CN103466870A - Material recovery method of wastewater containing high-concentration ammonia-nitrogen and heavy metal ions and treatment system - Google Patents
Material recovery method of wastewater containing high-concentration ammonia-nitrogen and heavy metal ions and treatment system Download PDFInfo
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Abstract
The invention relates to a material recovery method of wastewater containing high-concentration ammonia-nitrogen and heavy metal ions and a wastewater treatment system. The material recovery method comprises the following steps: regulating the pH value, ammonia stilling, precipitating, evaporating and the like. The invention further relates to the corresponding treatment system. After the adoption of alkali liquor to precipitate metal ions, sodium sulfide is continuously added to further remove the metal ions left in the waste liquor to reach the emission standard; stronger ammonia water, solid precipitates and the like produced during the wastewater treatment process are recovered to reduce the environmental harm effectively and produce certain economic benefits.
Description
Technical field
The present invention relates to water treatment field, relate to particularly a kind of material recycle method and Waste Water Treatment thereof containing ammonia nitrogen in high density and effluent containing heavy metal ions.
Background technology
Along with social development and scientific and technological progress, people are more and more deep in the exploration of chemical field, and industrial production wastewater various complexity, high density also produces thereupon.Such as in the industries such as metallurgy, plating, battery, often produce high-concentration ammonia nitrogenous wastewater, wherein also contain high density inorganic salt and heavy metal ion simultaneously.Although then ammonia nitrogen can adopt evaporation process that amino molecule is transferred to gas phase by pH value of solution is adjusted to alkalescence, thereby realize removing of ammonia nitrogen in water.Yet in water, exist when heavy metal ion that ammino closes can occur, ammonia and heavy metal ion formation coordinate bond, thereby, in the deamination process, not only need to overcome Intermolecular Forces, and also needing to destroy coordinate bond, separating difficulty improves greatly.
The Chinese invention patent that publication number is CN 102942280 A discloses the solution complexing method of heavy metal ammonia complex in a kind of high-concentration ammonia nitrogenous wastewater, comprise the steps: adding alkaline matter containing in the heavy metal high-concentration ammonia nitrogenous wastewater, make ammonium ion be converted into amino molecule, and have unnecessary hydroxide ion; The temperature distribution of controlling stripping tower by steam flow and the vapor pressure of control inputs stripping tower, make liquid certain temperature province in stripping tower keep certain residence time, the heavy metal ammonia complex is decomposed, heavy metal ion unnecessary hydroxide ion in waste water is combined, and generates precipitation.Yet still also has a certain amount of metal ion in the waste water that adopts the method to process, do not reach the standard of discharge, and the heavy metal ion in waste water and nitrogen element have use value mostly, in line with reducing valuable material in pollution, utilization of waste material and cost-saving principle reply waste water, processed reuse.Therefore develop processing recovery technology safer, economic, that be applicable to contain efficiently ammonia nitrogen in high density and effluent containing heavy metal ions; realize the recycling of trade effluent; refuse zero release up to standard, have important strategic importance and realistic meaning to environment protection, the standard of living that improves the people and the development of enterprise.
Summary of the invention
The objective of the invention is provides ammonia nitrogen and the heavy metal ion in a kind of effective removal trade effluent in order to overcome the deficiencies in the prior art, and the method that it is reclaimed.
