CN101486520B - Process for treating heavy metal wastewater - Google Patents
Process for treating heavy metal wastewater Download PDFInfo
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- CN101486520B CN101486520B CN2009101032687A CN200910103268A CN101486520B CN 101486520 B CN101486520 B CN 101486520B CN 2009101032687 A CN2009101032687 A CN 2009101032687A CN 200910103268 A CN200910103268 A CN 200910103268A CN 101486520 B CN101486520 B CN 101486520B
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- heavy metal
- metal wastewater
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- waste water
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Abstract
The invention relates to a heavy metal wastewater treatment method which comprises two main processes: firstly, chloro organic wastewater is collected and utilized and sufficiently mixed with a multi-thiocarbonate solution in accordance with the weight percentage of 1:2, and the pH value is adjusted to be 10 to 11; the mixture is sufficiently stirred under the function of microwave so as to synthesize multithio-organism. Afterward, the multithio-organism serves as a precipitator and is evenly mixed with the heavy metal wastewater to be treated in accordance with the weight percentage of 1.0 percent to 2.0 percent, so as to obtain flocculent precipitate. The method brings no secondary pollution, is characterized by simple operation and high treatment efficiency, has the advantages of usingwaste to treat waste and low cost, and is conducive to recycling heavy metal.
Description
Technical field
The present invention relates to processing to heavy metal wastewater thereby.
Background technology
Heavy metal (mercury, cadmium, lead, chromium etc.) waste water also still has stronger toxicity under the extremely low situation of concentration, therefore, remove the needs that heavy metal in the waste water just becomes environmental protection effectively; Because heavy metal is relatively more expensive, in decontamination, also to consider the recovery of heavy metal and the problem that resource utilization is utilized again again.
At present, the processing and the resource utilization method of heavy metal wastewater thereby are a lot, and they respectively have relative merits, and the sulfuration method is exactly one of them.The deficiency of existing sulfuration method is: be subjected to the influence of pH value easily and produce hydrogen sulfide when handling, cause secondary pollution; Aspect the heavy metal recovery, its heavy metal sulfide deposit seeds is also less, is unfavorable for reclaiming.
Summary of the invention
The technical problem to be solved in the present invention is, a kind of with low cost, non-secondary pollution is provided and helps the method for the processing heavy metal wastewater thereby of recycling.
The scheme that solve the technical problem is a kind of like this method of handling heavy metal wastewater thereby, and it comprises the steps:
(1) collects chloro-organic waste water and detect its chlorion volumetric molar concentration, be adjusted to 0.05mol/L～0.15mol/L;
(2) be 0.9mol/L polythio carbonate solution and chloro-organic waste water thorough mixing with concentration, regulate pH value to 10～11, wherein, the volumetric ratio of polythio carbonate solution and chloro-organic waste water is 2: 1;
(3) stir 30～60min under microwave action, wherein, microwave frequency is 2000～2800MHz, and microwave power is 600～1000W, and temperature of reaction is 60～100 ℃;
(4) get the polythio organism, precipitation, filtration are taken out, and standby as precipitation agent of handling heavy metal wastewater thereby it;
(5) in heavy metal wastewater thereby, add the polythio organism, mix, leave standstill the back and take out the flocks that contains heavy metal.Wherein, the weight percent of polythio organism and heavy metal wastewater thereby is selected between 1.0%～2.0% according to the weight percent of contained residual heavy metal in the heavy metal wastewater thereby.
As can be seen, the present invention has following advantage compared with prior art from scheme:
1, because the precipitation agent that adopts chloro-organic waste water to prepare to handle heavy metal wastewater thereby as raw material, so, both chloro-organic waste water had been carried out harmless treatment, it is fully used, not only with low cost, and the effect that the treatment of wastes with processes of wastes against one another is arranged, turn waste into wealth;
2, since be with the polythio organism as the precipitation agent of handling heavy metal wastewater thereby, so, not only avoided the secondary pollution that generation caused, and simple to operate because of hydrogen sulfide;
3, because to contain the solubility product of flocks of heavy metal less and particle is bigger, so heavy metal wastewater thereby after treatment not only is easy to reach the emission standard of country, simultaneously, can rapid subsidence to improve processing efficiency, also be beneficial to the recovery of heavy metal.
