CN102030440A - Mercury-polluted water treatment process - Google Patents
Mercury-polluted water treatment process Download PDFInfo
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- CN102030440A CN102030440A CN 201010566299 CN201010566299A CN102030440A CN 102030440 A CN102030440 A CN 102030440A CN 201010566299 CN201010566299 CN 201010566299 CN 201010566299 A CN201010566299 A CN 201010566299A CN 102030440 A CN102030440 A CN 102030440A
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Abstract
The invention relates to the field of sewage treatment, in particular to a treatment method of mercury-polluted water. The mercury-polluted water treatment process mainly comprises pretreatment and mercury removal, wherein the pretreatment is as follows: pretreatment is carried out on the collected polluted water, the suspended matter concentration in the water body is less than or equal to 100mg/L; mercury removal is as follows: (1) inorganic mercury is removed; (2) mercury and mercuric salt are removed by adsorption; secondary adsorption is carried out by an obligate zeolite and hydroxide radical activated carbon, wherein the hydroxide radical activated carbon further adsorbs inorganic mercuric salts in the polluted water; (3) mercury and mercuric salts are removed by ion exchange, and final treatment is carried out on mercury in the polluted water, so as to enable mercury ions in the treated polluted water to reach mercury discharge limit value 0.5mug/l. In the invention, the process is simple, organic mercury and inorganic mercury in the polluted water can be thoroughly removed effectively, so as to enable the mercury-containing concentration to reach emission standards.
Description
Technical field
The present invention relates to sewage treatment area, particularly contain the treatment process of Mercury sewage.
Background technology
Because industrial expansions such as rubber, make industrial sewage seriously be polluted with mercury as producing catalyzer, in the surface water concentration of mercury minimum be 879ng/l, maximum can reach 22563ng/L, its mercurous index also is difficult to reach emission standard (＜0.5 μ g/L) after common sewage disposal.Particularly, ripe engineering practice precedent is not arranged as yet at home at the mercury pollution water treatment of the organism that comprises organic mercury, the mercurous material of inorganic mercury two classes and higher concentration simultaneously, suspended substance.
Summary of the invention
The objective of the invention is to overcome above-mentioned not enough problem, a kind of mercury pollution water technology is provided, the mercury pollution of processing water is thoroughly effectively arranged, make it reach emission standard.
The technical scheme that the present invention is adopted for achieving the above object is: the mercury pollution water technology mainly comprises the removal of pre-treatment and mercury, wherein
Pre-treatment: the polluted water of collecting is carried out pre-treatment, make concentration of suspension≤100mg/L in the water body;
The removal of mercury: the removal of (1) inorganic mercury: the polluted water that contains inorganic mercury, after pre-treatment, enter oxidation pond, in oxidation pond, the particles settling that density is bigger is discharged to the bottom, and the sewage part adds medicament ammonium sulfide, coagulant aids (polyacrylamide) and flocculation agent (polymerize aluminum chloride) according to mercury concentration in the water; Hg
2++ S
2-Hg in the inorganic mercury salt in → HgS ↓ water
2+With the S in the ammonium sulfide
2-In conjunction with forming water-fast zunsober precipitation, be adsorbed on the surface of coagulating agent (polymerize aluminum chloride, polyacrylamide), be collected into sludge pipe;
(2) mercury and mercury salt are removed in absorption: through obligate zeolite and hydroxy kind gac secondary absorption, wherein obligate zeolite adsorption material contains the sulfenyl functional group, mercury salt in the water body there is certain exchange capacity, use has the sulfenyl of containing functional group obligate zeolite adsorption material, the oxidation pond water outlet promotes through pump and sends into the more medium filter that adopts obligate zeolite, quartz sand and other obligate filtrate, inorganic mercury salt in the water is adsorbed, tackles, simultaneously the suspended substance in the water is carried out part and remove, to reduce the subsequent disposal load;
The hydroxy kind gac: gac is primarily aimed at mercury salt and the part organic mercury adsorbs removal, the water outlet of zeolite filtration device (more medium filter) enters through pressure current has the hydroxy kind activated charcoal filter, realizes the further adsorption treatment of inorganic mercury salt in the sewage;
(3) mercury and mercury salt are removed in ion-exchange: the synthetic resins that contains sulfydryl that ion exchange resin adopts is primarily aimed at mercury salt and part organic mercury and carries out the ion-exchange removal; The water outlet of charcoal filter enters the ion exchange unit of the ion exchange resin that contains sulfydryl through pressure current, carries out the final processing to the mercury in the polluted water, and making the mercury ion of handling in the after stain water reach the mercury emissions limits value is 0.5 μ g/l.
