, after washing is completed, the hopper is lifted to be above the liquid level, and after water is drained, the hopper is sent into the next-stage washing tank. For example, as shown in fig. 2, when the number of stages of the step washing is 3.
The oxygen supply mode in the step (1) of the invention is that a top lance and a side lance are arranged in the converter, the side lance always maintains an oxygen blowing state before vanadium slag is poured into a sodium treatment tank, and the oxygen inlet amount is 200-500m 3 A/min; the lance position of the top lance is reduced to the lowest lance position, the distance from the bottom of the converter is 0.6 to 1m, and the oxygen inlet amount is 300 to 1500m 3 And (3) carrying out gun lifting after oxygen blowing of the top gun is completed, tilting the converter for 1-5 times back and forth, wherein the tilting angle range is 45-100 degrees, oxygen blowing of the side gun is kept in the tilting process, the tilting time is 2-4min, and the oxygen blowing aim is to improve the conversion rate of converting low-valence vanadium in vanadium slag into pentavalent vanadium.
Na in the step (2) of the invention 2 CO 3 Or NaOH is added in an amount of 6-20kg/t vanadium slag, preferably NaOH.
In the step (2) of the invention, the bottom of the sodium modification tank has a certain inclination, and the included angle between the bottom of the sodium modification tank and the horizontal plane is 10-30 degrees, so that iron beads can be conveniently deposited on one side.
The oxygen inlet amount of the sodium modification tank in the step (2) is 100-500m 3 /min。
In the step (3), the granularity of the porous vanadium slag is 2-20mm by adjusting the pressure and flow of the slag flushing liquid.
The water vapor generated in the slag flushing process in the step (3) is collected and then used for washing the tailings.
The filtering precision of the filter cloth in the step (4) is 5-100um.
The cyclic leaching reaction time in the step (4) is 60-180min, the liquid-slag mass ratio is 0.7-1.2, the concentration of NaOH in the leaching solution is 20-45%, and the leaching temperature is 80-120 ℃.
In the step (4) of the invention, after the vanadium concentration of the slurry at the bottom of the leaching tank reaches 25-40g/L, the slurry can be subjected to fine filtration separation.
The step washing in the step (5) is carried out in n stages, wherein n=2-5.
The step washing in the step (5) refers to the washing liquid of the n stages as the washing liquid of the (n-1) stage. The specific operation is that the washed liquid at the bottom of the n-level washing tank is pumped into the top of the (n-1) level washing tank, and vanadium slag in the (n-1) level hopper is sprayed; the washing liquid of the final stage is clean water, and the adding amount of the clean water of the final stage is the sum of the evaporation amount of the slag flushing liquid and the water quantity taken away by the tailings; the washing temperature of each stage is 70-95 ℃.
After the last stage of washing in the step (5), the hopper is lifted above the liquid level of the washing tank, and the tank is kept stand for a period of time, and after the water is drained, tailings are directly discharged into a tailings warehouse.
In the steps (4) and (5), in order to ensure the leaching effect in the leaching tank and the washing effect in the washing tank, hoppers on the leaching tank and the washing tank can move up and down to play a role in stirring, the moving frequency is 1-60 times/h, and the washing time of each stage is 60-180min.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The converter is utilized to directly fully oxidize vanadium slag, so that the conventional normal-temperature vanadium slag sodium roasting process in the vanadium extraction process is omitted, the process flow is simple, and the production energy consumption is greatly reduced.
(2) Porous vanadium slag is prepared by a water quenching method, vanadium is extracted by recycling leaching, tailings are washed by multistage washing, fluid conveyed by pumps at each stage is filtered solution, the slag amount is very small, and the abrasion to the pumps is small.
(3) And returning the NaOH solution after calcified vanadium precipitation to a slag flushing system, and returning the crystallization separation mother liquor to an ammonification vanadium precipitation process without generating wastewater.
Drawings
FIG. 1 shows a schematic flow diagram of a short-flow vanadium slag leaching method of the invention.
Fig. 2 shows a schematic of a step wash.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
(1) At the vanadium extraction end point of the converter, an oxygen lance is lifted to stop blowing oxygen, semisteel is poured into a semisteel tank, and then a side lance is started to introduce oxygen into the converter, wherein the oxygen introduction amount is 500m 3 A/min; then the gun position of the top gun is lowered to the lowest gun position of the converter, and is separated from the converter0.6m at the bottom, the oxygen inlet amount is 1500m 3 The oxygen introducing time is 1.5min; and after the completion, lifting the top lance, tilting the converter for 3 times forwards and backwards, wherein the tilting angle range is 100 degrees, and keeping the oxygen blowing of the side lance in the tilting process, wherein the tilting time is 3min.
