CN106745631A - A kind of method for removing Tungsten smelting fluorine in wastewater and arsenic - Google Patents
A kind of method for removing Tungsten smelting fluorine in wastewater and arsenic Download PDFInfo
- Publication number
- CN106745631A CN106745631A CN201710003587.5A CN201710003587A CN106745631A CN 106745631 A CN106745631 A CN 106745631A CN 201710003587 A CN201710003587 A CN 201710003587A CN 106745631 A CN106745631 A CN 106745631A
- Authority
- CN
- China
- Prior art keywords
- arsenic
- tungsten smelting
- fluorine
- tungsten
- waste water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a kind of method for removing Tungsten smelting fluorine in wastewater and arsenic, its technical characteristic is：To a certain amount of Tungsten smelting slag in fluorine-containing, arsenic Tungsten smelting waste water, is added, the Tungsten smelting slag is to smelt the metallurgical slag that Scheelite-Wolframite Mixed Mine is formed by NaOH and phosphoric acid/sodium phosphate, controls liquid-solid ratio and solution ph, can simultaneously be removed the fluorine in waste water, arsenic.The advantage of the invention is that " treatment of wastes with processes of wastes against one another ", using fluorine and arsenic in Tungsten smelting waste residue removal Tungsten smelting waste water, without adding other chemical reagent, it is simple to operate, industrialization is easily achieved, cost for wastewater treatment can be saved, the environment produced pollution while reduction debris dump is rivals in a contest.Tungsten smelting waste water after being processed using the method can qualified discharge：Funing tablet<10mg/L, arsenic concentration<0.5mg/L.
Description
Technical field
The present invention relates to industrial waste water treatment, in particular to a kind of Tungsten smelting wastewater processing technology neck
Domain.
Background technology
The usually association of the unit such as fluorine, arsenic is in tungsten mineral.Caustic digestion-ion-exchange treatment Scheelite-Wolframite Mixed Mine is China's tungsten smelting
The prevailing technology of refining, the technique first use basic pressure digestion decomposition method, with Scheelite-Wolframite Mixed Mine as raw material, add NaOH and
Phosphoric acid/sodium phosphate is reacted, and obtains Tungsten smelting slag and containing sodium tungstate solution, is entered through ion-exchange treatment again containing sodium tungstate solution
Row removal of impurities, transition.Limited by element property and technique, the harmful element such as fluorine, arsenic is generally separated with tungsten after ion exchange, is gone forward side by side
In entering waste water.The fluorine in wastewater, arsenic concentration are higher, need to be discharged after treatment.
Tungsten smelting waste water mainly uses chemical precipitation method fluorine removal and arsenic at present, such as adds aluminium salt fluorine removal and adds molysite arsenic removal, should
Method needs the expensive fluorine removal arsenic removal reagent of addition, and simultaneously can not remove fluorine and arsenic, on the one hand increases Tungsten smelting waste water
Processing cost, on the other hand made troubles to Tungsten smelting wastewater treatment operations.Therefore Tungsten smelting waste water is badly in need of low cost, operation
Simple handling process.
The content of the invention
It is an object of the invention to be directed to problem present in above-mentioned Tungsten smelting waste water treatment process, there is provided a kind of efficient letter
The method of single, low cost, step removal Tungsten smelting fluorine in wastewater and arsenic.
To achieve the above object, it is the invention provides a kind of method for removing Tungsten smelting fluorine in wastewater and arsenic including following
Step：According to liquid-solid ratio 1:1-5:1mL/g, be to Tungsten smelting slag, the Tungsten smelting slag is added in fluorine-containing, arsenic Tungsten smelting waste water
The metallurgical slag that Scheelite-Wolframite Mixed Mine is formed is smelted by NaOH and phosphoric acid/sodium phosphate, calcium hydroxy phosphate, hydroxide is mainly contained
Iron, manganous hydroxide, calcium hydroxide, calcium phosphate, it is 4-9, more than stirring reaction 30min under normal temperature and pressure, mistake to control solution ph
Tungsten smelting waste water after being purified after filter.
Further, described fluorine-containing, the waste water of Tungsten smelting containing arsenic are the waste water after waste liquid station carries tungsten and dephosphorization, its fluorine
Concentration is 10-80mg/L, and arsenic concentration is 0.5-15mg/L.