Described organic mercury and the inorganic mercury of in pretreated polluted water, containing, the wherein removal of mercury: at first carry out organomercurial removal before the removal technology of inorganic mercury: the main method that organomercurial removal is adopted in to polluted water is that organic mercury is carried out forced oxidation, behind the organomercurial transformation inorganic mercury, by the inorganic mercury treatment process it is handled again.
Described organomercurial removal: during water body concentration of suspension after pre-treatment≤100mg/L, water body is directly sent in the oxidation pond through promoting, organic mercury in the water body, organism are carried out oxidation, oxygenant adopts the high-pure chlorinedioxide of on-site preparation, behind forced oxidation, organism major part in the sewage is converted into inorganics, and organomercurial transformation becomes inorganic mercury.
Adopt the mode of matching while using that high-pure chlorinedioxide is provided in the described water treatment procedure, the dioxide peroxide preparation method is as follows: 5NaClO
2+ 4HCl=4ClO
2+ 2H
2O+5NaCl
The dioxide peroxide that produces directly leads to oxidation pond, and organic mercury in the water and other organic covalent linkage are destroyed, and forms new ionic linkage, finishes the conversion of organic mercury to inorganic mercury.
Described pre-treatment: when concentration of suspension＞3000mg/L, sewage no longer enters Sewage treatment systems, enters sludge treating system, and after sludge treatment dehydration or mummification, its discharge opeing enters Sewage treatment systems through collection;
As water inlet concentration of suspension＞100mg/L but≤during 3000mg/L, polluted water in the priming reservoir is sent into the coagulation air-float pretreatment unit through lift pump, sewage is finished combining of inorganic mercury and sulfide in air-floating apparatus, generate precipitation HgS, under the compressed-air actuated effect of gas blower, finish the synthetic of coagulating agent, and with the HgS sedimentation, after pre-treatment makes concentration of suspension≤100mg/L, carry out the removal of mercury again.
Technology of the present invention is simple, can be effectively and remove organic mercury and inorganic mercury in the polluted water completely, compare with similar water treatment method, and have outstanding feature:
1) to organomercurial removal: adopt the situ configuration high-pure chlorinedioxide that the organic mercury in the sewage is carried out forced oxidation, finish the conversion of organic mercury, come along with inorganic mercury then and remove to inorganic mercury.
2) sedimentation of inorganic mercury:, make the Hg in the water by adding ammonium sulfide
2+With the S in the ammonium sulfide
2-In conjunction with forming water-fast zunsober precipitation, strengthen sedimentation effect by adding coagulant aids polymerize aluminum chloride, flocculation agent polyacrylamide etc. simultaneously, realize the HgS sedimentation.
3) to the Filtration Adsorption of mercury in the polluted water:
Zeolite filtration: (zeolite filtration SH) drops into ferrous sulfate simultaneously and improves its work effect, realizes suspended substance in the water and part mercury salt are removed, and reduces the subsequent disposal load by containing the particular functional group.
Activated carbon filtration: (gac SH) is realized mercury salt and part organic mercury are adsorbed removal by containing the particular functional group.
Utilization has the strong binding property of the ion exchange resin of mercapto functional group to mercury, finally makes the mercurous concentration of water reach emission standard.
Description of drawings:
Fig. 1 is sewage treatment process figure of the present invention.
Fig. 2 is a sewage treatment process system architecture synoptic diagram of the present invention.
Embodiment:
Below in conjunction with specific embodiment the present invention is described in further detail, but the present invention is not limited to specific embodiment.
Embodiment 1
The mercury pollution water technology mainly comprises the removal of pre-treatment and mercury.
