CN112391537A - Method for extracting vanadium by using hydrochloric acid, sulfuric acid and vanadium-containing high-calcium high-phosphorus slag - Google Patents
Method for extracting vanadium by using hydrochloric acid, sulfuric acid and vanadium-containing high-calcium high-phosphorus slag Download PDFInfo
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- 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
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- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
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- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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- 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
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- 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
- C22B7/007—Wet processes by acid leaching
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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
The invention relates to the field of chemical industry, and discloses a method for extracting vanadium from hydrochloric acid, sulfuric acid and vanadium-containing high-calcium high-phosphorus slag, which comprises the following steps: (1) coarsely crushing vanadium-containing high-calcium high-phosphorus slag, adding water for wet milling, and filtering to obtain filter residue; (2) adding water into the filter residue to prepare slurry, adding hydrochloric acid to adjust the pH value, stirring for reaction, filtering to obtain filtrate and filter residue, and washing the filter residue to obtain filter residue A; (3) adding part of filter residue A into sulfuric acid, adjusting the pH value, reacting and filtering to obtain filtrate B and filter residue; (4) adding the residual filter residue A into the filtrate B, adjusting the pH value, reacting and filtering to obtain filtrate C and filter residue D; (5) adding an extracting agent into the filtrate C for extraction to obtain a vanadium-containing extracting agent and raffinate, and adding sulfuric acid into the vanadium-containing extracting agent for back extraction; (6) and roasting the filter residue D to obtain clinker, crushing the clinker, adding water, adding sulfuric acid to adjust the pH value, and leaching. The invention has simple process and good social and economic benefits.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for extracting vanadium from hydrochloric acid, sulfuric acid and vanadium-containing high-calcium high-phosphorus slag.
Background
The vanadium-containing high-calcium high-phosphorus slag is derived from the steel-making dephosphorization process of vanadium-titanium magnetite, the yield per year reaches more than 300 million tons, the vanadium oxide content is generally more than 1 weight percent, and the vanadium-containing high-calcium high-phosphorus slag is a very valuable metallurgical secondary resource and can be used as a potential important raw material for extracting vanadium. However, the contents of calcium oxide and phosphorus pentoxide in the vanadium-containing high-calcium high-phosphorus slag are generally more than 20 wt% and 1 wt%, which are far higher than the technical requirements of the vanadium extraction process, and in addition, the high content of calcium can greatly reduce the index of vanadium extraction and increase the cost of vanadium extraction.
In the production process of various fields of chemical industry, rare earth industry, metal smelting industry, waste regeneration treatment industry, titanium white by chlorination process and the like, waste hydrochloric acid with low concentration and impurities is generated. If the waste acid is not treated and is directly discharged, the environment is necessarily seriously polluted; if the waste hydrochloric acid is discharged after being neutralized, secondary pollution is generated, the treatment cost is increased, and the method is not economic. The titanium dioxide is produced by the enterprise combined sulfuric acid method of more than 90 percent in China, about 6 to 8 tons of concentrated waste acid with the sulfur acid of 20 percent can be produced when 1 ton of titanium dioxide is produced, the waste acid generally contains sulfuric acid, ferrous sulfate, titanium oxide and the like, and the preferred treatment scheme is to treat waste by waste and change waste into valuable.
The vanadium-containing converter steel slag can be combined with a pyrogenic process to recover partial vanadium resources, and in extraction and recovery of vanadium in the vanadium-containing converter steel slag, the process flow of the current vanadium-containing molten iron of the steel climbing and V in the vanadium-containing converter steel slag are aimed at2O5Content, provides a new technical idea and method for extracting vanadium from vanadium-containing converter steel slagThe process also carries out experimental research on the smelting of the vanadium-containing converter steel slag and the vanadium extraction of the high vanadium molten iron. The result shows that the mass fraction of vanadium in pig iron in the vanadium-containing converter steel slag smelted by the combined submerged arc furnace reaches 74.5 percent, vanadium extraction is carried out on the vanadium-containing pig iron, and V in vanadium slag2O5The mass fraction of the vanadium reaches 35.06 percent, and the effective extraction and the comprehensive recovery of vanadium resources are realized.
