CN101244859A - Method for processing heavy metal wastewater - Google Patents
Method for processing heavy metal wastewater Download PDFInfo
- Publication number
- CN101244859A CN101244859A CNA2007100484724A CN200710048472A CN101244859A CN 101244859 A CN101244859 A CN 101244859A CN A2007100484724 A CNA2007100484724 A CN A2007100484724A CN 200710048472 A CN200710048472 A CN 200710048472A CN 101244859 A CN101244859 A CN 101244859A
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- heavy metal
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Abstract
The invention relates to a removal method of heavy metal ion in wastewater, such as chrome, belonging to the technical field of wastewater treatment. The removal method is characterized in that nanometer FeSx is produced by culturing a compound bacteria comprising desulfovibrio Sp. CB1. 268, desulfotomaculum Sp. CB1.139, and desulfobacter Sp. CB1.168 in a culture medium comprising lactic acid proteinate, ferrite, sulfate, K, Mg, Ca, Cu, Mn, B, Si, and Mo under anaerobic or facultative, and alkaline condition at the temperature between 30 and 39 DEG C for thirty-six to 72 hours; the nanometer FeSx is dissociated into S<2-> and Fe<2+> under acidic condition, can reduce Cr<6+> to Cr<3+>, and generate unsolvable sedimentation of metal sulphides with Ni<2+>, Cu<2+>, Zn<2+>, and other elements; after the sedimentation is separated, the metal ions in the wastewater are removed. The removal method has the advantages of high removal efficiency and low cost.
Description
Technical field
The invention belongs to technical field of waste water processing, be specifically related to the removal method of heavy metal ion such as chromium in the waste water.
Background technology
The method of handling at present both at home and abroad heavy metal wastewater thereby has physics method, chemical method and biological process three major types, kind surplus in the of totally 20, and these methods cut both ways.Seeking more effective treatment process is the target that people yearn for all the time.Chinese patent ZL 93106616.6 " treating electroplating waste water with micro-organism method " has proposed the composite bacteria that four strain bacterium such as Fusobacterium nucleatum, Paracoccus denitrificans, blunt tarda and peptococcus anaerobius are formed first, to lower concentration (≤80mg/L) processing of Cr, Zn, Cu, Ni electroplating wastewater has effect preferably.Chinese patent ZL 96117479.X " administering compound function yeast, its cultural method and the using method thereof of electroplating wastewater " adopts five strain bacterium such as desulfurization bacterium, desulfovibrio, enterobacter cloacae, desulfurization enterobacteria and genus bacillus to form composite bacteria, theoretical basis and the practicality of removing heavy metal in the electroplating wastewater than patent ZL 93106616.6 are greatly improved, but the reaction residence time is long, and the pH value is limit in 5.0～7.5 scopes.Chinese patent ZL00112916.3 " biochemical process is administered the method for metallic wastewater " adopts desulfurization bacterium, enterobacter cloacae, desulfurization enterobacteria to form composite bacteria and proposes: " bacterium and waste water add the reaction tank reaction by 1: 10 volume ratio, add 0.05～5 kilogram of chemical reagent Na by waste water per ton again after the reaction
2S is or/and FeS removes the heavy metal ion in the waste water, and this method is to rely on to add Na basically
2S is or/and FeS removes the heavy metal ion in the waste water, its processing cost height, and have the secondary pollution problem of hydrogen sulfide.
Summary of the invention
Big in order to overcome mentioned microorganism method removal heavy metal ions in wastewater long reaction time, baterial cultivation pool and reaction tank volume, also to use Na
2S and FeS remove the defective of heavy metal ion, the invention provides a kind of by microorganism strains original position generation nanometer iron sulphide (FeS
x) material removes the method for heavy metal ion such as chromium in the waste water.
