CN102372377A - Method for advanced treatment of mercury-containing wastewater - Google Patents
Method for advanced treatment of mercury-containing wastewater Download PDFInfo
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- CN102372377A CN102372377A CN2011102829519A CN201110282951A CN102372377A CN 102372377 A CN102372377 A CN 102372377A CN 2011102829519 A CN2011102829519 A CN 2011102829519A CN 201110282951 A CN201110282951 A CN 201110282951A CN 102372377 A CN102372377 A CN 102372377A
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Abstract
The invention relates to a method for treating mercury-containing wastewater. The method comprises the following steps of: collecting the mercury-containing wastewater to a pH regulating reservoir; adjusting the pH value to be 9-11; pumping the mercury-containing wastewater into a reaction tank by a conveying pump; meanwhile, adding a Na2S solution in the reaction tank and fully reacting; adding a flocculating agent F<3+>; naturally precipitating the generated HgS flocculent precipitate; filtering the reacted supernate by a sand filter tank and enabling the filtered mercury-containing wastewater to feed into an advanced treatment device; feeding the precipitated HgS precipitate into a sludge concentrated tank and concentrating the precipitated HgS precipitate; and feeding the concentrated precipitate into a solid-liquid separating device for solid-liquid separation. According to the invention, the problem that pollution to the environment due to poor treatment effect of the mercury-containing wastewater caused by a synthetic work procedure for producing a polyvinyl chloride resin industrial furnace by adopting a current carbide method is solved; the invention has the advantages of simple and reasonable process, easiness for implementation, quick effect and the like; and the method can be widely applied to the treatment of the mercury-containing wastewater and is especially suitable for the advanced treatment of the mercury-containing wastewater in the production process of the polyvinyl chloride resin.
Description
Technical field:
The present invention relates to a kind of treatment process of mercury-containing waste water, particularly be applicable to the method that the mercury-containing waste water in the polyvinyl chloride resin production is handled.
Background technology:
Because the widespread use of SE; And very abundant increasingly mature with the carbide acetylene method Technology of China's calcium carbide resource; Make generated by polyvinyl chloride by calcium carbide industry fast development, yet also brought the serious environmental pollution problem when bringing great economic benefit, because with HgCl
2As catalyzer, inevitably cause the passage of mercury, the mercury pollution problem that thereupon causes also is on the rise.Though the harm of mercury-containing waste water is familiar with by people already, and has developed a lot of methods and handled, the processing data in most of document is the result of laboratory or pilot scale research, and it is still immature to be actually used in the engineering practice that mercury-containing waste water is handled in the industry.
Announced " a kind of three sections continuous processings are handled the method for mercury-containing waste water " among the Chinese patent CN 102010086A, its method is: PH is adjusted to 9-11 with mercury-containing waste water, is squeezed in the retort by pump, in retort, adds Hg: Na simultaneously
2The mass concentration ratio of S=1: 5-1: 20, mass concentration is the sinking agent Na of 0.5-0.6
2S solution fully reacts, and adds the inorganic flocculating agent that mass concentration is 0.01-0.03 then, and the HgS flocks natural sedimentation of generation is got off, and supernatant reaches emission standard after filtering, the HgS throw out decontamination mud thickener of post precipitation.But in this method processed waste water, still contain the mercury of lower concentration, can impact environment.
Summary of the invention:
Thereby the invention reside in the mercury-containing waste water poor processing effect that has solved the generation of present calcium carbide route production PVC RESINS industrial furnace synthesis procedure and cause the problem of environmental pollution, and then a kind of Hg is provided
2+Handle thoroughly, pollute little, technology advantages of simple, be prone to implement, the method for the advanced treatment mercury-containing waste water of instant effect.
The technical scheme that the present invention adopts is: a kind of method of advanced treatment mercury-containing waste water; Comprise PH equalizing tank, transferpump, retort, sludge thickener that is connected successively and the equipment for separating liquid from solid of handling mercury-containing sludge; It is characterized in that: be provided with the advanced treatment apparatus of sandfiltration pot and mercury-containing waste water after the retort, step is following:
(1) at first mercury-containing waste water is collected to the PH equalizing tank, PH is adjusted to 9-11;
(2) squeeze in the retort by transferpump, in retort, add Na simultaneously
2S solution fully reacts, and adds flocculation agent Fe then
3+, the HgS flocks natural sedimentation of generation is got off;
(3) reacted supernatant gets into the advanced treatment apparatus of mercury-containing waste water after sandfiltration pot filters,
(4) the HgS throw out decontamination mud thickener of post precipitation gets into equipment for separating liquid from solid and carries out solid-liquid separation after sludge thickener concentrates, the liquid after the separation returns the PH equalizing tank, and the solid barrelling sealing after the separation is collected.