In patent application CN200910300304.9, a vanadium-containing converter steel slag powder processing method and a vanadium-containing converter steel slag recycling method are provided, which are characterized in that the vanadium-containing converter steel slag powder is magnetically separated after being ball-milled. The method for recycling the vanadium-containing converter steel slag comprises the steps of crushing the vanadium-containing converter steel slag, carrying out magnetic separation to obtain large slag iron, leaving vanadium-containing high-calcium high-phosphorus slag powder, carrying out ball milling on the vanadium-containing converter steel slag powder, carrying out magnetic separation, and adding the obtained high-iron material into a sintering material. Aiming at the characteristics of low and unstable grade of vanadium-containing converter steel slag powder, a method of ball milling firstly and then magnetic separation is adopted to effectively separate iron and slag in the vanadium-containing converter steel slag powder, so that the iron-containing grade of the vanadium-containing converter steel slag powder is improved, the purpose of changing low-grade waste materials into high-quality iron-containing raw materials with high grade, namely high iron materials, is realized, and the high iron materials obtained after the treatment are added into a sintering furnace to be beneficial to sintering production. But the vanadium resource in the vanadium-containing converter steel slag is not effectively utilized.
In the vanadium extraction mechanism of vanadium-containing slag in the alkaline hydrothermal process, the process mechanism of recovering vanadium from vanadium-containing slag is researched aiming at the problems that the annual emission of vanadium extraction tailings and vanadium-containing high-calcium high-phosphorus slag is huge and cannot be comprehensively utilized. SEM analysis results show that vanadium in the vanadium extraction tailings is concentrated in a hematite phase and a pseudobrookite phase, and a part of vanadium is concentrated in a spodumene phase; the vanadium in the steel slag mainly exists in dicalcium silicate, tricalcium silicate and calcium ferrite phases and free oxides. According to the alkali solubility of the tetravalent vanadium and the pentavalent vanadium, 92 percent of vanadium in the vanadium extraction tailings and 94 percent of vanadium in the steel slag are alkali soluble. The influence experiment of the temperature and the alkali concentration on the vanadium-containing slag phase shows that the temperature has obvious damage effect on the silicate phase, and the alkali concentration and the decomposition rate of the silicate phase are in a linear increasing relationship. The vanadium-containing slag is decomposed by a NaOH medium hydrothermal process, and the leaching rate of vanadium is higher than 90%. However, the process has high requirements on equipment, the subsequent vanadium extraction process is complex, and a long distance is left from industrial application.
In the basic research on recycling of vanadium in vanadium-containing steel slag, the melting-cooling method is combined and SiO is respectively added into the slag2And Al2O3Modification studies were conducted to discuss the crystallization and growth of the vanadium rich phase. The research shows that SiO is added2In the vanadium-containing steel slag, vanadium is made of 2 CaO. SiO2(C2S) and 2 CaO. Fe2O3(C2F) The two phases are converted into concentrated Ca3[(V,P,Si)]O4]2In solid solution phase, wherein V2O5The mass fraction of (a) reaches 24.38%, but the size of the generated vanadium-enriched phase crystals is smaller; in the presence of Al2O3In the steel slag, vanadium is also enriched in Ca3[(V,P,Si)]O4]2In solid solution phase, wherein V2O5The mass fraction of (A) reaches 14.90%. Crystallization tests show that heterogeneous nucleation and homogeneous nucleation exist in vanadium-enriched phase nucleation, and the temperature is respectively 1350 ℃ and 1325 ℃; under the condition of 1300 ℃ heat preservation, the crystal of the vanadium-enriched phase grows from 6.24 mu m for 5min to 25.19 mu m for 580min, and the number of the crystal on the unit area is reduced.
Because the vanadium-containing high-calcium high-phosphorus slag contains extremely high calcium oxide, the vanadium extraction of the vanadium-containing high-calcium high-phosphorus slag by directly using the traditional process is infeasible.
Disclosure of Invention
The invention aims to solve the problem that vanadium resources in vanadium-containing high-calcium high-phosphorus slag are not fully extracted in the prior art, and provides a method for extracting vanadium by using hydrochloric acid, sulfuric acid and the vanadium-containing high-calcium high-phosphorus slag.
