CN103332773A - Method for removing mercury in waste water - Google Patents

Method for removing mercury in waste water Download PDF

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Publication number
CN103332773A
CN103332773A CN2013102974140A CN201310297414A CN103332773A CN 103332773 A CN103332773 A CN 103332773A CN 2013102974140 A CN2013102974140 A CN 2013102974140A CN 201310297414 A CN201310297414 A CN 201310297414A CN 103332773 A CN103332773 A CN 103332773A
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waste water
mercury
concentration
zvi
wastewater
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CN2013102974140A
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CN103332773B (en
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张进忠
王定勇
周欣
邱昕凯
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Southwest University
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Southwest University
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Abstract

The invention discloses a method for removing mercury in waste water. Firstly, the content of mercury in waste water is determined, then zero-valent iron powder is added into the waste water at a certain pH value and temperature, reaction is performed with oscillation, and with the progress of the reaction, precipitation appears in the waste water; when the precipitation is no longer increased, the reaction is finished, and the oscillation is stopped; precipitation separation is performed through a solid-liquid separation method, namely the mercury in the waste water is removed. According to the invention, the removal ratio of mercury is high, and under an optimal condition, the removal ratio can reach 99.83 percent. In the invention, follow-up treatment is simple, solid-liquid separation can be achieved only through filtering or settling, and the method is environmental-friendly. Moreover, the rate constant for removing the mercury in the waste water is high, and the highest rate constant can reach 0.0165min-1.