The method of described a kind of advanced treatment mercury-containing waste water, the advanced treatment apparatus of mercury-containing waste water comprise reduction reactor and the wet cyclone that links to each other successively; The uniform and stable flow velocity of mercury-containing waste water after sandfiltration pot filters is sent into reduction reactor; Filler in the reduction reactor is a metallic zinc; Mercury ion in reduction reactor in the mercury-containing waste water and metallic zinc generation reduction reaction; Separating out liquid mercury simple substance and the waste water after reduction gets into and carries out liquid liquid in the wet cyclone and separate; Mercury simple substance after separating is discharged by the bottom of wet cyclone and the barrelling sealing is collected, and the supernatant after the separation is come out by the top of wet cyclone, behind mercurous concentration≤0.5 μ g/l, discharges.Use the zinc granule reductive agent can make mercury ion be reduced into MERCURY METAL 99.99(500+500FLASKS), and reductive agent is cheap, loss is lacked in the solvent, and removal of mercury efficient is high, helps the processing of mercury-containing waste water.
The method of described a kind of advanced treatment mercury-containing waste water; Connect an adsorber behind the wet cyclone; Filler in the adsorber is a molecular sieve; Supernatant after the separation of coming out from the wet cyclone top gets into adsorber, and unreacted mercury ion is adsorbed the molecular sieve adsorption in the device in reduction reactor, behind the mercurous concentration of the waste water≤0.5 μ g/l after the absorption, discharges.Molecular sieve has stronger removal effect to divalence mercury; And bigger loading capacity arranged; Can use in the scope of reaction conditions (mercury concentration, PH, temperature, duration of contact etc.) broad, technological process is easy to control, easy to be implemented, and helps further improving the processing efficiency of mercury-containing waste water.
The method of described a kind of advanced treatment mercury-containing waste water; One waste water recycle pump is set behind the adsorber; Waste water after the absorption is sent waste water into reduction reactor again through the waste water recycle pump with uniform and stable flow velocity and is carried out reduction reaction; Carry out liquid liquid through wet cyclone and separate, the supernatant after the separation of coming out in the wet cyclone top gets into adsorber again, discharges behind the mercurous concentration of the supernatant after the separation≤0.5 μ g/l.
The method of described a kind of advanced treatment mercury-containing waste water, adsorber top connect a Gas Phase Adsorption device, are filled with gac in the Gas Phase Adsorption device.Use gac, help the mercury in the gas phase is adsorbed onto in the gac, reached the purpose of protection environment.
The method of described a kind of advanced treatment mercury-containing waste water, molecular sieve are reproducible, when molecular sieve reach absorption saturated after, feed steam in adsorber bottom molecular sieve regenerated, through discharging after mercuryvapour gets into the Gas Phase Adsorption device containing of molecular sieve.Utilize the steam waste heat in the chemical process molecular sieve is regenerated, but effective use of energy sources reduce production costs, reached the purpose of protection environment.
Filler in the method for described a kind of advanced treatment mercury-containing waste water, adsorber is 13X type molecular sieve, 5A type molecular sieve or solid activated carbon, the heavy metal chelate resin of spherical or column.Wherein 13X and 5A represent the model of molecular sieve respectively, and its aperture is respectively 10A and 5A.
Filler in the method for described a kind of advanced treatment mercury-containing waste water, reduction reactor is a metal, and the electropotential of its ionic state is lower than the electropotential of mercury ion.
Filler in the method for described a kind of advanced treatment mercury-containing waste water, reduction reactor is metallic zinc, metallic iron or the metallic aluminium of the spherical or column of 5-20mm.
The method of described a kind of advanced treatment mercury-containing waste water, uniform and stable flow velocity are 4-15m
3/ h.
