CN107620090A - The recovery method of vanadium and manganese in vanadium wastewater - Google Patents
The recovery method of vanadium and manganese in vanadium wastewater Download PDFInfo
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- CN107620090A CN107620090A CN201711084059.3A CN201711084059A CN107620090A CN 107620090 A CN107620090 A CN 107620090A CN 201711084059 A CN201711084059 A CN 201711084059A CN 107620090 A CN107620090 A CN 107620090A
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention relates to vanadium in vanadium wastewater and the recovery method of manganese, belongs to chemical metallurgy technical field.The technical problems to be solved by the invention are to provide the recovery method of vanadium and manganese in vanadium wastewater, and this method comprises the following steps：Vanadium wastewater is placed in electroplating bath, is passed through direct current ,+5 valency V are reduced to+4 valency V, pH to 6.0~7.0 is adjusted, separation of solid and liquid, produces containing vanadium slag；Contain+divalent Mn in the vanadium wastewater.After reclaiming vanadium, selenium dioxide is added in the liquid obtained to separation of solid and liquid, is electrolysed, produces manganese metal.The inventive method has advantages below：(1) promoter manganese in vanadium wastewater is reclaimed in a manner of High-purity manganese metal, vanadium therein is then formed containing vanadium slag, can return in main technique roasting；(2) reclaim the solution after vanadium, promoter manganese to can be used in calcification clinker acidic leaching, realize recycling for waste water.
Description
Technical field
The present invention relates to vanadium in vanadium wastewater and the recovery method of manganese, belongs to chemical metallurgy technical field.
Background technology
In vanadium oxide production, Converter Vanadium-bearing Slag is incorporated a certain amount of sodium salt or calcium salt after broken, ball milling, into rotary kiln
Or wedge furnance is calcined, the Low Valent Vanadium in vanadium slag is oxidized to water-soluble pentavalent vanadium, through leaching, precipitating, drying,
The processes such as reduction obtain vanadium oxide product.Wherein, the manganese in leaching process, raw material vanadium slag can enter solution jointly with vanadium
In, vanadium concentration therein is about 25~35g/L, manganese concentration is about 10~20g/L.In precipitation process, 99% vanadium is with more vanadic acid
Ammonium precipitation form is enriched with, and more than 99% manganese and about 1% vanadium are then stayed in precipitation waste water.Because manganese concentration is higher, precipitation
The recycling of waste water is relatively difficult.Have been reported that at present and Manganese in Waste Water ion concentration be reduced to by below 5g/L using neutralisation,
To ensure recycling for waste water, wastewater zero discharge is realized.The water treating method equipment and technology is ripe, easy to operate simple, but
The problems such as big wastewater treatment quantity of slag, vanadium and promoter manganese are not reclaimed effectively be present.
For vanadium wastewater caused by calcification baking technique, patent CN102838233A adjusts acid precipitation using milk of lime
Then waste water carries out separation of solid and liquid, obtains alkaline solution and gypsum tailings to alkalescence；Decalcifying agent is added into alkaline solution to be taken off
Calcium, separation of solid and liquid is then carried out, obtain supernatant liquor and decalcification slag；The pH value of supernatant liquor is adjusted to returning after 3~7 with sulfuric acid
Leaching process is returned to be recycled.Recycling for waste water is the method achieve, return can be effectively controlled and leach process
Solution in calcium ion concentration, avoid the formation of calcium sulfate precipitation, but substantial amounts of promoter manganese is not returned effectively in waste water
Receive, ore utilization ratio is low.
For vanadium wastewater caused by sodium roasting technique：Patent CN102051486A is using vanadium wastewater as vanadium bearing slag
Leaching agent, form complex precipitate using its contained ammonium ion and phosphate anion and magnesium ion, add dephosphorization agent and enter
Row deep phosphorous removal, so as to produce low-phosphorous vanadium liquid, realize the recycling of vanadium wastewater；Patent CN101812593A is by acid waste water
For being reduced, neutralizing, being concentrated by evaporation again after the cleaning of tailings in vanadium extraction, alkali used is neutralized in wastewater treatment process to reduce
Amount.