Description

A kind of method of removing Mercury in Wastewater
Technical field
The present invention relates to water technology, specifically refer to remove the method for Mercury in Wastewater, belong to water-treatment technology field.
Background technology
Mercury has stronger toxicity and biological accumulation in environment, can be converted into the stronger organic mercury of toxicity by biological and abiologic process, becomes the persistent pollutant of people's extensive concern.Mercury in the environment is mainly derived from " three wastes " of chlorine industry, plastics industry, electronic industry, amalgamate gold metallurgy and mercury fulminate production discharging, adopts the mercury in the methods processing waste water such as chemical precipitation, coagulation, ion-exchange, absorption, reduction and membrane sepn at present.But these method running cost height, clearance is lower or cause secondary pollution easily, presses for the new treatment technology of development Mercury in Wastewater.
Summary of the invention
At existing treatment technology above shortcomings, the purpose of this invention is to provide that a kind of clearance height, processing cost are low, the treatment process of non-secondary pollution.
The means that the present invention solves the problems of the technologies described above are achieved in that
A kind of method of removing Mercury in Wastewater is characterized in that: its treatment step is,
1) at first measures concentration, the wastewater volume of Mercury in Wastewater, obtain the content of Mercury in Wastewater;
2) the pH value of regulating waste water then is 4 ~ 6, is to add zeroth order iron powder (ZVI, 〉=98%) under 22 ~ 25 ℃ of conditions in waste water in temperature, presses Hg in the waste water 2+With the mass ratio of ZVI be the add-on that 1:10000 ~ 1:25000 determines ZVI, the reaction while vibrating along with the carrying out of reaction, precipitation occurs in the waste water; (this process was generally about 8 hours) reaction finishes the failure of oscillations when precipitation no longer increases;
3) with precipitate and separate, can remove the mercury in the waste water by solid-liquid isolation method (as filtration, sedimentation).
Preferably, the 2nd) go on foot when in waste water, adding ZVI, add humic acid (HA) simultaneously, according to Hg in the waste water 2+With the mass ratio of HA be the add-on that 1:10 ~ 1:30 determines HA.
If the 1st) pacing gets the concentration of Mercury in Wastewater greater than 0.10 mg * L -1, then earlier it is diluted to 0.08 ~ 0.10 mg * L -1, carry out the 2nd again) and the step.
The 1st) when Mercury in Wastewater concentration is decided in pacing, measure Cl in the waste water simultaneously -And Ca 2+Concentration, if Cl -Concentration is greater than 0.03 mol * L -1, perhaps Ca 2+Concentration is greater than 0.8 mmol * L -1The time, by handling, make Cl -Concentration is reduced to 0.025 ~ 0.03 mol * L -1, Ca 2+Concentration is reduced to 0.5 ~ 0.8 mmol * L -1
Described ZVI is analytical pure, and particle diameter is 0.15 ~ 0.2 mm.
Compared to existing technology, the present invention has following beneficial effect:
1, the clearance height of present method mercury.During lower concentration mercury (0.1 mg/L), the present invention shows special advantage in removing waste water, and the clearance under the optimal conditions can reach 99.83%, and flocculent precipitation can only reach 83.33%.
2, the present invention is to clearance and the Na of Mercury in Wastewater 2The S precipitator method (99.8%) are very approaching, but Na 2The S precipitator method are introduced excessive N a 2S has increased the salt content in the water outlet, and needing further to handle could qualified discharge.Subsequent disposal of the present invention is simple, only needs can realize solid-liquid separation by filtering or sedimentation, and the indissoluble material of excessive reduced iron powder and generation all can be removed fully, so the present invention can realize environmental friendliness.
3, the present invention's rate constant of removing Mercury in Wastewater is up to 0.0165 min -1, and bibliographical information only is 0.0042 min with the acid rate constant that contains mercury mining waste water of ZVI removal simulation -1, and the starting point concentration of the mercury-containing waste water of this method processing is 2.1 mg * L -1, and the ZVI consumption is far above the present invention.
Description of drawings
The scanning electron microscope diagram on ZVI surface before and after Fig. 1-the present invention handles.Wherein, (a) handle before; (b) processing contains Hg 2+Behind the waste water; (c) Cl -Handle when existing and contain Hg 2+Behind the waste water; (d) Cl -, Ca 2+Handle when existing and contain Hg 2+Behind the waste water; (e) Cl -, Ca 2+, handle when HA exists and contain Hg 2+Behind the waste water.