The present invention is in line with the purpose of protection environment, energy-saving and emission-reduction; The mercury-containing waste water of producing the generation of PVC RESINS industrial furnace synthesis procedure to calcium carbide route is difficult to handle this factor of environmental pollution; Through the filtering treatment process of chemical precipitation method, metallic reducing and molecular sieve adsorption, thereby treated mercury-containing waste water can be reached≤0.5 μ g/l; Adopt chemical reaction method treatment of high concentration mercury-containing waste water, utilize mercury ion to generate the sedimentary principle that is insoluble in water, make Hg with sulfide
2+Be converted into HgS, the HgS natural subsidence got off through adding flocculation agent; Adopt the metallic reducing method to handle the lower concentration mercury-containing waste water then, its speed of reaction is higher, can directly reclaim MERCURY METAL 99.99(500+500FLASKS), and the final barrelling sealing of the MERCURY METAL 99.99(500+500FLASKS) after separating is collected; Adopt the method for molecular sieve adsorption,, can use in the scope of reaction conditions broad because of molecular sieve has bigger loading capacity; And molecular sieve is renewable, thus reusable, prevent secondary pollution; And then reach the purpose of protecting environment, and also reduced production cost simultaneously, improved economic benefit.One aspect of the present invention makes mercury-containing waste water handle thoroughly, pollute little; On the other hand since in the native system filler reusable, invest for a short time, be prone to enforcement; Technology advantages of simple simultaneously can effectively reach the purpose of energy-saving and emission-reduction, protection environment.The present invention can be widely used in being specially adapted in the advanced treatment of the mercury-containing waste water in the polyvinyl chloride resin production in the processing of mercury-containing waste water.
Description of drawings:
Fig. 1 is the embodiments of the invention process flow sheet;
Among Fig. 1: 1 is that retort, 2 is that transferpump, 3 is that PH equalizing tank, 4 is that sludge thickener, 5 is that equipment for separating liquid from solid, 6 is that reduction reactor, 7 is that wet cyclone, 8 is that adsorber, 9 is that Gas Phase Adsorption device, 10 is that waste water recycle pump, 11 is a sandfiltration pot.
Embodiment:
In accompanying drawing 1; Present embodiment comprises the steps: to comprise PH equalizing tank 3, transferpump 2, retort 1, sludge thickener 4 that is connected successively and the equipment for separating liquid from solid 5 of handling mercury-containing sludge; Be provided with the advanced treatment apparatus of sandfiltration pot 11 and mercury-containing waste water after the retort; Step is following: at first mercury-containing waste water is collected to the PH equalizing tank, PH is adjusted to 9-11; Squeeze in the retort by transferpump, in retort, add Na simultaneously
2S solution fully reacts, and adds flocculation agent Fe then
3+, the HgS flocks natural sedimentation of generation is got off; Reacted supernatant gets into the advanced treatment apparatus of mercury-containing waste water after sandfiltration pot filters; The HgS throw out decontamination mud thickener of post precipitation; After sludge thickener concentrates, get into equipment for separating liquid from solid and carry out solid-liquid separation; Liquid after the separation returns the PH equalizing tank, and the solid barrelling sealing after the separation is collected.
Another embodiment difference is that the advanced treatment apparatus of mercury-containing waste water comprises the reduction reactor 6 and wet cyclone 7 that links to each other successively; The uniform and stable flow velocity of mercury-containing waste water after sandfiltration pot filters is sent into reduction reactor; Filler in the reduction reactor is a metallic zinc; Mercury ion in reduction reactor in the mercury-containing waste water and metallic zinc generation reduction reaction; Separating out liquid mercury simple substance and the waste water after reduction gets into and carries out liquid liquid in the wet cyclone and separate; Mercury simple substance after separating is discharged by the bottom of wet cyclone and the barrelling sealing is collected, and the supernatant after the separation is come out by the top of wet cyclone, behind mercurous concentration≤0.5 μ g/l, discharges.
Another embodiment difference is to connect an adsorber behind the wet cyclone; Filler in the adsorber is a molecular sieve; Supernatant after the separation of coming out from the wet cyclone top gets into adsorber; Unreacted mercury ion is adsorbed the molecular sieve adsorption in the device in reduction reactor, behind the mercurous concentration of the waste water≤0.5 μ g/l after the absorption, discharges.
Another embodiment difference is behind the adsorber waste water recycle pump to be set; Waste water after the absorption is sent waste water into reduction reactor again through the waste water recycle pump with uniform and stable flow velocity and is carried out reduction reaction; Carrying out liquid liquid through wet cyclone separates; Supernatant after the separation of coming out in the wet cyclone top gets into adsorber again, discharges behind the mercurous concentration of the supernatant after the separation≤0.5 μ g/l.
