CN102134640A - Method for leaching vanadium slag in converter by electro-catalytic oxidation - Google Patents
Method for leaching vanadium slag in converter by electro-catalytic oxidation Download PDFInfo
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- CN102134640A CN102134640A CN2011100487428A CN201110048742A CN102134640A CN 102134640 A CN102134640 A CN 102134640A CN 2011100487428 A CN2011100487428 A CN 2011100487428A CN 201110048742 A CN201110048742 A CN 201110048742A CN 102134640 A CN102134640 A CN 102134640A
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- leaching
- vanadium
- vanadium slag
- catalytic oxidation
- converter
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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 method discloses a method for leaching vanadium slag in a converter by electro-catalytic oxidation. In the method, the vanadium slag in the converter is mixed with MnSO4 and H2SO4 to obtain slurry and then leaching is conducted by non-membrane electro-catalytic oxidation; and after the leached ore slurry is filtered and separated, the vanadium in the obtained leaching solution is extracted through conventional ammonium salt (ammonium sulfate) vanadium precipitation so as to prepare vanadium pentoxide. During the leaching, the low-valent vanadium which is not easily leached in the vanadium slag is oxidized into high-valent vanadium which is easily leached by an anode-generated strong oxidant Mn3+ so that the leaching rate of the vanadium is improved by using an electro-catalytic oxidation method to leaching the vanadium slag, therefore, the problems of high energy consumption and high pollution in the traditional leaching methods are avoided, otherwise, the method is also suitable for the extraction of the vanadium in the raw materials including vanadium and the selective leaching of molybdenite concentrate; meanwhile, the method has the characteristics of being good in selectivity, moderate in technological condition, free of pollution and the like, therefore, a novel environmentally friendly wet decomposition method is provided.
Description
Technical field
The present invention relates to leach the method for vanadium with the converter vanadium slag.
Background technology
Vanadium (V) is important industrial raw material, is that raw material is produced Vanadium Pentoxide in FLAKES (V with the converter vanadium slag
2O
5) can either obtain the oxide compound of industrial available vanadium, also can restore vanadium easily.The method of leaching converter vanadium slag (to produce Vanadium Pentoxide in FLAKES) has several, and full wet method vanadium extraction is wherein polluted less.In full wet method vanadium extraction, direct pickling process commonly used, its concrete steps comprise: 1. use sulfuric acid (H
2SO
4) be mixed with pulp slurry with the converter vanadium slag; 2. stir, leave standstill to leach vanadylic sulfate (VOSO
4); 3. filter; 4. in the filtrate of sulfur acid vanadyl, add ammonium sulfate ［ (NH
4)
2SO
4(being ammonia salt precipitation method), to obtain containing ammonium poly-vanadate (NH
4VO
3) throw out; 5. filtration, washing precipitate get pure ammonium poly-vanadate; 6. calcining ammonium poly-vanadate in oxidizing atmosphere gets goods Vanadium Pentoxide in FLAKES (V
2O
5) step.Yet existing direct pickling process but exists the productive rate of Vanadium Pentoxide in FLAKES not high, i.e. the lower deficiency of the extraction yield of vanadium.Cause this insufficient key to be, its 2. in the step vanadylic sulfate leaching yield lower.
Summary of the invention
The objective of the invention is, the method for the higher leaching converter vanadium slag of a kind of vanadylic sulfate leaching yield is provided.
The method that realizes described goal of the invention is a kind of method with catalytic oxidation leaching converter vanadium slag, and aspect same as the prior art is that this method comprises with sulfuric acid and mixing with the converter vanadium slag to prepare the step (1) of pulp slurry.Its improvements are, in this step (1), the vitriolic percentage concentration is 30%～50%, and the converter vanadium slag was the powder shape behind 200 mesh sieves; The mass ratio of sulfuric acid and the contained vanadium of converter vanadium slag is 80: 1.5～2; Following steps are:
(2) step (1) gained pulp slurry is placed the leaching groove, connect power supply, to carry out electrocatalysis oxidation reaction; Wherein, anodic current density is 400～1000A/m
2, leaching temperature is 25～100 ℃, leaching time is 2～10h;
(3) pulp slurry behind step (2) electrocatalysis oxidation reaction is carried out solid-liquid separation, get the filtrate of sulfur acid vanadyl.
After the filtrate that obtains the sulfur acid vanadyl, step such as the ammonia salt precipitation method by routine and calcining prepares Vanadium Pentoxide in FLAKES again.
