CN102923874A - Method for processing wastewater containing heavy metal ions - Google Patents
Method for processing wastewater containing heavy metal ions Download PDFInfo
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- CN102923874A CN102923874A CN201110230799XA CN201110230799A CN102923874A CN 102923874 A CN102923874 A CN 102923874A CN 201110230799X A CN201110230799X A CN 201110230799XA CN 201110230799 A CN201110230799 A CN 201110230799A CN 102923874 A CN102923874 A CN 102923874A
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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 the water and compound thereof can be fish, circulate in other aquatic organisms and enrichment in the farm crop tissue, accumulation and participation biosphere, by drinking-water and food chain effect, can make heavy metal enrichment and poisoning in human body, even cause death.
The waste water that contains heavy metal ion is 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 heavy metal ion to be precipitated and remove by adding coagulating agent in waste water.Flocculation agent commonly used 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].When using aluminum salt flocculant, can cause aluminium in a large number discharging in the environment if settling dealt with improperly, might make the aluminium increased content in soil, the water body, cause secondary pollution.
2, oxidation reduction process
Oxidation reduction process is mainly for the treatment of the Cr in the waste water
6+, Cd
2+And Hg
2+Etc. heavy metal ion.Reductive agent commonly used has the SO of gaseous state
2, liquid hydrazine hydrate, solid-state sodium bisulfite and Sulfothiorine etc.At first in the pH value for carrying out the reducing heavy metal ion under the acidic conditions of 2-3, then add the alkaline matters such as lime, sodium hydroxide pH value is adjusted to 7.5-9.0, make the low price heavy metal ion precipitation removal after the reduction.The shortcoming of the method is that technical process is long, the treatment agent dosage is many, in the sewage after the processing salts contg high, secondary pollution arranged.
3, electrolytic process
Electrolytic process is to make heavy metal ion that oxidation and reduction reaction occur respectively on the male-female electrode in electrolyzer 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 the inorganic salt in the waste water can further strengthen current consumption, and vitriol and hydrochloride also can be decomposed into the poisonous hydrogen sulfide of stench and chlorine and cause secondary pollution in electrolysis.
4, the precipitator method
The precipitator method be by in waste water, add precipitation agent with heavy metal ion generation chemical reaction, generate the indissoluble material and also separate out, then precipitation separation is removed it.Precipitation agent commonly used has two kinds in alkaline matter and sulfide, and alkaline matter commonly used has CaO, Ca (OH)
2, NaOH, sulfide commonly used 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 to utilize heavy metal ion to make heavy metal ion concentrate in the separation method of organic phase at the different solubility of organic phase and aqueous phase.The method technique is simple, and existing problems are, the extraction agent loss amount is large, secondary pollution is arranged, processing cost is high.
6, membrane separation process
Membrane separation process is to utilize semi-permeable membranes that the most of water in the solution is infiltrated, and makes the concentrated treatment process of heavy metal ion solution.Membrane separating method commonly used 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 behind the membrane sepn not to be the solid heavy metal compound, but the heavy metal ion waste liquid that has been concentrated also need be done further harmless treatment.
7, biochemical process
Thereby biochemical process mainly is to use microorganism to make metal be precipitated out the method for heavy-metal ion removal with the form of metallic sulfide as sulfide sulfate reduction.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.At first add in the waste water sodium sulphite of solubility or potassium sulphide with the heavy metal ion reaction, generates tiny insoluble metal sulfide, add again aluminium salt and carry out coagulating sedimentation separation 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, such as Cr
6+Etc. invalid.In addition, when using sodium sulphite in acidic solution, the hydrogen sulfide that has foul smell is overflowed, and environment is caused secondary pollution.
Therefore, for the angle to environment protection, be badly in need of a kind of can be effective to contents of many kinds of heavy metal ion, and the sewage water treatment method that non-secondary pollution, processing efficiency are high, cost is low.
Summary of the invention
For existing above-mentioned technical problem in the 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 may further comprise the steps:
First step: at normal temperatures waste water is entered in the pH adjustment tank, so that the pH value of described waste water is adjusted to preset value;
Second step: the waste water after will processing through described first step enters sulfuration and resolves in the reactor, and adds the polysulfide precipitation agent, the heavy metal ion in the waste water is converted into the heavy metal ion insolubles separates out;
Third step: the waste water after will processing through described second step is drained in the flocculation tank, and adds flocculation agent so that the heavy metal ion insolubles of separating out and sulphur simple substance are realized flocculation sediment;
The 4th step: the waste water after will processing through described third step is drained in the settling tank and precipitates, and discharges supernatant liquor.
