CN105062495A - Heavy metal stabilizer - Google Patents
Heavy metal stabilizer Download PDFInfo
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- CN105062495A CN105062495A CN201510504522.XA CN201510504522A CN105062495A CN 105062495 A CN105062495 A CN 105062495A CN 201510504522 A CN201510504522 A CN 201510504522A CN 105062495 A CN105062495 A CN 105062495A
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Abstract
The invention discloses a heavy metal stabilizer which comprises sodium bentonite, zeolite powder, sulfydryl-iron base modified charcoal, reduced iron powder and calcium oxide. By carrying out sulfydryl-iron base modification on charcoal, the adsorption property of the heavy metal stabilizer to heavy metal is improved greatly; by mixing the sulfydryl-iron base modified charcoal with sodium bentonite, zeolite powder, reduced iron powder and calcium oxide, the heavy metal stabilizer is obtained. Compared with other materials, the heavy metal stabilizer has a better heavy metal adsorption property, can be applied to soil of different pH and combined pollution of multiple pollutants such as lead, zinc, copper, cadmium and arsenium at different degrees through reasonable proportioning, can simultaneously and effectively reduce exchangeable form quantity of pollutants such as lead, zinc, copper, cadmium and arsenium in soil, and is high in efficiency, stable and effective for a long term.
Description
Technical field
The present invention relates to technical field of environment pollution control, particularly relate to a kind of heavy metal stabilizer.
Background technology
Heavy metal pollution of soil refers to because mankind's activity makes heavy metal enter into soil, causes heavy metal in soil content apparently higher than background values and the phenomenon causing eco-environmental quality to decline.The heavy metal of contaminated soil mainly comprises the significant element of bio-toxicity as mercury (Hg), cadmium (Cd), plumbous (Pb), chromium (Cr) and metalloid arsenic (As) etc., and the element with certain toxicity is as zinc (Zn), copper (Cu), nickel (Ni) etc.Heavy metal contaminants movability in soil is very little, not easily with water leaching, is not microbiological deterioration, can enters human body, serious harm health of human body by food chain enrichment.Such as: after cadmium enters human body by food chain, can react with the specified protein in human body and multiple enzyme and make it to lose activity, and savings causes chronic poisoning in human organ, also can disturb copper, cobalt, zinc eubolism in vivo simultaneously, bring out various disease, even dead.
China's heavy metal pollution of soil situation is increasingly serious, by nearly 20,000,000 hm of cultivated area that Cd, Pb, As, Cr etc. pollute
2account for 1/5 of total area under cultivation, it is reported, the annual whole nation is underproduction grain yield more than 1,000 ten thousand tons because of heavy metal contamination, grain contaminated by heavy metals in addition also reaches 1,200 ten thousand tons every year, causes harm greatly and threaten national economy and fitness-for-all.Therefore, the control of heavy metal pollution of soil is more extremely urgent with reparation.