Fig. 2-ZVI of the present invention handles the x-ray diffraction pattern before the waste water.
Fig. 3-ZVI of the present invention handles the x-ray diffraction pattern behind the waste water.Wherein, (a) processing contains Hg 2+Behind the waste water; (b) Cl -Handle when existing and contain Hg 2+Behind the waste water; (c) Cl -, Ca 2+Handle when existing and contain Hg 2+Behind the waste water; (d) Cl -, Ca 2+, handle when HA exists and contain Hg 2+Behind the waste water.
Fig. 4-ZVI of the present invention removes Hg in the waste water 2+Mechanism of action figure.
Embodiment
The invention will be further described by reference to the accompanying drawings.
Strong, cheap and easy to get, the environmental friendliness of Zero-valent Iron (ZVI) reducing power, but the Fe (OH) of strong adsorption pollutent in reduction process, produced 2And Fe (OH) 3Deng flocks, be mainly used in the removal of halohydrocarbon, organochlorine pesticide, nitrate and some toxic heavy metals (as Cr, Cu, As and Pb etc.), yet there are no for the report of removing Mercury in Wastewater.The present invention uses it for the removal of Mercury in Wastewater, and its concrete treatment step is,
1) at first measures concentration, the wastewater volume of Mercury in Wastewater, obtain the content of Mercury in Wastewater;
2) the pH value of regulating waste water then is 4 ~ 6, is under 22 ~ 25 ℃ of conditions, according to Hg in the waste water in temperature 2+With the mass ratio of zeroth order iron powder (ZVI, 〉=98%, analytical pure, particle diameter 0.15 ~ 0.2 mm) be the ratio of 1:10000 ~ 1:25000, add ZVI, be 220 r * min at rotating speed -1The reaction while vibrating along with the carrying out of reaction, precipitation occurs in the waste water; (this process was generally about 8 hours) reaction finishes the failure of oscillations when precipitation no longer increases.
3) with precipitate and separate, can remove the mercury in the waste water by solid-liquid isolation method (as filtration, sedimentation).
In order further to improve the clearance of mercury, the 2nd) go on foot when in waste water, adding ZVI, according to Hg in the waste water 2+With the mass ratio of HA be the ratio of 1:10 ~ 1:30, can add HA simultaneously.
If the 1st) pacing gets Mercury in Wastewater concentration and is higher than 0.10 mg * L -1, then dilute waste water earlier, mercury concentration is reduced to 0.08 ~ 0.10 mg * L -1, carry out the 2nd again) and the step.Simultaneously the 1st) when Mercury in Wastewater concentration is decided in pacing, also measure Cl in the waste water -And Ca 2+Concentration.If Cl -Concentration is higher than 0.03 mol * L -1, perhaps Ca 2+Concentration is higher than 0.8 mmol * L -1The time, by handling, make Cl -Concentration is reduced to 0.025 ~ 0.03 mol * L -1, Ca 2+Concentration is reduced to 0.5 ~ 0.8 mmol * L -1
ZVI of the present invention removes Hg in the waste water 2+Optimum condition be: Hg in the waste water 2+Starting point concentration be 0.08 ~ 0.10 mg * L -1PH is 4.5 ~ 5.5; Temperature is 23 ~ 25 ℃; Cl in the waste water -And Ca 2+Concentration be respectively 0.028 ~ 0.03 mol * L -1, 0.5 ~ 0.8 mmol * L -1Hg in the waste water 2+With the mass ratio of ZVI be 1:10000 ~ 1:18000, Hg 2+With the mass ratio of HA be 1:12 ~ 1:18.
ZVI of the present invention removes Hg in the waste water 2+Top condition be: Hg in the waste water 2+Starting point concentration be 0.10 mg * L -1PH is 5; Temperature is 25 ℃; Cl in the waste water -And Ca 2+Concentration be respectively 0.03 mol * L -1, 0.5 ~ 0.8 mmol * L -1Hg in the waste water 2+With the mass ratio of ZVI be 1:16500, Hg 2+With the mass ratio of HA be 1:15.The clearance of mercury can reach 99.83% under this condition.
The present invention characterizes ZVI with SEM and XRD and changes at the surface topography of handling the waste water front and back and composition, tentatively inquires into ZVI and Hg 2+Mechanism of action.Wherein, the ZVI sample behind the processing waste water obtains through centrifugation, filtration, deionized water wash and lyophilize.
Utilize SEM and XRD to characterize ZVI and handle Hg 2+Surface topography and the composition of front and back solid sample change, and obtain as Fig. 1 ~ result shown in Figure 3.As can be seen from Figure 1, handle preceding ZVI surface relatively smoothly and be the gully shape, occur the obvious corrosion product after the processing.Fig. 1 (b) ~ (e) shows that ZVI handles and contains Hg 2+Behind the waste water, no matter whether contain Cl -, Ca 2+, many non-crystalline state flosss, some filaments and spicule all appear in HA, and the part gully is filled up by these non-crystalline states and crystalline state material; The crystal state of corrosion product is obviously good than Fig. 1 (b), (c) among Fig. 1 (d), (e), and reason may be to contain Ca among Fig. 1 (d), (e) 2+, promoted the formation of ferriferous oxide and oxyhydroxide crystal, these are thread, the needle-like crystal material mostly is common iron rot product FeOOH(pyrrhosiderite).