However, have not yet to see the report recycled to the vanadium in vanadium wastewater and promoter manganese.
The content of the invention
It is an object of the invention to provide vanadium in vanadium wastewater and the recovery method of manganese.
The invention provides the recovery method of vanadium in vanadium wastewater, comprise the following steps：Vanadium wastewater is placed in electroplating bath
In, direct current is passed through ,+5 valency V are reduced to+4 valency V, pH to 6.0~7.0 is adjusted, separation of solid and liquid, produces containing vanadium slag；It is described heavy
Contain+divalent Mn in vanadium waste.
Further, pH to 7.0 is adjusted.
Further, 10~30min is stirred when adjusting pH.
Further, the anode material of the electroplating bath is iron, carbon or pb-ag alloy.
Further, the negative electrode of the electroplating bath selects conductive material, such as stainless steel.
Further, the voltage of the direct current is 2~4V；Preferably 4V.
Further, the conduction time of the direct current is 10~30min；Preferably 30min.
Further, pH is adjusted using ammoniacal liquor or calcium oxide.
Further, the vanadium wastewater is caused by production vanadium oxide.
Further, the vanadium wastewater is by vanadium slag sodium roasting-water logging process for extracting vanadium or vanadium slag calcification baking-acid
Caused by leaching and vanadium extraction technique.
The invention provides the recovery method of manganese in vanadium wastewater, comprise the following steps：Vanadium is reclaimed according to methods described；To
Selenium dioxide is added in the liquid that separation of solid and liquid obtains, is electrolysed, produces manganese simple substance.
Further, the addition of the selenium dioxide is 0.01~0.02g/L.
Further, the current density of the electrolysis is 180~280A/m2。
Further, the electrolysis temperature is 20~30 DEG C.
Further, anode material is pb-ag alloy.
Further, cathode material is stainless steel.
The invention provides the approach of vanadium, promoter manganese in a kind of effectively recovery vanadium wastewater, there is advantages below：
(1) promoter manganese in vanadium wastewater is reclaimed into (purity reaches more than 99%) in the form of high-purity simple substance manganese, sunk
Vanadium in vanadium waste is then formed containing vanadium slag, be can return in main technique roasting, is equally realized recycling；
(2) reclaim the solution after vanadium, promoter manganese to can be used in calcification clinker acidic leaching, realize the circulation profit of waste water
With.
Brief description of the drawings
Fig. 1 is that the process chart of vanadium and manganese in vanadium wastewater is reclaimed in embodiment.
Embodiment
The raw material that is used in the specific embodiment of the invention, equipment are known product, are obtained by buying commercially available prod.
The invention provides the recovery method of vanadium in vanadium wastewater, this method comprises the following steps：Vanadium wastewater is placed in
In electroplating bath, direct current is passed through ,+5 valency V are reduced to+4 valency V, pH to 6.0~7.0 is adjusted, separation of solid and liquid, produces containing vanadium slag.
The generally simultaneously valency of presence+5 V and+divalent Mn in vanadium wastewater, also has substantial amounts of other metallic elements, by vanadium in addition
Extracted respectively with manganese, reclaim more difficulty.The pH of vanadium wastewater is 1.5~3.0, and it is tetravalence vanadium to be passed through direct current electroreduction pentavalent vanadium
PH afterwards is 2~4.Inventor has found that, when adjusting pH less than 4, tetravalence vanadium can not form precipitation and separate out by investigating；PH is
When 4~6, tetravalence vanadium precipitation is incomplete and is difficult to filter；When pH is higher than 7.5, bivalent manganese is easily precipitated into filter residue.Therefore,
Inventor realizes separation, the extraction of the vanadium, manganese in solution by adjusting pH to 6.0~7.0.
The effect of vanadium, promoter manganese in vanadium wastewater is reclaimed for proof the inventive method, below the explanation in the form of embodiment.