The present invention realizes in the following way:
On the basis of patent ZL93106616.6 and ZL 96117479.X, work out specific technology, with the composite bacteria that desulfovibrio CB1.268 (Desulfovibrio Sp.), desulfurization intestines shape bacterium CB1.139 (Desulfotomaculum Sp.) and desulfurization bacterium CB1.168 (Desulfobacter Sp.) form, can the many Iron sulfuret (FeS of produced in situ nanometer
x) material, detect FeS through x-electron diffraction energy spectrometer
xIn the formula, x=1.1～1.2, this FeS
xUnder acidic conditions, can remove the heavy metal ion in the waste water well.The bacterial strain ratio of components of this composite bacteria is: desulfovibrio CB 1.268 (DesulfovibrioSp.): desulfurization intestines shape bacterium CB 1.139 (Desulfotomaculum Sp.): desulfurization bacterium CB 1.168 (Desulfobacter Sp.)=1: 1: 1.The condition of this composite bacteria production nanometer iron sulphide is: anaerobism or double oxygen are cultivated, pH7.0～7.4,30～39 ℃ of temperature, contain lactic protein salt, 1%～10% (w/w) ferrous salt of 0.5%～5% (w/w) and 1%～10% (w/w) vitriol and K, Mg, Ca, Cu, Mn, B, Si, Mo element, cultivate and just produced nanometer Fe S in 36～72 hours
xThis nanometer Fe S
xLong 45～the 80nm of material, long-width ratio 15～20 is that bar is thread when amplifying 300,000 times, is lattice fringe and lattice particle when amplifying 400,000 times, dissociates into S under the acidic conditions of pH3～4
2-And Fe
2+S
2-And Fe
2+Ion all can reduce Cr preferably
6+Be Cr
3+, S
2-Also with Ni
2+, Cu
2+, Zn
2+Deng the metallic sulfide precipitation that generates indissoluble, through precipitation separation, these ions are removed.
It is as follows that the present invention handles the processing step of heavy metal wastewater thereby method:
In the cultivation device, add the substratum contain lactic protein salt, ferrous salt and vitriol and K, Mg, Ca, Cu, Mn, B, Si, Mo element, regulate pH7.0～7.4, add composite fungus agent, 30～39 ℃ of controlled temperature, anaerobism or double oxygen were cultivated 36～72 hours, contained nanometer Fe S with what generate
xFermented liquid transfer in the reactor, transfer pH3～4, treat nanometer Fe S
xAfter the heavy metal wastewater thereby reaction, add NaOH and transfer pH6～8, the heavy metal ion in the waste water generates the precipitation of indissoluble, through precipitation separation, reaches the purpose of removing metal ion in the waste water.
S
2-And Fe
2+With Cr
6+, Ni
2+, Cu
2+, Zn
2+Deng reaction see that ionic reaction formula (1) is to (9).
S
2-With Cr
6+Reaction as shown in the formula:
FeS
x+H
+→Fe
2++S
2- (1)
HCrO
4 -+S
2-→S↓+H
2O+Cr
3+ (2)
Cr
2O
7 2-+S
2-→S↓+H
2O+Cr
3+?(3)
Reaction formula (2), (3) show FeS
xThe S that acidolysis produces
2-Reduction Cr
6+Be Cr
3+, after reaction finishes, transfer pH6～7, Cr with NaOH
3+Generate Cr (OH) with OH-
3Precipitation, through solid-liquid separation, Cr
6+Be removed.
Fe
2+With Cr
6+Reaction formula as follows:
Fe
2++Cr
2O
7 2-→Cr
3++Fe
3+ (4)
Reaction (4) shows FeS
xThe Fe that acidolysis produces
2+Reduction Cr
6+Be Cr
3+, after reaction finishes, transfer pH6～7 with NaOH, generate Cr (OH)
3Precipitation, through solid-liquid separation, Cr
6+Be removed.
FeS also can be directly and CrO
4 2-And Cr
2O
7 2-Reaction makes its Cr
6+Be reduced to Cr
3+:
CrO
4 2-+FeS
x→Cr
3++Fe
3++S↓ (5)
Cr
2O
7 2-+FeS
x→Cr
3++Fe
3++S↓?(6)
After reaction finishes, transfer pH6～7, Cr with NaOH
3+Generate Cr (OH) with OH-
3Precipitation, through solid-liquid separation, Cr
6+Be removed.
Secondly, nanometer Fe S
xThe S that acidolysis produces
2-Also with Ni
2+, Cu
2+, Zn
2+Sulfide precipitation Deng generating indissoluble through precipitation separation, makes Ni
2+, Cu
2+, Zn
2+Be removed, reaction formula is as follows:
Ni
2++S
2-→NiS↓ (7)
Cu
2++S
2-→CuS↓ (8)
Zn
2++S
2-→ZnS↓ (9)
From nickelous sulfide solubility product: α 1.6 * 10
-24, β 2.5 * 10
-22, γ 2 * 10
-26With cupric sulfide solubility product: Cu
2S 6 * 10
-48, CuS 6 * 10
-36And zinc sulphide solubility product: α 1.6 * 10
-24, β 2.5 * 10
-22As can be known, the solubleness of these ionic sulfide is very little, and it remains in solution metal ionic concentration all below the GB emission standard after generating sulfide precipitation.
Once more, nanometer Fe S
xIn Fe
2+Be oxidized to Fe
3+, transferring pH6～7 o'clock with NaOH, Fe
3+Generate Fe (OH)
3Precipitation, Fe (OH)
3Precipitation has fine absorption and mixes (wadding) and coagulate effect, makes the inorganic and organism of a little be adsorbed removal, makes stable effluent quality up to standard.
