CN105036413B - A kind of handling process of waste water containing thallium - Google Patents
A kind of handling process of waste water containing thallium Download PDFInfo
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- CN105036413B CN105036413B CN201510453225.7A CN201510453225A CN105036413B CN 105036413 B CN105036413 B CN 105036413B CN 201510453225 A CN201510453225 A CN 201510453225A CN 105036413 B CN105036413 B CN 105036413B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 59
- 229910052716 thallium Inorganic materials 0.000 title claims abstract description 47
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 25
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000945 filler Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 229910001385 heavy metal Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000000701 coagulant Substances 0.000 abstract description 5
- 230000001112 coagulating effect Effects 0.000 abstract description 4
- 238000004062 sedimentation Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 230000015271 coagulation Effects 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- -1 thallium ion Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- JRIGVWDKYXCHMG-UHFFFAOYSA-N (5-arsoroso-2-hydroxyphenyl)azanium;chloride Chemical compound Cl.NC1=CC([As]=O)=CC=C1O JRIGVWDKYXCHMG-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 240000006909 Tilia x europaea Species 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical group O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229950008475 oxophenarsine Drugs 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 208000026015 thallium poisoning Diseases 0.000 description 1
- 229910021516 thallium(I) hydroxide Inorganic materials 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a kind of handling process of waste water containing thallium.A kind of handling process of waste water containing thallium, including step：1）Adjust the pH of waste water containing thallium raw water；2）Above-mentioned waste water is mixed with iron carbon filler, fully reaction；3）The pH of waste water of the regulation by the processing of upper step, adds metal agent for capturing, fully reaction；4）Coagulant, coagulating sedimentation, filtering are added into the waste water by the processing of upper step.Present invention process is very good to the removal effect of thallium in waste water containing thallium, and clearance can reach 99.99%.
Description
Technical field
The present invention relates to a kind of handling process of waste water containing thallium.
Background technology
Thallium is III A races element, and in easily entering environment in the smelting process of coal-fired, fuel oil and other ores, thallium exists
There are two kinds of oxidation state in nature：Tl+And Tl3+, for thallium to the toxicity of mammal more than Hg, Pb and As etc., toxicity is arsenic oxide arsenoxide
More than 3 times.Thallium typically exists in nature water body with the form stable of monovalence and its compound, it is difficult to natural subsidence.
With China's expanding economy, exploitation of mineral resources dynamics continues to increase, will bag during mineral resource utilization
Include the heavy metal release including thallium to enter in environment, the problem of environmental pollution thus triggered is on the rise.Tectonic In Southwestern Guizhou due to containing
Thallium environmental pollution caused by thallium mercury ore develops, causing this area, hundreds of people is poisoned in wide area twice in history
Phenomenon, successively more people die from thallium poisoning.It is dirty to have shown obvious thallium in production history for many years for Yunnan Nanhua As-tl Deposit
Contaminate effect.Cement plant also once occurred for former federal republic of germany, and nearby resident causes fairly large poisoning existing because eating the crop of high thallium content
As.
The research to thallium has had upper century-old history in the world, and the thinking handled it is divided into two kinds, Yi Zhongshi
Thallium is converted into the purpose that insoluble compound reaches removal, the methods of one kind is directly by adsorbing, filtering reaches removal
Purpose, comparatively removal effect is more thorough for the former.According to detection and analysis, the thallium from smeltery's discharge is mainly Tl+Deposit
Due to Tl+Hydroxide TlOH be dissolved in water, common lime precipitation method can not settle, conventional method be strengthen oxygen
Change Coagulation Method, i.e., first by Tl+It is oxidized to Tl3+, Tl (OH) is then generated by Coagulation Method3Precipitation reaches the purpose of removal.
