CN108178372A - A kind of method for removing chlorinated exhaust and absorbing vanadium in abraum salt - Google Patents
A kind of method for removing chlorinated exhaust and absorbing vanadium in abraum salt Download PDFInfo
- Publication number
- CN108178372A CN108178372A CN201711473434.3A CN201711473434A CN108178372A CN 108178372 A CN108178372 A CN 108178372A CN 201711473434 A CN201711473434 A CN 201711473434A CN 108178372 A CN108178372 A CN 108178372A
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- CN
- China
- Prior art keywords
- vanadium
- abraum salt
- chlorinated exhaust
- absorbing
- liquid
- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/62—Heavy metal 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F7/00—Aeration of stretches of water
Abstract
The invention belongs to industrial waste water treatments, and in particular to a kind of method for removing chlorinated exhaust and absorbing vanadium in abraum salt.The technical problems to be solved by the invention are to provide a kind of method for removing chlorinated exhaust and absorbing vanadium in abraum salt.This method includes the following steps：The pH value for adding in hydrochloric acid control abraum salt is reacted for 2~4, is then removed free chlorine, is carried out separation of solid and liquid.The method of the present invention can realize that chlorinated exhaust absorbs the content of vanadium in effluent brine and handled from 20ppm~500ppm to less than 0.02ppm, and the foreign matter of vanadium removed in waste water so as to effectively stablize avoids environmental pollution, realizes that industrial waste salt removes the application of vanadium.
Description
Technical field
The invention belongs to industrial waste water treatments, and in particular to a kind of chlorinated exhaust that removes absorbs vanadium in abraum salt
Method.
Background technology
Titanium production industry field produces titanium tetrachloride process, due to mining heritages vanadium using fluidizing chlorination or fused salt chlorimation
Content is high, and the content of vanadium that sodium hydroxide is absorbed in chlorinated exhaust in generation waste liquid is higher, and the recycling of abraum salt solution must be driven off
Vanadium.It is probed by many experiments, the vanadium in abraum salt cannot be removed effectively by various resins, exchange membrane, it is necessary to using chemistry
The method of reaction precipitation removes, but there is no method that can handle the vanadium in chlorinated exhaust absorption waste liquid at present.
Invention content
Due to there is no the prior art that can handle the vanadium in chlorinated exhaust absorption waste liquid at present, the present invention provides a kind of new
Remove chlorinated exhaust absorbing liquid in vanadium method.The present inventor is probed by many experiments, the vanadium in the effluent brine mainly with
The form of sodium vanadate exists, and under conditions of hydrochloric acid adjusting pH is added to be 2~4 outside, sodium vanadate reacts the more sodium vanadates of generation with hydrochloric acid
Precipitation, the precipitation may filter that using the filter cloth of 1000 mesh of ＞, it can be ensured that vanadium is less than 0.02mg/L in the filtrate after filtering, from
And effectively that stablizes removes the vanadium in abraum salt, realizes that industrial waste salt removes the application of vanadium.
The technical problems to be solved by the invention are to provide a kind of method for removing chlorinated exhaust and absorbing vanadium in abraum salt.The party
Method includes the following steps：The pH value that abraum salt is adjusted with hydrochloric acid is reacted for 2~4, then removes free chlorine, separation of solid and liquid is
It can.
Specifically, above-mentioned removing chlorinated exhaust is absorbed in abraum salt in the method for vanadium, the hydrochloric acid for mass concentration 30% into
Product acid.
Specifically, above-mentioned removing chlorinated exhaust is absorbed in abraum salt in the method for vanadium, the reaction time is 1~2h.
Specifically, it is removed by the way of nitrogen gas stirring is passed through in the method for vanadium in above-mentioned removing chlorinated exhaust absorption abraum salt
Remove free chlorine.The mixing time is 5~10min.
Preferably, above-mentioned removing chlorinated exhaust is absorbed in abraum salt in the method for vanadium, and solid-liquid point is carried out using chamber filter press
From, use filter cloth for 1000 mesh more than.
The purpose of the present invention is removing the vanadium after chlorinated exhaust is absorbed using sodium hydroxide in gained effluent brine, use is additional
Hydrochloric acid mode chemical subtraction, strictly controls solution ph, it is ensured that except the stability and economy of vanadium effect.The method of the present invention controls
The pH of solution ranging from 2~4,1~2h of reaction time, more vanadic acid sodium hydrates and the metatitanic acid suspended matter in solution of generation are total to
Coagulation drops, and forms the solid of diameter bigger, i.e., can effectively remove solid using the filter cloth more than 1000 mesh；To improve filter operation
Condition with nitrogen gas stirring after solution reaction, further removes the free chlorine in solution, at the same make precipitation mix after convenient for pump dnockout
Filtering avoids further acid adding from dechlorinating, and solid containing vanadium is caused to dissolve, and ensures except vanadium effect.The method of the present invention can realize chlorination tail
Content of vanadium in aspiration effluent brine is handled from 20ppm~500ppm to less than 0.02ppm, so as to effectively stable removing waste water
In foreign matter of vanadium, avoid environmental pollution, realize that industrial waste salt removes the application of vanadium.