(2) After the oxidation process is completed, 15 tons of molten vanadium slag is poured into a sodium treatment tank, 180kg of NaOH is added, oxygen is introduced into the sodium treatment tank, and the oxygen introduction amount is 500m 3 Mixing vanadium slag and sodium salt thoroughly, and further oxidizing vanadium slag; in the mixing process of vanadium slag and sodium salt, iron beads are settled at the bottom of the sodium modification tank.
(3) After the vanadium slag and the sodium salt are uniformly mixed, a right discharge port is opened to discharge the vanadium slag, then the porous vanadium slag is obtained through impact and granulation of slag flushing liquid and discharged into a leaching tank, and the granularity of the porous vanadium slag is 2-10mm through adjusting the hydraulic pressure and flow of the slag flushing.
(4) The leaching tank is internally provided with a hopper capable of moving up and down, the outside of the hopper is of a basket-shaped structure, the filter cloth is lined, the filter cloth filtering precision is 100um, slag flushing liquid flows to the bottom of the leaching tank through the filter cloth, then the slag flushing liquid is pumped out by a slag flushing pump and is recycled as slag flushing liquid, the circulating leaching time is 180min, the concentration of NaOH in the leaching liquid is 35%, the mass ratio of the slag flushing liquid is 1.2, and the leaching temperature is 120 ℃.
(5) Setting a four-stage washing tank, putting a hopper into the washing tank step by step for step washing, wherein the washing time of each stage is 180min, the up-and-down movement frequency of the hopper is 30 times/h, after washing, lifting the hopper to be above the liquid level, after water is drained, sending the hopper into a next-stage washing tank, and after washing and draining of the last stage, directly discharging tailings into a tailings warehouse, wherein the water quantity of the last stage is 6 tons.
And (3) detecting: the vanadium leaching rate of the embodiment is 88.93 percent.
Example 2
(1) At the vanadium extraction end point of the converter, an oxygen gun is lifted to stop blowing oxygen, semisteel is poured into a semisteel tank, and then a side gun is started to introduce oxygen into the converter, wherein the oxygen introduction amount is 400m 3 A/min; then the top lance position is lowered to the lowest lance position of the converter, and the oxygen inlet amount is 1200m at a position 0.6m away from the bottom of the converter 3 The oxygen introducing time is 1.5min; lifting after completionThe top lance is tilted for 4 times in the front and back of the converter, the tilting angle range is 90 degrees, the oxygen blowing of the side lance is kept in the tilting process, and the tilting time is 2min.
(2) After the oxidation process is completed, 15 tons of molten vanadium slag are poured into a sodium treatment tank, and 100kg of Na is added 2 CO 3 Introducing oxygen into a sodium treatment tank with oxygen inlet amount of 300m 3 Mixing vanadium slag and sodium salt thoroughly, and further oxidizing vanadium slag; in the mixing process of vanadium slag and sodium salt, iron beads are settled at the bottom of the sodium modification tank.
(3) After the vanadium slag and the sodium salt are uniformly mixed, a right discharge port is opened to discharge the vanadium slag, then the porous vanadium slag is obtained through impact and granulation of slag flushing liquid and discharged into a leaching tank, and the granularity of the porous vanadium slag is 5-15mm through adjusting the hydraulic pressure and flow of the slag flushing.
(4) The leaching tank is internally provided with a hopper capable of moving up and down, the outside of the hopper is of a basket-shaped structure, the filter cloth is lined, the filter cloth filtering precision is 10um, slag flushing liquid flows to the bottom of the leaching tank through the filter cloth, then is pumped away by a primary pump and is recycled as slag flushing liquid, the circulating leaching time is 120min, the concentration of NaOH in the leaching liquid is 30%, the mass ratio of slag to liquid is 1:1, and the leaching temperature is 90 ℃.
(5) Setting three-stage washing tanks, putting the hopper into the washing tanks step by step for step washing, wherein the washing time of each stage is 120min, the up-and-down moving frequency of the hopper is 20 times/h, lifting the hopper to be above the liquid level after washing is finished, after water is drained, sending the hopper into the next-stage washing tank, and directly discharging tailings into a tailings warehouse after washing and draining at the last stage. The amount of washing water was 6.4 tons.
And (3) detecting: the vanadium leaching rate of this example is 87.32%.