Prior art has the disadvantage that：In conventional oxidation Coagulation Method technique, oxidation is key point,
Because only that by Tl+Exhaustive oxidation is Tl3+, follow-up coagulating sedimentation ability is more preferable, thallium more is converted into precipitation, removal
Effect can be only achieved most preferably.Conventional oxidation agent is such as：Potassium permanganate, postassium hypochlorite etc., they are same oxidation thallium ion
When, it can be that solution brings new ion such as chlorion, Manganate ions etc. again, the corrosivity of solution, and oxidation can be increased
The used in amounts of agent will be controlled, the very few oxidation not reached, and another pollution can at most be caused by crossing.
Secondly, oxidation effect has bottleneck, with reaction Tl+-2e→Tl3+Continuous progress, Tl3+Concentration constantly carries
Height can cause reaction to be more difficult to carry out to the right, and this is also that oxidation Coagulation Method can not be lifted further to the clearance of thallium
Reason, and in iron-carbon micro-electrolysis reaction, occur to have Fe while redox reaction2+Generation, Fe2+Make with coagulation
With so Tl of oxidation generation3+Meeting part coagulating sedimentation, above-mentioned reaction is set to be easier to carry out toward the right, more fully Tl+
It is oxidized to Tl3+.Meanwhile Fe2+As solution enters follow-up coagulation-settlement process, there is facilitation to coagulating.
The content of the invention
It is an object of the invention to provide a kind of handling process of waste water containing thallium.
The technical solution used in the present invention is：
A kind of handling process of waste water containing thallium, including step：
1）Adjust the pH of waste water containing thallium raw water；
2）Above-mentioned waste water is mixed with iron carbon filler, fully reaction；
3）The pH of waste water of the regulation by the processing of upper step, adds metal agent for capturing, fully reaction；
4）Flocculant and coagulant, precipitation, filtering are added into the waste water by the processing of upper step.
Step 1）In, it is 2.5-3.5 to adjust pH with sulfuric acid solution.
In iron carbon filler：Iron, carbon mass ratio are 1-4：1.
The particle diameter of iron carbon filler is 0.5-2cm.
Iron carbon filler is before use, by following pre-treatment：Washed by iron carbon filler alkali liquid washing, then with acid solution, most
Water cleans afterwards.
Iron carbon filler, waste water containing thallium raw water volume ratio are 1：1.
Step 3）In, adjust pH to 9-10 with alkali metal hydroxide.
Described flocculant is PAM；Described coagulant is PAC.
PAC dosage is 180-220ppm；PAM dosage is 40-60ppm.
Step 2）In, reaction time 1h-2h；Step 3）In, reaction time 5-8min；Step 4）In, the sedimentation time
For 0.5-1h.
The beneficial effects of the invention are as follows：Present invention process is very good to the removal effect of thallium in waste water containing thallium, clearance energy
Reach 99.99%.
Embodiment
A kind of handling process of waste water containing thallium, including step：
1）Adjust the pH of waste water containing thallium raw water；
2）Above-mentioned waste water is mixed with iron carbon filler, fully reaction；
3）The pH of waste water of the regulation by the processing of upper step, adds metal agent for capturing, fully reaction；
4）Flocculant and coagulant, precipitation, filtering are added into the waste water by the processing of upper step.
Preferably, step 1）In, it is 2.5-3.5 to adjust pH with sulfuric acid solution.
Preferably, in iron carbon filler：Iron, carbon mass ratio are 1-4：1；The particle diameter of iron carbon filler is 0.5-2cm.
Preferably, iron carbon filler is before use, by following pre-treatment：By iron carbon filler alkali liquid washing, then use acid solution
Washing, last water cleaning.
Preferably, iron carbon filler, waste water containing thallium raw water volume ratio are 1：1.
Preferably, step 3）In, adjust pH to 9-10 with alkali metal hydroxide；It is further preferred that adjusted with NaOH
PH to 9-10.
Preferably, described flocculant is PAM；Described coagulant is PAC.