For solving above technical problem, a kind of technical scheme that the present invention takes is: a kind for the treatment of process containing ammonia nitrogen in high density and effluent containing heavy metal ions, and it comprises the following steps:
(a) adjust the pH value: in described waste water, add alkali lye, its pH value is adjusted to 9.5 ~ 11, and fully react to obtain one-level supernatant liquor and precipitation with heavy metal ion wherein, after filtration, reclaim after mummification, the filtrate of gained and one-level supernatant liquor are merged into mixed solution to described precipitation;
(b) ammonia still process is processed: add alkali lye in the described mixed solution of step (a), regulating the pH value is 9 ~ 10, and heating evaporation mixed solution subsequently carries out Distillation recovery to ammonia wherein;
(c) precipitation process: in the water outlet after processing to step (b), add respectively sodium sulphite, coagulating agent, flocculation agent, staticly settle to obtain secondary supernatant and mud, further remove heavy metal ion and the solid particulate matter in waste water, after filtration, reclaim after mummification, the filtrate of gained and secondary supernatant merge described mud;
(d) evaporation process: the water outlet of step (c) gained is carried out to evaporation process, after processing, a gained part is the crystallization concentrated solution, another part is phlegma, described crystallization concentrated solution is through centrifugation, the salt recycling is analysed in crystallization, and parting liquid re-starts evaporation process, described phlegma, add thimerosal, recycle after sterilizing or efflux;
Optimally, in described step (a), heavy metal ion is one or more in cupric ion, molybdenum ion, nickel ion, zine ion, silver ions, platinum ion, cobalt ion, cadmium ion, can with OH
-and sodium sulphite formation precipitation, be conducive to the removal of metal ion.
Optimally, in described step (c), the add-on of sodium sulphite, coagulating agent, flocculation agent is respectively 20 ~ 100ppm, 30 ~ 100ppm, 1 ~ 10ppm, saves consumption, reduces costs.
Optimally, in described step (c), mixed solution adopts saturation steam to be heated, and facilitates the operation of subsequent step.
The present invention also provides a kind for the treatment of system containing ammonia nitrogen in high density and effluent containing heavy metal ions, it comprises the collecting tank connected successively, pH adjusts pond, criticize the formula settling tank, reservoir, ammonia steaming device, the coagulating groove, the flocculation reaction groove, sludge sump, intermediate pool, triple-effect evaporation plant, deep bed filter, oxidation trough, thereby wherein said pH adjusts pond and regulates the pH value of waste water for receiving alkali lye, described coagulating groove, the flocculation reaction groove is respectively used to receive sodium sulphite, coagulating agent and flocculation agent, make metal ion residual in waste water, solid particles sediment is got off, purify water, thereby described oxidation trough carries out sterilization and disinfection for receiving thimerosal to waste water, with triple-effect evaporation plant, circulation is connected for the importing of the parting liquid by producing intermediate pool described intermediate pool, it also comprise connect batch formula settling tank and reservoir for the strainer that precipitation carried out to solid-liquid separation, be connected sludge sump and intermediate pool for mud being carried out to the strainer of solid-liquid separation.
Optimally, described ammonia steaming device comprises rich or poor ammoniacal liquor interchanger, ammoniacal liquor well heater, ammonia still, condensate cooler, strong aqua groove, gaseous effluent cooler, wherein said rich or poor ammoniacal liquor interchanger, gaseous effluent cooler are connected with reservoir, coagulating groove respectively, described rich or poor ammoniacal liquor interchanger, ammoniacal liquor well heater, ammonia still, condensate cooler, strong aqua groove connect successively, optimized the structure of ammonia steaming device, be conducive to effective removal of ammonia nitrogen in waste water, and the convenient recovery to ammonia nitrogen.
Because technique scheme is used, the present invention compared with prior art has following advantages: the present invention contains the treatment process of ammonia nitrogen in high density and effluent containing heavy metal ions after using alkali lye to be precipitated metal ion, continue to add sodium sulphite, further remove residual metal ion in waste liquid, make it reach the standard of discharge; On the other hand, by recyclings such as the strong aqua that produces in wastewater treatment process, solid precipitations, can effectively reduce the harm that environment is produced, and produce certain economic benefit.