The method according to this invention, described method is carried out under 10-40 ℃ temperature.
The method according to this invention, the heavy metal ion in the 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 precipitate and separate is out from waste water with these heavy metal ion.
According to the present invention, at first waste water is entered in the pH adjustment tank, and add simultaneously acid or alkaline matter to regulate the pH value of waste water, preferably, described pH adjustment tank has whipping appts to realize faster, the more equably adjusting of pH value.In one embodiment, regulate the pH value by adding acid and/or alkaline matter in described first step, wherein said acid is hydrochloric acid or sulfuric acid, and the alkaline matter that adds is Ca (OH)
2, a kind of among CaO or the NaOH, to regulate the pH value of waste water.In another embodiment, in described first step, the pH value is adjusted to 4-11, be preferably 6-9.
According to the present invention, the waste water after will processing through described first step enters continuously sulfuration and resolves in the reactor, and adds simultaneously the polysulfide precipitation agent, carries out vulcanization reaction.In one embodiment, the polysulfide precipitation agent that adds in described second step is Me
xS
n, the Me in the 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 that adds is Na
2S
n, K
2S
nAnd MgS
nIn a kind of.In addition, preferably, this sulfuration is resolved reactor and is had whipping appts, and for example mechanical stirring or pneumatic blending are with the accelerated reaction process.
Resolve in the reactor in sulfuration, heavy metal ion and the sulphur formation insolubles that reacts, thus heavy metal ion is separated from waste water, with MgS
nBe 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 one the step finish the redox of the contents of many kinds of heavy metal ion in the waste water and reaction is resolved in sulfuration and with its precipitation with separate out from water.
According to one embodiment of present invention, the add-on of described polysulfide precipitation agent for total molar ratio computing of the heavy metal ion in sulphur and the 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 the flocculation tank with the reacted waste water of polysulfide precipitation agent, and add simultaneously flocculation agent and make the tiny heavy metal ion insolubles in the waste water form the floc sedimentation of bulk, thereby can in subsequent disposal, successfully separate.According to one embodiment of present invention, the flocculation agent that adds in described third step is anion-polyacrylamide or non-ionic polyacrylamide.Experiment according to the contriver, discovery is when adopting anion-polyacrylamide or non-ionic polyacrylamide as flocculation agent, can be to above-mentioned heavy metal ion insolubles, the sulphur simple substance that particularly produces in second step produces very good throwing out, shortened thus flocculation time, thereby can in subsequent disposal, successfully separate.
In one embodiment, the add-on of described flocculation agent is the 5-50 mg/litre, is preferably the 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 the 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 removing the heavy metal ion in the 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, the using polypropylene acid amides is done the flocculation agent non-secondary pollution, and polyacrylamide is more suitable for having accelerated flocculation rate in the flocculation of sulphur simple substance than aluminium salt, Ferric Salt Flocculants, shortened the settling time, and the draining after processing can be satisfied the highest permission emission standard of the heavy metal contaminants of stipulating in the 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 contents of many kinds of heavy metal ion is arranged of different concns and/or only have a kind of heavy metal ion.In addition, because the heavy metal ion in the waste water has elemental sulfur to generate in the process that forms the sulfide insolubles, its surface has certain adsorption, can remove simultaneously the pollutent of the part macromole bio-refractory in the waste water, is conducive to be connected with biochemical treatment.
Description of drawings
To and come with reference to the accompanying drawings the present invention is described in more detail based on different embodiment hereinafter.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 the sewage treatment technology process synoptic diagram that contains heavy metal ion according to of the present invention.The waste water 10 that at first will contain heavy metal ion enters in the pH adjustment tank 1, under agitation adds acid or alkaline matter 11 simultaneously to regulate the pH value of waste water 10.Then will regulate waste water after the pH value and enter sulfuration and resolve in the reactor 2, and under agitation add polysulfide precipitation agent 21 simultaneously and resolve reaction to vulcanize, and heavy metal ion is converted into insolubles and will separate out.Subsequently waste water is entered in the flocculation tank 3, and add flocculation agent 31 so that tiny insolubles forms large floc sedimentation.At last waste water is drained in the settling tank 4, in settling tank 4, the bulk floc sedimentation that contains heavy metal deposits to the bottom of settling tank 4, and supernatant liquid 41 can discharge to carry out other processing.