Embodiment
A kind of method of handling heavy metal wastewater thereby.This treatment process comprises the steps:
(1) collects chloro-organic waste water and detect its chlorion volumetric molar concentration, be adjusted to 0.05mol/L～0.15mol/L;
(2) be 0.9mol/L polythio carbonate solution and chloro-organic waste water thorough mixing with concentration, regulate pH value to 10～11, wherein, the volumetric ratio of polythio carbonate solution and chloro-organic waste water is 2: 1;
(3) stir 30～60min under microwave action, wherein, microwave frequency is 2000～2800MHz, and microwave power is 600～1000W, and temperature of reaction is 60～100 ℃;
(4) get the polythio organism, precipitation, filtration are taken out, and standby as precipitation agent of handling heavy metal wastewater thereby it;
(5) in heavy metal wastewater thereby, add the polythio organism, mix, leave standstill the back and take out the flocks that contains heavy metal.Wherein, the weight percent of polythio organism and heavy metal wastewater thereby, weight percent according to contained residual heavy metal in the heavy metal wastewater thereby is selected (it will be apparent to those skilled in the art that should can make heavy metal precipitation degree of being entirely) between 1.0%～2.0%.In the heavy metal wastewater thereby, residual heavy metal be in mercury (Hg), manganese (Mn), copper (Cu), zinc (Zn), nickel (Ni), chromium (Cr), cadmium (Cd), the cobalt (Co) etc. one or more.
Further, the chloro-organic waste water of collecting in step (1) is a kind of, two or more the waste water that contains in chloro alkane, chloro-alkenes and the chlorination aromatic hydrocarbon.
Say that further in step (1), the concentration after its chloro-organic waste water is regulated is 0.125mol/L.
Again further, the polythio carbonate in the step (2) is trithiocarbonate or pentathiosulfate salt.Those skilled in the art is fully aware of, when selecting polythio carbonate for use, will select solubility certainly, for example: trithiocarbonic acid sodium (Na
2CS
3), sodium pentathiosulfate (Na
2CS
5) etc.
For the benefit of those skilled in the art understand the present invention better, disclose experimental verification process of the present invention and result as follows:
Checking example 1
Preparation polythio organism:
(1) collects Chongqing enterprise's chloro-organic waste water (mainly containing unsaturated chloro-alkenes such as dichlorobutylene, trichloro-butene, dichloroprene etc.), after the sampling analysis its concentration adjustment is arrived 0.05mol/L;
(2) be the trithiocarbonic acid sodium solution of 0.9mol/L with concentration,, regulate pH value to 10～11 according to 2: 1 volumetric ratios and chloro-organic waste water thorough mixing;
(3) stir 60min under microwave action, wherein, microwave frequency is 2000MHz, and microwave power is 600W, and temperature of reaction is 60 ℃;
(4) get the polythio organism, precipitation, filtration are taken out, and standby as the precipitation agent of processing heavy metal wastewater thereby.
Handle heavy metal wastewater thereby:
(5) this routine heavy metal wastewater thereby is, residual heavy metal content is the trade effluent of Mn:309.5, Cu:88.4, Zn:75.4, Ni:45.4 (mg/L).According to the weight percent of this trade effluent 1.0%, step (4) synthetic polythio organism is added, mix, leave standstill the back and take out the flocks that contains wherein.
Detect treated trade effluent, wherein the content of residual heavy metal is Mn:0.98, Cu:0.45, Zn:0.74, Ni:0.31 (mg/L), reaches the emission standard of country.
Checking example two
(1) Chongqing enterprise chloro-organic waste water (mainly containing many chloroparaffins such as tetrachloro butane, pentachloro-butane etc.) is carried out after the sampling analysis its concentration adjustment being arrived 0.075mol/L;
(2) be the trithiocarbonic acid sodium solution of 0.9mol/L with concentration,, regulate pH value to 10～11 according to 2: 1 volumetric ratios and chloro-organic waste water thorough mixing;
(3) stir 55min under microwave action, wherein, microwave frequency is 2200MHz, and microwave power is 700W, and temperature of reaction is 70 ℃;
(4) get the polythio organism, precipitation, filtration are taken out, and standby as the precipitation agent of processing heavy metal wastewater thereby.