As can be seen, the present invention in its committed step (leaching vanadylic sulfate) process, increases catalytic oxidation on existing direct pickling process basis from scheme.Behind catalytic oxidation, just can the high price vanadium that the difficult low price vanadium that leaches in the converter vanadium slag is oxidized to easy leaching (promptly all be present in the filtrate with the vanadylic sulfate form).So, with the ammonium salt precipitation time, there is a large amount of vanadium to be converted into ammonium poly-vanadate with regard to having guaranteed, and then can obtains more Vanadium Pentoxide in FLAKES, promptly improved recovery (extraction) rate of vanadium.Obviously, the present invention is not only applicable to the wet method of converter vanadium slag and decomposes, but also the selectivity that is applicable to extraction that other contains vanadium in the vanadium raw materials and molybdenum glance concentrate leaches, characteristics such as have equally also that selectivity is good, the rate of recovery is high, processing condition are gentle and pollution-free are that a kind of eco-friendly wet method is decomposed novel method.
The present invention is further illustrated below in conjunction with embodiment.
Embodiment
With the method for catalytic oxidation leaching converter vanadium slag, this method comprises with sulfuric acid and mixing with the converter vanadium slag to prepare the step (1) of pulp slurry.The present invention is in this step (1), and the vitriolic percentage concentration is 30%～50%, and the converter vanadium slag was the powder shape behind 200 orders (0.075mm) sieve; The mass ratio of sulfuric acid and the contained vanadium of converter vanadium slag is 80: 1.5～2; Following steps are:
(2) step (1) gained pulp slurry is placed the leaching groove, connect power supply, to carry out electrocatalysis oxidation reaction; Wherein, anodic current density is 400～1000A/m
2Leaching temperature is 25～100 ℃, and leaching time is that 2～10h(it will be apparent to those skilled in the art that the length of leaching time is relevant with the size and the leaching temperature of anodic current density, big in anodic current density, when leaching temperature is higher, leaching time is just shorter; Otherwise leaching time is just longer.Certainly, to allow low price vanadium as much as possible be changed into the high price vanadium degree of being of easy leaching by Catalytic Oxygen);
(3) pulp slurry behind step (2) electrocatalysis oxidation reaction is carried out solid-liquid separation, get the filtrate of sulfur acid vanadyl.
To those skilled in the art, understand the content of above-mentioned disclosure after, can understand and realized the present invention.
For the leaching yield (certainly, also being the extraction yield of vanadium finally) that further improves vanadylic sulfate, in this embodiment, also adding in the described pulp slurry of step (1) has manganous sulfate (MnSO
4), the mass ratio of contained vanadium is 1.2～3: 1 in this manganous sulfate and this pulp slurry.
After in pulp slurry, having added manganous sulfate, because Mn in the manganous sulfate
2+Can generate strong oxidizer Mn in anodic oxidation
3+, in conjunction with using Mn
3+Original position is in time handled the converter vanadium slag, can make the low price vanadium when being oxidized to the high price vanadium, and is faster.
For obtaining reliable and better effect, in this embodiment, also adopted following measure.Specifically: the used leaching flowing current separation of step (2) is leached groove with no barrier film, and the anode of catalytic oxidation electrode used therein is selected the quad alloy of Pt-Ir-Ta-Sn oxide coating for use, and negative electrode is selected 1Cr18Ni9Ti Austenitic stainless steel for use.Consider that from the efficient aspect anodic current density is at 800～1000A/m
2Between select, leaching temperature is selected between 80～100 ℃, leaching time is controlled between 3～6h.
The present invention has passed through laboratory proofing.For calculating the leaching yield of vanadium, when checking, after the filtrate that obtains the sulfur acid vanadyl, also continue to adopt the operation of following steps.
(4) step (3) gained pH value of filtrate is adjusted to 2～4, is adding ammonium sulfate ［ (NH then
4)
2SO
4After fully stir, must contain ammonium poly-vanadate (NH
4VO
3) mixed solution; Wherein, the consumption of ammonium sulfate, to guarantee that the vanadium in step (3) the gained filtrate can all transform into ammonium poly-vanadate degree of being (also promptly: the consumption of ammonium sulfate, determine by the vanadic acid root amount in the mixed solution)---for avoiding introducing other impurity sexual elements, when regulating step (3) gained pH value of filtrate, also regulate (, add ammoniacal liquor and be adjusted to 2～4) because of this pH value of filtrate before regulating is too little by adding ammoniacal liquor;
(5) leave standstill, settling step (4) gained mixed solution; Filter, use clear water washing precipitate 1～2 time then, get ammonium poly-vanadate (filtrate is handled in addition);
(6) in oxidizing atmosphere at 500～600 ℃ of following calcining ammonium poly-vanadates, the goods Vanadium Pentoxide in FLAKES---it will be apparent to those skilled in the art that calcination time, should all be converted into Vanadium Pentoxide in FLAKES with whole ammonium poly-vanadates certainly and be as the criterion.
