CN102923874B - Method for processing wastewater containing heavy metal ions - Google Patents
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- CN102923874B CN102923874B CN201110230799.XA CN201110230799A CN102923874B CN 102923874 B CN102923874 B CN 102923874B CN 201110230799 A CN201110230799 A CN 201110230799A CN 102923874 B CN102923874 B CN 102923874B
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Abstract
The invention relates to a method for processing wastewater containing heavy metal ions, and belongs to the chemical field. The method comprises the following steps: 1, discharging the wastewater to a pH adjustment tank at normal temperature in order to adjust the pH value of the wastewater to a predetermined value; 2, discharging the wastewater obtained after step 1 to a curing precipitation reactor, adding a polysulfide precipitating agent to covert the heavy metal ions in the wastewater into insoluble substances of the heavy metal ions, and precipitating the insoluble substances of the heavy metal ions while precipitating elementary sulfur; 3, discharging the wastewater obtained after step 2 to a flocculating tank, adding a flocculating agent to flocculate the insoluble substances of the heavy metal ions and the elementary sulfur; and 4, discharging the wastewater obtained after step 3 to a precipitating tank, precipitating, and discharging the obtained supernatant. The method has the advantages of high removal rates of a plurality of the heavy metal ions, no secondary pollution, low cost, and easy realization.
Description
Technical field
The present invention relates to a kind of method of processing trade effluent, more specifically, relate to a kind of method of processing heavy metal ion-containing waste water.
Background technology
Heavy metal ion in water and compound thereof can be fish, enrichment, accumulation participate in biosphere and circulate in other aquatic organisms and in farm crop tissue, by drinking-water and food chain effect, can make heavy metal enrichment and poisoning in human body, even cause death.
Containing the waste water of heavy metal ion mainly from the waste water of the various factories such as pickling waste waters, Steel Plant's pickling waste waters and the electrolysis of the washing water of Electroplate Factory's plating piece, the draining of tunnel, mine, non-ferrous metal metallurgy, Non-ferrous Metals Processing Factory, Effect of Catalysis In Petrochemistry agent, agricultural chemicals, medicine, paint, dyestuff.
The method of processing at present heavy metal ion-containing waste water mainly contains:
1, coagulant sedimentation
Coagulant sedimentation is by adding coagulating agent heavy metal ion is precipitated and remove in waste water.Conventional flocculation agent is aluminium salt and molysite, and aluminium salt mainly contains: Tai-Ace S 150 [Al
2(SO
4)
318H
2o], alum [Al
2(SO
4)
3k
2sO
412H
2o], sodium aluminate [Na
3alO
3], aluminum chloride [AlCl
3] and aluminium chlorohydroxide [Al
n(OH)
mcl
(3n-m)].Molysite mainly contains: ferrous sulfate [FeSO
4], ferric sulfate [Fe
2(SO
4)
3] and iron trichloride [FeCl
3].While using aluminum salt flocculant, if settling is dealt with improperly and can be caused aluminium to discharge in a large number, likely make the aluminium increased content in soil, water body in environment, cause secondary pollution.
2, oxidation reduction process
Oxidation reduction process is mainly for the treatment of the Cr in waste water
6+, Cd
2+and Hg
2+etc. heavy metal ion.Conventional reductive agent has the SO of gaseous state
2, liquid hydrazine hydrate, solid-state sodium bisulfite and Sulfothiorine etc.First under the acidic conditions that is 2-3 in pH value, carry out reducing heavy metal ion, then add the alkaline matter such as lime, sodium hydroxide that pH value is adjusted to 7.5-9.0, the low price heavy metal ion precipitation after reduction is removed.The shortcoming of the method is that technical process is long, treatment agent dosage is many, in sewage after treatment salts contg high, have a secondary pollution.