The improvement restorative procedure of heavy metal pollution of soil, according to the difference of Processing tecchnics and principle, contaminated soil is administered recovery technique and can be divided into: engineering control measure and physical chemistry repair two large classes.Engineering control measure mainly comprises: soil moved in improve the original, soil removal and replacement, go table soil and deep ploughing the measure such as to dig; Physical chemistry reparation mainly comprises: curing/stabilizing, electro reclamation, complexing drip washing, steam lixiviate, redox, agricultural reparation, biological restoration etc.Soil moved in improve the original method, adds a large amount of untainted soil in contaminated soil, covers its surface or mixes uniformly, and this method can not fundamentally be polluted by removal heavy metal, and cost is high, more likely destroys soil structures, causes soil fertility to decline.Phytoremediation, by heavy metal super-enriched plant, transfers to plant by this heavy metal from the soil body, but the phytoremediation cycle is long, can only be applied to root system of plant scope extremely, the reparation of polluting for deep layer is more difficult; The growth of plant is easily subject to the restriction of the factor such as weather and geology, cannot large-arealy on a large scale repair on the spot; There is pollutent and enter natural risk by the food chain of " plant-animal ".Chemical leaching method, refer to promote pollutant dissolution or migration in edatope by chemical/biological chemical solvents, solution containing pollutent is extracted from soil, carry out the technology of separation and sewage disposal again, this method processing cost is very high, and cannot predict removal effect and lasting repair time, removal effect is limited by place geological condition, if extracting solution is chosen improper, probably cause secondary pollution.Electromotion repairing technique method, heavy metal in soil is transported to electrode vessel by electrodialysis under electric field action, then collected by gathering system, and further focus on, this method is only applicable to the little region of pollution range, and be unsuitable for acidic conditions, and the complicacy of edatope makes it often fall flat.Curing/stabilizing recovery technique, the method of physics or chemistry is used to be fixed up by the toxic heavy metal in soil, or heavy metal is changed into the inactive form of chemical property, stop it to move in the environment, spread, thus reduction heavy metal toxicity, can realize contaminated soil innoxious while, reach soil to reduce perhaps not increase-volume, thus improving overall efficiency and the economy of contaminated soil/Hazardous wastes process disposal system, curing/stabilizing technology is especially expected to the main force becoming heavy metal pollution of soil recovery technique field.But current most of heavy metal stabilizer only has effect for a kind of or a few heavy metal, effectively cannot process the problem of the compound pollution of various heavy, need research and development a kind of to all effective heavy metal stabilizer of various heavy.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of to all effective heavy metal stabilizer of various heavy.
The technical solution used in the present invention is:
A kind of heavy metal stabilizer, comprises sodium bentonite, zeolite powder, sulfydryl-iron-based modification biological charcoal, reduced iron powder, and at least one in calcium oxide or calcium hydroxide.
Preferably, each constituent mass mark is respectively sodium bentonite 25%-50%, zeolite powder 20%-50%, sulfydryl-iron-based modification biological charcoal 10%-25%, reduced iron powder 5%-25%, calcium oxide or calcium hydroxide surplus.
Preferably, the preparation method of described sulfydryl-iron-based modification biological charcoal, comprises the following steps:
S1: prepare mercapto-complex solution;
S2: prepare poly-hydroxy iron polymers soln;
S3: prepare charcoal suspension;
S4: mercapto-complex solution and poly-hydroxy iron polymers soln are added stirring reaction in charcoal suspension simultaneously;
S5: reaction gained solution centrifugal, centrifugal gained solid drying is also calcined;
S6: the solid after cleaning calcining is dry.
Preferably, described mercapto-complex liquid quality fraction is 5-15%, described poly-hydroxy iron polymer solution concentration is 0.1-0.5mol/L, described charcoal suspension quality mark is 1-2%, and the volume ratio of described poly-hydroxy iron polymers soln, described charcoal suspension and described mercapto-complex solution is 40:20:(1-2.5).
Preferably, described mercapto-complex is any one in γ-mercaptopropyl trimethoxysilane, acetylcysteine, Mercaptamine, Gelucystine, Thiovanic acid.
Preferably, described S5 calcining temperature is 400-500 DEG C.
Preferably, described sodium bentonite is natural sodium bentonite or artificial sodium bentonite, and in described wilkinite, smectite content is more than or equal to 60%.
Preferably, described zeolite powder is at least one in the natural zeolites such as clinoptilolite, mordenite, euthalite, stilbite and chabazite.
Preferably, described charcoal take plant refuse as raw material, carbonizes and obtain at 300-900 DEG C.
A restorative procedure for heavy-metal contaminated soil, comprises the following steps:
S1: analysis heavy metal Heavy Metals in Contaminated Soils constituent content and exchange state amount;
S2: add heavy metal stabilizer, balance and stability;
Wherein, described heavy metal stabilizer is described above.