In the converter vanadium slag of using when carrying out above-mentioned checking, content of vanadium is 8.76%, and mainly with V
2O
3Form exists.Converter vanadium slag consumption is 20g, respectively with the sulfuric acid of different concns, and the different mass of press sulfuric acid and the contained vanadium of converter vanadium slag than (usefulness " MnSO
4: V " expression) three groups of pulp slurry of preparation.Be 1 group respectively: the sulfuric acid percentage concentration is 30%, MnSO
4: V=80: 1.5; 2 groups: the sulfuric acid percentage concentration is 40%, MnSO
4: V=80: 1.8; 3 groups: the sulfuric acid percentage concentration is 30%, MnSO
4: V=80: 2.(6) step carried out in retort furnace during calcining ammonium poly-vanadate, and setting calcining temperature is 600 ℃, and calcination time is 2 hours.At last, calculate the extraction yield of vanadium, with respectively to whether comparing by the catalytic oxidation method according to the Vanadium Pentoxide in FLAKES that obtains; To before catalytic oxidation, whether adding manganous sulfate compare.Checking is the result be shown in the following table.
Proof list 1:
Proof list 2:
Proof list 3:
Annotate:
1. the certificate parameter in above each table all is to allow with the higher used data of mode of efficient at test conditions.After those skilled in the art finished watching the full content of this specification sheets disclosure, necessarily clear: under the industrial production situation, just in case a certain condition does not allow, for example, anodic current density can only reach 400A/m for some reason
2The time, except that leaching temperature being got 25～100 ℃ higher limit, leaching time also will be between 2～10h the capping value.
2. " routine " in above each table is the Comparative Examples by catalytic oxidation not.
As can be seen, compare with direct pickling process of the prior art from checking, have increased significantly at vanadium extraction yield of the present invention, after further having added manganous sulfate, its increase rate is bigger.
Claims (3)
1. leach the method for converter vanadium slag with catalytic oxidation, this method comprises with sulfuric acid and mixing with the converter vanadium slag to prepare the step (1) of pulp slurry, it is characterized in that, in this step (1), the vitriolic percentage concentration is 30%～50%, and the converter vanadium slag was the powder shape behind 200 mesh sieves; The mass ratio of sulfuric acid and the contained vanadium of converter vanadium slag is 80: 1.5～2; Following steps are:
(2) step (1) gained pulp slurry is placed the leaching groove, connect power supply, to carry out electrocatalysis oxidation reaction; Wherein, anodic current density is 400～1000A/m
2, leaching temperature is 25～100 ℃, leaching time is 2～10h;
(3) pulp slurry behind step (2) electrocatalysis oxidation reaction is carried out solid-liquid separation, get the filtrate of sulfur acid vanadyl.
2. according to the described method with catalytic oxidation leaching converter vanadium slag of claim 1, it is characterized in that adding has manganous sulfate in the described pulp slurry of step (1), the mass ratio of contained vanadium is 1.2～3: 1 in this manganous sulfate and this pulp slurry.