3, electrolytic process
Electrolytic process is in electrolyzer, to make heavy metal ion oxidation and reduction reaction occur respectively on male-female electrode and make heavy metal ion be reduced to a kind for the treatment of process of metal.The method advantage is that technical maturity, floor space are little, shortcoming is that current consumption is large, wastewater treatment capacity is little, and inorganic salt in waste water can further strengthen current consumption, vitriol and hydrochloride also can be decomposed into hydrogen sulfide that stench is poisonous and chlorine and cause secondary pollution in electrolysis.
4, the precipitator method
The precipitator method be by waste water, add precipitation agent with heavy metal ion generation chemical reaction, generate indissoluble material and also separate out, then precipitation separation is removed.Conventional precipitation agent has two kinds, alkaline matter and sulfide, and conventional alkaline matter has CaO, Ca (OH)
2, NaOH, conventional sulfide has Na
2s, NaHS etc.The problem that the method exists is that reaction precipitation speed is slow, precipitation threshold is poor, it is not thorough to separate, processing efficiency is low, draining is alkalescence etc.
5, solvent extration
Solvent extration is utilize the different solubility of heavy metal ion in organic phase and water and make heavy metal ion concentrate in the separation method of organic phase.The method technique is simple, and existing problems are, extraction agent loss amount is large, have secondary pollution, processing cost is high.
6, membrane separation process
Membrane separation process is to utilize semi-permeable membranes that the most of water in solution is infiltrated, and makes the concentrated treatment process of heavy metal ion solution.Conventional membrane separating method has the methods such as diffusion dialysis, electrodialysis, reverse osmosis and ultrafiltration.The advantage of membrane separating method is normal-temperature operation, do not add chemical reagent, non-secondary pollution etc.; Shortcoming is after membrane sepn not to be solid heavy metal compound, but the heavy metal ion waste liquid being concentrated also needs to do further harmless treatment.
7, biochemical process
Biochemical process is mainly to use microorganism that thereby sulfate reduction is precipitated out to the method for heavy-metal ion removal for sulfide makes metal with the form of metallic sulfide.The method advantage is to utilize micro-reduction to process heavy metal ion, and cost is lower; Shortcoming is that sludge yield is large and aftertreatment is difficult, and investment is large.
Chinese patent CN101269893A discloses a kind for the treatment of process of removing heavy metal ions in wastewater.First to adding in waste water the sodium sulphite of solubility or potassium sulphide to react with heavy metal ion, generate tiny insoluble metal sulfide, then add aluminium salt to carry out coagulating sedimentation to separate removal heavy metal sulfide.The shortcoming of the method is to not generating the material that is insoluble in water with sodium sulphite or potassium sulphide, as Cr
6+etc. invalid.In addition, use sodium sulphite in acidic solution time, the hydrogen sulfide that has foul smell is overflowed, and environment is caused to secondary pollution.
Therefore, for the angle to environment protection, being badly in need of one can be effective to contents of many kinds of heavy metal ion, and non-secondary pollution, processing efficiency is high, cost is low sewage water treatment method.
Summary of the invention
For existing above-mentioned technical problem in prior art, the present invention proposes a kind of method of processing heavy metal ion-containing waste water, it is effective to contents of many kinds of heavy metal ion, and non-secondary pollution, processing efficiency is higher, cost is also lower.
The method according to this invention, it comprises the following steps:
First step: at normal temperatures waste water is entered in pH adjustment tank, so that the pH value of described waste water is adjusted to preset value;
Second step: will enter sulfuration through described first step waste water after treatment and resolve in reactor, and add polysulfide precipitation agent, and the heavy metal ion in waste water will be converted into heavy metal ion insolubles and separate out;
Third step: will be drained in flocculation tank through described second step waste water after treatment, and add flocculation agent so that the heavy metal ion insolubles of separating out and sulphur simple substance are realized flocculation sediment;
The 4th step: will be drained in settling tank and precipitate through described third step waste water after treatment, and discharge supernatant liquor.
The method according to this invention, described method is carried out at the temperature of 10-40 ℃.