The invention has the beneficial effects as follows: the invention provides a kind of heavy metal stabilizer, comprise sodium bentonite, zeolite powder, sulfydryl-iron-based modification biological charcoal, reduced iron powder, calcium oxide.By carrying out sulfydryl-iron-based modification to charcoal, substantially increase the absorption property of its heavy metal, by sulfydryl-iron-based modification biological charcoal is mixed with sodium bentonite, zeolite powder, reduced iron powder, calcium oxide, obtain heavy metal stabilizer, comparatively other materials has better heavy metal adsorption performance, different pH soil, the multi-pollutant combined pollution such as lead, zinc, copper, cadmium, arsenic is in various degree applicable to through rational proportion, effectively can reduce the exchangeable species amount of the pollutents such as Lead In Soil, zinc, copper, cadmium, arsenic, efficiency is high and effectively steady in a long-term simultaneously.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of charcoal before modified.
Fig. 2 is the scanning electron microscope (SEM) photograph of sulfydryl-iron-based modification biological charcoal.
Fig. 3 is the energy spectrogram of charcoal before modified.
Fig. 4 is the energy spectrogram of sulfydryl-iron-based modification biological charcoal.
Embodiment
1, the preparation of heavy metal stabilizer
Prepare sulfydryl-iron-based modification biological charcoal according to the following steps: 1) prepare mercapto-complex solution: measure 0.5ml γ-mercaptopropyl trimethoxysilane, by volume γ-mercaptopropyl trimethoxysilane: ethanol: water=0.5:9:0.5 prepares γ-mercaptopropyl trimethoxysilane solution 10mL; 2) poly-hydroxy iron polymers soln is prepared: take 40.4gFe (NO
3)
39H2O is dissolved in 1L water, obtains 1L0.1molL
-1fe (NO
3)
3solution; Take 16gNa
2cO
3join prepared 1L0.1molL
-1feNO
3in solution, stir 2h; By the solution that obtains as 80 DEG C of aging 24h in thermostatic drier, stand-by; 3) prepare charcoal suspension: the charcoal taking 4g drying joins in 200mL deionized water, stirs, obtain the charcoal suspension that massfraction is 2%; 4) measure 400mL poly-hydroxy iron polymers soln and 10mL γ-mercaptopropyl trimethoxysilane solution, join in 200mL2% charcoal suspension gradually at ambient temperature, stirring reaction 2h simultaneously; 5) will react gained solution centrifugal, and get centrifugal gained solid and move into crucible after complete drying at 105 DEG C in thermostatic drying chamber, sealing, calcines 2h at 400-500 DEG C; 6) take out calcining solid after cooling, by washed with de-ionized water 2 ~ 3 times, grinding after dry at 60 ~ 80 DEG C in thermostatic drying chamber, crosses 100 mesh sieves, obtains sulfydryl-iron-based modification biological charcoal.
Take 4g natural sodium bentonite, sulfydryl that 2g zeolite powder, 2g aforesaid method prepare-iron-based modification biological charcoal, 1g reduced iron powder, 1g calcium oxide, mixed grinding, crosses 100 mesh sieves and obtains heavy metal-polluted soil stabilization agent.
The analysis of 2, sulfydryl-iron-based modification biological charcoal
Get sulfydryl-iron-based modification biological charcoal that aforesaid method prepares, use scanning electron microscope-energy spectrometer (SEM-EDS) to analyze charcoal rear surface form and constituent content change before modified.Fig. 1 is charcoal scanning electron microscope (SEM) photograph before modified, in Fig. 1, a amplifies 1000 times of figure under Electronic Speculum, b amplifies 2000 times of figure under Electronic Speculum, c amplifies 5000 times of figure under Electronic Speculum, d amplifies 10000 times of figure under Electronic Speculum, Fig. 2 is the modified scanning electron microscope (SEM) photograph of charcoal, in Fig. 2, a amplifies 1000 times of figure under Electronic Speculum, b amplifies 2000 times of figure under Electronic Speculum, c amplifies 5000 times of figure under Electronic Speculum, d amplifies 10000 times of figure under Electronic Speculum, Fig. 3 is charcoal energy spectrogram before modified, Fig. 4 be charcoal modified can spectrogram, in Fig. 1-4, small character and watermark are analyzing and testing system and automatically generate, there is no essential meaning.Analyze the physico-chemical property of sulfydryl-iron-based modification biological charcoal.Its pH is 6.5 ~ 8.5, ash oontent 3.0 ~ 6.0%, organic carbon content 40 ~ 75%, specific surface area>=1000m
2/ g.Analyze charcoal rear surface element before modified, obtain result as table 1.Can find out, sulfydryl-iron-based modification biological charcoal because of sulfydryl electronegative, therefore have better reflecting effect to the electron beam of SEM, make it obviously brighten on photo.Sulfydryl-iron-based modification biological charcoal particle becomes large simultaneously, and surface is cotton-shaped increases, and Fe, S, Si constituent content then increases considerably.The surface that result illustrates iron-based, sulfydryl is attached to charcoal preferably, effectively can increase reduction, the adsorptive power of charcoal heavy metal.