Example 3
(1) At the vanadium extraction end point of the converter, an oxygen gun is lifted to stop blowing oxygen, semisteel is poured into a semisteel tank, and then a side gun is started to introduce oxygen into the converter, wherein the oxygen introduction amount is 300m 3 A/min; then the top lance position is lowered to the lowest lance position of the converter, and the oxygen inlet amount is 1000m at a position 0.8m away from the bottom of the converter 3 The oxygen introducing time is 3min; after the completion, lifting the top lance, tilting the converter for 2 times forwards and backwards, wherein the tilting angle range is 70 degrees, and keeping the side lance blowing in the tilting processOxygen and tilting time was 2min.
(2) After the oxidation process was completed, 15 tons of molten vanadium slag was poured into a sodium treatment tank, and 130kg of Na was added 2 CO 3 Introducing oxygen into the sodium treatment tank with oxygen inlet amount of 200m 3 Mixing vanadium slag and sodium salt thoroughly, and further oxidizing vanadium slag; in the mixing process of vanadium slag and sodium salt, iron beads are settled at the bottom of the sodium modification tank.
(3) After the vanadium slag and the sodium salt are uniformly mixed, a right discharge port is opened to discharge the vanadium slag, then the porous vanadium slag is obtained through impact and granulation of slag flushing liquid and discharged into a leaching tank, and the granularity of the porous vanadium slag is 2-15mm through adjusting the hydraulic pressure and flow of the slag flushing.
(4) The leaching tank is internally provided with a hopper capable of moving up and down, the outside of the hopper is of a basket-shaped structure, the filter cloth is lined, the filter cloth filtering precision is 20um, slag flushing liquid flows to the bottom of the leaching tank through the filter cloth, then is pumped out by a primary pump and is recycled as slag flushing liquid, the circulating leaching time is 90min, the concentration of NaOH in the leaching liquid is 25%, the liquid-slag mass ratio is 0.7, and the leaching temperature is 80 ℃.
(5) Setting three-stage washing tanks, putting the hopper into the washing tanks step by step for step washing, wherein the washing time of each stage is 90min, the up-and-down moving frequency of the hopper is 30 times/h, lifting the hopper to be above the liquid level after washing is finished, after water is drained, sending the hopper into the next-stage washing tank, and discharging tailings into a tailings warehouse after washing and draining at the last stage. The amount of washing water in the final stage was 7.1 tons.
And (3) detecting: the vanadium leaching rate of this example is 86.75%.
Example 4
(1) At the vanadium extraction end point of the converter, an oxygen gun is lifted to stop blowing oxygen, semisteel is poured into a semisteel tank, and then a side gun is started to introduce oxygen into the converter, wherein the oxygen introduction amount is 200m 3 A/min; then the lance position of the top lance is lowered to the lowest lance position of the converter, and the oxygen inlet amount is 800m at a position 1m away from the bottom of the converter 3 The oxygen introducing time is 3min; and after the completion, lifting the top lance, tilting the converter for 1 time forwards and backwards, wherein the tilting angle range is 45 degrees, and keeping the oxygen blowing of the side lance in the tilting process, wherein the tilting time is 1min.
(2) After the oxidation process is completedPouring 15 tons of molten vanadium slag into a sodium treatment tank, adding 90kg of NaOH, and introducing oxygen into the sodium treatment tank, wherein the oxygen introducing amount is 100m 3 Mixing vanadium slag and sodium salt thoroughly, and further oxidizing vanadium slag; in the mixing process of vanadium slag and sodium salt, iron beads are settled at the bottom of the sodium modification tank.
(3) After the vanadium slag and the sodium salt are uniformly mixed, a right discharge port is opened to discharge the vanadium slag, then the porous vanadium slag is obtained through impact and granulation of slag flushing liquid and discharged into a leaching tank, and the granularity of the porous vanadium slag is 5-20mm through adjusting the hydraulic pressure and flow of the slag flushing.
(4) The leaching tank is internally provided with a hopper capable of moving up and down, the outside of the hopper is of a basket-shaped structure, the filter cloth is lined, the filter cloth filtering precision is 50um, slag flushing liquid flows to the bottom of the leaching tank through the filter cloth, then is pumped away by a primary pump and is recycled as slag flushing liquid, the circulating leaching time is 60min, the concentration of NaOH in the leaching liquid is 20%, the liquid-slag mass ratio is 1.1, and the leaching temperature is 90 ℃.