The method according to this invention, the heavy metal ion in described waste water comprises Pb
2+, Hg
2+, Cd
2+, Cr
6+, Cr
3+, As
3+, Fe
2+, Fe
3+, Cu
2+, Zn
2+, Ni
2+, Al
3+in one or more.Method of the present invention can a step by these heavy metal ion, from waste water, precipitate and separate is out.
According to the present invention, first waste water is entered in pH adjustment tank, and adds acid or alkaline matter to regulate the pH value of waste water simultaneously, preferably, described pH adjustment tank have whipping appts with realize pH value sooner, adjusting more equably.In one embodiment, in described first step, by adding acid and/or alkaline matter to regulate pH value, wherein said acid is hydrochloric acid or sulfuric acid, and the alkaline matter adding is Ca (OH)
2, one in CaO or NaOH, to regulate the pH value of waste water.In another embodiment, in described first step, pH value is adjusted to 4-11, be preferably 6-9.
According to the present invention, will enter continuously sulfuration through described first step waste water after treatment and resolve in reactor, and add polysulfide precipitation agent simultaneously, carry out vulcanization reaction.In one embodiment, the polysulfide precipitation agent adding in described second step is Me
xs
n, the Me in formula is Na, K or Mg, and S is element sulphur, and x is 1-2, and n is 2-5.In another embodiment, the polysulfide precipitation agent adding is Na
2s
n, K
2s
nand MgS
nin one.In addition, preferably, this sulfuration is resolved reactor and is had whipping appts, and for example mechanical stirring or pneumatic blending are with accelerated reaction process.
Resolve in reactor in sulfuration, heavy metal ion and the sulphur formation insolubles that reacts, thus heavy metal ion is separated from waste water, with MgS
nfor example
MgS
n+2/3O
2→MgS
2O
3+(n-2)S↓
Cr
6++3/2MgS
2O
3+3/2H
2O→3/2MgSO
4+Cr
3++3/2S↓+3H
+
Cr
3++3OH
-→Cr(OH)
3↓
Ni
2++MgS
2O
3+H
2O→MgSO
4+NiS↓+2H
+
Al
3++3OH
-→Al(OH)
3↓
Therefore, can a step complete the redox of the contents of many kinds of heavy metal ion in waste water and reaction is resolved in sulfuration and by its precipitation with separate out from water.
According to one embodiment of present invention, the add-on of described polysulfide precipitation agent be total molar ratio computing take the heavy metal ion in sulphur and waste water as S: Me=1: 1-4: 1, be preferably S: Me=1.5: 1-3: 1.According to another embodiment of the invention, the reaction times of polysulfide precipitation agent and heavy metal ion is 20-120 minute, is preferably 30-90 minute.
According to the present invention, will be through entering in flocculation tank with the reacted waste water of polysulfide precipitation agent, and add flocculation agent to make the tiny heavy metal ion insolubles in waste water form the floc sedimentation of bulk simultaneously, thus can in subsequent disposal, successfully separate.According to one embodiment of present invention, the flocculation agent adding in described third step is anion-polyacrylamide or non-ionic polyacrylamide.According to contriver's experiment, find in the time adopting anion-polyacrylamide or non-ionic polyacrylamide as flocculation agent, can be to above-mentioned heavy metal ion insolubles, the sulphur simple substance particularly producing in second step produces very good throwing out, shorten thus flocculation time, thereby can in subsequent disposal, successfully separate.
In one embodiment, the add-on of described flocculation agent is 5-50 mg/litre, is preferably 10-30 mg/litre.According to another embodiment of the invention, in described third step, flocculation time is 1-10 minute, is preferably 3-5 minute.
According to the present invention, the waste water that adds flocculation agent is entered in settling tank, precipitate.Under the effect of flocculation agent, the bulk floc sedimentation that contains heavy metal ion deposits to the bottom of settling tank, and supernatant liquid is discharged, thereby realizes the heavy metal ion of removing in waste water.According to one embodiment of present invention, in described the 4th step, sedimentation time is 30-180 minute, is preferably 60-120 minute.