The unmodified charcoal of table 1 and sulfydryl-iron-based modification biological carbon surface results of elemental analyses (At%)
3, heavy metal stabilizer single component each with it is to the removal ability contrast experiment of cadmium, arsenic
Use Cd (NO
3)
24H
2o and 1000ppm arsenic standard solution preparation cadmium, arsenic concentration are respectively the mixing solutions of 100ppm, 50ppm; Measure 50mL mixing solutions respectively in five 100mL Erlenmeyer flasks, take heavy metal stabilization agent that 0.1g aforesaid method prepares respectively, 0.1g sodium bentonite, 0.1g zeolite, the unmodified charcoal of 0.1g, 0.1g sulfydryl-iron-based modification biological charcoal add Erlenmeyer flask; Shaken at room temperature 180min, filters, gets the concentration that filtrate uses inductive coupling plasma emission spectrograph (ICP-OES) respectively, Atomic Fluorescence Spectroscopy (AFS) (AFS) measures cadmium in solution, arsenic.Obtain result as follows, the adsorption rate of heavy metal stabilization agent to cadmium, arsenic that aforesaid method prepares is respectively 98.4%, 99.1%; The adsorption rate of sodium bentonite to cadmium, arsenic is respectively 22.5%, 8.9%; The adsorption rate of zeolite powder to cadmium, arsenic is respectively 14.2%, 10.1%; The adsorption rate of unmodified charcoal to cadmium, arsenic is respectively 16.8%, 7.7%; The adsorption rate of sulfydryl-iron-based modification biological charcoal cadmium, arsenic is respectively 73.1%, 92.5%.The adsorptive power of the modified heavy metal of visible charcoal significantly strengthens, and the removal ability of heavy metal stabilization agent heavy metal that visible aforesaid method prepares obviously is better than each independent component, there is synergistic effect between each component that heavy metal-polluted soil stabilization agent of the present invention is chosen.
4, the impact experiment of concentration, pH heavy metal stablizer removal cadmium, arsenic
Use Cd (NO
3)
24H
2o and 1000ppm arsenic standard solution prepares three groups of different concns mixing solutionss, and its concentration is respectively Cd1000ppm and As500ppm, Cd100ppm and As50ppm, Cd10ppm and As5ppm; Three groups of different concns mixing solutionss measure 50mL mixing solutions respectively in three 100mL Erlenmeyer flasks, use 1molL
-1naOH and 1molL
-1hCl regulates the three bottles of pH often organizing mixing solutions to be respectively pH=5.0,7.0,9.0; In the Erlenmeyer flask regulating pH value, add the heavy metal stabilization agent that 0.5g aforesaid method prepares respectively, vibrate under room temperature condition 180min; Filter, get filtrate and use ICP-OES, AFS to measure cadmium, arsenic concentration in filtrate respectively, obtain experimental result as 2.
Table 2 concentration, pH heavy metal stablizer remove cadmium, arsenic affect experimental result
Note: do not detect in solution after absorption, therefore think adsorption rate 100%.