Demonstration project shows: nanometer Fe S
xRemoving heavy metal ions in wastewater is that chemical method is (as using chemical reagent Na
2SO
3Or FeSO
4) 2 times of clearance.To Cr
6+Clearance reach 99.99%, to Ni
2+, Cu
2+, Zn
2+Clearance reach 99.9%.Cr in the treat effluent
6+＜0.1mg/L, Ni
2+, Cu
2+＜0.5mg/L, Zn
2+＜0.2mg/L.So the inventive method has characteristics such as place to go efficient height, cost be low.
Composite bacteria of the present invention has generated nanometer Fe S after 36～72 hours incubation growth
x, with the nanometer Fe S that is generated
xAnd mixture such as bacterial classification, through concentrate, sealing, packing can be standby.
Description of drawings
Accompanying drawing is the process flow diagram that nanometer Fe S of the present invention handles heavy metal wastewater thereby.
Among the figure: 1,2 are the cultivation device; 3 is the waste liquid equalizing tank; 4,5 is reactor; 6 is strainer; 7 is clean water basin; 8 for cultivating foundation trench; 9 is sludge sump; 10 is the metal recovery device; 11 is innoxious mud cake.
At cultivation device 1, the 2 nanometer Fe S that producexMaterial with enter reactor 4 from the waste water of wastewater equalization pond 3, follow into reactor 5 and carry out two-stage reaction, be filtered again rear qualified discharge 7, or reuse 8, add culture medium to recycle-water and enter cultivation device 1 or 2, in pH7.0～7.4,30～39 ℃, cultivate and produced nanometer Fe S in 36～72 hoursxFor using. The mud of filter 6 advances sludge-tank 9, to recover 10 acid addings Crome metal, copper, zinc, nickel are reclaimed in dissolving, and harmless mud cake 11 can be made fertilizer.
Embodiment
Below in conjunction with Figure of description, the invention will be further described.
Embodiment one: certain cold Zha Chang workshop contains the high chromium concentration wastewater treatment
The substratum that in the cultivation device, adds the vitriol contain 0.5% lactic protein salt, 1% ferrous salt and 1% and K, Mg, Ca, Cu, Mn, B, Si, Mo element, regulate pH7.0～7.4, add composite fungus agent, 30 ℃ of controlled temperature, anaerobism or double oxygen were cultivated 36 hours, generated to contain nanometer Fe S
xMixture, for using.
Per hour handle 0.4m
3High chromium concentration waste water, waste water (W) and biological nano FeS
x(BN) ratio is 2: 1, through static mixing, reactor reaction 30min.Add 1 ‰ positively charged ion Polyscrylamide (PAM) flocculation sediment and filtration treatment, measure chromium and sulfide in the water.Total chromium in the water outlet (TCr≤0.17mg/L) and sexavalent chrome (Cr as seen from Table 1
6+≤ 0.05mg/L) all be better than first grade discharging mark (TCr1.5mg/L, the Cr of GB
6+0.5mg/L), do not detect S in the water outlet
2-The Cr rate of recovery in the mud is greater than 97.0%.
The cold bundle chromate waste water of table 1 result unit: mg/L
Annotate: ND is not for detecting.
Embodiment two: the processing of drop liquid is oozed on certain chromium slag mountain
The substratum that in the cultivation device, adds the vitriol contain 5% lactic protein salt, 10% ferrous salt and 10% and K, Mg, Ca, Cu, Mn, B, Si, Mo element, regulate pH7.0～7.4, add composite fungus agent, 35 ℃ of controlled temperature, anaerobism or double oxygen were cultivated 48 hours, generated to contain nanometer Fe S
xMixture, for using.
This oozes drop liquid and contains Cr
6+5500mg/L, TCr 5800mg/L, pH14 per hour handles 9m
3Ooze drop liquid, W/BN=1: 1.Through static mixing, reactor reaction, precipitation and filtration treatment the results are shown in table 2.As seen TCr≤0.21mg/L and Cr in the water outlet
6+≤ 0.05mg/L all is better than the first discharge standard of GB, does not detect S in the water outlet
2-The Cr rate of recovery in the mud is greater than 97.5%.
Drop liquid result unit: mg/L is oozed on certain chromium slag mountain of table 2
Annotate: ND is not for detecting.
Embodiment three: certain mining industry liquid waste disposal
The substratum that in the cultivation device, adds the vitriol contain 3% lactic protein salt, 6% ferrous salt and 6% and K, Mg, Ca, Cu, Mn, B, Si, Mo element, regulate pH7.0～7.4, add composite fungus agent, 39 ℃ of controlled temperature, anaerobism or double oxygen were cultivated 72 hours, generated to contain nanometer Fe S
xMixture, for using.