Pre-treatment: existing polluted water water body is mixed, mixed polluted water is sent to by lift pump carries out sewage disposal in the priming reservoir 1, at first through data analysis and in conjunction with on-the-spot water sample actual measurement, mixed solution total mercury maximum concentration is 12522 ng/L, serves as according to determining this cover sewage treatment process segmentation controlling index with this concentration.
To mixed polluted water, according to the suspension content in the water, organic content etc. adopt different pretreatment technology, stop up because of suspended substance in operational process to prevent treatment unit.
1) when the concentration of suspension in the water body≤100mg/L, water body is directly sent into oxidation pond 3 water treatment systems and is gone mercury to handle through promoting;
2) as water inlet concentration of suspension＞100mg/L but≤during 3000mg/L, adopting increases pretreatment technology, pre-treatment is mainly: the polluted water in the priming reservoir 1 is sent into coagulation air-float pretreatment unit 2 No. one through lift pump, sewage is finished combining of inorganic mercury and sulfide in air-floating apparatus, generate precipitation HgS, under the compressed-air actuated effect of gas blower, finish the synthetic of coagulating agent, and with the HgS sedimentation.After pre-treatment made floating substrate concentration≤100mg/L, the water treatment system that enters behind the oxidation pond 3 went mercury to handle;
3) when concentration of suspension＞3000mg/L, sewage no longer enters Sewage treatment systems, enters sludge treating system, and after sludge treatment dehydration or mummification, its discharge opeing enters Sewage treatment systems through collection, by 1) or 2) go on foot and carry out pre-treatment.
Removal: after testing in the water body based on inorganic mercury, organic mercury does not almost have, and mainly carries out the removal to inorganic mercury in the polluted water.
(1) adopts the removal of coagulating sedimentation to mercury and mercury salt
Be difficult to the dissolved characteristic according to zunsober, mercury be converted into sulfide can make the mercury precipitation very effectively.By adding coagulating agent, utilize coprecipitation to raise the efficiency.According to practical experience and test, when under best deposition condition, working and adding coagulating agent aluminium salt and be used for coprecipitation, mercury concentration can be reduced to 0.5 –, 5 μ g/l.
The water outlet that is specially oxidation pond 3 enters coagulation air-float device 4 No. two, reaches by No. two coagulation air-float devices the inorganic mercury in the oxidation pond water outlet is carried out the coagulation removal.
Coagulation air-float device (comprising No. one and No. two) mainly comprises coil pipe type reactor, swash plate air supporting etc., coil pipe type reactor.The swash plate air-floating apparatus is made up of hybrid reaction section (not drawing in the schematic diagram), air dissolving system (air dissolved pump, dissolving, pneupress system, dissolved air release) and pond body [zone of action, disengaging zone (comprising Ji Zhaqu, cloth pool, swash plate disengaging zone, catchment area, mud collection area)].Fill with clear water before the air-floating apparatus work.After the startup, pneupress system provides the pressurized air that is not less than 0.6MPa, and air dissolved pump enters working order then, and when the discharge pressure of air dissolved pump surpasses 0.5MPa, and behind the stable 5min (air dissolving system works better), air-floating apparatus begins water inlet (former water).Former water with enter the backflow dissolved air water of zone of action and the microbubble thorough mixing of release thereof by reliever, suspended substance combines with microbubble and forms air float body, enter the cloth pool, this moment, bigger air float body rose to Ji Zhaqu rapidly, less air float body enters the swash plate disengaging zone, according to shallow pool principle, the most of air float body in these air float bodies will be removed at this.The particle that density is bigger will sink down into the air-floating apparatus bottom, by mud scraper it be discharged.Sewage part after the processing is got back in the system as recirculation water, and most of water (water outlet) will enter the next stage processing unit.
On the coagulation air-float device, be furnished with medicine mixing tank 9, medicament is added on the medicine mixing tank after deployed.According to mercury concentration appropriateness allotment in the former water sample.
In the schema: medicament 1 is an ammonium sulfide, with Hg
2+In conjunction with, generate sulfide precipitation and remove inorganic mercury
Hg
2+?+?S
2-?→?HgS↓
Medicament 2 is a polymerize aluminum chloride, and this medicament is a coagulant aids.
