CN105036413A - Treatment process for wastewater containing thallium - Google Patents
Treatment process for wastewater containing thallium Download PDFInfo
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- CN105036413A CN105036413A CN201510453225.7A CN201510453225A CN105036413A CN 105036413 A CN105036413 A CN 105036413A CN 201510453225 A CN201510453225 A CN 201510453225A CN 105036413 A CN105036413 A CN 105036413A
- Authority
- CN
- China
- Prior art keywords
- waste water
- treatment process
- containing thallium
- water containing
- carbon filler
- 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
- 239000002351 wastewater Substances 0.000 title claims abstract description 65
- 229910052716 thallium Inorganic materials 0.000 title claims abstract description 53
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 52
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000945 filler Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000000701 coagulant Substances 0.000 claims abstract description 7
- 238000004062 sedimentation Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000001117 sulphuric acid Substances 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000005189 flocculation Methods 0.000 claims description 6
- 230000016615 flocculation Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 230000001112 coagulating effect Effects 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 7
- 230000015271 coagulation Effects 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 231100000567 intoxicating Toxicity 0.000 description 2
- 230000002673 intoxicating effect Effects 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 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
- -1 Manganate ions Chemical class 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
- 238000010521 absorption reaction 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method 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
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910003438 thallium oxide Inorganic materials 0.000 description 1
- 208000026015 thallium poisoning Diseases 0.000 description 1
- 229910021516 thallium(I) hydroxide Inorganic materials 0.000 description 1
Abstract
The invention discloses a treatment process for wastewater containing thallium. The treatment process comprises the following steps: 1), adjusting the pH value of raw water of the wastewater containing thallium; 2) mixing the wastewater with an iron-carbon filler to enable the wastewater and the iron-carbon filler to react sufficiently; 3) adjusting the pH value of the treated wastewater, adding a metal collecting agent to enable the mixture to react sufficiently; 4) adding a coagulant into the treated wastewater to realize coagulating sedimentation, and carrying out filtering. The treatment process has a good removal effect on thallium in the wastewater containing thallium, and the removal rate can reach 99.99%.
Description
Technical field
The present invention relates to a kind for the treatment of process of waste water containing thallium.
Background technology
Thallium is III A race element, and be easy in entered environment in the smelting process of fire coal, fuel oil and other ore, thallium has two kinds of oxidation state: Tl at occurring in nature
+and Tl
3+, thallium is greater than Hg, Pb and As etc. to mammiferous toxicity, and toxicity is arsenic oxide arsenoxide more than 3 times.Thallium generally exists with the form stable of monovalence and compound thereof in nature water body, is difficult to natural subsidence.
Along with China's expanding economy, exploitation of mineral resources dynamics continues to increase, and enters in environment in mineral resource utilization process by the heavy metal release comprising thallium, and the problem of environmental pollution caused thus is on the rise.Tectonic In Southwestern Guizhou is owing to developing the thallium environmental pollution caused containing thallium mercury ore, and cause this area's hundreds of people generation intoxicating phenomenon in twice wide area in history, successively many people die from thallium poisoning.Yunnan Nanhua As-tl Deposit, in production history for many years, has shown obvious thallium pollution effect.Also once to there is near cement mill resident because of the crop eating high thallium content and caused fairly large intoxicating phenomenon in former federal republic of germany.
In the world the research of thallium is had to the history of upper a century, two kinds are divided into its thinking processed, a kind of is thallium is converted into the object that insoluble compound reaches removal, be the object directly being reached removal by methods such as absorption, filtrations, removal effect is more thorough comparatively speaking for the former.Analyze according to detection, be mainly Tl from the thallium of smeltery's discharge
+exist, due to Tl
+oxyhydroxide TlOH water-soluble, common lime precipitation method can not sedimentation, and conventional method is oxidation Coagulation Method, namely first by Tl
+be oxidized to Tl
3+, then generate Tl (OH) by Coagulation Method
3precipitation reaches the object of removal.
There is such shortcoming in prior art: in conventional oxidation Coagulation Method technique, oxidation is key point, because only have Tl
+exhaustive oxidation is Tl
3+, follow-up coagulating sedimentation could better, more thallium is converted into precipitation, the effect of removal just can reach the best.Conventional oxidation agent is as potassium permanganate, potassium hypochlorite etc., they are while thallium oxide ion, new ion can be brought as chlorion, Manganate ions etc. for solution again, the corrodibility of solution can be increased, and the used in amounts of oxidation agent will control, the very few oxygenizement do not reached, crosses and can cause another kind of pollution at most.
Secondly, oxidation effect has bottleneck, along with reaction Tl
+-2e → Tl
3+constantly carry out, Tl
3+concentration improves constantly and reaction can be made to the right to be more difficult to carry out, and this is also the reason that oxidation Coagulation Method can not promote further to the clearance of thallium, and in iron-carbon micro-electrolysis reaction, has Fe while there is redox reaction
2+generation, Fe
2+there is coagulation, the Tl of oxidation generation like this
3+meeting part coagulating sedimentation, makes above-mentioned reaction more easily carry out, more fully Tl toward the right
+be oxidized to Tl
3+.Meanwhile, Fe
2+along with solution enters follow-up coagulation-settlement process, there is promoter action to coagulating.
Summary of the invention
The object of the present invention is to provide a kind for the treatment of process of waste water containing thallium.
The technical solution used in the present invention is:
A treatment process for waste water containing thallium, comprises step:
1) pH of the former water of waste water containing thallium is regulated;
2) above-mentioned waste water is mixed with iron carbon filler, fully react;
3) regulate the pH through the waste water of upper step process, add metal trapping agent, fully react;
4) in the waste water through upper step process, add flocculation agent and coagulating agent, precipitate, filter.
In step 1), pH is regulated to be 2.5-3.5 with sulphuric acid soln.
In iron carbon filler: iron, carbon mass ratio are 1-4:1.
The particle diameter of iron carbon filler is 0.5-2cm.
Before iron carbon filler uses, the pre-treatment through following: by iron carbon filler alkali liquid washing, then wash by acid solution, last water cleaning.
The former water volume ratio of iron carbon filler, waste water containing thallium is 1:1.
In step 3), regulate pH to 9-10 with alkali metal hydroxide.
Described flocculation agent is PAM; Described coagulating agent is PAC.
The dosage of PAC is 180-220ppm; The dosage of PAM is 40-60ppm.
Step 2) in, the reaction times is 1h-2h; In step 3), the reaction times is 5-8min; In step 4), sedimentation time is 0.5-1h.
The invention has the beneficial effects as follows: present invention process is very good to the removal effect of thallium in waste water containing thallium, and clearance can reach 99.99%.
Embodiment
A treatment process for waste water containing thallium, comprises step:
1) pH of the former water of waste water containing thallium is regulated;
2) above-mentioned waste water is mixed with iron carbon filler, fully react;
3) regulate the pH through the waste water of upper step process, add metal trapping agent, fully react;
4) in the waste water through upper step process, add flocculation agent and coagulating agent, precipitation, filters.
Preferably, in step 1), pH is regulated to be 2.5-3.5 with sulphuric acid soln.
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, before iron carbon filler uses, the pre-treatment through following: by iron carbon filler alkali liquid washing, then wash by acid solution, last water cleaning.
Preferably, iron carbon filler, the former water volume ratio of waste water containing thallium are 1:1.
Preferably, in step 3), regulate pH to 9-10 with alkali metal hydroxide; Preferred further, regulate pH to 9-10 with NaOH.
Preferably, described flocculation agent is PAM; Described coagulating agent is PAC.
Preferably, the dosage of PAC is 180-220ppm; The dosage of PAM is 40-60ppm; Namely the dosage of the dosage of PAC to be its concentration in the waste water after step 3) process be 180-220ppm, PAM is its concentration in the waste water after step 3) process is 40-60ppm; Preferred further, the dosage of PAC is 200ppm; The dosage of PAM is 50ppm.
Preferably, step 2) in, the reaction times is 1h-2h; In step 3), the reaction times is 5-8min; In step 4), the precipitin reaction time is 0.5-1h.
Below in conjunction with specific embodiment, the present invention is described further:
embodiment 1:
A kind for the treatment of process of waste water containing thallium (thallium content is: 800 μ g/L), comprises step:
1) pH to 2.5-3.5 of waste water containing thallium is regulated with the sulphuric acid soln that concentration is 5wt%;
2) iron carbon filler (Fe/C mass ratio is 3, and iron carbon filler particle diameter the is 0.5-2cm) sodium hydroxide solution that concentration is 5wt% is washed, then be the sulphuric acid soln washing of 5wt% by concentration, last water cleaning;
3) by the waste water of step 1) with through step 2) (consumption of iron carbon filler is: it with the volume ratio of former water is: 1:1) mix, fully react 1h for the iron carbon filler that processes;
4) regulate through the pH to 9-10 of the waste water of upper step process with NaOH, adding the mass concentration that heavy metal chelating agent TMT15(makes it in waste water is 0.5%), fully react 5min;
5) in the waste water through upper step process, add PAC and PAM, the add-on of PAC is: to be the add-on of 200ppm, PAM be the concentration in waste water: the concentration in waste water is 50ppm; Precipitation 0.5h, filters.
Result is as follows:
table 1:
embodiment 2:
A kind for the treatment of process of waste water containing thallium (thallium content is: 1406.5 μ g/L), comprises step:
1) pH to 2.5-3.5 of waste water containing thallium is regulated with the sulphuric acid soln that concentration is 5wt%;
2) iron carbon filler (Fe/C mass ratio is 3, and iron carbon filler particle diameter the is 0.5-2cm) sodium hydroxide solution that concentration is 5wt% is washed, then be the sulphuric acid soln washing of 5wt% by concentration, last water cleaning;
3) by the waste water of step 1) with through step 2) (consumption of iron carbon filler is: it with the volume ratio of former water is: 1:1) mix, fully react 1h for the iron carbon filler that processes;
4) regulate through the pH to 9-10 of the waste water of upper step process with NaOH, adding the mass concentration that heavy metal chelating agent TMT15(makes it in waste water is 0.5%), fully react 5min;
5) in the waste water through upper step process, add PAC and PAM, the add-on of PAC is: to be the add-on of 200ppm, PAM be the concentration in waste water: the concentration in waste water is 50ppm; Precipitation 0.5h, filters.
Result is as follows:
table 2:
embodiment 3:
A kind for the treatment of process of waste water containing thallium (thallium content is: 9 μ g/L), comprises step:
1) pH to 2.5-3.5 of waste water containing thallium is regulated with the sulphuric acid soln that concentration is 5wt%;
2) iron carbon filler (Fe/C mass ratio is 3, and iron carbon filler particle diameter the is 0.5-2cm) sodium hydroxide solution that concentration is 5wt% is washed, then be the sulphuric acid soln washing of 5wt% by concentration, last water cleaning;
3) by the waste water of step 1) with through step 2) (consumption of iron carbon filler is: it with the volume ratio of former water is: 1:1) mix, fully react 1h for the iron carbon filler that processes;
4) regulate through the pH to 9-10 of the waste water of upper step process with NaOH, adding the mass concentration that heavy metal chelating agent TMT15(makes it in waste water is 0.1%), fully react 5min;
5) in the waste water through upper step process, add PAC and PAM, the add-on of PAC is: to be the add-on of 200ppm, PAM be the concentration in waste water: the concentration in waste water is 50ppm; Precipitation 1h, filters.
Result is as follows:
table 3:
Can find out: present invention process is very good to the removal effect of thallium, and iron-carbon micro-electrolysis process also has certain removal effect to thallium, and clearance can reach 99.99%.
Claims (10)
1. a treatment process for waste water containing thallium, is characterized in that: comprise step:
1) pH of the former water of waste water containing thallium is regulated;
2) above-mentioned waste water is mixed with iron carbon filler, fully react;
3) regulate the pH through the waste water of upper step process, add metal trapping agent, fully react;
4) in the waste water through upper step process, add flocculation agent and coagulating agent, precipitate, filter.
2. the treatment process of a kind of waste water containing thallium according to claim 1, is characterized in that: in step 1), regulates pH to be 2.5-3.5 with sulphuric acid soln.
3. the treatment process of a kind of waste water containing thallium according to claim 1, is characterized in that: in iron carbon filler: iron, carbon mass ratio are 1-4:1.
4. the treatment process of a kind of waste water containing thallium according to claim 1, is characterized in that: the particle diameter of iron carbon filler is 0.5-2cm.
5. the treatment process of a kind of waste water containing thallium according to claim 1, is characterized in that: before iron carbon filler uses, the pre-treatment through following: by iron carbon filler alkali liquid washing, then washs by acid solution, last water cleaning.
6. the treatment process of a kind of waste water containing thallium according to claim 3 or 4, is characterized in that: the former water volume ratio of iron carbon filler, waste water containing thallium is 1:1.
7. the treatment process of a kind of waste water containing thallium according to claim 1, is characterized in that: in step 3), regulates pH to 9-10 with alkali metal hydroxide.
8. the treatment process of a kind of waste water containing thallium according to claim 1, is characterized in that: described flocculation agent is PAM; Described coagulating agent is PAC.
9. the treatment process of a kind of waste water containing thallium according to claim 1 or 8, is characterized in that: the dosage of PAC is 180-220ppm; The dosage of PAM is 40-60ppm.
10. the treatment process of a kind of waste water containing thallium according to claim 1, is characterized in that: step 2) in, the reaction times is 1h-2h; In step 3), the reaction times is 5-8min; In step 4), sedimentation time is 0.5-1h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510453225.7A CN105036413B (en) | 2015-07-29 | 2015-07-29 | A kind of handling process of waste water containing thallium |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510453225.7A CN105036413B (en) | 2015-07-29 | 2015-07-29 | A kind of handling process of waste water containing thallium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105036413A true CN105036413A (en) | 2015-11-11 |
| CN105036413B CN105036413B (en) | 2017-12-05 |
Family
ID=54443463
Family Applications (1)
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN111807573A (en) * | 2020-07-16 | 2020-10-23 | 湖南中湘春天环保科技有限公司 | Treatment device and method for thallium-containing wastewater |
| 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 |
| WO2023036053A1 (en) * | 2021-09-07 | 2023-03-16 | 中冶长天国际工程有限责任公司 | Cooperative treatment method and treatment system for high-salt solid waste ash and acidic wastewater of steel plant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| WO2023036053A1 (en) * | 2021-09-07 | 2023-03-16 | 中冶长天国际工程有限责任公司 | Cooperative treatment method and treatment system for high-salt solid waste ash and acidic 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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| Publication number | Publication date |
|---|---|
| CN105036413B (en) | 2017-12-05 |
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