As can be seen from Figures 2 and 3, handle the preceding diffraction crest that reduced iron powder is only arranged in the time of 44.70 ~ 45.02 °; ZVI handles and contains Hg 2+Behind the waste water, Fe appears in the time of 35.38 ~ 36.78 ° 3O 4-Fe 2O 3The diffraction crest; At Cl -, Ca 2+, when HA exists, ZVI handles and to contain Hg 2+Behind the waste water, then in many places such as 14.02 ~ 14.41 °, 18.14 ~ 18.42 °, 30.12 ~ 30.32 ° and 43.00 ~ 43.38 ° FeOOH, Fe appear 3O 4-Fe 2O 3The diffraction crest, and the diffraction crest of FeO appears in the time of 36.18 ~ 36.46 °, prove that handling ZVI surface, back forms and assembled pyrrhosiderite, magnetite and hematite crystals, these materials can adsorb, a part of Hg in flocculation and the co-precipitation waste water 2+, promote Hg 2+Removal, but can make the ZVI surface passivation behind a large amount of the formation, cause Hg in the waste water 2+Clearance descend.
ZVI of the present invention removes Hg separately 2+Mainly contain two kinds of mechanism of action: the one, reductive action, Hg 2+Mainly by ZVI it is reduced to simple substance mercury or the lower mercury shape of toxicity is removed; The 2nd, absorption, co-precipitation, Hg 2+Mainly by the Fe that produces after the ZVI corrosion 2+, Fe 3+The oxide compound that forms and oxyhydroxide absorption are removed with co-precipitation, namely except the reductive action of ZVI, ferriferous oxide be adsorbed on removal Hg 2+Process in also play an important role.In fact, under mild acid conditions, ZVI removes Hg in the waste water 2+The existing redox of mechanism of action absorption, flocculation, coprecipitation process are arranged again, the principal reaction that relates to may have:
Fe + 2H + → Fe 2+ + H 2↑ (1)
Fe + 2H 2O → Fe 2+ + H 2↑+ 2OH - (2)
Hg 2+ + Fe → Hg 0 + Fe 2+ (3)
Hg 2+ + 2Fe 2+ → Hg 0 + 2Fe 3+ (4)
Fe 3+ + Fe 2+ + 5OH - → Fe(OH) 2↓+ Fe(OH) 3↓ (5)
4Fe 2+ + 8OH - + O 2 → 4FeOOH + 2H 2O (6)
Fe 2+ + FeOOH + 2OH - → Fe 2O 3↓+ H 2O (7)
Fe (OH) 2+ O 2→ FeOOH or Fe 3O 4↓ (8)
Fe 2O 3-Fe 3O 4 + Hg 2+ → Fe 2O 3-Fe 3O 4-Hg 2+ (9)
In reaction formula (3) and (4), all produce Hg 0, but remove Hg at ZVI 2+After x-ray diffraction pattern in do not find Hg 0The diffraction crest, its reason may be because Hg 0Instability, highly volatile, volatilization loss in the treating processes of ZVI sample.
Hg in the waste water of ZVI of the present invention 2+Have one to remove process fast, meet the pseudo first order reaction kinetic equation, the maximum rate constant is 0.0165 min -1
ZVI of the present invention removes Hg in the waste water 2+Mechanism mainly be redox reaction, ferriferous oxide and the oxyhydroxide that reaction generates can further adsorb, flocculation sediment Hg 2+
There is Cl in the trade effluent mostly -, Ca 2+Deng ionogen and natural organic matter, can influence removal speed and the clearance of pollutent in the waste water of ZVI usually.Work as Cl -, Ca 2+Concentration be respectively 0.01 mol * L -1, 0.25 mmol * L -1The time, can suppress Hg 2+Removal; Cl -And Ca 2+Concentration be respectively 0.03 mol * L -1, 0.5 ~ 0.8 mmol * L -1The time, to Hg 2+Removal promoter action is arranged; The existence of HA can improve Hg in the waste water 2+Clearance, along with the rising of HA concentration, clearance begins to descend.
Work as Cl -, Ca 2+, during the HA Individual existence, Hg 2+The removal process all meets the pseudo first order reaction dynamic characteristic, removes speed and obviously improves.Work as Cl -+ Ca 2+, Cl -+ HA, Cl -+ Ca 2+When+HA exists, Hg in the waste water 2+Clearance do not significantly improve, obviously improve but remove speed, the removal process all meets the pseudo first order reaction dynamic characteristic.Work as Cl -, Ca 2+, when HA exists jointly, Hg in ZVI and the waste water 2+Mechanism of action as shown in Figure 4.
Above-mentioned example only be that explanation the present invention does for example, and be not to be restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other multi-form variation and change on the basis of the above description, can't give exhaustive here to all embodiments.Everyly belong to the row that apparent variation that technical solution of the present invention amplifies out or change still are in protection scope of the present invention.