As shown in Table 2, the heavy metal stabilization agent that aforesaid method prepares is within the scope of the pH of 6 ~ 9, and the clearance of heavy metal when being respectively 100ppm, 50ppm to cadmium in water, arsenic concentration can reach more than 96%; When being respectively 1000ppm, 500ppm to cadmium in water, arsenic concentration, Cd clearance reaches more than 51%, As clearance and reaches more than 77%, proves that heavy metal stabilization agent of the present invention is under different pH, has very high heavy metal and stablizes constraint capacity.
5, to the reparative experiment of cadmium pollution soil
Layout and gather somewhere contaminated soil sample, measure total cadmium of contaminated soil, available Cd content; Take 500g (air-dry, to cross 10 mesh sieves) contaminated soil, add the stabilized metal agent that 5g aforesaid method prepares wherein, control water ratio and be about 50%, stir, maintenance under room temperature condition; Sample after 2,5,14 days in maintenance respectively, use diethyl pentetic acid (DTPA) to extract soil available Cd, and use ICP-OES to measure soil available Cd content.
After measured, after maintenance stablizes 2,5,14 days, effective cadmium content of soil is respectively decline 67.1%, 73.5%, 73.6%.Visible heavy metal stabilizer of the present invention effectively can reduce available Cd in actual contaminated soil, and has reparation speed and preferably repair ability faster.
6, to the reparative experiment of the tailings containing various heavy
Layout and gather the plumbous zinc tailings in Chenzhou, Hunan Province mining area, measure each total metals of tailings, available state amount and Leaching; Take 500g tailings sample (air-dry, cross 10 mesh sieves), according to massfraction be sodium bentonite 25%, zeolite powder 25%, aforesaid method prepare sulfydryl-iron-based modification biological charcoal 10%, reduced iron powder 25%, calcium oxide 15% proportioning be mixed to get heavy metal stabilizer, get this stabilized metal agent of 25g, control water ratio and be about 40%, stir; Room temperature maintenance is after 5 days, and sampling natural air drying, measures its Leaching by HJ/T299-2007.
With do not add compared with heavy metal stabilization agent process, tailings sample each Leaching of Heavy Metals amount density loss is clearly.Wherein, plumbous leaching concentration declines 89.43%, and the leaching concentration of zinc declines 97.30%, and the leaching concentration of arsenic declines 71.49%, and the leaching concentration of cadmium declines 76.18%, and the leaching concentration of copper declines 92.11%.This illustrates that heavy metal-polluted soil stabilization agent of the present invention can fetter effectively to the zinc in soil, arsenic, cadmium, a few heavy metal species of copper, applied widely.
7, to the reparative experiment of various heavy polluted river channel bed mud
By massfraction be sodium bentonite 25%, zeolite powder 40%, aforesaid method prepare sulfydryl-iron-based modification biological charcoal 15%, reduced iron powder 15%, calcium oxide 5% the agent of proportioning mixed preparing heavy metal stabilization; Massfraction by 2% adds heavy metal stabilizer in certain pollution of river bed mud, in this bed mud, zinc, copper, nickel, chromium total amount are respectively 905mg/kg, 2133mg/kg, 1255mg/kg, 1863mg/kg, after stirring, waterflooding 2-3cm, does blank simultaneously; Maintenance samples after stablizing 7 days, after sample natural air drying, uses DTPA to extract soil available zinc, copper, nickel, chromium, and uses ICP-OES to measure.
After measured, and do not add compared with heavy metal stabilization agent process, in bed mud, each heavy metal bio-available Zn concentration declines clearly.Wherein, Available zinc content declines 54.92%, and Available Cu content declines 85.23%, and active nickel content declines 71.37%, and available state chromium content declines 76.54%.Result proves, heavy metal stabilizer of the present invention can make the multi-metal bio-available Zn concentration in heavy metal polluted bed mud significantly reduce.