Medicament 3 is a polyacrylamide, and this medicament is a flocculation agent.
Hg in the inorganic mercury salt in the water
2+With the S in the ammonium sulfide
2-In conjunction with forming water-fast zunsober precipitation, be adsorbed on the surface of coagulating agent, the latter floats on the water surface under compressed-air actuated effect, be collected into sludge pipe by coagulation air-float device scraper plate.
(2) adopt of the removal of obligate sorbing material to mercury and mercury salt
Obligate zeolite adsorption material: it has the sulfenyl of containing functional group, and the mercury salt in the water body is had certain exchange capacity, uses to have the sulfenyl of containing functional group obligate zeolite adsorption material, can realize the clearance of mercury salt is improved about 20 ~ 30%.The water outlet warp of No. two coagulation air-float devices 4 and middle priming reservoir 5, pump promote sends into the more medium filter 6 that adopts obligate zeolite, quartz sand and other obligate filtrate, inorganic mercury salt in the water is adsorbed, tackles, simultaneously the suspended substance in the water is carried out part and remove, to reduce the subsequent disposal load.
The hydroxy kind gac: gac is primarily aimed at mercury salt and the part organic mercury adsorbs removal.Also be the optimal adsorption material to mercury salt and mercury, use has hydroxy kind charcoal absorption material can improve about 30% to the clearance of mercury salt.The water outlet of zeolite filtration device (more medium filter 6) enters through pressure current has hydroxy kind activated charcoal filter 7, realizes the further adsorption treatment of inorganic mercury salt in the sewage.
(3) adopt the removal of ion-exchange to mercury and mercury salt
The synthetic resins that contains sulfydryl that ion exchange resin adopts is primarily aimed at mercury salt and part organic mercury and carries out the ion-exchange removal.Sulfydryl on the resin has very strong adsorptive power to mercury ion.Concerning the synthetic resins that contains sulfydryl, one liter of resin can hold 100g mercury before saturated, and saturated resin can be reused or dispose.Before using ion exchange column, water must filter to avoid the plug ion exchange column.Resin choice ion-exchange is fit to remove the low-down mercury of concentration, and the mercury residual concentration is about 0.4 –, 0.5 μ g/l under top condition.
The water outlet of charcoal filter 7 enters the ion exchange unit 8 of the ion exchange resin that contains sulfydryl through pressure current, carries out the final processing to the mercury in the polluted water, and making the mercury ion of handling in the after stain water reach the mercury emissions limits value is 0.5 μ g/l.
Produce mud in the native system and enter the sludge disposal system handles.
Embodiment 2
The mercury pollution water technology mainly comprises the removal of pre-treatment and mercury.
Pre-treatment: with embodiment 1.
The removal of mercury: contain organic mercury and inorganic mercury after testing in the water body simultaneously, at first will carry out organomercurial removal, carry out the removal of inorganic mercury again.
Organomercurial removal: the main method that organomercurial removal in the polluted water is adopted is that organic mercury is carried out forced oxidation, behind the organomercurial transformation inorganic mercury, by the inorganic mercury treatment process it is handled again.
Because the water body in the on-the-spot sedimentation basin is in first valve state, the suspended substance amount of body top, pond water body is all very low, during concentration of suspension≤100mg/L, water body is directly sent in the oxidation pond through promoting, organic mercury in the water body, organism are carried out oxidation, and oxygenant adopts the high-pure chlorinedioxide of on-site preparation, behind forced oxidation, organism major part in the sewage is converted into inorganics, and organomercurial transformation becomes inorganic mercury.
Surpassing 10% according to the aerial volumetric concentration of dioxide peroxide just has explosivity, but is foolproof characteristics at the aqueous solution, adopts the mode of matching while using that high-pure chlorinedioxide is provided in the water treatment procedure, and the dioxide peroxide preparation method is as follows: 5NaClO
2+ 4HCl=4ClO
2+ 2H
2O+5NaCl
The dioxide peroxide that produces directly leads to oxidation pond, and organic mercury in the water and other organic covalent linkage are destroyed, and forms new ionic linkage, finishes the conversion of organic mercury to inorganic mercury.