In order to achieve the aim, the invention provides a method for extracting vanadium from hydrochloric acid, sulfuric acid and vanadium-containing high-calcium high-phosphorus slag, which comprises the following steps:
(1) coarsely crushing the vanadium-containing high-calcium high-phosphorus slag until the granularity is less than 5mm, then adding water for wet grinding, and then filtering to obtain filter residue with the granularity less than 0.175 mm;
(2) adding water into the filter residue obtained in the step (1) to prepare slurry, then adding hydrochloric acid, adjusting the pH value to 4-7, stirring for reaction, filtering to obtain filtrate and filter residue, and washing the filter residue to obtain filter residue A;
(3) adding part of the filter residue A into sulfuric acid, adjusting the pH value to 0.1-0.8, reacting for 30-120min, and filtering to obtain filtrate B and filter residue;
(4) adding the residual filter residue A into the filtrate B, adjusting the pH value to 2-4, reacting for 30-120min, and filtering to obtain filtrate C and filter residue D;
(5) adding an extracting agent into the filtrate C for extraction to obtain a vanadium-containing extracting agent and raffinate, and then adding sulfuric acid into the vanadium-containing extracting agent for back extraction to obtain a vanadium-containing solution;
(6) and roasting the filter residue D to obtain clinker, crushing the clinker until the granularity is less than 0.125mm, adding water, adding sulfuric acid to adjust the pH value, and leaching under the stirring condition to obtain vanadium-containing leaching solution.
Preferably, in the step (1), the vanadium-containing high-calcium high-phosphorus slag is slag obtained during dephosphorization of vanadium-containing molten iron, and the content of vanadium pentoxide in the vanadium-containing high-calcium high-phosphorus slag is 1-10 wt%.
Preferably, in the step (2), the liquid-solid ratio of the water to the filter residue is 0.5-5 mL/g.
Preferably, in step (2), the concentration of the hydrochloric acid is 10 to 30% by weight.
Preferably, in step (5), the extractant contains at least one of P204 and P507.
Preferably, in step (5), the extractant further comprises TBP and sulfonated kerosene.
Preferably, in the step (5), the concentration of the sulfuric acid is 1 to 3 mol/L.
Preferably, in the step (6), the roasting temperature is 820-1050 ℃, and the roasting time is 30-180 min.
Preferably, in step (6), sulfuric acid is added to adjust the pH to 0.8-3.
Preferably, in the step (6), the temperature of the leaching is 50-60 ℃, and the time of the leaching is 30-180 min.
The method of the invention treats the vanadium-containing high-calcium high-phosphorus slag in advance, improves the grade of the vanadium-containing high-calcium high-phosphorus slag, and finally combines a blank roasting acid leaching vanadium extraction process to fully extract vanadium resources in the vanadium-containing high-calcium high-phosphorus slag.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for extracting vanadium by using hydrochloric acid, sulfuric acid and vanadium-containing high-calcium high-phosphorus slag, which comprises the following steps:
(1) coarsely crushing the vanadium-containing high-calcium high-phosphorus slag until the granularity is less than 5mm, then adding water for wet grinding, and then filtering to obtain filter residue with the granularity less than 0.175 mm;
(2) adding water into the filter residue obtained in the step (1) to prepare slurry, then adding hydrochloric acid, adjusting the pH value to 4-7, stirring for reaction, filtering to obtain filtrate and filter residue, and washing the filter residue to obtain filter residue A;
(3) adding part of the filter residue A into sulfuric acid, adjusting the pH value to 0.1-0.8, reacting for 30-120min, and filtering to obtain filtrate B and filter residue;
(4) adding the residual filter residue A into the filtrate B, adjusting the pH value to 2-4, reacting for 30-120min, and filtering to obtain filtrate C and filter residue D;
(5) adding an extracting agent into the filtrate C for extraction to obtain a vanadium-containing extracting agent and raffinate, and then adding sulfuric acid into the vanadium-containing extracting agent for back extraction to obtain a vanadium-containing solution;
(6) and roasting the filter residue D to obtain clinker, crushing the clinker until the granularity is less than 0.125mm, adding water, adding sulfuric acid to adjust the pH value, and leaching under the stirring condition to obtain vanadium-containing leaching solution.