8, to the reparative experiment containing various heavy contaminated soil
Heavy metal stabilization agent is obtained by the proportioning mixed preparing of massfraction sodium bentonite 25%, zeolite powder 20%, sulfydryl-iron-based modification biological charcoal 25%, reduced iron powder 25%, calcium oxide 5%; Massfraction by 2% adds heavy metal stabilizer in contaminated soil, in this contaminated soil, lead, zinc, arsenic, copper, cadmium total amount are respectively 5511mg/kg, 5204mg/kg, 514.9mg/kg, 439.0mg/kg, 123.8mg/kg, and keep water ratio to be about 40%; 5 days plantation sensitive crop romaine lettuce are afterwards stablized in room temperature maintenance; Separately do controlled trial, identical contaminated soil does not add heavy metal stabilizer, directly plants romaine lettuce; Growth of Lettuce was gathered in the crops after 40 days, got edible portion as test sample, and in sample, lead, zinc, arsenic, copper, cadmium content measure by GB/T5009.11 ~ 15-2003.
After measured, the lead that the romaine lettuce edible portion of planting absorbs, zinc, arsenic, copper, cadmium content reduce 74.7%, 73.2%, 66.9%, 55.8%, 87.8% than control group respectively, romaine lettuce volume increase simultaneously 27.4%.Result proves, heavy metal-polluted soil stablizer of the present invention pollutes lead, zinc, arsenic, copper, cadmium in rehabilitating soil etc. and has extraordinary effect, can significantly reduce its transfer ability.
Claims (10)
1. a heavy metal stabilizer, is characterized in that, comprises sodium bentonite, zeolite powder, sulfydryl-iron-based modification biological charcoal, reduced iron powder, and at least one in calcium oxide or calcium hydroxide.
2. heavy metal stabilizer according to claim 1, it is characterized in that, each constituent mass mark is respectively sodium bentonite 25%-50%, zeolite powder 20%-50%, sulfydryl-iron-based modification biological charcoal 10%-25%, reduced iron powder 5%-25%, calcium oxide or calcium hydroxide surplus.
3. heavy metal stabilizer according to claim 1, is characterized in that, the preparation method of described sulfydryl-iron-based modification biological charcoal, comprises the following steps:
S1: prepare mercapto-complex solution;
S2: prepare poly-hydroxy iron polymers soln;
S3: prepare charcoal suspension;
S4: mercapto-complex solution and poly-hydroxy iron polymers soln are added stirring reaction in charcoal suspension simultaneously;
S5: reaction gained solution centrifugal, centrifugal gained solid drying is also calcined;
S6: the solid after cleaning calcining is dry.
4. heavy metal stabilizer according to claim 3, it is characterized in that, described mercapto-complex liquid quality fraction is 5-15%, described poly-hydroxy iron polymer solution concentration is 0.1-0.5mol/L, described charcoal suspension quality mark is 1-2%, and the volume ratio of described poly-hydroxy iron polymers soln, described charcoal suspension and described mercapto-complex solution is 40:20:(1-2.5).
5. heavy metal stabilizer according to claim 3, is characterized in that, described mercapto-complex is any one in γ-mercaptopropyl trimethoxysilane, acetylcysteine, Mercaptamine, Gelucystine, Thiovanic acid.
6. heavy metal stabilizer according to claim 3, is characterized in that, described S5 calcining temperature is 400-500 DEG C.
7. heavy metal stabilizer according to claim 1, is characterized in that, described sodium bentonite is natural sodium bentonite or artificial sodium bentonite, and in described wilkinite, smectite content is more than or equal to 60%.
8. heavy metal stabilizer according to claim 1, is characterized in that, described zeolite powder is at least one in the natural zeolites such as clinoptilolite, mordenite, euthalite, stilbite and chabazite.
9. heavy metal stabilizer according to claim 1, is characterized in that, described charcoal take plant refuse as raw material, carbonizes and obtain at 300-900 DEG C.
10. a restorative procedure for heavy-metal contaminated soil, is characterized in that, comprises the following steps:
S1: analysis heavy metal Heavy Metals in Contaminated Soils constituent content and exchange state amount;
S2: add heavy metal stabilizer, balance and stability;
Wherein, described heavy metal stabilizer is as described in any one of claim 1-9.
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