3. according to claim 1 or 2 described methods with catalytic oxidation leaching converter vanadium slag, it is characterized in that, the used leaching groove of step (2) is no barrier film leaching groove, the anode of catalytic oxidation electrode used therein is the quad alloy of Pt-Ir-Ta-Sn oxide coating, and negative electrode is a 1Cr18Ni9Ti Austenitic stainless steel; Anodic current density is at 800～1000A/m
2Between, leaching temperature is between 80～100 ℃, and leaching time is 3～6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100487428A CN102134640A (en) | 2011-03-01 | 2011-03-01 | Method for leaching vanadium slag in converter by electro-catalytic oxidation |
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|---|---|---|---|
| CN2011100487428A CN102134640A (en) | 2011-03-01 | 2011-03-01 | Method for leaching vanadium slag in converter by electro-catalytic oxidation |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329954A (en) * | 2011-08-09 | 2012-01-25 | 重庆大学 | Method for pretreating vanadium slag of converter by alkaline leaching and desiliconizing under action of electric field |
| CN102534229A (en) * | 2011-12-08 | 2012-07-04 | 重庆大学 | Method for selectively leaching vanadium from vanadium-bearing converter slag |
| CN102732730A (en) * | 2012-06-28 | 2012-10-17 | 江苏龙源催化剂有限公司 | Recovery method for vanadium component in selective catalytic reduction denitration catalyst |
| CN103060843A (en) * | 2012-12-29 | 2013-04-24 | 中国科学院过程工程研究所 | Method for synchronously extracting vanadium and chromium by electrochemically decomposing vanadium slag in potassium hydroxide solution |
| CN104342567A (en) * | 2014-11-05 | 2015-02-11 | 攀枝花兴辰钒钛有限公司 | Method for extracting vanadium from high-calcium vanadium containing material |
| CN109722546A (en) * | 2018-12-31 | 2019-05-07 | 南京格洛特环境工程股份有限公司 | The extraction process of valuable metal in a kind of steel slag |
| CN110117714A (en) * | 2019-05-29 | 2019-08-13 | 北京科技大学 | A kind of method of room temperature saturated oxalic acid solution Anodic electrolysis Leaching Vanadium |
| CN110306043A (en) * | 2019-07-01 | 2019-10-08 | 北京科技大学 | The method that room temperature electroxidation leaches vanadium in magnetic vanadium iron spinel-type powder vanadium concentrate |
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| CN1936037A (en) * | 2006-10-19 | 2007-03-28 | 昆明理工大学 | Method for oxidizing-converting-leaching vanadium from converter steelmaking extracted vanadium slag under pressure field |
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2011
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1936037A (en) * | 2006-10-19 | 2007-03-28 | 昆明理工大学 | Method for oxidizing-converting-leaching vanadium from converter steelmaking extracted vanadium slag under pressure field |
Non-Patent Citations (2)
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| 《华东理工大学学报》 20021231 李登新等 "煤系黄铁矿的电解催化氧化和动力学研究" 第621-624页 1-3 第28卷, 第6期 * |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329954A (en) * | 2011-08-09 | 2012-01-25 | 重庆大学 | Method for pretreating vanadium slag of converter by alkaline leaching and desiliconizing under action of electric field |
| CN102534229A (en) * | 2011-12-08 | 2012-07-04 | 重庆大学 | Method for selectively leaching vanadium from vanadium-bearing converter slag |
| CN102534229B (en) * | 2011-12-08 | 2013-03-27 | 重庆大学 | Method for selectively leaching vanadium from vanadium-bearing converter slag |
| CN102732730A (en) * | 2012-06-28 | 2012-10-17 | 江苏龙源催化剂有限公司 | Recovery method for vanadium component in selective catalytic reduction denitration catalyst |
| CN102732730B (en) * | 2012-06-28 | 2013-11-06 | 江苏龙源催化剂有限公司 | Recovery method for vanadium component in selective catalytic reduction denitration catalyst |
| CN103060843A (en) * | 2012-12-29 | 2013-04-24 | 中国科学院过程工程研究所 | Method for synchronously extracting vanadium and chromium by electrochemically decomposing vanadium slag in potassium hydroxide solution |
| CN103060843B (en) * | 2012-12-29 | 2017-09-29 | 中国科学院过程工程研究所 | A kind of method that electrochemical decomposition vanadium slag synchronously extracts vanadium chromium in potassium hydroxide solution |
| CN104342567A (en) * | 2014-11-05 | 2015-02-11 | 攀枝花兴辰钒钛有限公司 | Method for extracting vanadium from high-calcium vanadium containing material |
| CN109722546A (en) * | 2018-12-31 | 2019-05-07 | 南京格洛特环境工程股份有限公司 | The extraction process of valuable metal in a kind of steel slag |
| CN110117714A (en) * | 2019-05-29 | 2019-08-13 | 北京科技大学 | A kind of method of room temperature saturated oxalic acid solution Anodic electrolysis Leaching Vanadium |
| CN110117714B (en) * | 2019-05-29 | 2020-03-17 | 北京科技大学 | Method for leaching vanadium by anode electrolysis in normal-temperature saturated oxalic acid solution |
| CN110306043A (en) * | 2019-07-01 | 2019-10-08 | 北京科技大学 | The method that room temperature electroxidation leaches vanadium in magnetic vanadium iron spinel-type powder vanadium concentrate |
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Application publication date: 20110727 |