In the invention, the vanadium-containing high-calcium high-phosphorus slag is slag obtained when the vanadium-containing molten iron is subjected to dephosphorization operation, and the content of vanadium pentoxide in the vanadium-containing high-calcium high-phosphorus slag is 1-10 wt%. Specifically, the content of vanadium pentoxide in the vanadium-containing high-calcium high-phosphorus slag may be 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%.
In the invention, in the step (2), the liquid-solid ratio of the water to the filter residue is 0.5-5 mL/g. Specifically, the liquid-solid ratio of the water to the filter residue can be 0.5mL/g, 1mL/g, 1.5mL/g, 2mL/g, 2.5mL/g, 3mL/g, 3.5mL/g, 4mL/g, 4.5mL/g, or 5 mL/g.
In the present invention, the concentration of the hydrochloric acid is 10 to 30% by weight. Specifically, the concentration of the hydrochloric acid may be 10 wt%, 13 wt%, 15 wt%, 17 wt%, 20 wt%, 23 wt%, 25 wt%, 27 wt%, or 30 wt%.
In the present invention, the source of hydrochloric acid is not particularly limited, and may be derived from industrial hydrochloric acid or waste hydrochloric acid.
In particular embodiments, in step (2), the pH may be adjusted to 4, 4.5, 5, 5.5, 6, 6.5 or 7.
In the invention, in the step (2), the chlorine content in the filter residue A is less than 0.1 wt%.
In the invention, in the step (2), the filtrate and the filter residue are obtained after filtration, the filter residue is washed by water, and the washed water can be added into the filter residue obtained in the step (1) to prepare slurry.
In the invention, in the step (3), the source of the sulfuric acid has no special requirement, and the sulfuric acid can be derived from industrial sulfuric acid, and can also be derived from waste sulfuric acid, such as titanium dioxide waste acid and the like.
In particular embodiments, in step (3), the pH may be adjusted to 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, or 0.8.
In a specific embodiment, in step (3), the reaction time after adjusting the pH may be 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, or 120 min.
In particular embodiments, in step (4), the pH may be adjusted to 2, 2.5, 3, 3.5, or 4.
In a specific embodiment, in the step (4), the reaction time after the pH adjustment may be 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120 min.
In the present invention, in the step (5), the extractant is an extractant subjected to saponification treatment with sodium hydroxide.
In the present invention, in the step (5), the extractant contains at least one of P204 and P507. Preferably, the extractant further comprises TBP and sulfonated kerosene.
In the present invention, in the step (5), the concentration of the sulfuric acid is 1 to 3 mol/L. Specifically, the concentration of the sulfuric acid may be 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, or 3 mol/L.
In the invention, in the step (5), the vanadium-containing solution obtained after the back extraction can be used for oxidizing and precipitating vanadium or used for directly precipitating tetravalent vanadium.
In the invention, in the step (6), the roasting temperature is 820-1050 ℃, and the roasting time is 30-180 min. Specifically, the roasting temperature can be 820 ℃, 850 ℃, 870 ℃, 890 ℃, 900 ℃, 920 ℃, 950 ℃, 970 ℃, 990 ℃, 1000 ℃ or 1050 ℃, and the roasting time can be 30min, 50min, 70min, 90min, 110min, 130min, 150min, 170min or 180 min.
In the present invention, in step (6), sulfuric acid is added to adjust the pH to 0.8 to 3. Specifically, the pH value may be adjusted to 0.8, 1, 1.3, 1.5, 1.7, 2.3, 2.5, 2.7 or 3.
In the invention, in the step (6), the leaching temperature is 50-60 ℃, and the leaching time is 30-180 min. Specifically, the leaching temperature may be 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃ or 60 ℃, and the leaching time may be 30min, 50min, 70min, 90min, 110min, 130min, 150min, 170min or 180 min.
The method of the invention processes the vanadium-containing high-calcium high-phosphorus slag in advance, improves the grade of the vanadium-containing high-calcium high-phosphorus slag, and finally combines a blank roasting acid leaching vanadium extraction process to fully extract vanadium resources in the vanadium-containing high-calcium high-phosphorus slag. The method changes waste resources of the vanadium-containing high-calcium high-phosphorus slag into valuable, has the advantages of simple and easy process, low equipment requirement, convenient operation, low cost and the like, can utilize the waste hydrochloric acid and the waste sulfuric acid with high and low concentrations, can also utilize the waste hydrochloric acid and the waste sulfuric acid containing a small amount of impurities, recycles and recycles the waste acid, solves numerous environmental problems, and can effectively utilize the waste acid resources, thereby realizing the three-win of economic benefit, social benefit and environmental benefit.