(5) Setting three-stage washing tanks, putting the hopper into the washing tanks step by step for step washing, wherein the washing time of each stage is 60min, the up-and-down moving frequency of the hopper is 30 times/h, after washing, lifting the hopper to be above the liquid level, after water is drained, sending the hopper into the next-stage washing tank, and after washing and draining, directly discharging tailings into a tailings warehouse at the last stage. The amount of washing water in the final stage was 6.2 tons.
And (3) detecting: the vanadium leaching rate of this example is 85.25%.
Example 5
(1) At the vanadium extraction end point of the converter, an oxygen gun is lifted to stop blowing oxygen, semisteel is poured into a semisteel tank, and then a side gun is started to introduce oxygen into the converter, wherein the oxygen introduction amount is 400m 3 A/min; then the top lance position is lowered to the lowest lance position of the converter, and the oxygen inlet amount is 1200m at a position 0.6m away from the bottom of the converter 3 The oxygen introducing time is 3min; and after the completion, lifting the top lance, tilting the converter for 3 times forwards and backwards, wherein the tilting angle range is 100 degrees, and keeping the oxygen blowing of the side lance in the tilting process, wherein the tilting time is 4min.
(2) After the oxidation process is completed, 15 tons of molten vanadium slag is poured into a sodium modification tank, 120kg of NaOH is added, oxygen is introduced into the sodium modification tank, and the oxygen introduction amount is increased200m of 3 Mixing vanadium slag and sodium salt thoroughly, and further oxidizing vanadium slag; in the mixing process of vanadium slag and sodium salt, iron beads are settled at the bottom of the sodium modification tank.
(3) After the vanadium slag and the sodium salt are uniformly mixed, a right discharge port is opened to discharge the vanadium slag, then the porous vanadium slag is obtained through impact and granulation of slag flushing liquid and discharged into a leaching tank, and the granularity of the porous vanadium slag is 2-20mm through adjusting the hydraulic pressure and flow of the slag flushing.
(4) The leaching tank is internally provided with a hopper capable of moving up and down, the outside of the hopper is of a basket-shaped structure, the filter cloth is lined, the filter cloth filtering precision is 10um, slag flushing liquid flows to the bottom of the leaching tank through the filter cloth and is pumped out by a primary pump to be used as slag flushing liquid for recycling, the circulating leaching time is 60min, the liquid-slag mass ratio is 0.9, the concentration of NaOH in the leaching liquid is 30%, and the leaching temperature is 120 ℃.
(5) Setting a second-stage washing tank, putting the hopper into the washing tank step by step for step washing, wherein the washing time of each stage is 60min, the up-and-down moving frequency of the hopper is 20 times/h, lifting the hopper to be above the liquid level after washing is finished, after water is drained, sending the hopper into a next-stage washing tank, and directly discharging tailings into a tailings warehouse after washing and draining at the last stage. The amount of washing water in the final stage was 6.6 tons.
And (3) detecting: the vanadium leaching rate of the embodiment is 85.74 percent.
The balance relationship between the mass ratio of the liquid slag and the use amount in the cyclic leaching process is shown in table 1.
Table 1 System Water usage balance calculation
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (9)
1. A short-process vanadium slag leaching method, characterized in that the method comprises the following steps:
(1) Stopping oxygen blowing at the vanadium extraction end point of the converter, pouring semisteel into a semisteel tank, adjusting the oxygen supply mode in the converter, and converting low-valence vanadium in the vanadium slag into pentavalent vanadium to obtain oxidized molten vanadium slag;
(2) Pouring the oxidized molten vanadium slag into a sodium treatment tank, and adding sodium salt Na 2 CO 3 Or NaOH is used for sodium treatment of vanadium slag, and oxygen is blown in for stirring and oxidation, so that residual iron beads in the vanadium slag are settled at the bottom of the tank;
(3) Discharging vanadium slag after the vanadium slag and sodium salt are uniformly mixed, flushing and granulating by using slag flushing liquid to obtain porous vanadium slag, discharging the porous vanadium slag into a leaching tank, and stopping oxygen blowing after all the vanadium slag in the sodium treatment tank is discharged;
(4) A hopper capable of moving up and down is arranged in the leaching tank, the outside of the hopper is of a basket-shaped structure, filter cloth is lined, slag flushing liquid flows to the bottom of the reaction tank through the filter cloth to form bottom slurry, and if the vanadium concentration in the bottom slurry does not reach a preset value, the bottom slurry is extracted to be used as slag flushing liquid for circulating leaching; if the vanadium concentration of the bottom slurry reaches a preset value, carrying out fine filtration and separation on the bottom slurry to obtain sodium vanadate filtrate and fine tailings;
(5) The hopper is gradually put into a washing tank for step washing to finish the leaching of vanadium slag, wherein,
the oxygen supply mode in the step (1) is that a top lance and a side lance are arranged in the converter, the side lance is kept in an oxygen blowing state before molten vanadium slag is poured into a sodium treatment tank, and the oxygen inlet amount is 200m 3 /min-500m 3 A/min; the top lance position is reduced to the lowest lance position, and the oxygen inlet amount is 300m at the position 0.6m-1m away from the bottom of the converter 3 /min-1500m 3 And/min, wherein the oxygen introducing time is 1min-4min, the lance is lifted after the oxygen blowing of the top lance is completed, and the converter is arranged in front and backTilting for 1-5 times, wherein the tilting angle range is 45-100 degrees, oxygen blowing of the side gun is kept in the tilting process, and the tilting time is 2-4 min.
