CN110983040A - Method for precipitating vanadium in acidic vanadium-rich solution without ammonia - Google Patents
Method for precipitating vanadium in acidic vanadium-rich solution without ammonia Download PDFInfo
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- CN110983040A CN110983040A CN201911227308.9A CN201911227308A CN110983040A CN 110983040 A CN110983040 A CN 110983040A CN 201911227308 A CN201911227308 A CN 201911227308A CN 110983040 A CN110983040 A CN 110983040A
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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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
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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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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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
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Abstract
The invention belongs to the field of wet metallurgy, and particularly relates to a method for precipitating vanadium in an acidic vanadium-rich solution without ammonia, which comprises the following steps: 1) controlling the sulfuric acid concentration of the acid vanadium-rich solution to be 1-10%, adding an oxidant until vanadium is completely oxidized, adding a certain amount of poly-vanadic acid as seed crystal, and introducing CO2Heating to precipitate vanadium; preserving heat, and completely filtering the precipitated vanadium; 2) filtering residue, adding 0.5-5% sulfuric acid water solution, heating and stirring, and introducing CO2Washing and filtering, leaching the washed and filtered filter residue with clear water, washing and firing to obtain the industrial vanadium pentoxide. The invention has the beneficial effects that: the method of the invention has no ammonia precipitation and complete vanadium precipitation, solves the emission of ammonia nitrogen wastewater and ammonia-containing toxic waste gas from the source and has no environmental pollution.
Description
Technical Field
The invention belongs to the field of wet metallurgy, and particularly relates to a method for precipitating vanadium in an acidic vanadium-rich solution without ammonia.
Background
The acidic vanadium-rich solution refers to acid leaching vanadium-containing acidic solution, which is extracted, separated and enriched by a solvent, acid leaching is carried out on sulfuric acid stripping solution of dilute sulfuric acid stripping or vanadium-containing high-grade material, and V is contained in solid-liquid separation2O5More than 20g/L of vanadium-rich acidic solution, the acidic vanadium-rich solution containing V2O5Generally, the vanadium precipitation process is 20g/L-120g/L, the conventional vanadium precipitation process is to completely oxidize vanadium by adding an oxidant into an acidic vanadium-rich solution, adjust the pH value of the acidic vanadium-rich solution to about 2.0 by adopting ammonia water or ammonium bicarbonate to adjust the alkali, and heat and precipitate vanadium to produce ammonium polyvanadate. The vanadium precipitation process generates a large amount of ammonia nitrogen wastewater and toxic ammonia-containing waste gas due to the addition of ammonia salt, and has great potential environmental protection hazards.
Disclosure of Invention
The invention aims to solve the problem that the method for precipitating vanadium in the acid vanadium-rich solution without ammonia is provided by the prior art, the emission of ammonia nitrogen wastewater and ammonia-containing toxic waste gas is solved from the source, and the method is free from environmental pollution.
The technical scheme adopted by the invention for solving the problems is as follows: a method for precipitating vanadium in an acidic vanadium-rich solution without ammonia comprises the following steps:
1) controlling the sulfuric acid concentration of the acid vanadium-rich solution to be 1-10%, adding an oxidant until vanadium is completely oxidized, adding a certain amount of poly-vanadic acid as seed crystal, and introducing CO2Heating to precipitate vanadium; preserving heat, and completely filtering the precipitated vanadium;
2) filtering residue, adding 0.5-5% sulfuric acid water solution, heating and stirring, and introducing CO2Washing and filtering, leaching the washed and filtered filter residue with clear water, washing and firing to obtain the industrial vanadium pentoxide.
According to the scheme, the concentration of the sulfuric acid in the acidic vanadium-rich solution is preferably controlled to be 1-5%.
According to the scheme, introducing CO in the step 1)2The amount is 5-50L/min.
According to the scheme, the heating in the step 2) is 60-100 ℃, and CO is introduced2The amount is 5-50L/min.
The theory principle is as follows: CO 22Is an acidic gas, has high solubility in water to form carbonic acid H2CO3,
Carbon dioxide solubility at 25 ℃ under standard atmospheric pressure (volume ratio) 1: 0.759, 60 ℃ is (volume ratio) 1: 0.359.
Vanadium can polymerize under acidic conditions to precipitate polyvanadate, but under high acid conditions the reaction is a reversible reaction and vanadium precipitation is difficult to complete.
When a large amount of CO is introduced2Since carbonic acid is a weak acid, the acid concentration of the solution is not changed, but large acid can be providedAmount of H+The reaction is driven to the right to complete the vanadium precipitation under high acid conditions.
Under the condition of high acid, other impurities hardly precipitate, so that the quality of the vanadium is ensured.