Specific embodiment
The present invention removes chlorinated exhaust and absorbs in abraum salt in the method for vanadium, and a large amount of sodium chloride, content of vanadium are contained in effluent brine
For 2~400mg/L, vanadium mainly exists with vanadic acid na form；There are a large amount of suspended solid particles in acid condition, add hydrochloric acid control
When the pH value of solution is 2~4, sodium vanadate reacts generation Na with hydrochloric acid2O·5V2O5·2H2O is precipitated, heavy with suspended solid copolymerization
Drop；After sodium vanadate fully reacts precipitation, with 5~10min of nitrogen gas stirring, the free chlorine in solution, Ran Houzai are further removed
Using the chamber filter press filtering more than 1000 mesh, the filtrate that content of vanadium is less than 0.02mg/L is obtained.
Specifically, the method that chlorinated exhaust removes vanadium using the abraum salt generated after sodium hydroxide elution, includes the following steps：
(1) continuous acid adding operation is carried out using baffling titanium mixer, according to pH value 2~4, adjust automatically acid adding flow；
(2) mixed liquor is reacted in ceramic reactor or titanium reactor after acid adding, reactor Liquid level for 40~
60%, reaction release the gases such as great amount of carbon dioxide and chlorine go the elution of negative pressure tail gas handle, liquid using it is enterprising, under go out mode
It is back to back liquid；
(3) go out the liquid alternated of reactor to be placed in two plastic stand tanks, treat a jar liquid level reach 80~
When 90%, stop charging, stand 1~2h of reaction, after time of repose reaches, using 5~10min of nitrogen gas stirring, stand tank and give up
Gas removes exhaust treatment system, after free chlorine is made further to remove and be sufficiently stirred with solution, is carried out with pump dnockout to chamber filter press
Filtering；
(4) chamber filter press filter process, filtering early period turbid solution requirement, which returns, stands tank, after filtrate is limpid, cleaning
Lautertuns, switching collect filtrate, after filtering clear up filter residue can directly remove slag factory landfill or the intermediate raw material as sulfate process titanium dioxide
It recycles, with cleaning waste water cleaning filter cloth is collected, ejected wash water is handled into collecting pit periodic filtering.
Embodiment 1
Certain chlorination workshop uses content of titanium dioxide to be produced under cryogenic conditions for 13%~20% low-grade titanium carbide slag
TiCl4The abraum salt that generates of tail gas Alkali absorption, the main component of abraum salt is as shown in table 1：
Chlorination production technology generate alkaline tail gas wastewater eluting contain a large amount of Ca, Mg, Al, Fe, Co, Cu, V, Ti, Cr,
The nonmetallic inclusions such as the metal impurities such as Ni and Si, its impurity content of before processing use the inspections such as Inductively coupled plasma optical emission spectrometer
It surveys, the results are shown in Table 1：
1 effluent brine main component of table
| Ingredient | pH | Free chlorine | Sodium carbonate | V | Ti |
| Content | 9~11 | 3.5% | 2.4% | 50ppm | 0.012% |
The present invention removes the industrial operation method that chlorinated exhaust absorbs vanadium in abraum salt liquid, and process is：
1st, it due to containing a large amount of sodium hypochlorite in effluent brine, needs to decompose dechlorination with outer acid adding, to decompose after avoiding acid adding
The chlorine of releasing gets into the air, it is ensured that dechlorination effect.Production is abundant into titanium mixer using pump conveying abraum salt and hydrochloric acid
Mixing according to mixer outlet pH meter testing result, controls PH ranging from 2~4.
2nd, mixed liquid enters in closed reactor, micro-negative pressure operation is used in reactor, it is ensured that react generation
A large amount of gases are taken away in time, avoid exploding.The reaction time control of mixed liquor is 1~1.5h, and the liquid of reactor controls
Ranging from 40%~50%, liquid after reaction is from reactor bottom continuous discharge.The gas phase of reactor accesses calcium tail gas leaching processed
Wash system, decompose generation chlorine absorbed with calcium hydroxide after remove to prepare calcium chloride, exhaust system negative pressure is -100~-500pa.
3rd, mixed liquor is put into filled in taper knockout drum after switch, in the knockout drum after filling reaction sedimentation 3~4h, make life
Into Na2O·5V2O5·2H2O is precipitated fully is copolymerized sedimentation with metatitanic acid solid particle, from the muddy of conical lower portion discharge about 10%
Turbid goes to treat press filtration pond；Compressed air aeration is passed through from bottom, residual free chlorine is made fully to take out of again, aeration time is 2~3h,
The easy lye fluid-tight of the gas that aeration process generates absorbs trough and receives.