Compared with prior art, the invention has the beneficial effects as follows: method of the present invention is carried out under normal temperature, normal pressure, working method is simple, using polypropylene acid amides does flocculation agent non-secondary pollution, and polyacrylamide is more suitable for having accelerated flocculation rate in the flocculation of sulphur simple substance compared with aluminium salt, Ferric Salt Flocculants, shortened the settling time, and draining after treatment can meet the highest permission emission standard of the heavy metal contaminants stipulating in GB8978-1996 standard.And method of the present invention is applied widely, the waste water that can be used for processing the waste water that has contents of many kinds of heavy metal ion of different concns and/or only have a kind of heavy metal ion.In addition, because having elemental sulfur in the process that forms sulfide insolubles, the heavy metal ion in waste water generates, its surface has certain adsorption, can remove the pollutent of the part macromole bio-refractory in waste water simultaneously, is conducive to be connected with biochemical treatment.
Accompanying drawing explanation
Hereinafter by the embodiment based on different and with reference to accompanying drawing, the present invention is described in more detail.Wherein:
Fig. 1 is the process flow diagram for the treatment of in accordance with the present invention heavy metal ion-containing waste water.
Embodiment
Below in conjunction with accompanying drawing, a kind of method of processing heavy metal ion-containing waste water of the present invention is described further.
Fig. 1 is according to the sewage treatment technology process schematic diagram containing heavy metal ion of the present invention.First the waste water that contains heavy metal ion 10 is entered in pH adjustment tank 1, under agitation add acid or alkaline matter 11 to regulate the pH value of waste water 10 simultaneously.Then by regulating the waste water after pH value to enter in sulfuration parsing reactor 2, under agitation add polysulfide precipitation agent 21 to resolve reaction to vulcanize simultaneously, heavy metal ion is converted into insolubles and separates out.Subsequently waste water is entered in flocculation tank 3, and add flocculation agent 31 so that tiny insolubles forms large floc sedimentation.Finally waste water is drained in settling tank 4, in settling tank 4, deposits to the bottom of settling tank 4 containing the bulk floc sedimentation of heavy metal, supernatant liquid 41 can discharge to carry out other processing.
Embodiment 1:
Under the condition of 18 ℃, will contain Pb
2+, Hg
2+, Zn
2+, Cu
2+enter etc. the waste water of heavy metal ion in the pH adjustment tank with whipping appts, add continuously Ca (OH) simultaneously
2the pH value of waste water is adjusted to 8 ± 0.5.Then, waste water is entered in the sulfuration parsing reactor with mechanical stirring device, add continuously chemical formula is Na simultaneously
2s
3sodium polysulphide, its add-on is take total molar ratio computing of sulphur and heavy metal ions in wastewater as S: Me=2: 1.Waste water is resolved in reactor and is reacted after 60 minutes in the sulfuration with mechanical stirring device, enters in the flocculation tank with whipping appts, and under agitation add continuously anion-polyacrylamide, its add-on is 15 milligrams of every liter of waste water simultaneously.Waste water stopped after 3 minutes in flocculation tank, entered in settling tank, in settling tank, in precipitation, stopped after 90 minutes, and supernatant liquor is discharged.Analytical results is in table 1.
Table 1
| Heavy metal ion | Pb 2+ | Hg 2+ | Cu 2+ | Zn 2+ |
| Concentration mg/L before processing | 68.9 | 43.1 | 109.3 | 79 |
| Concentration mg/L after processing | 0.84 | 0.05 | 0.9 | 0.97 |
Embodiment 2:
Under the condition of 20 ℃, will contain Pb
2+, Cr
3+, As
3+, Cu
2+, Zn
2+enter etc. the waste water of heavy metal ion in the pH adjustment tank with whipping appts, add continuously NaOH that the pH value of waste water is adjusted to 7 ± 0.5 simultaneously.Then, waste water is entered to the sulfuration with mechanical stirring device and resolve in reactor, add continuously chemical formula is the sodium polysulphide of Na2S4 simultaneously, and its add-on is take total molar ratio computing of sulphur and heavy metal ions in wastewater as S: Me=3: 1.Waste water is resolved in reactor and is reacted after 90 minutes in the sulfuration with mechanical stirring device, enters in the flocculation tank with whipping appts, and under agitation add continuously non-ionic polyacrylamide, its add-on is 20 milligrams of every liter of waste water simultaneously.Waste water stopped after 4 minutes in flocculation tank, entered in settling tank, in settling tank, in precipitation, stopped after 75 minutes, and supernatant liquor is discharged.Analytical results is in table 2.