The accompanying drawing explanation
Accompanying drawing 1 is the treatment system connection diagram of the present invention containing ammonia nitrogen in high density and effluent containing heavy metal ions;
Accompanying drawing 2 is the connection diagram of the present invention containing ammonia steaming device in the treatment system of ammonia nitrogen in high density and effluent containing heavy metal ions;
Wherein: 1, collecting tank; 2, pH adjusts pond; 3, criticize the formula settling tank; 4, reservoir; 5, ammonia steaming device; 501, rich or poor ammoniacal liquor interchanger; 502, ammoniacal liquor well heater; 503, ammonia still; 504, condensate cooler; 505, strong aqua groove; 506, gaseous effluent cooler; 6, coagulating groove; 7, flocculation reaction groove; 8, sludge sump; 9, intermediate pool; 10, triple-effect evaporation plant; 11, deep bed filter; 12, oxidation trough; 13, strainer; 13 ', strainer.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiment of the invention is elaborated:
Press Waste Water Treatment annexation as shown in Figure 1-2, at first the ammonia nitrogen in high density of generation and effluent containing heavy metal ions importing collecting tank 1 are mixed, then import pH and adjust pond 2, add NaOH solution and regulate pH to 9.5 ~ 11, fully mix under agitation condition, make the heavy metal ion Cu in waste water
2+same OH
-react and generate the Cu (OH) that is insoluble in water
2, waste water enters batch formula settling tank 3 and is precipitated afterwards, and the one-level supernatant liquor of generation imports in reservoir 4, and Cu (OH)
2precipitation is extracted out through the mud suction unit, and after filter 13 filters, filtrate enters reservoir 4, filters the Cu (OH) obtained
2solid is recycled after mummification.
Readjust the pH to 9 of waste water ~ 10 to adding NaOH solution in reservoir 4, then it is imported in ammonia steaming device 5.As shown in Figure 2, the waste water that contains ammonia nitrogen in high density is through rich or poor ammoniacal liquor interchanger 501, with the ammonia still process steam heat exchange from ammonia still 502, the waste water that will contain ammonia nitrogen in high density is heated to 60 ℃, then deliver to ammoniacal liquor well heater 502 use saturation steams and be heated 98 ℃, enter ammonia still 503, in ammonia still 503 by the saturation steam straight run distillation, form ammonia vapour and enter condensate cooler 504, be cooled to strong aqua (12 ~ 18%) with recirculated cooling water and certainly flow to the 505 collection reuses of strong aqua groove.Ammonia still process steam in ammonia still 502 is in rich or poor ammoniacal liquor interchanger 501 after heat exchange, and temperature is down to approximately 70 ℃ and is entered gaseous effluent cooler 506, imports coagulating groove 6 after being water-cooled to below 40 ℃ by circulating cooling.
Add sodium sulphite in coagulating groove 6, further remove cupric ion residual in waste water, dosing coagulant PAC, make solid particulate form larger particulate matter simultaneously.6 water outlets of coagulating groove are imported in flocculation reaction groove 7, add flocculation agent PAM, make particulate matter in waste water form the larger more particle of free settling, precipitated in settling tank 8.The 8 top gravity flows of secondary supernatant autoprecipitation pond are flowed out and are entered intermediate pool 9, and the mud that precipitation produces is extracted out through the mud draw-out device, and through filter 13 ' filtration treatment, filtrate enters intermediate pool 9, and filter residue reclaims after mummification;
In intermediate pool 9, water outlet pumps into evaporative crystallization in triple-effect evaporator 10, a gained part is nitrate, nitrite crystallization concentrated solution, import through centrifugal from device 6 through centrifugation, filter out solid crystal, recycle, mother liquor returns to triple-effect evaporator 5 and continues evaporative crystallization; Another part is phlegma, imports in deep bed filter 11, enters after filtering oxidizing reaction groove 12, adds sodium hypochlorite phlegma is carried out after the degree of depth sterilization reuse or effluxes.
Utilize aforesaid method and system to process certain chemical plant wastewater, the water quality before and after processing is as follows:
COD wherein
crorganic substance relative content in the water that means to adopt potassium dichromate standard method to calculate, NH
3-N means ammonia-nitrogen content, and T-N means total nitrogen content, and SS means solid suspension content.As seen from the above table, after adopting aforesaid method and system to be processed waste water, the nitrogen-removing rate of waste water is more than 95%, and solid suspended solid clearance is more than 80%, and the clearance of cupric ion, more than 99%, has reached the standard of recycling or discharging.