4th, treated, and supernatant liquid goes chamber filter press to filter, it is desirable that filter cloth is not less than 1000 mesh, and filter pressure is more than
0.3Mpa says and is related to that equipment and materials is acidproof and oxidation corrosion；The liquid that 30min is filtered before filter process comes back for mistake again
It filters, the liquid filtered after 30min is the qualified clear liquid of removal of impurities, and filtered fluid main component is as shown in table 2 below.
Clear liquid ingredient after the processing of table 2
| Ingredient | pH | Free chlorine | Sodium chloride | V | Ti |
| Content | 2~4 | 150ppm | 16% | ＜ 0.02ppm | ＜ 100ppm |
Claims (6)
1. remove the method that chlorinated exhaust absorbs vanadium in abraum salt, it is characterised in that：Include the following steps：Abraum salt is adjusted with hydrochloric acid
PH value is reacted for 2~4, then removes free chlorine, separation of solid and liquid.
2. the method according to claim 1 for removing chlorinated exhaust and absorbing vanadium in abraum salt, it is characterised in that：The hydrochloric acid is
30% finished acid of mass concentration.
3. the method according to claim 1 for removing chlorinated exhaust and absorbing vanadium in abraum salt, it is characterised in that：During the reaction
Between be 1~2h.
4. the method according to claim 1 for removing chlorinated exhaust and absorbing vanadium in abraum salt, it is characterised in that：Using being passed through nitrogen
The mode of gas agitating removes free chlorine.
5. the method for removing chlorinated exhaust and absorbing vanadium in abraum salt according to claim 1 or 4, it is characterised in that：It is described to stir
The time is mixed as 5~10min.
6. the method according to claim 1 for removing chlorinated exhaust and absorbing vanadium in abraum salt, it is characterised in that：Using box pressure
Filter carry out separation of solid and liquid, use filter cloth for 1000 mesh more than.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711473434.3A CN108178372A (en) | 2017-12-29 | 2017-12-29 | A kind of method for removing chlorinated exhaust and absorbing vanadium in abraum salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711473434.3A CN108178372A (en) | 2017-12-29 | 2017-12-29 | A kind of method for removing chlorinated exhaust and absorbing vanadium in abraum salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108178372A true CN108178372A (en) | 2018-06-19 |
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| CN201711473434.3A Pending CN108178372A (en) | 2017-12-29 | 2017-12-29 | A kind of method for removing chlorinated exhaust and absorbing vanadium in abraum salt |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012019265A1 (en) * | 2010-08-09 | 2012-02-16 | Vale S.A. | A method for treating liquid effluents and recovering metals |
| CN102476880A (en) * | 2010-11-26 | 2012-05-30 | 攀钢集团钢铁钒钛股份有限公司 | Treatment method of wastewater with sedimentated vanadium |
| US20120193295A1 (en) * | 2011-01-31 | 2012-08-02 | Rahul Shankar Bhaduri | Method for treating effluent waters |
| CN105603221A (en) * | 2016-03-17 | 2016-05-25 | 攀钢集团攀枝花钢钒有限公司 | Method for precipitating vanadium from high-vanadium high-sodium solution |
| CN106893877A (en) * | 2017-02-27 | 2017-06-27 | 中南大学 | A kind of method that vanadium chromium is extracted in the chromic acid mixed salt solution from vanadium |
-
2017
- 2017-12-29 CN CN201711473434.3A patent/CN108178372A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012019265A1 (en) * | 2010-08-09 | 2012-02-16 | Vale S.A. | A method for treating liquid effluents and recovering metals |
| CN102476880A (en) * | 2010-11-26 | 2012-05-30 | 攀钢集团钢铁钒钛股份有限公司 | Treatment method of wastewater with sedimentated vanadium |
| US20120193295A1 (en) * | 2011-01-31 | 2012-08-02 | Rahul Shankar Bhaduri | Method for treating effluent waters |
| CN105603221A (en) * | 2016-03-17 | 2016-05-25 | 攀钢集团攀枝花钢钒有限公司 | Method for precipitating vanadium from high-vanadium high-sodium solution |
| CN106893877A (en) * | 2017-02-27 | 2017-06-27 | 中南大学 | A kind of method that vanadium chromium is extracted in the chromic acid mixed salt solution from vanadium |
Non-Patent Citations (3)
| Title |
|---|
| 李洪桂: "《稀有金属冶金原理及工艺》", 31 January 1981, 冶金工业出版社 * |
| 肖亮: "钒溶液沉钒工艺研究进展", 《第三届钒产业先进技术研讨与交流会论文集》 * |
| 郭宇杰等: "《工业废水处理工程》", 31 October 2016, 东华理工大学出版社 * |
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Application publication date: 20180619 |