Further, it is 5-7 to control solution ph.
Further, the Tungsten smelting fluorine in wastewater concentration after the purification<10mg/L, arsenic concentration<0.5mg/L.
It is prevailing technology in the art at present, the technique that NaOH and phosphoric acid/sodium phosphate smelt Scheelite-Wolframite Mixed Mine
The Tungsten smelting slag of middle formation mainly contains calcium hydroxy phosphate, iron hydroxide, manganous hydroxide, calcium hydroxide, calcium phosphate, its specific group
It is extremely complex into, composition and crystal formation, it is impossible to Accurate Determining, thus be difficult by, stacked usually as waste residue.
In the present invention, using the knowable composition of some of Tungsten smelting slag and characteristic, after using it for treatment Tungsten smelting
Fluorine-containing, the arsenic Tungsten smelting waste water produced in continuous technique, realize " treatment of wastes with processes of wastes against one another ".Wherein, the calcium hydroxy phosphate in Tungsten smelting slag is
Fluorapatite in scheelite is decomposed under the conditions of high-alkali and formed, its faintly acid and it is weakly alkaline under the conditions of have very with fluorine ion
Strong binding ability, the hydroxyl generation minimum fluorapatite of solubility product in fluorine energy substituted hydroxy calcium phosphate, fluorapatite can be
Stable existence in water, so as to reach defluorination effect.Meanwhile, containing a certain amount of iron hydroxide in Tungsten smelting slag again, can turn into useless
The natural agent of removing arsenic from water.
In the present invention, because the component of Tungsten smelting slag is difficult to determine, its addition and reaction condition cannot be calculated, this hair
It is bright to find to can reach the purpose for effectively removing fluorine removal and arsenic by controlling the method for liquid-solid ratio and solution ph.It is preferred that controlling pH value of solution
It is 5-7 to be worth, the influence that can further avoid other impurities in Tungsten smelting slag from bringing, while improving the clearance of fluorine and arsenic.Utilize
Tungsten smelting fluorine in wastewater concentration after method treatment of the present invention<10mg/L, arsenic concentration<0.5mg/L, if single treatment without
Method realizes that can carry out secondary repetition is processed, and finally realizes qualified discharge.
The present invention uses Tungsten smelting Slag treatment Tungsten smelting waste water, while having reached the purpose for going fluorine removal and arsenic.The method is easy
In the industrialized production for realizing normal temperature and pressure lower short time, the fluorine removal arsenic removal of short route, accomplish " treatment of wastes with processes of wastes against one another ", reduce waste residue
Heap is rivals in a contest the environment produced pollution, economic and environment-friendly；And other chemical reagent need not be added, it is with low cost, it is simple to operate, give up
Water can reach National Industrial wastewater discharge standard after treatment.
Specific embodiment
It is intended to make the present invention with reference to embodiments further describe, is not intended to limit the present invention.Without departing substantially from this hair
On the premise of bright spirit, any improvement done to the present invention and replacement are within the scope of protection of the invention.
Embodiment 1：
Take that 1L is fluorine-containing, arsenic Tungsten smelting waste water, its initial Funing tablet is that 12.18mg/L, initial arsenic concentration are 1.53mg/L, is added
0.2kg Tungsten smelting slags, it is 6.5 or so to control solution ph, and 30min is reacted at normal temperatures, is stirred with agitating paddle, after reaction terminating
Filtering, measures the Funing tablet in filtrate for 7.876mg/L, and arsenic concentration is 0.18mg/L.
Embodiment 2：
Take that 4L is fluorine-containing, arsenic Tungsten smelting waste water, its initial Funing tablet is that 33.79mg/L, initial arsenic concentration are 5.18mg/L, is added
2kg Tungsten smelting slags, it is 7 or so to control solution ph, and 40min is reacted at normal temperatures, is stirred with agitating paddle, mistake after reaction terminating
Filter, measures the Funing tablet in filtrate for 5.593mg/L, and arsenic concentration is 0.30mg/L.
Embodiment 3：
Take that 200mL is fluorine-containing, arsenic Tungsten smelting waste water, its initial Funing tablet is that 46.30mg/L, initial arsenic concentration are 7.18mg/L,
0.15kg Tungsten smelting slags are added, it is 6 or so to control solution ph, and 30min is reacted at normal temperatures, is stirred with agitating paddle, reaction is eventually
Filtered after only, measure the Funing tablet in filtrate for 8.909mg/L, arsenic concentration is 0.48mg/L.