The removal of inorganic mercury: (1) adopts the removal of coagulating sedimentation to mercury and mercury salt; (2) adopt of the removal of obligate sorbing material to mercury and mercury salt; (3) adopt the removal of ion-exchange to mercury and mercury salt, the technology that adopts with embodiment 1 is identical.
According to technological design, each processing unit controlling index such as following table
Table 1: each processing unit segmentation controlled variable
For guaranteeing the water treatment effect, behind the treatment facility commissioning test, the each processing unit water sample is carried out not timing every day and detect, detect index and mainly comprise mercury and suspended substance etc., according to the water sample analysis result in the process, all satisfy the controlling index requirement.
Claims (5)
1. mercury pollution water technology, it is characterized in that: it mainly comprises the removal of pre-treatment and mercury, wherein
Pre-treatment: the polluted water of collecting is carried out pre-treatment, make concentration of suspension≤100mg/L in the water body;
The removal of mercury: the removal of (1) inorganic mercury: the polluted water that contains inorganic mercury, after pre-treatment, enter oxidation pond, in oxidation pond, the particles settling that density is bigger is discharged to the bottom, and the sewage part adds medicament ammonium sulfide, coagulant aids (polyacrylamide) and flocculation agent (polymerize aluminum chloride) according to mercury concentration in the water; Hg
2++ S
2-Hg in the inorganic mercury salt in → HgS ↓ water
2+With the S in the ammonium sulfide
2-In conjunction with forming water-fast zunsober precipitation, be adsorbed on the surface of coagulating agent (polymerize aluminum chloride, polyacrylamide), be collected into sludge pipe;
(2) mercury and mercury salt are removed in absorption: through obligate zeolite and hydroxy kind gac secondary absorption, wherein obligate zeolite adsorption material contains the sulfenyl functional group, mercury salt in the water body there is certain exchange capacity, use has the sulfenyl of containing functional group obligate zeolite adsorption material, the oxidation pond water outlet promotes through pump and sends into the more medium filter that adopts obligate zeolite, quartz sand and other obligate filtrate, inorganic mercury salt in the water is adsorbed, tackles, simultaneously the suspended substance in the water is carried out part and remove, to reduce the subsequent disposal load;
The hydroxy kind gac: gac is primarily aimed at mercury salt and the part organic mercury adsorbs removal, the water outlet of zeolite filtration device (more medium filter) enters through pressure current has the hydroxy kind activated charcoal filter, realizes the further adsorption treatment of inorganic mercury salt in the sewage;
(3) mercury and mercury salt are removed in ion-exchange: the synthetic resins that contains sulfydryl that ion exchange resin adopts is primarily aimed at mercury salt and part organic mercury and carries out the ion-exchange removal; The water outlet of charcoal filter enters the ion exchange unit of the ion exchange resin that contains sulfydryl through pressure current, carries out the final processing to the mercury in the polluted water, and making the mercury ion of handling in the after stain water reach the mercury emissions limits value is 0.5 μ g/l.
2. mercury pollution water technology according to claim 1, it is characterized in that: in pretreated polluted water, contain organic mercury and inorganic mercury, the wherein removal of mercury: at first carry out organomercurial removal before the removal technology of inorganic mercury: the main method that organomercurial removal is adopted in to polluted water is that organic mercury is carried out forced oxidation, behind the organomercurial transformation inorganic mercury, by the inorganic mercury treatment process it is handled again.
3. mercury pollution water technology according to claim 2, it is characterized in that: described organomercurial removal: during water body concentration of suspension after pre-treatment≤100mg/L, water body is directly sent in the oxidation pond through promoting, organic mercury in the water body, organism are carried out oxidation, oxygenant adopts the high-pure chlorinedioxide of on-site preparation, behind forced oxidation, the organism major part in the sewage is converted into inorganics, and organomercurial transformation becomes inorganic mercury.