Embodiment 1:
Under 18 ℃ condition, will contain Pb
2+, Hg
2+, Zn
2+, Cu
2+Waste water etc. heavy metal ion enters in the pH adjustment tank with whipping appts, adds continuously simultaneously Ca (OH)
2The pH value of waste water is adjusted to 8 ± 0.5.Then, waste water is entered the sulfuration with mechanical stirring device resolve in the reactor, adding chemical formula continuously simultaneously is Na
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 the reactor internal reaction after 60 minutes in the sulfuration with mechanical stirring device, enters in the flocculation tank with whipping appts, under agitation adds continuously anion-polyacrylamide simultaneously, and its add-on is 15 milligrams of every liter of waste water.Waste water enters in the settling tank stop 3 minutes in flocculation tank after, stops after 90 minutes in the precipitation in settling tank, and supernatant liquor is discharged.Analytical results sees 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 20 ℃ condition, will contain Pb
2+, Cr
3+, As
3+, Cu
2+, Zn
2+Waste water etc. heavy metal ion enters in the pH adjustment tank with whipping appts, adds continuously simultaneously NaOH the pH value of waste water is adjusted to 7 ± 0.5.Then, waste water is entered the sulfuration with mechanical stirring device resolve in the reactor, adding chemical formula continuously simultaneously is the sodium polysulphide of Na2S4, 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 the reactor internal reaction after 90 minutes in the sulfuration with mechanical stirring device, enters in the flocculation tank with whipping appts, under agitation adds continuously non-ionic polyacrylamide simultaneously, and its add-on is 20 milligrams of every liter of waste water.Waste water enters in the settling tank stop 4 minutes in flocculation tank after, stops after 75 minutes in the precipitation in settling tank, and supernatant liquor is discharged.Analytical results sees 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 28 ℃ condition, will contain Pb
2+, Hg
2+, Zn
2+, Ni
2+Waste water etc. heavy metal ion enters in the pH adjustment tank with whipping appts, adds continuously simultaneously NaOH the pH value of waste water is adjusted to 9 ± 0.5.Then, waste water is entered the sulfuration with mechanical stirring device resolve in the reactor, adding chemical formula continuously simultaneously is Na
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 the reactor internal reaction after 45 minutes in the sulfuration with mechanical stirring device, enters in the flocculation tank with whipping appts, under agitation adds continuously anion-polyacrylamide simultaneously, and its add-on is 15 milligrams of every liter of waste water.Waste water enters in the settling tank stop 5 minutes in flocculation tank after, stops after 90 minutes in the precipitation in settling tank, and supernatant liquor is discharged.Analytical results sees 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 31 ℃ condition, will contain Cd
2+, Cr
6+, Cr
3+, Ni
2+Waste water etc. heavy metal ion enters in the pH adjustment tank with whipping appts, adds continuously simultaneously Ca (OH)
2The pH value of waste water is adjusted to 8 ± 0.5.Then, waste water is entered the sulfuration with air stirrer resolve in the reactor, adding chemical formula continuously simultaneously is K
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 the reactor internal reaction after 90 minutes in the sulfuration with air stirrer, enters in the flocculation tank with whipping appts, under agitation adds continuously anion-polyacrylamide simultaneously, and its add-on is 10 milligrams of every liter of waste water.Waste water enters in the settling tank stop 8 minutes in flocculation tank after, stops after 150 minutes in the precipitation in the pond, and supernatant liquor is discharged.Analytical results sees 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 30 ℃ condition, will contain Zn
2+, Ni
2+, Cd
2+, Cr
6+, Cr
3+Waste water etc. heavy metal ion enters in the pH adjustment tank, and the sulfuric acid of adding 1% adjusts to 6.5 ± 0.5 with the pH value of waste water continuously simultaneously.Then, waste water is entered the sulfuration with air stirrer resolve in the reactor, adding chemical formula continuously simultaneously is K
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 the reactor internal reaction after 90 minutes in the sulfuration with mechanical stirring device, enters in the flocculation tank with whipping appts, adds continuously simultaneously anion-polyacrylamide under mechanical stirring, and its add-on is 15 milligrams of every liter of waste water.Waste water enters in the settling tank stop 4 minutes in flocculation tank after, stops after 120 minutes in the precipitation in settling tank, and supernatant liquor is discharged.Analytical results sees 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 25 ℃ condition, will contain Pb