The invention has the beneficial effects that:
1. the method of the invention has no ammonia precipitation and complete vanadium precipitation, solves the discharge of ammonia nitrogen wastewater and ammonia-containing toxic waste gas from the source and has no environmental pollution;
2. the adoption of the invention can save the investment of ammonia distillation equipment by precipitating vanadium without ammonia;
3. the invention has no ammonia to precipitate vanadium, and the vanadium precipitation mother liquor can be recycled because no chemical reagent is added. Firstly, vanadium in the vanadium precipitation mother liquor can be completely recovered without loss, and the total recovery rate of vanadium is improved; secondly, residual acid in the vanadium precipitation mother liquor and sulfuric acid generated by chemical reaction are fully utilized, and 1.5-2.5 tons of sulfuric acid can be saved in each ton of refined vanadium;
4. the poly-vanadic acid without ammonia precipitation is free of ammonia, so that the ignition time of vanadium pentoxide is shortened without deaminizing during ignition of vanadium pentoxide, and the energy consumption is reduced.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
a production enterprise producing 2500 tons of vanadium pentoxide in one year takes vanadium-containing stone coal as a raw material, adds fluorite as an auxiliary leaching agent, uses dilute sulfuric acid as a leaching agent, heats the vanadium-containing stone coal by steam, stirs and leaches the vanadium-containing stone coal in a leaching tank for 2 hours, filters the vanadium-containing stone coal, adjusts alkali of acid leaching liquid by calcium carbonate powder, extracts the acid leaching liquid by a P204+ TBP + white oil solvent, back-extracts the acid leaching liquid by dilute acid and a back-extraction liquid V2O5The content is 80-90% g/L, and the concentration of sulfuric acid is 3-5%. The original vanadium precipitation process comprises the following steps: oxidizing vanadium completely with sodium chloride as oxidant, regulating pH value to 2.0 with ammonia water, and heating to precipitate vanadium. Vanadium precipitation mother liquor containing V2O51.0-1.5g/L, adding lime to adjust the pH value to 7-8, filtering, adjusting the pH value of the filtrate to 11, feeding the filtrate into an ammonia distillation system to distill ammonia and recover dilute ammonia water for recycling in a vanadium precipitation working section, wherein the annual operation cost of the ammonia distillation system is 1200 ten thousand yuan, and the vanadium loss in annual vanadium precipitation mother liquor is more than 30 tons of refined vanadium.
The process adopts an ammonia-free vanadium precipitation process through technical improvement: controlling the sulfuric acid concentration of the stripping solution to be less than 5%, and adding solid sodium chlorate in an amount which is 0.24 times of the total vanadium amount to completely oxidize the vanadium per m3The back extraction solution is added with 5kg/m of poly-vanadic acid3Introducing 25L/minCO2Heating to above 90 deg.C to precipitate vanadium, maintaining the temperature for 0.5h, and filtering. Vanadium precipitation mother liquor containing V2O52-3g/L of the mixed acid is completely recycled for the acid preparation in the leaching section.
Filtering with 1-2% dilute sulfuric acid water at a solid-to-liquid ratio of 1:10, and introducing 20L/minCO2Heating to 80 ℃ by using steam under the condition of stirring, filtering, leaching and washing the filter residue for 2-3 times by using clear water in a suction filtration disc, and burning for 1h at 500 ℃ in a vanadium pentoxide burning furnace to obtain orange vanadium pentoxide with the concentration of more than 98.5 percent.
Example 2: an enterprise for extracting vanadium from vanadium-containing steel slag adopts a V-containing steel slag2O516-25% vanadium-containing steel slag is used as raw material, the original process adopts the steps of adding soda ash and sodium chloride into rotary kiln roasting slag, ball-milling, water-soaking and extracting vanadium, the water-soaking liquor is regulated by sulfuric acidpH value to about 2.0 as V2O5Ammonium sulfate in an amount of 1.5 times is added, and the mixture is heated to precipitate vanadium so as to produce ammonium polyvanadate. The technical improvement is carried out because the environmental protection does not reach the standard.
The vanadium-containing steel slag is not roasted and ball-milled to-120 meshes, and is leached by heating and stirring sulfuric acid, and V is leached by circulation leaching2O5Enriching to above 40g/L, controlling sulfuric acid concentration to below 5%, adding sodium chloride 0.24 times of the total amount of low-valence vanadium, and oxidizing to complete vanadium oxidation2Adding 10kg/m of poly-vanadic acid into the vanadium-containing solution3Introducing 30L/min CO2Heating to boil, and keeping the temperature for 1h until the vanadium precipitation is complete, wherein the vanadium precipitation mother liquor contains V2O53-4g/L of the acid is completely recycled for the acid complex in the leaching section.
Filtering with 2-3% diluted sulfuric acid water at a solid-to-liquid ratio of 1:10, introducing CO2Heating steam for 25L/min stirring and washing to 60 deg.C, filtering, leaching the filter residue with clear water in a filter disc for 2-3 times, and burning at 750 deg.C in a vanadium burning furnace to produce vanadium flake and vanadium flake V2O5The content is more than 98.0 percent.