The present invention will be described in detail below by way of examples. The scope of the invention is not limited thereto.
The vanadium-containing high-calcium high-phosphorus slag used in the examples and the comparative examples is slag obtained when the vanadium-containing molten iron is subjected to dephosphorization, and the main chemical composition table is shown in table 1, and the chemical composition tables of the waste hydrochloric acid and the titanium white waste acid are shown in tables 2 and 3.
TABLE 1 table of main chemical composition of vanadium-containing high calcium high phosphorus slag/weight%
Table 2 waste hydrochloric acid chemical composition table/weight%
| Chemical composition | HCl | Ti | Fe |
| Content (wt.) | 15 | 26 | 15 |
TABLE 3 titanium dioxide waste acid chemical composition table/g.L-1
Example 1
(1) Taking 5000g of vanadium-containing high-calcium high-phosphorus slag in the table 1, coarsely crushing the slag until the granularity is less than 5mm, then adding 1500mL of water, carrying out wet milling in a wet ball mill, and then filtering to obtain 4500g of filter residue with the granularity less than 120 meshes;
(2) taking 500g of filter residue obtained in the step (1), adding 300mL of water to prepare slurry, then adding 700mL of waste hydrochloric acid shown in table 2, adjusting the pH value to 4, stirring for reaction for 2h, filtering to obtain filtrate and filter residue, and washing the filter residue with water to obtain 390g of filter residue A (V)2O52.52 wt%, chlorine content in residue a is less than 0.1 wt%);
(3) adding 200g of filter residue A into 500mL of titanium white waste acid shown in Table 3, adjusting the pH value to 0.1, reacting for 40minFiltration gave 450mL of filtrate B (V)2O5Content 9.2g/L) and residue (V)2O5Content 0.26 wt%);
(4) adding the residual filter residue A into the filtrate B, adjusting pH to 2.5, reacting for 30min, and filtering to obtain 400mL filtrate C (V)2O5Content of 8.4g/L) and 200g of residue D (V)2O5Content 2.68 wt%);
(5) extracting 400mL of filtrate C with 100mL of sodium hydroxide saponified extractant (15 vol% P204+10 vol% TBP +75 vol% sulfonated kerosene) for 5min, and separating with separating funnel to obtain vanadium-containing extractant and raffinate (V)2O5Content of 0.4g/L), then adding 50mL of sulfuric acid with concentration of 1mol/L into the vanadium-containing extractant for back extraction, wherein the back extraction temperature is 25 ℃, and the back extraction time is 30min, thus obtaining 50mL of vanadium-containing solution (V)2O5The content is 63 g/L);
(6) roasting 100g of filter residue D at 820 ℃ for 180min to obtain clinker, crushing the clinker to a granularity of less than 0.125mm, adding 200mL of water, adding sulfuric acid to adjust the pH value to 0.8, leaching under stirring at 50 ℃ for 180min to obtain 180mL of vanadium-containing leaching solution (V is the leaching solution with a temperature of 50 ℃ for 180 min)2O5The content is 13.4g/L), and the leaching rate is 90 percent.
In this example, V in the vanadium-containing solution obtained in step (5)2O5The content of V in the vanadium-containing leaching solution obtained in the step (6) is 63g/L2O5The content is 13.4g/L, and the leaching rate is 90 percent.