Another embodiment difference is that the adsorber top connects a Gas Phase Adsorption device, is filled with gac in the Gas Phase Adsorption device.
Another embodiment difference is that molecular sieve is reproducible, when molecular sieve reach absorption saturated after, feed steam in adsorber bottom molecular sieve regenerated, through discharging after mercuryvapour gets into the Gas Phase Adsorption device containing of molecular sieve.
Another embodiment difference is that the filler in the adsorber is a globular 13X type molecular sieve.
Another embodiment difference is that the filler in the adsorber is the 5A type molecular sieve of column.
Another embodiment difference is that the filler in the reduction reactor is the metallic zinc of 10mm column.
Another embodiment difference is that the filler in the reduction reactor is a 5mm globular metallic aluminium.
Another embodiment difference is that uniform and stable flow velocity is 5m
3/ h.
Another embodiment difference is that uniform and stable flow velocity is 15m
3/ h.
Below be workflow of the present invention and principle:
From mercury-containing waste waters such as the mercurous abraum salt acid that produces in the generated by polyvinyl chloride by calcium carbide production, waste lyes, be collected to the PH equalizing tank, regulate its PH and be adjusted to 9-11; Squeeze in the retort by transferpump; In retort, add the heavy metal sinking agent simultaneously and fully react, and then add inorganic flocculating agent, the HgS flocks natural sedimentation of generation is got off; The supernatant that produces; Filter the back through sandfiltration pot and get into reduction reactor, the metallic zinc generation reduction reaction of the mercury ion in reduction reactor in the mercury-containing waste water and reactor drum filling is separated out the waste water of liquid mercury simple substance after reducing and is got into and carry out liquid liquid in the wet cyclone and separate; Mercury simple substance after separating is discharged and the barrelling sealing by the bottom of wet cyclone; Supernatant after the separation is by the top of the wet cyclone adsorber that comes out to get into again, and unreacted mercury ion is adsorbed the adsorbent of molecular sieve absorption in the device in reduction reactor, and the waste water after the absorption is sent into reduction reactor again through the waste water of waste water recycle pump after with underproof absorption again and continued circulating reaction then; And guarantee uniform and stable circular flow; After the mercury-containing waste water concentration of waste water circulating-pump outlet is lower than 0.005ppm, open the valve of pump discharge, waste water is sent into composite wastewater treatment plant of full factory handle.The mercury-containing sludge that in retort, settles down is then from flowing into sludge thickener; Arrive equipment for separating liquid from solid through sludge pump again; Gained filtrating is returned the PH equalizing tank, the sedimentation removal of mercury that circulates reaction, and the gained filter cake leaves the useless storehouse of danger in; Unified transporting, thus reach the purpose that the removal of mercury reduces environmental pollution.
After molecular sieve adsorption reaches capacity, feed steam from the bottom and carry out regenerative process, the mercurous gas that comes out in the top gets into the Gas Phase Adsorption device by charcoal absorption, thereby reaches the purpose of protection environment.
Claims (10)
1. the method for an advanced treatment mercury-containing waste water; Comprise PH equalizing tank, transferpump, retort, sludge thickener that is connected successively and the equipment for separating liquid from solid of handling mercury-containing sludge; It is characterized in that: be provided with the advanced treatment apparatus of sandfiltration pot and mercury-containing waste water after the retort, step is following:
(1) at first mercury-containing waste water is collected to the PH equalizing tank, PH is adjusted to 9-11;
(2) squeeze in the retort by transferpump, in retort, add Na simultaneously
2S solution fully reacts, and adds flocculation agent Fe then
3+, the HgS flocks natural sedimentation of generation is got off;
(3) reacted supernatant gets into the advanced treatment apparatus of mercury-containing waste water after sandfiltration pot filters,
(4) the HgS throw out decontamination mud thickener of post precipitation gets into equipment for separating liquid from solid and carries out solid-liquid separation after sludge thickener concentrates, the liquid after the separation returns the PH equalizing tank, and the solid barrelling sealing after the separation is collected.
2. the method for a kind of advanced treatment mercury-containing waste water according to claim 1 is characterized in that: the advanced treatment apparatus of mercury-containing waste water comprises reduction reactor and the wet cyclone that links to each other successively; The uniform and stable flow velocity of mercury-containing waste water after sandfiltration pot filters is sent into reduction reactor; Filler in the reduction reactor is a metallic zinc; Mercury ion in reduction reactor in the mercury-containing waste water and metallic zinc generation reduction reaction; Separating out liquid mercury simple substance and the waste water after reduction gets into and carries out liquid liquid in the wet cyclone and separate; Mercury simple substance after separating is discharged by the bottom of wet cyclone and the barrelling sealing is collected, and the supernatant after the separation is come out by the top of wet cyclone, qualified back qualified discharge.