Claims (4)
1. A method for precipitating vanadium in an acidic vanadium-rich solution without ammonia comprises the following steps:
1) controlling the sulfuric acid concentration of the acid vanadium-rich solution to be 1-10%, adding an oxidant until vanadium is completely oxidized, adding a certain amount of poly-vanadic acid as seed crystal, and introducing CO2Heating to precipitate vanadium; preserving heat, and completely filtering the precipitated vanadium;
2) filtering residue, adding 0.5-5% sulfuric acid water solution, heating and stirring, and introducing CO2Washing and filtering, leaching the washed and filtered filter residue with clear water, washing and firing to obtain the industrial vanadium pentoxide.
2. The method of claim 1, wherein the concentration of sulfuric acid in the acidic vanadium-rich solution is controlled to be 1-5%.
3. The method for ammonia-free vanadium precipitation of acidic vanadium-rich solution according to claim 1, characterized in that the CO is introduced in the step 1)2The amount is 5-50L/min.
4. The method for ammonia-free vanadium precipitation of the acidic vanadium-rich solution according to claim 1, wherein the heating in the step 2) is 60-100 ℃, and the CO is introduced2The amount is 5-50L/min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911227308.9A CN110983040A (en) | 2019-12-04 | 2019-12-04 | Method for precipitating vanadium in acidic vanadium-rich solution without ammonia |
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| CN201911227308.9A CN110983040A (en) | 2019-12-04 | 2019-12-04 | Method for precipitating vanadium in acidic vanadium-rich solution without ammonia |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112030011A (en) * | 2020-08-12 | 2020-12-04 | 杨秋良 | Method for producing vanadium pentoxide by one-step vanadium precipitation of vanadium-containing material by full-wet method |
| CN114250372A (en) * | 2021-12-24 | 2022-03-29 | 辽宁东野环保产业开发有限公司 | Method for recovering vanadium in waste catalyst |
| CN114480843A (en) * | 2021-12-24 | 2022-05-13 | 辽宁东野环保产业开发有限公司 | Application of industrial white oil as synergist in extraction process |
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| CN106011471A (en) * | 2016-06-15 | 2016-10-12 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for extracting vanadium from acid-leaching vanadium solution |
| CN106337135A (en) * | 2015-07-16 | 2017-01-18 | 陕西五洲矿业股份有限公司 | Novel method for producing vanadium pentoxide through ammonium-free vanadium precipitation |
| CN108642271A (en) * | 2018-05-30 | 2018-10-12 | 武汉理工大学 | A kind of method that novel vanadium-containing shale produces vanadium dioxide without ammonia-sinking vanadium |
| CN110106346A (en) * | 2019-06-24 | 2019-08-09 | 攀钢集团研究院有限公司 | The method that Sodium Carbonate Leaching roasting clinker prepares vanadium oxide |
| CN110157927A (en) * | 2019-03-27 | 2019-08-23 | 杨秋良 | A kind of no ammonium precipitation vanadium method |
| CN110358935A (en) * | 2019-08-15 | 2019-10-22 | 攀钢集团钒钛资源股份有限公司 | The method of vanadium and sodium is recycled from sodium vanadate solution |
-
2019
- 2019-12-04 CN CN201911227308.9A patent/CN110983040A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106337135A (en) * | 2015-07-16 | 2017-01-18 | 陕西五洲矿业股份有限公司 | Novel method for producing vanadium pentoxide through ammonium-free vanadium precipitation |
| CN106011471A (en) * | 2016-06-15 | 2016-10-12 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for extracting vanadium from acid-leaching vanadium solution |
| CN108642271A (en) * | 2018-05-30 | 2018-10-12 | 武汉理工大学 | A kind of method that novel vanadium-containing shale produces vanadium dioxide without ammonia-sinking vanadium |
| CN110157927A (en) * | 2019-03-27 | 2019-08-23 | 杨秋良 | A kind of no ammonium precipitation vanadium method |
| CN110106346A (en) * | 2019-06-24 | 2019-08-09 | 攀钢集团研究院有限公司 | The method that Sodium Carbonate Leaching roasting clinker prepares vanadium oxide |
| CN110358935A (en) * | 2019-08-15 | 2019-10-22 | 攀钢集团钒钛资源股份有限公司 | The method of vanadium and sodium is recycled from sodium vanadate solution |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112030011A (en) * | 2020-08-12 | 2020-12-04 | 杨秋良 | Method for producing vanadium pentoxide by one-step vanadium precipitation of vanadium-containing material by full-wet method |
| CN114250372A (en) * | 2021-12-24 | 2022-03-29 | 辽宁东野环保产业开发有限公司 | Method for recovering vanadium in waste catalyst |
| CN114480843A (en) * | 2021-12-24 | 2022-05-13 | 辽宁东野环保产业开发有限公司 | Application of industrial white oil as synergist in extraction process |
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Application publication date: 20200410 |