Example 2
(1) Taking 5000g of vanadium-containing high-calcium high-phosphorus slag in the table 1, coarsely crushing the slag until the granularity is less than 3mm, then adding 1000mL of water into a wet ball mill for wet milling, and then filtering to obtain 4200g of filter residue with the granularity less than 120 meshes;
(2) taking 500g of filter residue obtained in the step (1), adding 300mL of water to prepare slurry, then adding 600mL of waste hydrochloric acid shown in table 2, adjusting the pH value to 7, stirring for reaction for 2h, filtering to obtain filtrate and filter residue, and washing the filter residue with water to obtain 445g of filter residue A (V)2O52.46 wt%, chlorine content in residue a is less than 0.1 wt%);
(3) adding 250g of filter residue A into 500mL of titanium dioxide waste acid shown in Table 3, adjusting the pH value to 0.8, reacting for 100min, and filtering to obtain 440mL of filtrate B (V)2O5Content of 10.9g/L) and residue (V)2O5Content 0.38 wt%);
(4) adding the residual filter residue A into the filtrate B, adjusting pH to 3.0, reacting for 40min, and filtering to obtain 410mL filtrate C (V)2O5Content of 8.2g/L) and 220g of residue D (V)2O5Content 3.0 wt%);
(5) extracting 400mL of filtrate C with 100mL of sodium hydroxide saponified extractant (15 vol% P507+10 vol% TBP +75 vol% sulfonated kerosene) for 5min, and separating with separating funnel to obtain vanadium-containing extractant and raffinate (V)2O5Content of 0.5g/L), then adding 40mL of sulfuric acid with concentration of 2mol/L into the vanadium-containing extractant for back extraction, wherein the back extraction temperature is 25 ℃, and the back extraction time is 30min, thus obtaining 40mL of vanadium-containing solution (V)2O5The content is 77 g/L);
(6) roasting 100g of filter residue D at 1050 ℃ for 30min to obtain clinker, crushing the clinker until the granularity is less than 0.125mm, adding 200mL of water, adding sulfuric acid to adjust the pH value to 1.8, leaching under stirring at 60 ℃ for 120min to obtain 160mL of vanadium-containing leaching solution (V is the leaching solution with the granularity of 60 mm, and the leaching time is the leaching time of 120min2O5The content is 15.94g/L), and the leaching rate is 85 percent.
In this example, V in the vanadium-containing solution obtained in step (5)2O5The content of V in the vanadium-containing leaching solution obtained in the step (6) is 77g/L2O5The content is 15.94g/L, and the leaching rate is 85 percent.
Example 3
(1) Taking 5000g of vanadium-containing high-calcium high-phosphorus slag in the table 1, coarsely crushing the slag until the granularity is less than 2mm, then adding 2000mL of water into the slag to perform wet milling in a wet ball mill, and then filtering the slag to obtain 4000g of filter residue with the granularity less than 160 meshes;
(2) taking 500g of filter residue obtained in the step (1), and adding 300m of filter residuePreparing water L into slurry, adding 550mL of waste hydrochloric acid shown in Table 2, adjusting pH to 5, stirring for reaction for 2h, filtering to obtain filtrate and residue, and washing the residue with water to obtain 430g of residue A (V)2O52.50 wt%, chlorine content in residue a is less than 0.1 wt%);
(3) adding 250g of filter residue A into 500mL of titanium dioxide waste acid shown in Table 3, adjusting the pH value to 0.5, reacting for 60min, and filtering to obtain 420mL of filtrate B (V)2O5Content of 14.1g/L) and residue (V)2O5Content 0.1 wt%);
(4) adding the residual filter residue A into the filtrate B, adjusting pH to 2.8, reacting for 40min, and filtering to obtain 410mL filtrate C (V)2O5Content of 10.1g/L) and 200g of residue D (V)2O5Content 3.3 wt%);
(5) taking 400mL of filtrate C, adding 100mL of sodium hydroxide saponified extractant (15 vol% P204+10 vol% TBP +75 vol% sulfonated kerosene) for extraction for 10min, and separating with a separating funnel to obtain vanadium-containing extractant and raffinate (V)2O5Content of 0.8g/L), then adding 60mL of sulfuric acid with concentration of 1.5mol/L into the vanadium-containing extractant for back extraction, wherein the back extraction temperature is 25 ℃, and the back extraction time is 40min, thus obtaining 60mL of vanadium-containing solution (V)2O5The content is 62 g/L);
(6) roasting 100g of filter residue D at the roasting temperature of 950 ℃ for 70min to obtain clinker, crushing the clinker to the granularity of less than 0.125mm, adding 300mL of water, adding sulfuric acid to adjust the pH value to 1.7, leaching under the stirring condition at the leaching temperature of 60 ℃ for 120min to obtain 180mL of vanadium-containing leaching solution (V is the leaching solution with the granularity of less than 0.125 mm), and leaching for 120min2O5The content is 16.13g/L), and the leaching rate is 88 percent.