Table 2
| Heavy metal ion | Pb 2+ | Cr 3+ | As 3 | Cu 2+ | Zn 2+ |
| Concentration mg/L before processing | 43 | 101 | 43 | 133 | 81 |
| Concentration mg/L after processing | 0.93 | 0.39 | 0.42 | 0.6 | 0.85 |
Embodiment 3:
Under the condition of 28 ℃, will contain Pb
2+, Hg
2+, Zn
2+, Ni
2+enter etc. the waste water of heavy metal ion in the pH adjustment tank with whipping appts, add continuously NaOH that the pH value of waste water is adjusted to 9 ± 0.5 simultaneously.Then, waste water is entered in the sulfuration parsing reactor with mechanical stirring device, add continuously chemical formula is Na simultaneously
2s
2sodium polysulphide, its add-on is take total molar ratio computing of sulphur and heavy metal ions in wastewater as S: Me=2.5: 1.Waste water is resolved in reactor and is reacted after 45 minutes in the sulfuration with mechanical stirring device, enters in the flocculation tank with whipping appts, and under agitation add continuously anion-polyacrylamide, its add-on is 15 milligrams of every liter of waste water simultaneously.Waste water stopped after 5 minutes in flocculation tank, entered in settling tank, in settling tank, in precipitation, stopped after 90 minutes, and supernatant liquor is discharged.Analytical results is in table 3.
Table 3
| Heavy metal ion | Pb 2+ | Hg 2+ | Zn 2+ | Ni 2+ |
| Concentration mg/L before processing | 52 | 21 | 181 | 56 |
| Concentration mg/L after processing | 0.63 | 0.045 | 0.76 | 0.64 |
Embodiment 4:
Under the condition of 31 ℃, will contain Cd
2+, Cr
6+, Cr
3+, Ni
2+enter etc. the waste water of heavy metal ion in the pH adjustment tank with whipping appts, add continuously Ca (OH) simultaneously
2the pH value of waste water is adjusted to 8 ± 0.5.Then, waste water is entered in the sulfuration parsing reactor with air stirrer, add continuously chemical formula is K simultaneously
2s
4potassium polysulfide, its add-on is take total molar ratio computing of sulphur and heavy metal ions in wastewater as S: Me=1.5: 1.Waste water is resolved in reactor and is reacted after 90 minutes in the sulfuration with air stirrer, enters in the flocculation tank with whipping appts, and under agitation add continuously anion-polyacrylamide, its add-on is 10 milligrams of every liter of waste water simultaneously.Waste water stopped after 8 minutes in flocculation tank, entered in settling tank, in pond, in precipitation, stopped after 150 minutes, and supernatant liquor is discharged.Analytical results is in table 4.