Preferably, PAC dosage is 180-220ppm；PAM dosage is 40-60ppm；That is PAC dosage is
It is passing through step 3）The concentration in waste water after processing is 180-220ppm, and PAM dosage is passing through step 3 for it）Place
The concentration in waste water after reason is 40-60ppm；It is further preferred that PAC dosage is 200ppm；PAM dosage is
50ppm。
Preferably, step 2）In, reaction time 1h-2h；Step 3）In, reaction time 5-8min；Step 4）In, sink
The shallow lake reaction time is 0.5-1h.
With reference to specific embodiment, the present invention is described further：
Embodiment 1：
A kind of waste water containing thallium（Thallium content is：800μg/L）Handling process, including step：
1）The pH to 2.5-3.5 for the sulfuric acid solution regulation waste water containing thallium for being 5wt% with concentration；
2）By iron carbon filler（Fe/C mass ratioes are 3, and iron carbon filler particle diameter is 0.5-2cm）The hydroxide for being 5wt% with concentration
Sodium solution washs, then the sulfuric acid solution for being 5wt% with concentration washs, last water cleaning；
3）By step 1）Waste water with pass through step 2）The iron carbon filler of processing（The dosage of iron carbon filler is：Itself and raw water
Volume ratio be：1:1）Mixing, fully reacts 1h；
4）The pH to 9-10 of the waste water handled by upper step is adjusted with NaOH, adds heavy metal chelating agent TMT15（Make its
Mass concentration in waste water is 0.5%）, fully react 5min；
5）PAC is added into the waste water by the processing of upper step and PAM, PAC addition are：Concentration in waste water is
200ppm, PAM addition is：Concentration in waste water is 50ppm；Precipitate 0.5h, filtering.
Result is as follows：
Table 1：
Embodiment 2：
A kind of waste water containing thallium（Thallium content is：1406.5μg/L）Handling process, including step：
1）The pH to 2.5-3.5 for the sulfuric acid solution regulation waste water containing thallium for being 5wt% with concentration；
2）By iron carbon filler（Fe/C mass ratioes are 3, and iron carbon filler particle diameter is 0.5-2cm）The hydroxide for being 5wt% with concentration
Sodium solution washs, then the sulfuric acid solution for being 5wt% with concentration washs, last water cleaning；
3）By step 1）Waste water with pass through step 2）The iron carbon filler of processing（The dosage of iron carbon filler is：Itself and raw water
Volume ratio be：1:1）Mixing, fully reacts 1h；
4）The pH to 9-10 of the waste water handled by upper step is adjusted with NaOH, adds heavy metal chelating agent TMT15（Make its
Mass concentration in waste water is 0.5%）, fully react 5min；
5）PAC is added into the waste water by the processing of upper step and PAM, PAC addition are：Concentration in waste water is
200ppm, PAM addition is：Concentration in waste water is 50ppm；Precipitate 0.5h, filtering.
Result is as follows：
Table 2：
Embodiment 3：
A kind of waste water containing thallium（Thallium content is：9μg/L）Handling process, including step：
1）The pH to 2.5-3.5 for the sulfuric acid solution regulation waste water containing thallium for being 5wt% with concentration；
2）By iron carbon filler（Fe/C mass ratioes are 3, and iron carbon filler particle diameter is 0.5-2cm）The hydroxide for being 5wt% with concentration
Sodium solution washs, then the sulfuric acid solution for being 5wt% with concentration washs, last water cleaning；
3）By step 1）Waste water with pass through step 2）The iron carbon filler of processing（The dosage of iron carbon filler is：Itself and raw water
Volume ratio be：1:1）Mixing, fully reacts 1h；
4）The pH to 9-10 of the waste water handled by upper step is adjusted with NaOH, adds heavy metal chelating agent TMT15（Make its
Mass concentration in waste water is 0.1%）, fully react 5min；
5）PAC is added into the waste water by the processing of upper step and PAM, PAC addition are：Concentration in waste water is
200ppm, PAM addition is：Concentration in waste water is 50ppm；Precipitate 1h, filtering.
Result is as follows：
Table 3：
It can be seen that：Present invention process is very good to the removal effect of thallium, and iron-carbon micro-electrolysis process also has necessarily to thallium
Removal effect, clearance can reach 99.99%.