Handle heavy metal wastewater thereby:
(5) this routine heavy metal wastewater thereby is, residual heavy metal content is the trade effluent of Mn:208.4, Cr:112.5, Zn:92.5, Co:37.3 (mg/L).According to the weight percent of this trade effluent 1.2%, step (4) synthetic polythio organism is added, mix, leave standstill the back and take out the flocks that contains wherein.
Detect treated trade effluent, wherein the content of residual heavy metal is Mn:0.55, Cr:0.055, Zn:0.28, Co:0.27 (mg/L), reaches the emission standard of country.
Checking example three
(1) chloro-organic waste water (mainly containing chlorinated aromatic hydrocarbons such as dichlorobenzene, trichlorobenzene, toluene(mono)chloride and main derivative nitro Benzene Chloride thereof etc.) to Chongqing enterprise carries out after the sampling analysis its concentration adjustment being arrived 0.1mol/L;
(2) be the trithiocarbonic acid sodium solution of 0.9mol/L with concentration,, regulate pH value to 10～11 according to 2: 1 volumetric ratios and chloro-organic waste water thorough mixing;
(3) stir 50min under microwave action, wherein, microwave frequency is 2400MHz, and microwave power is 800W, and temperature of reaction is 80 ℃;
(4) get the polythio organism, precipitation, filtration are taken out, and standby as the precipitation agent of processing heavy metal wastewater thereby.
Handle heavy metal wastewater thereby:
(5) this routine heavy metal wastewater thereby is, residual heavy metal content is the trade effluent of Cu:312.5, Cr:104.6, Mn:77.3, Cd:49.5 (mg/L).According to the weight percent of this trade effluent 1.5%, step (4) synthetic polythio organism is added, mix, leave standstill the back and take out the flocks that contains wherein.
Detect treated trade effluent, wherein the content of residual heavy metal is Cu:0.35, Cr:0.23, Mn:0.793, Cd:0.059 (mg/L), reaches the emission standard of country.
Checking example four
(1) chloro-organic waste water (mainly containing chlorinated aromatic hydrocarbons such as dichlorobenzene, trichlorobenzene, toluene(mono)chloride and main derivative nitro Benzene Chloride thereof etc.) to Chongqing enterprise carries out after the sampling analysis its concentration adjustment being arrived 0.125mol/L;
(2) be the pentathiosulfate sodium solution of 0.9mol/L with concentration,, regulate pH value to 10～11 according to 2: 1 volumetric ratios and chloro-organic waste water thorough mixing;
(3) stir 45min under microwave action, wherein, microwave frequency is 2600MHz, and microwave power is 900W, and temperature of reaction is 90 ℃;
(4) get the polythio organism, precipitation, filtration are taken out, and standby as the precipitation agent of processing heavy metal wastewater thereby.
Handle heavy metal wastewater thereby:
(5) this routine heavy metal wastewater thereby is, residual heavy metal content is the trade effluent of Cr:332.5, Cu:114.6, Mn:87.3, Ni:38.5 (mg/L).According to the weight percent of this trade effluent 1.7%, step (4) synthetic polythio organism is added, mix, leave standstill the back and take out the flocks that contains wherein.
Detect treated trade effluent, wherein the content of residual heavy metal is Cr:0.236, Cu:0.46, Mn:0.15, Ni:0.21 (mg/L), reaches the emission standard of country.
Checking example five
(1) chloro-organic waste water (mainly containing chlorinated aromatic hydrocarbons such as dichlorobenzene, trichlorobenzene, toluene(mono)chloride and main derivative nitro Benzene Chloride thereof etc.) to Chongqing enterprise carries out after the sampling analysis its concentration adjustment being arrived 0.15mol/L;
(2) be the pentathiosulfate sodium solution of 0.9mol/L with concentration,, regulate pH value to 10～11 according to 2: 1 volumetric ratios and chloro-organic waste water thorough mixing;
(3) stir 30min under microwave action, wherein, microwave frequency is 2800MHz, and microwave power is 1000W, and temperature of reaction is 100 ℃;
(4) get the polythio organism, precipitation, filtration are taken out, and standby as the precipitation agent of processing heavy metal wastewater thereby.