Table 4
| Heavy metal ion | Cd 2+ | Cr 6+ | Cr 3+ | Ni 2+ |
| Concentration mg/L before processing | 32.6 | 49 | 21 | 39.3 |
| Concentration mg/L after processing | 0.079 | 0.36 | 0.8 | 0.87 |
Embodiment 5:
Under the condition of 30 ℃, will contain Zn
2+, Ni
2+, Cd
2+, Cr
6+, Cr
3+enter in pH adjustment tank etc. the waste water of heavy metal ion, add continuously 1% sulfuric acid that the pH value of waste water is adjusted to 6.5 ± 0.5 simultaneously.Then, waste water is entered in the sulfuration parsing reactor with air stirrer, add continuously chemical formula is K simultaneously
2s
5potassium polysulfide, its add-on is take total molar ratio computing of sulphur and heavy metal ions in wastewater as S: Me=2.5: 1.Waste water is resolved in reactor and is reacted after 90 minutes in the sulfuration with mechanical stirring device, enters in the flocculation tank with whipping appts, and under mechanical stirring, add continuously anion-polyacrylamide, its add-on is 15 milligrams of every liter of waste water simultaneously.Waste water stopped after 4 minutes in flocculation tank, entered in settling tank, in settling tank, in precipitation, stopped after 120 minutes, and supernatant liquor is discharged.Analytical results is in table 5.
Table 5
| Heavy metal ion | Zn 2+ | Ni 2+ | Cd 2+ | Cr 6+ | Cr 3+ |
| Concentration mg/L before processing | 150.6 | 40.3 | 18.1 | 43.3 | 18 |
| Concentration mg/L after processing | 0.3 | 0.9 | 0.087 | 0.33 | 0.27 |
Embodiment 6:
Under the condition of 25 ℃, will contain Pb
2+, Cd
2+, As
3+, Cu
2+, Ni
2+enter in pH adjustment tank etc. the waste water of heavy metal ion, add continuously NaOH solution that the pH value of waste water is adjusted to 8.5 ± 0.5 simultaneously.Then, waste water is entered in the sulfuration parsing reactor with mechanical stirring device, add continuously chemical formula is MgS simultaneously
3many magnesium sulfides, its add-on is take total molar ratio computing of sulphur and heavy metal ions in wastewater as S: Me=2: 1.Waste water is resolved in reactor and is reacted after 60 minutes in the sulfuration with mechanical stirring device, enters in the flocculation tank with whipping appts, and under agitation add continuously non-ionic polyacrylamide, its add-on is 20 milligrams of every liter of waste water simultaneously.Waste water stopped after 3 minutes in flocculation tank, entered in settling tank, in settling tank, in precipitation, stopped after 90 minutes, and supernatant liquor is discharged.Analytical results is in table 6.
Table 6
| Heavy metal ion | Pb 2+ | Cd 2+ | As 3+ | Cu 2+ | Ni 2+ |
| Concentration mg/L before processing | 38.1 | 30.2 | 90.3 | 81 | 46 |
| Concentration mg/L after processing | 0.73 | 0.073 | 0.49 | 0.83 | 0.37 |
Can see by above-described embodiment, the method according to this invention, very high to the clearance of contents of many kinds of heavy metal ion, the concentration of the heavy metal ion in waste water is reduced to the 1mg/L of being less than after treatment by dozens or even hundreds of mg/L before treatment, even lower than 0.1mg/L.In addition, method non-secondary pollution of the present invention, cost also lower, be easy to realize.
Although invention has been described with reference to preferred embodiment, without departing from the scope of the invention, can carry out various improvement and can replace material wherein with equivalent it.The present invention is not limited to disclosed specific embodiment in literary composition, but comprises all technical schemes in the scope that falls into claim.
Claims (14)
1. a method of processing heavy metal ion-containing waste water, it comprises the following steps:
First step: at normal temperatures waste water is entered in pH adjustment tank, so that the pH value of described waste water is adjusted to preset value;
Second step: will enter sulfuration through described first step waste water after treatment and resolve in reactor, and add polysulfide precipitation agent, and the heavy metal ion in waste water will be converted into heavy metal ion insolubles and separate out, and also have during this period sulphur simple substance to separate out;
Third step: will be drained in flocculation tank through described second step waste water after treatment, and add flocculation agent so that the heavy metal ion insolubles of separating out and sulphur simple substance are realized flocculation sediment;
The 4th step: will be drained in settling tank and precipitate through described third step waste water after treatment, discharge supernatant liquor,
Wherein, in described step 1, the pH value of waste water is adjusted to 6-9,
The polysulfide precipitation agent adding in described second step is Me
xs
n, in formula, Me is Na, K or Mg, and S is element sulphur, and x is 1-2, and n is 2-5, the add-on of described polysulfide precipitation agent is that total molar ratio computing take the heavy metal ion in sulphur and waste water is as S:Me=1:1-4:1.