Above-described embodiment is only explanation technical conceive of the present invention and characteristics, and its purpose is to allow the person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (6)
1. the treatment process containing ammonia nitrogen in high density and effluent containing heavy metal ions, it is characterized in that: it comprises the following steps:
(a) adjust the pH value: in described waste water, add alkali lye, its pH value is adjusted to 9.5 ~ 11, and fully react to obtain one-level supernatant liquor and precipitation with heavy metal ion wherein, after filtration, reclaim after mummification, the filtrate of gained and one-level supernatant liquor are merged into mixed solution to described precipitation;
(b) ammonia still process is processed: add alkali lye in the described mixed solution of step (a), regulating the pH value is 9 ~ 10, and heating evaporation mixed solution subsequently carries out Distillation recovery to ammonia wherein;
(c) precipitation process: in the water outlet after processing to step (b), add respectively sodium sulphite, coagulating agent, flocculation agent, staticly settle to obtain secondary supernatant and mud, further remove heavy metal ion and the solid particulate matter in waste water, after filtration, reclaim after mummification, the filtrate of gained and secondary supernatant merge described mud;
(d) evaporation process: the water outlet of step (c) gained is carried out to evaporation process, after processing, a gained part is the crystallization concentrated solution, another part is phlegma, described crystallization concentrated solution is through centrifugation, the salt recycling is analysed in crystallization, and parting liquid re-starts evaporation process, described phlegma, add thimerosal, recycle after sterilizing or efflux.
2. the treatment process containing ammonia nitrogen in high density and effluent containing heavy metal ions according to claim 1, it is characterized in that: in described step (a), heavy metal ion is one or more in cupric ion, molybdenum ion, nickel ion, zine ion, silver ions, platinum ion, cobalt ion, cadmium ion.
3. the treatment process containing ammonia nitrogen in high density and effluent containing heavy metal ions according to claim 1, it is characterized in that: in described step (c), the add-on of sodium sulphite, coagulating agent, flocculation agent is respectively 20 ~ 100ppm, 30 ~ 100ppm, 1 ~ 10ppm.
4. the treatment process containing ammonia nitrogen in high density and effluent containing heavy metal ions according to claim 1, it is characterized in that: in described step (c), mixed solution adopts saturation steam to be heated.
5. the treatment system containing ammonia nitrogen in high density and effluent containing heavy metal ions, it is characterized in that: it comprises the collecting tank (1) connected successively, pH adjusts pond (2), criticize formula settling tank (3), reservoir (4), ammonia steaming device (5), coagulating groove (6), flocculation reaction groove (7), sludge sump (8), intermediate pool (9), triple-effect evaporation plant (10), deep bed filter (11), oxidation trough (12), wherein said pH adjusts pond (2) thereby the pH value of regulating waste water for receiving alkali lye, described coagulating groove (6), flocculation reaction groove (7) is respectively used to receive sodium sulphite, coagulating agent and flocculation agent, make metal ion residual in waste water, solid particles sediment is got off, purify water, described oxidation trough (12) thus for receiving thimerosal, waste water is carried out to sterilization and disinfection, with triple-effect evaporation plant (10), circulation is connected for the importing of the parting liquid by producing intermediate pool (9) described intermediate pool (9), it also comprise connect batch formula settling tank (3) and reservoir (4) for the strainer (13) that precipitation carried out to solid-liquid separation, be connected sludge sump (8) and intermediate pool (9) for mud being carried out to the strainer (13 ') of solid-liquid separation.
6. the treatment system containing ammonia nitrogen in high density and effluent containing heavy metal ions according to claim 5, it is characterized in that: described ammonia steaming device (5) comprises rich or poor ammoniacal liquor interchanger (501), ammoniacal liquor well heater (502), ammonia still (503), condensate cooler (504), strong aqua groove (505), gaseous effluent cooler (506), wherein said rich or poor ammoniacal liquor interchanger (501), gaseous effluent cooler (506) respectively with reservoir (4), coagulating groove (6) is connected, described rich or poor ammoniacal liquor interchanger (501), ammoniacal liquor well heater (502), ammonia still (503), condensate cooler (504), strong aqua groove (505) connects successively.
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