2. The short-process vanadium slag leaching method according to claim 1, wherein in step (2), na 2 CO 3 Or the addition amount of NaOH is 6kg/t-20kg/t vanadium slag; the sodium treatment tank is a sodium treatment tank with the bottom having an included angle of 10-30 degrees with the horizontal plane; the amount of oxygen blown into the sodium modification tank is 100m 3 /min-500m 3 /min。
3. The short-process vanadium slag leaching method according to claim 1 or 2, wherein the porous vanadium slag in step (3) has a particle size of 2mm to 20mm.
4. The short-process vanadium slag leaching method according to claim 1 or 2, wherein the cyclic leaching reaction time in the step (4) is 60-180min, the mass ratio of liquid slag is 0.7-1.2, the concentration of NaOH in the leaching solution is 20-45%, and the leaching temperature is 80-120 ℃.
5. The short-process vanadium slag leaching method according to claim 1 or 2, wherein the predetermined value of the vanadium concentration in step (4) is 25g/L to 40g/L; the filtering precision of the filter cloth is 5-100um.
6. The short-process vanadium slag leaching method according to claim 1 or 2, wherein the number of stages of the cascade washing is n, n=2-5.
7. The short-process vanadium slag leaching method according to claim 6, wherein the step washing comprises the steps of taking washing liquid after n-level washing as washing liquid of (n-1), spraying vanadium slag in a (n-1) level hopper, taking the washing liquid of the n-level as clear water, adding the washing clear water of the n-level as the sum of evaporation amount of slag flushing liquid and water taken away by tailings, and washing at each level at 70-95 ℃.
8. The short-process vanadium slag leaching method according to claim 6, wherein after the nth stage of washing, the hopper is lifted to be above the liquid level of the washing tank, and after standing, the tailings are directly discharged into a tailings warehouse after the water is drained.
9. The short-process vanadium slag leaching method according to claim 1 or 2, further comprising moving the hoppers in the leaching tank and the washing tank up and down at a frequency of 1 to 60 times/h, each stage washing time being 60 to 180 minutes.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2147620C1 (en) * | 1999-03-16 | 2000-04-20 | ОАО "Нижнетагильский металлургический комбинат" | Method of processing high-calcium vanadium-containing materials |
| CN104294055A (en) * | 2014-09-22 | 2015-01-21 | 河北钢铁股份有限公司承德分公司 | Method for extracting vanadium from vanadium slag |
| CN110042193A (en) * | 2019-05-16 | 2019-07-23 | 成都先进金属材料产业技术研究院有限公司 | The converter producing of calcium system vanadium slag and its subsequent leaching extraction vanadium method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2147620C1 (en) * | 1999-03-16 | 2000-04-20 | ОАО "Нижнетагильский металлургический комбинат" | Method of processing high-calcium vanadium-containing materials |
| CN104294055A (en) * | 2014-09-22 | 2015-01-21 | 河北钢铁股份有限公司承德分公司 | Method for extracting vanadium from vanadium slag |
| CN110042193A (en) * | 2019-05-16 | 2019-07-23 | 成都先进金属材料产业技术研究院有限公司 | The converter producing of calcium system vanadium slag and its subsequent leaching extraction vanadium method |
Non-Patent Citations (1)
| Title |
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| 吴诰 ; 潘鹏 ; 范鹤林 ; 王瑞祥 ; 徐志峰 ; .钒渣提钒研究现状及发展趋势.江西冶金.2020,(04),全文. * |
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