2. method according to claim 1, is characterized in that, the add-on of described polysulfide precipitation agent is that total molar ratio computing take the heavy metal ion in sulphur and waste water is as S:Me=1.5:1-3:1.
3. method according to claim 1, is characterized in that, the reaction times of polysulfide precipitation agent and heavy metal ion is 20-120 minute.
4. method according to claim 3, is characterized in that, the reaction times of polysulfide precipitation agent and heavy metal ion is 30-90 minute.
5. method according to claim 1, is characterized in that, the flocculation agent adding in described third step is anion-polyacrylamide or non-ionic polyacrylamide.
6. method according to claim 5, is characterized in that, the add-on of described flocculation agent is 5-50 mg/litre.
7. method according to claim 6, is characterized in that, the add-on of described flocculation agent is 10-30 mg/litre.
8. method according to claim 5, is characterized in that, in described third step, flocculation time is 1-10 minute.
9. method according to claim 8, is characterized in that, in described third step, flocculation time is 3-5 minute.
10. method according to claim 1, is characterized in that, in described the 4th step, sedimentation time is 30-180 minute.
11. methods according to claim 10, is characterized in that, in described the 4th step, sedimentation time is 60-120 minute.
12. methods according to claim 1, is characterized in that, in described first step, by adding acid and/or alkaline matter to regulate pH value, wherein said acid is hydrochloric acid or sulfuric acid, and the alkaline matter adding is Ca (OH)
2, one in CaO or NaOH.
13. methods according to claim 1, is characterized in that, described method is carried out at the temperature of 10-40 ℃.
14. according to the method described in any one in claim 1 to 13, it is characterized in that, the heavy metal ion in described waste water comprises Pb
2+, Hg
2+, Cd
2+, Cr
6+, Cr
3+, As
3+, Fe
2+, Fe
3+, Cu
2+, Zn
2+, Ni
2+, Al
3+in one or more.
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| CN103151088A (en) * | 2013-03-28 | 2013-06-12 | 南京大学宜兴环保研究院 | Composite flocculating agent for processing radioactive elements iron, cobalt, manganese and silver in nuclear waste water and processing method |
| CN103714875B (en) * | 2013-12-30 | 2016-06-22 | 中国原子能科学研究院 | Ag colloid removal device in a kind of nuclear waste water |
| CN103991995A (en) * | 2014-06-04 | 2014-08-20 | 孙伟 | Comprehensive utilization method for iron and steel smelting dust washing wastewater |
| CN104692561B (en) * | 2015-03-11 | 2017-08-04 | 北京矿冶研究总院 | Advanced treatment method of thallium-containing wastewater |
| CN107226567A (en) * | 2016-03-23 | 2017-10-03 | 上海第二工业大学 | A kind of sulfide precipitation method handled for effluent containing heavy metal ions |
| CN106348415A (en) * | 2016-10-09 | 2017-01-25 | 东莞市台腾环保材料科技有限公司 | QCL-T complexing breaking agent and preparation method thereof |
| CN109604312A (en) * | 2019-01-09 | 2019-04-12 | 北京金隅琉水环保科技有限公司 | A kind of method of trap heavy metals during flying dust water-washing pre-treatment |
| CN110184466B (en) * | 2019-05-31 | 2022-03-25 | 中运建设控股有限公司 | Method for leaching valuable heavy metals in river and lake water body |
| CN112694159A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Wastewater treatment agent containing metal sulfide and wastewater treatment method |
| CN114804412B (en) * | 2022-04-15 | 2023-11-10 | 桂林电子科技大学 | Treatment process of mixed waste liquid of water quality on-line monitoring equipment |
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