Claims (5)

1. method of removing Mercury in Wastewater is characterized in that: its treatment step is,
1) at first measures concentration, the wastewater volume of Mercury in Wastewater, obtain the content of Mercury in Wastewater;
2) the pH value of regulating waste water then is 4 ~ 6, is to add zeroth order iron powder (ZVI) under 22 ~ 25 ℃ of conditions in waste water in temperature, presses Hg in the waste water 2+With the mass ratio of ZVI be the add-on that 1:10000 ~ 1:25000 determines ZVI, the reaction while vibrating along with the carrying out of reaction, precipitation occurs in the waste water; Reaction finishes the failure of oscillations when precipitation no longer increases;
3) by solid-liquid isolation method with precipitate and separate, can remove the mercury in the waste water.
2. the method for removal Mercury in Wastewater according to claim 1 is characterized in that: the 2nd) go on foot when adding ZVI in waste water, add humic acid (HA) simultaneously, according to Hg in the waste water 2+With the mass ratio of HA be the add-on that 1:10 ~ 1:30 determines HA.
3. the method for removal Mercury in Wastewater according to claim 1 is characterized in that: if the 1st) pacing gets Hg in the waste water 2+Concentration is greater than 0.10 mg * L -1, then earlier it is diluted to 0.08 ~ 0.10 mg * L -1, carry out the 2nd again) and the step.
4. the method for removal Mercury in Wastewater according to claim 1 is characterized in that: the 1st) when Mercury in Wastewater concentration is decided in pacing, measure Cl in the waste water simultaneously -And Ca 2+Concentration, if Cl -Concentration is greater than 0.03 mol * L -1, perhaps Ca 2+Concentration is greater than 0.8 mmol * L -1The time, by handling, make Cl -Concentration is reduced to 0.025 ~ 0.03 mol * L -1, Ca 2+Concentration is reduced to 0.5 ~ 0.8 mmol * L -1
5. the method for removal Mercury in Wastewater according to claim 1, it is characterized in that: described ZVI is analytical pure, particle diameter is 0.15 ~ 0.2 mm.
CN201310297414.0A 2013-07-16 2013-07-16 Method for removing mercury in waste water Expired - Fee Related CN103332773B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105668754A (en) * 2016-03-10 2016-06-15 湘潭大学 Method for removing trace of heavy metal and nonmetal impurities in waste acid cleaning liquor
CN105948329A (en) * 2016-06-28 2016-09-21 中钢集团天澄环保科技股份有限公司 Treatment device and method for mercury-containing wastewater in chlor-alkali industry
CN108687114A (en) * 2018-05-16 2018-10-23 扬州杰嘉工业固废处置有限公司 A kind of Organomercurial waste is stable and cures disposing technique
CN110282784A (en) * 2019-07-26 2019-09-27 合肥九一化工科技有限公司 A kind of laboratory waste liquid processing method

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JP2002224676A (en) * 2001-01-31 2002-08-13 Nippon Denkai Kk Method for treating waste water
CN103112918A (en) * 2013-02-20 2013-05-22 同济大学 Integrated process for treating heavy metal wastewater

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002224676A (en) * 2001-01-31 2002-08-13 Nippon Denkai Kk Method for treating waste water
CN103112918A (en) * 2013-02-20 2013-05-22 同济大学 Integrated process for treating heavy metal wastewater

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105668754A (en) * 2016-03-10 2016-06-15 湘潭大学 Method for removing trace of heavy metal and nonmetal impurities in waste acid cleaning liquor
CN105948329A (en) * 2016-06-28 2016-09-21 中钢集团天澄环保科技股份有限公司 Treatment device and method for mercury-containing wastewater in chlor-alkali industry
CN108687114A (en) * 2018-05-16 2018-10-23 扬州杰嘉工业固废处置有限公司 A kind of Organomercurial waste is stable and cures disposing technique
CN108687114B (en) * 2018-05-16 2021-05-11 扬州杰嘉工业固废处置有限公司 Mercury-containing reagent waste stabilization and solidification treatment process
CN110282784A (en) * 2019-07-26 2019-09-27 合肥九一化工科技有限公司 A kind of laboratory waste liquid processing method

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