Wherein, the main component of vanadium wastewater used is (content, g/L) as follows, and its pH is 1.5~3.0, produces the work of vanadium wastewater
Skill is referring to background section first paragraph.
| V | Mn | P | Fe | Mg | SO4 2- |
| 0.1-0.4 | 10-20 | 0-0.02 | 0-0.2 | 3-8 | 50-80 |
Embodiment 1 is using the vanadium and manganese in the inventive method recovery vanadium wastewater
Vanadium wastewater 5000mL (10.50g/L containing manganese, vanadium 0.10g/L) is taken, is put into electroplating bath, the anode material of electroplating bath
Expect that for iron staff, cathode material be stainless steel, be passed through direct current, control voltage 2V, time 10min, with ammoniacal liquor regulation system
Acidity is filtrated to get the first filtrate (10.20g/L containing manganese, vanadium 0.008g/L) and containing vanadium slag to 6.0 after stirring 10min；To first
Selenium dioxide 0.01g/L is added in filtrate, is passed through direct current, carries out electrolysis procedure, anode material is that (lead content is pb-ag alloy
0.2~1.0%, silver content is 0.02~0.05%), cathode material is stainless steel, current density 180A/m2, the temperature of electrolysis
Spend for 20 DEG C, obtain manganese metal 35.4g (product purity 99.88%) and electrolysis waste solution (containing manganese 2.30g/L).
Embodiment 2 is using the vanadium and manganese in the inventive method recovery vanadium wastewater
Vanadium wastewater 5000mL (16.10g/L containing manganese, vanadium 0.25g/L) is taken, is put into electroplating bath, the anode material of electroplating bath
Expect that for iron staff, cathode material be stainless steel, be passed through direct current, control voltage 4V, time 20min, body adjusted with calcium oxide
It is acidity to 6.5, the first filtrate (15.85g/L containing manganese, vanadium 0.010g/L) is filtrated to get and containing vanadium slag after stirring 15min；To
Selenium dioxide 0.015g/L is added in one filtrate, is passed through direct current, carries out electrolysis procedure, anode material is pb-ag alloy, negative electrode
Material is stainless steel, current density 240A/m2, the temperature of electrolysis is 25 DEG C, and obtaining manganese metal 56.8g, (product purity is
And electrolysis waste solution (containing manganese 3.40g/L) 99.91%).
Embodiment 3 is using the vanadium and manganese in the inventive method recovery vanadium wastewater
Vanadium wastewater 5000mL (19.80g/L containing manganese, vanadium 0.46g/L) is taken, is put into electroplating bath, the anode material of electroplating bath
Expect that for iron staff, cathode material be stainless steel, be passed through direct current, control voltage 4V, time 30min, with ammoniacal liquor regulation system
Acidity is filtrated to get the first filtrate (19.47g/L containing manganese, vanadium 0.012g/L) and containing vanadium slag to 7.0 after stirring 30min；To first
Selenium dioxide 0.02g/L is added in filtrate, is passed through direct current, carries out electrolysis procedure, anode material is pb-ag alloy, cathode material
For stainless steel, current density 280A/m2, the temperature of electrolysis is 30 DEG C, and obtaining manganese metal 65.3g, (product purity is
And electrolysis waste solution (containing manganese 4.90g/L) 99.91%).
The resultant metal manganese composition that embodiment 1~3 obtains is shown in Table 1, and the composition containing vanadium slag that processing procedure obtains is shown in Table 2, contains
Vanadium slag can return in the roasting of main technique.