2+, Cd
2+, As
3+, Cu
2+, Ni
2+Waste water etc. heavy metal ion enters in the pH adjustment tank, adds continuously simultaneously NaOH solution the pH value of waste water is adjusted to 8.5 ± 0.5.Then, waste water is entered the sulfuration with mechanical stirring device resolve in the reactor, adding chemical formula continuously simultaneously is MgS
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 the reactor internal reaction after 60 minutes in the sulfuration with mechanical stirring device, enters in the flocculation tank with whipping appts, under agitation adds continuously non-ionic polyacrylamide simultaneously, and its add-on is 20 milligrams of every liter of waste water.Waste water enters in the settling tank stop 3 minutes in flocculation tank after, stops after 90 minutes in the precipitation in settling tank, and supernatant liquor is discharged.Analytical results sees 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, clearance to contents of many kinds of heavy metal ion is very high, the concentration of the heavy metal ion in the waste water by the dozens or even hundreds of mg/L before processing be reduced to after the processing less than 1mg/L, even be 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 wherein material with equivalent it.The present invention is not limited to disclosed specific embodiment in the literary composition, but comprises all technical schemes in the scope that falls into claim.
Claims (12)
1. method of processing heavy metal ion-containing waste water, it may further comprise the steps:
First step: at normal temperatures waste water is entered in the pH adjustment tank, so that the pH value of described waste water is adjusted to preset value;
Second step: the waste water after will processing through described first step enters sulfuration and resolves in the reactor, and adds the polysulfide precipitation agent, the heavy metal ion in the waste water is converted into the heavy metal ion insolubles separates out, and also has during this period sulphur simple substance to separate out;
Third step: the waste water after will processing through described second step is drained in the flocculation tank, and adds flocculation agent so that the heavy metal ion insolubles of separating out and sulphur simple substance are realized flocculation sediment;
The 4th step: the waste water after will processing through described third step is drained in the settling tank and precipitates, and discharges supernatant liquor.
2. method according to claim 1 is characterized in that, the polysulfide precipitation agent that adds in described second step is Me
xS
n, Me is Na, K or Mg in the formula, and S is element sulphur, and x is 1-2, and n is 2-5.
3. method according to claim 2 is characterized in that, the add-on of described polysulfide precipitation agent for total molar ratio computing of the heavy metal ion in sulphur and the waste water as S: Me=1: 1-4: 1, be preferably S: Me=1.5: 1-3: 1.
4. according to claim 1,2 or 3 described methods, it is characterized in that the reaction times of polysulfide precipitation agent and heavy metal ion is 20-120 minute, be preferably 30-90 minute.
5. method according to claim 1 is characterized in that, the flocculation agent that adds in described third step is anion-polyacrylamide or non-ionic polyacrylamide.
6. method according to claim 1 or 5 is characterized in that the add-on of described flocculation agent is the 5-50 mg/litre, is preferably the 10-30 mg/litre.
7. according to claim 1,5 or 6 described methods, it is characterized in that in described third step, flocculation time is 1-10 minute, is preferably 3-5 minute.
8. method according to claim 1 is characterized in that, in described the 4th step, sedimentation time is 30-180 minute, is preferably 60-120 minute.
9. method according to claim 1 is characterized in that, regulates the pH value by adding acid and/or alkaline matter in described first step, and wherein said acid is hydrochloric acid or sulfuric acid, and the alkaline matter that adds is Ca (OH)
2, a kind of among CaO or the NaOH.
10. according to claim 1 or 9 described methods, it is characterized in that, in described first step, the pH value is adjusted to 4-11, be preferably 6-9.
11. method according to claim 1 is characterized in that, described method is carried out under 10-40 ℃ temperature.
12. according to the described method of above-mentioned each claim, it is characterized in that the heavy metal ion in the 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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