This waste liquid contains Cr
6+1280mg/L, V3800mg/L, 1m is per hour handled in pH2～3
3Waste liquid, W/BN=1: 3.Through static mixing, reactor reaction, precipitation and filtration treatment the results are shown in table 3.As seen Cr in the water outlet
6+≤ 0.05mg/L, TCr≤0.15mg/L, V≤0.01mg/L all is better than the first discharge standard in GB and Sichuan Province, does not detect S in the water outlet
2-The Cr rate of recovery in the mud is greater than 96%, and the rate of recovery of vanadium is greater than 93%.
Drop liquid result unit: mg/L is oozed on certain chromium slag mountain of table 2
Annotate: ND is not for detecting; * Sichuan Province's standard.
Claims (3)
1. method of handling heavy metal wastewater thereby, it is characterized in that: the composite bacteria of utilizing desulfovibrio CB1.268 (Desulfovibrio Sp.), desulfurization intestines shape bacterium CB1.139 (Desulfotomaculum Sp.) and desulfurization bacterium CB1.168 (Desulfobacter Sp.) to form, in the substratum that contains lactic protein salt, ferrous salt and vitriol and K, Mg, Ca, Cu, Mn, B, Si, Mo element, under the alkaline condition, 30～39 ℃ of temperature, anaerobism or double oxygen were cultivated 36～72 hours, produced nanometer Fe S
xThis nanometer Fe S
xUnder acidic conditions, dissociate into S
2-And Fe
2+, reduction Cr
6+Be Cr
3+, with Ni
2+, Cu
2+, Zn
2+Deng the metallic sulfide precipitation that generates indissoluble,, reach the purpose of removing metal ion in the waste water through precipitation separation.
2. a kind of method of handling heavy metal wastewater thereby according to claim 1 is characterized in that: the bacterial strain proportion of composing of described composite fungus agent is: desulfovibrio CB 1.268 (DesulfovibrioSp.): desulfurization intestines shape bacterium CB 1.139 (Desulfotomaculum Sp.): desulfurization bacterium CB 1.168 (Desulfobacter Sp.)=1: 1: 1; The weight percent of nutritive salt is in the substratum: lactic protein salt 0.5%～5%, ferrous salt 1%～10%, vitriol 1%～10%; Alkaline condition pH7.0～7.4, acidic conditions pH3～4, the nanometer Fe S of generation
xMiddle x=1.1～1.2.
3. a kind of method of handling heavy metal wastewater thereby according to claim 1, its processing step is as follows:
In the cultivation device, add the substratum contain lactic protein salt, ferrous salt and vitriol and K, Mg, Ca, Cu, Mn, B, Si, Mo element, regulate pH7.0～7.4, add composite fungus agent, 30～39 ℃ of controlled temperature, anaerobism or double oxygen were cultivated 36～72 hours, contained nanometer Fe S with what generate
xFermented liquid transfer in the reactor, transfer pH3～4, treat nanometer Fe S
xAfter the heavy metal wastewater thereby reaction, add NaOH and transfer pH6～8, the heavy metal ion in the waste water generates the precipitation of indissoluble, through precipitation separation, reaches the purpose of removing metal ion in the waste water.
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|---|---|---|---|
| CN200710048472A CN100584771C (en) | 2007-02-13 | 2007-02-13 | A kind of method of handling heavy metal wastewater thereby |
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|---|---|---|---|
| CN200710048472A CN100584771C (en) | 2007-02-13 | 2007-02-13 | A kind of method of handling heavy metal wastewater thereby |
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| CN101244859A true CN101244859A (en) | 2008-08-20 |
| CN100584771C CN100584771C (en) | 2010-01-27 |
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| US4522723A (en) * | 1984-06-01 | 1985-06-11 | Kerr-Mcgee Corporation | Process for the removal and recovery of heavy metals from aqueous solutions |
| CN1079083C (en) * | 1996-03-14 | 2002-02-13 | 中国科学院成都生物研究所 | Compound functional bacteria for treatment of various electroplating wastes |
| EP1016633A1 (en) * | 1998-12-29 | 2000-07-05 | Pâques Bio Systems B.V. | Process for the treatment of waste water containing heavy metals |
| CN1162355C (en) * | 2000-05-10 | 2004-08-18 | 裴锡理 | Biochemical process of treating metal-containing waste water |
| CN1290779C (en) * | 2004-02-13 | 2006-12-20 | 成都科泰技术有限公司 | Process for treating and controlling waste water containing high concentration hazard rubbish chromium by high efficient function bacteria |
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- 2007-02-13 CN CN200710048472A patent/CN100584771C/en not_active Expired - Fee Related
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