The resultant metal manganese composition of table 1
| Constituent content (%w/w) | Mn | C | S | P | Si | Fe | Se |
| Embodiment 1 | 99.88 | 0.01 | 0.017 | 0.0004 | 0.01 | 0.003 | 0.08 |
| Embodiment 2 | 99.91 | 0.01 | 0.005 | 0.0004 | 0.01 | 0.002 | 0.06 |
| Embodiment 3 | 99.91 | 0.01 | 0.006 | 0.0004 | 0.01 | 0.002 | 0.06 |
The main component containing vanadium slag of table 2
| Content (%w/w) | MnO | V | Fe2O3 | CaO |
| Embodiment 1 | 10.0 | 15.0 | 10.0 | 0.4 |
| Embodiment 2 | 9.6 | 14.2 | 9.4 | 15.6 |
| Embodiment 3 | 17.0 | 23.6 | 11.5 | 0.5 |
The detection method of content of any of the above composition uses national standard or professional standard, refers to GB/T8654.1, GB/
T8654.3、GB/T8654.5、GB/T8654.6、GB/T8654.8、GB/T8654.10、YB/T547.3-2014、YB/
T547.1-2014、GB/T1506-2002。
Claims (10)
1. the recovery method of vanadium in vanadium wastewater, it is characterized in that：Comprise the following steps：Vanadium wastewater is placed in electroplating bath, led to
Enter direct current ,+5 valency V are reduced to+4 valency V, pH to 6.0~7.0 is adjusted, separation of solid and liquid, produces containing vanadium slag；The vanadium wastewater
In contain+divalent Mn.
2. recovery method as claimed in claim 1, it is characterized in that：Adjust pH to 7.0.
3. recovery method as claimed in claim 1, it is characterized in that：The anode material of the electroplating bath is that iron, carbon or lead silver close
Gold.
4. recovery method as claimed in claim 1, it is characterized in that：The voltage of the direct current is 2~4V；Preferably 4V.
5. recovery method as claimed in claim 1, it is characterized in that：The conduction time of the direct current is 10~30min；It is preferred that
For 30min.
6. recovery method as claimed in claim 1, it is characterized in that：Using ammoniacal liquor or calcium oxide regulation pH.
7. recovery method as claimed in claim 1, it is characterized in that：The vanadium wastewater meets at least one of following：
The vanadium wastewater is caused by production vanadium oxide；
The vanadium wastewater is by vanadium slag sodium roasting-water logging process for extracting vanadium or vanadium slag calcification baking-process for extracting vanadium by acid leaching production
Raw.
8. the recovery method of manganese in vanadium wastewater, it is characterized in that：Comprise the following steps：According to claim 1~7 any one institute
State method recovery vanadium；Selenium dioxide is added in the liquid obtained to separation of solid and liquid, is electrolysed, produces manganese simple substance.
9. recovery method as claimed in claim 8, it is characterized in that：The addition of the selenium dioxide is 0.01~0.02g/L.
10. recovery method as claimed in claim 8, it is characterized in that：The electrolytic condition meets at least one of following：
Current density is 180~280A/m2；
Electrolysis temperature is 20~30 DEG C；
Anode material is pb-ag alloy；
Cathode material is stainless steel.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111719053A (en) * | 2020-06-29 | 2020-09-29 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for extracting vanadium and manganese by roasting vanadium slag |
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| CN86106414A (en) * | 1986-11-07 | 1988-05-04 | 冶金工业部钢铁研究总院 | Electrolytic method for treating wastewater containing vanadium and chromium |
| CN103966437A (en) * | 2014-05-14 | 2014-08-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for removing phosphorous from acid solution containing vanadium |
| CN104058523A (en) * | 2013-10-31 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium oxide production industrial wastewater processing method |
| CN105219969A (en) * | 2015-11-19 | 2016-01-06 | 攀钢集团西昌钢钒有限公司 | Vanadium wastewater and tailings in vanadium extraction is utilized to extract the method for manganese metal |
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2017
- 2017-11-07 CN CN201711084059.3A patent/CN107620090A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106414A (en) * | 1986-11-07 | 1988-05-04 | 冶金工业部钢铁研究总院 | Electrolytic method for treating wastewater containing vanadium and chromium |
| CN104058523A (en) * | 2013-10-31 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium oxide production industrial wastewater processing method |
| CN103966437A (en) * | 2014-05-14 | 2014-08-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for removing phosphorous from acid solution containing vanadium |
| CN105219969A (en) * | 2015-11-19 | 2016-01-06 | 攀钢集团西昌钢钒有限公司 | Vanadium wastewater and tailings in vanadium extraction is utilized to extract the method for manganese metal |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111719053A (en) * | 2020-06-29 | 2020-09-29 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for extracting vanadium and manganese by roasting vanadium slag |
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