Handle heavy metal wastewater thereby:
(5) this routine heavy metal wastewater thereby is, residual heavy metal content is the trade effluent of Mn:232.6, Zn:134.8, Cu:98.6, Hg:3.5 (mg/L).According to the weight percent of this trade effluent 2.0%, step (4) synthetic polythio organism is added, mix, leave standstill the back and take out the flocks that contains wherein.
Detect treated trade effluent, wherein the content of residual heavy metal is Mn:0.64, Zn:0.15, Cu:0.45, Hg:0.0009 (mg/L), reaches the emission standard of country.
Claims (5)
1. a method of handling heavy metal wastewater thereby is characterized in that this treatment process comprises the steps:
(1) collects chloro-organic waste water and detect its chlorion volumetric molar concentration, be adjusted to 0.05mol/L～0.15mol/L;
(2) be 0.9mol/L polythio carbonate solution and chloro-organic waste water thorough mixing with concentration, regulate pH value to 10～11, wherein, the volumetric ratio of polythio carbonate solution and chloro-organic waste water is 2: 1;
(3) stir 30～60min under microwave action, wherein, microwave frequency is 2000～2800MHz, and microwave power is 600～1000W, and temperature of reaction is 60～100 ℃;
(4) get the polythio organism, precipitation, filtration are taken out, and standby as precipitation agent of handling heavy metal wastewater thereby it;
(5) in heavy metal wastewater thereby, add the polythio organism, mix, leave standstill the back and take out the flocks that contains heavy metal;
Wherein, the weight percent of polythio organism and heavy metal wastewater thereby is selected between 1.0%～2.0% according to the weight percent of contained residual heavy metal in the heavy metal wastewater thereby.
2. according to the method for the described processing heavy metal wastewater thereby of claim 1, it is characterized in that: the described chloro-organic waste water of collecting in step (1) is one or both the waste water that contains in chloro alkane, chloro-alkenes and the chlorination aromatic hydrocarbon.
3. according to the method for claim 1 or 2 described processing heavy metal wastewater therebies, it is characterized in that: in step (1), the concentration after described chloro-organic waste water is regulated is 0.125mol/L.
4. according to the method for claim 1 or 2 described processing heavy metal wastewater therebies, it is characterized in that: at the polythio carbonate described in the step (2) is trithiocarbonate or pentathiosulfate salt.
5. according to the method for the described processing heavy metal wastewater thereby of claim 3, it is characterized in that: at the polythio carbonate described in the step (2) is trithiocarbonate or pentathiosulfate salt.
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| CN2009101032687A CN101486520B (en) | 2009-02-26 | 2009-02-26 | Process for treating heavy metal wastewater |
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|---|---|---|---|
| CN2009101032687A CN101486520B (en) | 2009-02-26 | 2009-02-26 | Process for treating heavy metal wastewater |
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| CN101486520B true CN101486520B (en) | 2010-09-22 |
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| CN101850358B (en) * | 2010-06-13 | 2011-11-16 | 南京工业大学 | Method for restoring organochlorine contaminated soil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4612125A (en) * | 1985-06-20 | 1986-09-16 | Cx/Oxytech, Inc. | Method for removing heavy metal from wastewater streams |
| CN1054403A (en) * | 1990-02-28 | 1991-09-11 | 友联石油公司 | Solid thiocatbonate and production thereof and using method |
| CN101302017A (en) * | 2008-06-23 | 2008-11-12 | 重庆大学 | Synthetic method of sodium pentathiosulfate |
-
2009
- 2009-02-26 CN CN2009101032687A patent/CN101486520B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4612125A (en) * | 1985-06-20 | 1986-09-16 | Cx/Oxytech, Inc. | Method for removing heavy metal from wastewater streams |
| CN1054403A (en) * | 1990-02-28 | 1991-09-11 | 友联石油公司 | Solid thiocatbonate and production thereof and using method |
| CN101302017A (en) * | 2008-06-23 | 2008-11-12 | 重庆大学 | Synthetic method of sodium pentathiosulfate |
Non-Patent Citations (2)
| Title |
|---|
| JP特开平7-90112A 1995.04.04 |
| 李炳智等.氯代硝基苯类废水臭氧化动力学和机理.《化工学报》.2008,第59卷(第8期),2111-2120. * |
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