Embodiment 4：
Take that 8L is fluorine-containing, arsenic Tungsten smelting waste water, its initial Funing tablet is that 60.38mg/L, initial arsenic concentration are 9.09mg/L, is added
8kg Tungsten smelting slags, it is 5 or so to control solution ph, and 30min is reacted at normal temperatures, is stirred with agitating paddle, mistake after reaction terminating
Filter, measures the Funing tablet in filtrate for 9.475mg/L, and arsenic concentration is 0.38mg/L.
Embodiment 5：
Take that 10L is fluorine-containing, arsenic Tungsten smelting waste water, its initial Funing tablet is that 78.91mg/L, initial arsenic concentration are 12.67mg/L, plus
Enter 12.5kg Tungsten smelting slags, 40min is reacted at normal temperatures, it is 5.5 or so to control solution ph, is stirred with agitating paddle, and reaction is eventually
Filtered after only, measure the Funing tablet in filtrate for 8.053mg/L, arsenic concentration is 0.42mg/L.
Claims (4)
1. a kind of method for removing Tungsten smelting fluorine in wastewater and arsenic, it is characterised in that comprise the following steps：According to liquid-solid ratio 1:1-
5:1mL/g, to Tungsten smelting slag is added in fluorine-containing, arsenic Tungsten smelting waste water, the Tungsten smelting slag is by NaOH and phosphoric acid/phosphorus
Sour sodium smelts the metallurgical slag that Scheelite-Wolframite Mixed Mine is formed, and mainly contains calcium hydroxy phosphate, iron hydroxide, manganous hydroxide, hydroxide
Calcium, calcium phosphate, it is 4-9, more than stirring reaction 30min under normal temperature and pressure, the tungsten after being purified after filtering to control solution ph
Smelting wastewater.
2. method according to claim 1, it is characterised in that described fluorine-containing, the waste water of Tungsten smelting containing arsenic is by waste liquid
Station carries the waste water after tungsten and dephosphorization, and its Funing tablet is 10-80mg/L, and arsenic concentration is 0.5-15mg/L.
3. method according to claim 1, it is characterised in that it is 5-7 to control solution ph.
4. method according to claim 1, it is characterised in that the Tungsten smelting fluorine in wastewater concentration after the purification<10mg/
L, arsenic concentration<0.5mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710003587.5A CN106745631B (en) | 2017-01-04 | 2017-01-04 | Method for removing fluorine and arsenic in tungsten smelting wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710003587.5A CN106745631B (en) | 2017-01-04 | 2017-01-04 | Method for removing fluorine and arsenic in tungsten smelting wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106745631A true CN106745631A (en) | 2017-05-31 |
| CN106745631B CN106745631B (en) | 2020-02-14 |
Family
ID=58949395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710003587.5A Active CN106745631B (en) | 2017-01-04 | 2017-01-04 | Method for removing fluorine and arsenic in tungsten smelting wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106745631B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563016A (en) * | 2019-10-09 | 2019-12-13 | 江西理工大学 | Method for treating waste gas containing fluorine and chlorine by using white tungsten slag |
| CN111517353A (en) * | 2020-04-07 | 2020-08-11 | 厦门钨业股份有限公司 | Method for extracting calcium fluoride from scheelite smelting slag |
| CN114524553A (en) * | 2022-03-16 | 2022-05-24 | 赣州八0一钨业有限公司 | Process for treating heavy metal wastewater by using alkaline-boiling tungsten slag |
| CN115925066A (en) * | 2022-09-26 | 2023-04-07 | 中国有色集团（广西）平桂飞碟股份有限公司 | Method for removing fluorine and arsenic from discharged wastewater of ammonium paratungstate workshop |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410562A (en) * | 2002-04-10 | 2003-04-16 | 株洲硬质合金集团有限公司 | United decomposition technology of tungstite, wolframite alkali decomposition |
| CN1455008A (en) * | 2003-05-16 | 2003-11-12 | 自贡硬质合金有限责任公司 | Method of producing sodium tungstate solution using scheelite powder as raw material |
| CN103601311A (en) * | 2013-08-16 | 2014-02-26 | 崇义章源钨业股份有限公司 | Method for removing fluorine, phosphor, and arsenic from tungsten ion exchange wastewater |