4. mercury pollution water technology according to claim 3 is characterized in that: adopt the mode of matching while using that high-pure chlorinedioxide is provided in the described water treatment procedure, the dioxide peroxide preparation method is as follows: 5NaClO
2+ 4HCl=4ClO
2+ 2H
2O+5NaCl
The dioxide peroxide that produces directly leads to oxidation pond, and organic mercury in the water and other organic covalent linkage are destroyed, and forms new ionic linkage, finishes the conversion of organic mercury to inorganic mercury.
5. according to the arbitrary described mercury pollution water technology of claim 1-4, it is characterized in that: described pre-treatment: when concentration of suspension＞3000mg/L, sewage no longer enters Sewage treatment systems, enter sludge treating system, after sludge treatment dehydration or mummification, its discharge opeing enters Sewage treatment systems through collection;
As water inlet concentration of suspension＞100mg/L but≤during 3000mg/L, polluted water in the priming reservoir is sent into the coagulation air-float pretreatment unit through lift pump, sewage is finished combining of inorganic mercury and sulfide in air-floating apparatus, generate precipitation HgS, under the compressed-air actuated effect of gas blower, finish the synthetic of coagulating agent, and with the HgS sedimentation, after pre-treatment makes concentration of suspension≤100mg/L, carry out the removal of mercury again.
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| CN102344212A (en) * | 2011-07-04 | 2012-02-08 | 北京中科百旺环保科技有限公司 | Technology for removing mercury from mercury-containing waste alkali |
| CN102381749A (en) * | 2011-09-09 | 2012-03-21 | 天辰化工有限公司 | Method for treating low-concentration mercury-containing wastewater |
| CN102936070A (en) * | 2012-12-06 | 2013-02-20 | 赵建军 | Method for treating mercury-containing wastewater during PVC (Polyvinyle Chloride) production through two-step process |
| CN104108815A (en) * | 2014-08-01 | 2014-10-22 | 何华 | Treatment method for methyl mercury polluted water |
| CN104496081A (en) * | 2014-12-23 | 2015-04-08 | 重庆澄露环境工程有限公司 | Mercury-containing wastewater treatment method and treatment device |
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| CN102381749A (en) * | 2011-09-09 | 2012-03-21 | 天辰化工有限公司 | Method for treating low-concentration mercury-containing wastewater |
| CN102936070A (en) * | 2012-12-06 | 2013-02-20 | 赵建军 | Method for treating mercury-containing wastewater during PVC (Polyvinyle Chloride) production through two-step process |
| CN104108815A (en) * | 2014-08-01 | 2014-10-22 | 何华 | Treatment method for methyl mercury polluted water |
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| CN106830435B (en) * | 2017-03-09 | 2019-11-05 | 杭州职业技术学院 | A kind of mercurous sewage water treatment method |
| CN109775884A (en) * | 2017-11-13 | 2019-05-21 | 武汉中地金盾水务工程有限公司 | A kind of mercury-containing waste water treatment process |
| CN108439642A (en) * | 2018-04-16 | 2018-08-24 | 中国石油工程建设有限公司 | A kind of gas water high concentration mercury efficient removal system and method |
| CN108623047A (en) * | 2018-06-11 | 2018-10-09 | 西南石油大学 | One kind containing Mercury sewage and mercury-containing sludge processing method |
| CN111606402A (en) * | 2020-05-18 | 2020-09-01 | 太仓市新星轻工助剂厂 | Efficient preparation method of water treatment polyaluminum sulfate chloride |
| CN113501594A (en) * | 2021-07-09 | 2021-10-15 | 中南大学 | Method for recovering mercury from high-mercury-content waste liquid |
| CN113501594B (en) * | 2021-07-09 | 2022-04-19 | 中南大学 | Method for recovering mercury from high-mercury-content waste liquid |
| CN115490375A (en) * | 2022-10-02 | 2022-12-20 | 四川树霖科技集团有限公司 | Treatment method of mercury-containing gas field water with high salt content and high COD (chemical oxygen demand) |
| CN116924622A (en) * | 2023-08-11 | 2023-10-24 | 北京博朗德科技有限公司 | Mercury-containing sewage purifying equipment |
| CN116924622B (en) * | 2023-08-11 | 2024-03-29 | 北京博朗德科技有限公司 | Mercury-containing sewage purifying equipment |
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Application publication date: 20110427 |