3. the method for a kind of advanced treatment mercury-containing waste water according to claim 2; It is characterized in that: connect an adsorber behind the wet cyclone; Filler in the adsorber is a molecular sieve; Supernatant after the separation of coming out from the wet cyclone top gets into adsorber, and unreacted mercury ion is adsorbed the molecular sieve adsorption in the device in reduction reactor, the qualified back of the waste water after absorption qualified discharge.
4. the method for a kind of advanced treatment mercury-containing waste water according to claim 3; It is characterized in that: a waste water recycle pump is set behind the adsorber; Waste water after the absorption is sent waste water into reduction reactor again through the waste water recycle pump with uniform and stable flow velocity and is carried out reduction reaction; Carry out liquid liquid through wet cyclone and separate, the supernatant after the separation of coming out in the wet cyclone top gets into adsorber again, the qualified back of the supernatant after separation qualified discharge.
5. the method for a kind of advanced treatment mercury-containing waste water according to claim 4 is characterized in that: the adsorber top connects a Gas Phase Adsorption device, is filled with gac in the Gas Phase Adsorption device.
6. the method for a kind of advanced treatment mercury-containing waste water according to claim 3; It is characterized in that: molecular sieve is reproducible; When molecular sieve reach absorption saturated after; Feed steam in the adsorber bottom molecular sieve is regenerated, through discharging after mercuryvapour gets into the Gas Phase Adsorption device containing of molecular sieve.
7. the method for a kind of advanced treatment mercury-containing waste water according to claim 6 is characterized in that: the filler in the adsorber is 13X type molecular sieve, 5A type molecular sieve or solid activated carbon, the heavy metal chelate resin of spherical or column.
8. the method for a kind of advanced treatment mercury-containing waste water according to claim 2 is characterized in that: the filler in the reduction reactor is a metal, and the electropotential of its ionic state is lower than the electropotential of mercury ion.
9. the method for a kind of advanced treatment mercury-containing waste water according to claim 8 is characterized in that: the filler in the reduction reactor is metallic zinc, metallic iron or the metallic aluminium of the spherical or column of 5-20mm.
10. according to the method for claim 2 or 4 described a kind of advanced treatment mercury-containing waste waters, it is characterized in that: described uniform and stable flow velocity is 4-15m
3/ h.
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| CN102633296A (en) * | 2012-05-04 | 2012-08-15 | 新疆大学 | Method for preparing mercuric sulfide (HgS) quantum dots by using 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 |
| CN103936187A (en) * | 2014-03-15 | 2014-07-23 | 新疆天业（集团）有限公司 | Method for advanced treatment of mercury-containing wastewater |
| CN105084598A (en) * | 2015-08-28 | 2015-11-25 | 马鞍山市桓泰环保设备有限公司 | Treatment method of treatment device for mercury, cadmium and lead-contained liquid waste |
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| 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 |
| CN103936187A (en) * | 2014-03-15 | 2014-07-23 | 新疆天业（集团）有限公司 | Method for advanced treatment of mercury-containing wastewater |
| CN106348484A (en) * | 2015-07-17 | 2017-01-25 | 许中石 | Novel deep mercury removal process |
| CN105084598A (en) * | 2015-08-28 | 2015-11-25 | 马鞍山市桓泰环保设备有限公司 | Treatment method of treatment device for mercury, cadmium and lead-contained liquid waste |
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| CN106495363A (en) * | 2016-12-07 | 2017-03-15 | 云南大地绿坤环保科技有限公司 | A kind of processing method of mercurous waste liquid |
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| 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 |
| CN108218096A (en) * | 2018-04-08 | 2018-06-29 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of mercurous high-salt wastewater processing system and method for carbide production vinyl chloride |
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| CN112777850A (en) * | 2020-12-15 | 2021-05-11 | 上海傲江生态环境科技有限公司 | Treatment method and treatment system for mercury-containing high-concentration organic pesticide wastewater |
| CN112777850B (en) * | 2020-12-15 | 2023-10-10 | 上海傲江生态环境科技有限公司 | Treatment method and treatment system for high-concentration organic pesticide wastewater containing mercury |
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