Claims (1)
1. a kind of handling process of waste water containing thallium, including step：
1) sulfuric acid solution for being 5wt% with concentration adjusts the pH to 2.5-3.5 of waste water containing thallium；
2) sodium hydroxide solution that iron carbon filler is 5wt% with concentration is washed, then the sulfuric acid solution for being 5wt% with concentration is washed
Wash, last water cleaning；
3) waste water of step 1) is mixed with the iron carbon filler by step 2) processing, fully reacts 1h；
4) pH to 9-10 of the waste water handled by upper step is adjusted with NaOH, adds heavy metal chelating agent TMT15, fully reaction
5min；
5) PAC is added into the waste water by the processing of upper step and PAM, PAC addition are：Concentration in waste water is
200ppm, PAM addition is：Concentration in waste water is 50ppm；Precipitate 0.5h, filtering；
The thallium content of the waste water containing thallium raw water is：800μg/L；
In step 2), iron carbon filler Fe/C mass ratioes are 3, and iron carbon filler particle diameter is 0.5-2cm；
In step 3), the dosage of iron carbon filler and the volume ratio of raw water are：1:1；
In step 4), heavy metal chelating agent TMT15 makes its mass concentration in waste water be 0.5%.
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| CN105540946A (en) * | 2015-12-14 | 2016-05-04 | 株洲冶炼集团股份有限公司 | Process for removing thallium through microelectrolysis treatment of thallium-containing heavy metal wastewater |
| CN105417794A (en) * | 2015-12-14 | 2016-03-23 | 株洲冶炼集团股份有限公司 | Microelectrolysis and coagulation linkage treatment device for thallium-containing heavy metal wastewater |
| CN111807573B (en) * | 2020-07-16 | 2022-06-14 | 湖南中湘春天环保科技有限公司 | Treatment device and method for thallium-containing wastewater |
| CN114702188B (en) * | 2021-09-07 | 2023-10-10 | 中冶长天国际工程有限责任公司 | Method and system for cooperatively treating high-salt solid waste ash and acid wastewater of steel plant |
| CN115286139A (en) * | 2022-08-10 | 2022-11-04 | 铜陵铜冠环保科技有限公司 | Compound preparation method and application of industrial wastewater thallium removal agent |
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| CN104773878A (en) * | 2015-04-28 | 2015-07-15 | 韶关朗润环保科技有限公司 | Method for removing trace of thallium in sewage |
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| CN1301219C (en) * | 2005-10-08 | 2007-02-21 | 广州大学 | Treatment of thallium and heavy metal containing mixed waste water drained by sulfuric acid plant |
| CN103086569B (en) * | 2013-01-08 | 2014-09-10 | 华南理工大学 | Method for detoxifying, emission-reducing and deeply treating wastewater of electronic electroplating industry |
| CN103693819B (en) * | 2014-01-02 | 2015-03-04 | 中南大学 | Thallium-containing heavy metal wastewater advanced treatment method |
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| 铁炭微电解催化氧化-絮凝法去除铜冶炼废水中砷的研究;张瑾;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20120315(第03期);第16页第1.5节、第40-42页第4.8-4.9节、第63-64页第5.4节、第65-67页第6.1-6.2节 * |
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Date of cancellation: 20221124 Granted publication date: 20171205 Pledgee: Guangzhou Caold financing Company limited by guarantee Pledgor: GUANGZHOU JINLONGFENG ENVIRONMENTAL PROTECTION EQUIPMENT ENGINEERING CO.,LTD. Registration number: Y2020980005622 |
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Denomination of invention: A Treatment Process for Thallium Containing Wastewater Effective date of registration: 20221125 Granted publication date: 20171205 Pledgee: Guangzhou Caold financing Company limited by guarantee Pledgor: GUANGZHOU JINLONGFENG ENVIRONMENTAL PROTECTION EQUIPMENT ENGINEERING CO.,LTD. Registration number: Y2022440000321 |