In this example, V in the vanadium-containing solution obtained in step (5)2O5The content of V in the vanadium-containing leaching solution obtained in the step (6) is 62g/L2O5The content is 16.13g/L, and the leaching rate is 88 percent.
Comparative example 1
The process is carried out according to the method of example 1, except that the operation of step (1) is not carried out, and the same mass of vanadium-containing high-calcium high-phosphorus slag which is not subjected to coarse crushing, wet grinding and filtering is directly taken in step (2) and added with water to prepare slurry.
V in the vanadium-containing solution obtained in the comparative example2O5The content is 7.05g/L, and V in the obtained vanadium-containing leaching solution2O5The content is 31g/L, and the leaching rate is 44 percent.
The results show that the method can fully extract vanadium resources in the vanadium-containing high-calcium high-phosphorus slag, has the advantages of simple and easy process, low equipment requirement, convenient operation, wide application range, low cost and good social and economic benefits.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for extracting vanadium by using hydrochloric acid, sulfuric acid and vanadium-containing high-calcium high-phosphorus slag is characterized by comprising the following steps:
(1) coarsely crushing the vanadium-containing high-calcium high-phosphorus slag until the granularity is less than 5mm, then adding water for wet grinding, and then filtering to obtain filter residue with the granularity less than 0.175 mm;
(2) adding water into the filter residue obtained in the step (1) to prepare slurry, then adding hydrochloric acid, adjusting the pH value to 4-7, stirring for reaction, filtering to obtain filtrate and filter residue, and washing the filter residue to obtain filter residue A;
(3) adding part of the filter residue A into sulfuric acid, adjusting the pH value to 0.1-0.8, reacting for 30-120min, and filtering to obtain filtrate B and filter residue;
(4) adding the residual filter residue A into the filtrate B, adjusting the pH value to 2-4, reacting for 30-120min, and filtering to obtain filtrate C and filter residue D;
(5) adding an extracting agent into the filtrate C for extraction to obtain a vanadium-containing extracting agent and raffinate, and then adding sulfuric acid into the vanadium-containing extracting agent for back extraction to obtain a vanadium-containing solution;
(6) and roasting the filter residue D to obtain clinker, crushing the clinker until the granularity is less than 0.125mm, adding water, adding sulfuric acid to adjust the pH value, and leaching under the stirring condition to obtain vanadium-containing leaching solution.
2. The method according to claim 1, wherein in the step (1), the vanadium-containing high-calcium high-phosphorus slag is slag obtained when molten iron containing vanadium is dephosphorized, and the content of vanadium pentoxide in the vanadium-containing high-calcium high-phosphorus slag is 1-10 wt.%.
3. The method as claimed in claim 1, wherein in the step (2), the liquid-solid ratio of the water to the filter residue is 0.5-5 mL/g.
4. The method according to claim 1, wherein the hydrochloric acid has a concentration of 10 to 30% by weight in step (2).
5. The method of claim 1, wherein in step (5), the extractant comprises at least one of P204 and P507.
6. The process of claim 1 or 5, wherein in step (5), the extractant further comprises TBP and sulfonated kerosene.
7. The method according to claim 1, wherein the concentration of the sulfuric acid in the step (5) is 1 to 3 mol/L.
8. The method as claimed in claim 1, wherein in step (6), the calcination temperature is 820-1050 ℃, and the calcination time is 30-180 min.
9. The method as claimed in claim 1, wherein in step (6), sulfuric acid is added to adjust the pH to 0.8-3.
10. The method as claimed in claim 1, wherein, in the step (6), the temperature of the leaching is 50-60 ℃, and the time of the leaching is 30-180 min.
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| CN109516499A (en) * | 2018-11-30 | 2019-03-26 | 攀钢集团研究院有限公司 | The method that high phosphorus solution containing vanadium produces vanadium oxide |
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| CN101412539A (en) * | 2008-11-18 | 2009-04-22 | 攀钢集团研究院有限公司 | Clean production process for vanadium oxide |
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| CN103397209A (en) * | 2013-07-16 | 2013-11-20 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for extracting vanadium from high-calcium and high-phosphorus vanadium slag |
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