| US20140235910A1 (en) * | 2012-12-28 | 2014-08-21 | Eni S.P.A. | Integrated process for the production of biofuels from solid urban waste |
-
2017
- 2017-01-04 CN CN201710003587.5A patent/CN106745631B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410562A (en) * | 2002-04-10 | 2003-04-16 | 株洲硬质合金集团有限公司 | United decomposition technology of tungstite, wolframite alkali decomposition |
| CN1455008A (en) * | 2003-05-16 | 2003-11-12 | 自贡硬质合金有限责任公司 | Method of producing sodium tungstate solution using scheelite powder as raw material |
| US20140235910A1 (en) * | 2012-12-28 | 2014-08-21 | Eni S.P.A. | Integrated process for the production of biofuels from solid urban waste |
| CN103601311A (en) * | 2013-08-16 | 2014-02-26 | 崇义章源钨业股份有限公司 | Method for removing fluorine, phosphor, and arsenic from tungsten ion exchange wastewater |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563016A (en) * | 2019-10-09 | 2019-12-13 | 江西理工大学 | Method for treating waste gas containing fluorine and chlorine by using white tungsten slag |
| CN111517353A (en) * | 2020-04-07 | 2020-08-11 | 厦门钨业股份有限公司 | Method for extracting calcium fluoride from scheelite smelting slag |
| CN114524553A (en) * | 2022-03-16 | 2022-05-24 | 赣州八0一钨业有限公司 | Process for treating heavy metal wastewater by using alkaline-boiling tungsten slag |
| CN115925066A (en) * | 2022-09-26 | 2023-04-07 | 中国有色集团（广西）平桂飞碟股份有限公司 | Method for removing fluorine and arsenic from discharged wastewater of ammonium paratungstate workshop |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106745631B (en) | 2020-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104099474B (en) | A kind of electroplating sludge recycles technique | |
| CN106745631A (en) | A kind of method for removing Tungsten smelting fluorine in wastewater and arsenic | |
| CN104016398B (en) | A kind of method that dilute sulfuric acid utilized in industrial wastewater produces sulfate | |
| CN103073126A (en) | Treatment method of kaolin mineral processing waste water | |
| CN102001762A (en) | Process method of a selenium-containing discharge water | |
| CN108584901B (en) | Method for recovering ceramic-grade iron phosphate from polymetallic hazardous wastes | |
| CN102642953B (en) | Treatment method for high-salinity heavy-metal-containing production sewage | |
| CN107162273A (en) | A kind of processing method of arsenic-containing waste water | |
| US20200190627A1 (en) | Method for decomposing medium-/low-grade scheelite | |
| CN108396158A (en) | A kind of processing method of the complex salt crystal object of electrolytic manganese process | |
| CN107641724A (en) | One kind improves WO in scheelite3The method of leaching rate | |
| CA2677939C (en) | Method and system for removing manganese from waste liquors | |
| CN113249597A (en) | Method for purifying rare earth solution | |
| EP3325414B1 (en) | Improved effluent treatment process for sulphate removal | |
| CN103539242A (en) | Method used for reducing calcium content of rare earth industrial wastewater | |
| CN103667695A (en) | Method for extracting arsenic from gold ore | |
| CN104071954A (en) | Method of treating high-iron red mud by alkaline process for deep dealkalization and iron enrichment | |
| CN108862370A (en) | A method of nano zine oxide being produced under zinc ammonia complexing environment using containing zinc ore crude | |
| CN103601311B (en) | Method for removing fluorine, phosphor, and arsenic from tungsten ion exchange wastewater | |
| CN105347546A (en) | Treatment method and system of waste water produced by acid preparation from pyrite | |
| CN100590077C (en) | Method for preparing copper arsenite or copper arsenate by using arsenic-containing waste water | |
| CN110760700A (en) | Clean production method for zero discharge of wastewater in ammonium molybdate production process | |
| CN106746402B (en) | Method for treating arsenic-removing sludge | |
| KR101293283B1 (en) | Method for removing fluoride from waste water containing fluoroboric acid | |
| CN113292087B (en) | Treatment method for evaporative crystallization of alumina production system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |