CN105130041A - Improved treatment method of acidic waste water containing heavy metals - Google Patents
Improved treatment method of acidic waste water containing heavy metals Download PDFInfo
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- CN105130041A CN105130041A CN201510360292.4A CN201510360292A CN105130041A CN 105130041 A CN105130041 A CN 105130041A CN 201510360292 A CN201510360292 A CN 201510360292A CN 105130041 A CN105130041 A CN 105130041A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 56
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 49
- 230000002378 acidificating effect Effects 0.000 title abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 31
- 238000005189 flocculation Methods 0.000 claims abstract description 27
- 230000016615 flocculation Effects 0.000 claims abstract description 27
- 238000005273 aeration Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004571 lime Substances 0.000 claims abstract description 15
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 14
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 27
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N activated carbon Substances [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005352 clarification Methods 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000010802 sludge Substances 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000010979 pH adjustment Methods 0.000 abstract 2
- 239000000839 emulsion Substances 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 238000007790 scraping Methods 0.000 abstract 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
The invention discloses an improved treatment method of acidic waste water containing heavy metals; the treatment method comprises the following processes and steps: (1) blast aeration: carrying out blast aeration oxidation treatment on mine acidic waste water containing the heavy metals in an aeration tank with the aeration time of 30-50 min, wherein an aeration system adopts a ceramic-prepared microporous aeration head; (2) pH adjustment: carrying out pH adjustment and neutralizing treatment with a lime emulsion, and adjusting and controlling the pH value to be 8.0-8.5; (3) flocculation treatment with the flocculant dosage of 8-12 mg/L and the hydraulic retention time of 25 min-40 min; (4) standing precipitation: allowing most of bottom mud subjected to standing precipitation in a precipitation tank to synchronously return to a water pool and a flocculation tank, and scraping the rest part to a mud bucket by a mud scraper and discharging, wherein the backflow ratio of backflow slurry of the bottom mud is (8-10):1; and (5) physical and chemical adsorption treatment. The method can greatly reduce the consumption amount of a neutralizing agent and a flocculant, the amount of eventually produced sludge is substantially reduced, the content of the heavy metal elements in the sludge is increased significantly, the concentration treatment of the sludge is facilitated, the production process is simple, and the production cost is low.
Description
Technical field
The invention belongs to technical field of sewage treatment and utilization, be specifically related to a kind for the treatment of process of acid waste water containing heavy metal, acid heavy metal wastewater after making it process reaches " integrated wastewater discharge standard " (GB8978-1996) emission standard, is specially adapted to the application that Mine production acid heavy metal wastewater is administered.
Background technology
Oneself is more and more subject to concern and the attention of the whole society due to its persistence for the heavy metal contamination produced in mining process and harm.And refuse dump heavy metal drenches the major way the pollution being mine heavy metal.Refuse dump is stored up in process, due to ore body often association various heavy and sulfide mineral, in recovery process, these mineral are under the acting in conjunction of air, water and bacterium, form sulfuric acid ~ ferric sulphate solution, and the many kinds of metal ions in stripping ore, thus produce the heavy metal wastewater thereby of cupric, lead, zinc, cadmium, arsenic etc.It has following characteristics: (1) in acid, and contains contents of many kinds of heavy metal ion; (2) water quantity reduction fluctuation is large.
At present, the treatment process of acid heavy metal wastewater major part adopts neutralisation, by adding and medicament control pH carry out heavy metal ion and carry out sedimentation removal.Conventional technique is lower concentration bed mud reflux technique (LDS), this technique in and the consumption of medicament large, the final sludge quantity produced is more, and easily limits by condition the control of pH and the removal effect of heavy metal and cause final treatment effect fluctuation larger.In recent years the HDS technique of Introduced From Abroad is risen at home, and major part is in conceptual phase, and part case history is Combined concrete, and between each processing unit, the backflow concentration of linking and bed mud is still immature.
In order to solve the technical barrier of acid heavy metal wastewater process; Chinese patent application 201010153695.9 discloses a kind for the treatment of process and treatment system thereof of thereof for acidic waste water containing heavy metals; comprise the following steps: first by powdered carbon, iron filings mixing; add the zeolite through modification again; be placed in Inner electrolysis pond; to be transported in this Inner electrolysis pond by waste water after pre-treatment, under aeration condition, react 10 ~ 30min; Make water outlet directly enter electrochemical reaction cell, in pond, the spacing of pole plate is 0.6 ~ 1.4cm, reaction 5s ~ 5min; Water outlet is carried out precipitating, solid-liquid separation.This treatment system comprise be connected successively equalizing tank, Inner electrolysis pond, electrochemical reaction cell, settling tank and filtering basin; Inner electrolysis is provided with reaction bed in pond, the filtrate of filling zeolite, powdered carbon and iron filings composition in reaction bed; Be equiped with electrochemical reactor in electrochemical reaction cell, in filtering basin, be equiped with surface film strainer.This invention disposal methods is effective, but complex treatment process, processing cost is higher.
The high problem of bed mud water ratio is when remained with bed mud backflow in the shortcoming that reagent consumption is large, bed mud is many and current HDS technique in order to solve in LDS technique, this technique is furtherd investigate original technique and repeatedly test in place, and the treatment process successfully researching and developing the backflow of high density bed mud is effectively administered acid heavy metal wastewater.
The treatment process of high density bed mud backflow, by accurately controlling mixing time and reflux ratio, in efficiency utilization and medicament, repeatedly refluxes to bed mud simultaneously, greatly reduces output and its water ratio of bed mud.Accurately controlled the flow process of waste water simultaneously by the control to the pH of waste water and supporting auxiliary facility of on-line checkingi and robot, reduce the impact in wastewater treatment process and fluctuation to greatest extent, reach object that is efficient, stabilizing treatment acid heavy metal wastewater.
Summary of the invention
Object of the present invention is exactly for the above-mentioned problems in the prior art, and a kind for the treatment of process that significantly can reduce medicament usage quantity, reduce cost for wastewater treatment, follow-on acid waste water containing heavy metal that processing efficiency is high is provided, a new approach is opened up in the process up to standard for acid waste water containing heavy metal.
For realizing above-mentioned purpose of the present invention, the technique of the treatment process employing of a kind of follow-on acid waste water containing heavy metal of the present invention, step, technical parameter are:
(1) blast aeration: by mine acid waste water containing heavy metal blast aeration oxide treatment in aeration tank, aeration time 30 ~ 50min; Aerating system adopts pottery micro porous aeration head processed, and bubble is small, aeration is even, can improve oxygen utilization rate and water treatment efficiency, and aeration oxygen blast simultaneously can remove sulfide, improve anaerobic environment.
(2) pH regulator: the waste water after aerating oxidation feeds in neutralization tank, adds the basic agent into configuring with volume pump---lime slurry carries out pH regulator, neutralizing treatment, regulate, control ph between 8.0 ~ 8.5, being good between 8.0-8.5.Now heavy metal will form throw out and other complex compounds hard to tolerate with hydroxide root.
The lime slurry adopted is even by lime under agitation with lime under agitation tank, and weight concentration controls about 10%, is good with 8% ~ 15% scope.
(3) flocculation treatment: the waste water after pH regulator is fed in flocculation basin and adds flocculation agent and carry out flocculation treatment, flocculation dosage 8 ~ 12mg/L, hydraulic detention time is 25min ~ 40min;
(4) staticly settle: feed in settling tank through the waste water of pH regulator, neutralizing treatment and flocculation treatment and staticly settle; The bed mud major part staticly settled in settling tank synchronously turns back in middle pond, flocculation basin, and remainder adopts mud scraper to scrape and discharges to bucket; The slurry of bed mud backflow backflows than 8 ~ 10:1, and the weight concentration of bed mud controls in 25% ~ 30% scope, controls SO in waste water
4 2-content>=25g/L, there is not knot calcium phenomenon in whole technical process.Can effectively extend automation instrument life-span and accuracy rate aborning, ensure the carrying capacity of a pipeline and produce normal operation, improve processing efficiency.
(5) materialization adsorption treatment: staticly settle the some time until waste water after waste water clarification, supernatant liquor enters physical adsorption device---activated carbon filtration system, carries out advanced treatment to wherein remaining heavy metal, obtains the clear water meeting environmental protection or agricultural requirement.Heavy metal and organic concentration in advanced water treatment, activated carbon filtration system adsorption rate remains on 80% ~ 85%.
The above-mentioned bed mud turned back in neutralization tank is controlling in (0.8 ~ 1.2) with the mass ratio turning back to the bed mud in flocculation basin: 1 scope.
Acid heavy metal wastewater after process can reach " integrated wastewater discharge standard " (GB8978-1996) secondary standard.
The principle of the treatment process of a kind of follow-on acid waste water containing heavy metal of the present invention is: because mine is more containing the sulfide in acidic substance, heavy metal wastewater thereby, under having a large amount of sulfide existent condition, major part heavy metal element forms sulfide precipitation with sulfide in water, but this precipitation easily produces hydrolysis phenomena, heavy metal element and sulfide in overflow water are exceeded standard; And when under the low condition of Sulfide in water content, the hydroxide root in heavy metal element and lime forms complex-precipitation, highly stable very difficult hydrolysis in water, solubleness is less than sulfide precipitation.
Therefore, by heavy metal element precipitation in water if want, reduce its hydrolysis phenomena to greatest extent, first must remove the sulfide in overflow water, at feeding lime make it produce hydroxide throw out and indissoluble complex compound thereof that pole is insoluble in water.
After the treatment process of a kind of follow-on acid waste water containing heavy metal of the present invention adopts above process program, have the following advantages:
(1) in greatly reducing and the consumption of medicament and flocculation agent, as compared to " blast aeration---in---staticly settle---materialization with coagulation adsorb " technique of routine, neutralization milk of lime consumption reduces more than 60%, flocculant usage minimizing more than 40%;
(2) the final sludge quantity produced significantly reduces, and the content of Heavy Metals in Sludge element significantly improves, thus is convenient to focusing on of mud;
(3) more common HDS technique decreases line clogging;
(4) production technique is simple, and production cost is low.
Accompanying drawing explanation
Fig. 1 is the Technology Roadmap of the treatment process of a kind of follow-on acid waste water containing heavy metal of the present invention;
Fig. 2 is the treatment facility contact figure of the treatment process of inventing a kind of follow-on acid waste water containing heavy metal.
Embodiment
For further describing the present invention, below in conjunction with embodiment, for a more detailed description to the treatment process of a kind of follow-on acid waste water containing heavy metal of the present invention.
The inventive method is adopted to process the acid waste water containing heavy metal that certain Mine production of East China is discharged.The water quality of the acid waste water containing heavy metal that this refuse dump is discharged is as shown in table 1.
Table 1 refuse dump waste water quality table (unit: except mg/L, pH)
| Sample | pH | Cu 2+ | Fe 3+ | Zn 2+ | SO4 2- |
| Content | 2.8 | 30-400 | 300-500 | 10-30 | 3240 |
Treatment process, step and technical parameter are as follows:
(1) blast aeration: by mine acid waste water containing heavy metal blast aeration oxide treatment in aeration tank, aeration time 40min; Aerating system adopts pottery micro porous aeration head processed.
(2) pH regulator: the waste water after aerating oxidation feeds in neutralization tank, adds the basic agent into configuring with volume pump---and lime slurry carries out pH regulator, neutralizing treatment, and adjustment, control ph are between 8.0 ~ 8.5.The lime slurry adopted is even by lime under agitation with lime under agitation tank, and weight concentration controls in 8% ~ 15% scope.
(3) flocculation treatment: fed in flocculation basin by the waste water after pH regulator and add flocculation agent PAM or polymerize aluminum chloride carries out flocculation treatment, flocculation dosage 8 ~ 12mg/L, hydraulic detention time is 30min.
(4) staticly settle: feed in settling tank through the waste water of pH regulator, neutralizing treatment and flocculation treatment and staticly settle; The bed mud major part staticly settled in settling tank synchronously turns back in middle pond, flocculation basin, and remainder adopts mud scraper to scrape and discharges to bucket; The slurry of bed mud backflow backflows than 8 ~ 10:1, and wherein turning back to bed mud in neutralization tank with the mass ratio turning back to the bed mud in flocculation basin is good at 1:1.The weight concentration of bed mud controls in 25% ~ 30% scope, controls SO in waste water
4 2-content>=25g/L.
Tested by pH value and sour water metal ion settlement relationship: in sour water, can each metal ion generate precipitation of hydroxide, depends mainly on the height of pH value, pH value is 8.0 or higher time, and in waste water, each metal ion is all effectively precipitated.
The slurry of described bed mud backflow backflow than refer to per minute backflow in bed mud amount and per minute produce and the ratio of the bed mud amount of discharging, its ratio is different, slurry concentration is made a significant impact, when slurry backflows than during for 10 ~ 8:1, slurry concentration can be improved rapidly and stability contorting between 25% ~ 30%, meet processing requirement.
(5) materialization adsorption treatment: after the waste water clarification staticly settled, supernatant liquor enters physical adsorption device---activated carbon filtration system, carries out advanced treatment to wherein remaining heavy metal, obtains the clear water meeting environmental protection or agricultural requirement.
Practical application shows, the acid heavy metal wastewater after process can reach " integrated wastewater discharge standard " (GB8978-1996) secondary standard.As compared to " blast aeration---in---staticly settle---materialization with coagulation adsorb " technique of routine, neutralization milk of lime consumption decreases 62.5%, flocculant usage decreases 42.8%, achieve and fall drug effect fruit significantly, cost for wastewater treatment also significantly reduces, and achieves beyond thought technology and economical effectiveness.
Claims (3)
1. a treatment process for follow-on acid waste water containing heavy metal, is characterized in that adopting following technique, step:
(1) blast aeration: by mine acid waste water containing heavy metal blast aeration oxide treatment in aeration tank, aeration time 30 ~ 50min; Aerating system adopts pottery micro porous aeration head processed;
(2) pH regulator: the waste water after aerating oxidation feeds in neutralization tank, adds the basic agent into configuring with volume pump---and lime slurry carries out pH regulator, neutralizing treatment, and adjustment, control ph are between 8.0 ~ 8.5;
(3) flocculation treatment: the waste water after pH regulator is fed in flocculation basin and adds flocculation agent and carry out flocculation treatment, flocculation dosage 8 ~ 12mg/L, hydraulic detention time is 25min ~ 40min;
(4) staticly settle: feed in settling tank through the waste water of pH regulator, neutralizing treatment and flocculation treatment and staticly settle; The bed mud major part staticly settled in settling tank synchronously turns back in middle pond, flocculation basin, and remainder adopts mud scraper to scrape and discharges to bucket; The slurry of bed mud backflow backflows than 8 ~ 10:1, and the weight concentration of bed mud controls in 25% ~ 30% scope, controls SO in waste water
4 2-content>=25g/L;
(5) materialization adsorption treatment: after the waste water clarification staticly settled, supernatant liquor enters physical adsorption device---activated carbon filtration system, carries out advanced treatment to wherein remaining heavy metal, obtains the clear water meeting environmental protection or agricultural requirement.
2. the treatment process of a kind of follow-on acid waste water containing heavy metal as claimed in claim 1, is characterized in that: the lime slurry lime under agitation tank adopted in (2) step is even by lime under agitation, and weight concentration controls in 8% ~ 15% scope.
3. the treatment process of a kind of follow-on acid waste water containing heavy metal as claimed in claim 1 or 2, is characterized in that: turn back to the bed mud in neutralization tank and turn back to the mass ratio of the bed mud in flocculation basin in (0.8 ~ 1.2): 1 scope.
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| CN109626647A (en) * | 2019-01-07 | 2019-04-16 | 浙江财经大学 | Commercial metal sewage water treatment method based on flocfloatation precipitating |
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| CN112678987A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Treatment method and application of high-COD high-phosphorus heavy metal-containing sewage |
| CN112811541A (en) * | 2019-11-18 | 2021-05-18 | 腾冲华辉火山灰开发有限公司 | High-concentration wastewater medicament compounding device and method |
| CN111617732A (en) * | 2020-06-10 | 2020-09-04 | 中国地质大学（武汉） | Method for in-situ preparation of heavy metal adsorbent based on high-iron-manganese acidic pit wastewater and application |
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Application publication date: 20151209 |