CN107011918A - A kind of sulfhydrylation bentonite of restoration of soil polluted by heavy metal and preparation method thereof - Google Patents
A kind of sulfhydrylation bentonite of restoration of soil polluted by heavy metal and preparation method thereof Download PDFInfo
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Abstract
Administered and recovery technique field the present invention relates to heavy-metal contaminated soil, and in particular to a kind of for sulfhydrylation bentonite of restoration of soil polluted by heavy metal and preparation method thereof.A kind of sulfhydrylation bentonite is disclosed, is mixed by bentonite, the ethanol solution of 3 mercaptopropyl trimethoxysilanes, sodium metasilicate and water, after stirring reaction, scrubbed, filtering, drying are made.Obtained sulfhydrylation bentonite is cheap, and adsorption rate is high, and desorption efficiency is low, and adsorption capacity is big；In preparation method, sulfhydryl modified dose of consumption is significantly reduced, reduces and is carried out in cost, and this modified alta-mud original soil, simplify modified technique.
Description
Technical field
Administered and recovery technique field the present invention relates to heavy-metal contaminated soil, and in particular to a kind of repairing heavy metal pollution
Sulfhydrylation bentonite of soil and preparation method thereof.
Background technology
It is increasingly serious the problem of heavy metal pollution with the fast development of industry, because its toxicity is big, easily accumulation, once
It is difficult to remove into water body and soil environment, causes serious Heavy-Metal-Contaminated Environments problem.Therefore, develop a kind of honest and clean
Valency, efficient heavy-metal adsorption material turn into the hot issue of current research.Bentonite resource is abundant, cheap and easy to get, has
Stronger ion-exchange capacity and absorption property, but its absorption property need to be improved, accordingly, it would be desirable to change to bentonite
Property processing.
Zhang Yiping exists《Organic modified bentonite Study on adsorption properties》(Zhejiang Educational College's journal, in November, 2008, the
6 phases) in a text, the acidifying of sodium form bentonite enriching hydrochloric acid is disclosed, then enter with the toluene solution of 3- mercaptopropyl trimethoxysilanes
Row reaction prepares the bentonitic method of sulfydryl.Wherein, the mass ratio of sodium form bentonite and 3- mercaptopropyl trimethoxysilanes is 1:1
(i.e. bentonite:Silane coupler=1:5mmol), and need in toluene solution flow back 24 hours.
The research work that the present inventor's early stage is participated in, the Chinese patent of Application No. 201210139593.0 is disclosed
A kind of preparation method of sulfydryl-montmorillonite composite material.This kind of method needs first handle montmorillonite with hydrochloric acid activation, then with 3-
The ethanol solution reaction of mercaptopropyl trimethoxysilane, obtains sulfydryl-montmorillonite composite material.Wherein montmorillonite and 3- mercapto propyl group
The ratio between trimethoxy silane is 1:1.The research shows that sulfhydryl modified bentonite is to cadmium, and lead, nickel advantages of good adsorption effect is not having
Under conditions of interfering ion is present, its saturated adsorption capacity is respectively Cd2+68.49mg/g、Pb2+208.33mg/g、Ni2+
35.84mg/g, modified bentonite is greatly improved to the adsorption capacity of cadmium, improves 40~50 times.
The problem of generally existing 3- mercaptopropyl trimethoxysilane usage amounts are more in the existing sulfhydryl modified technology of bentonite,
The ratio between bentonite and modifying agent are essentially all 1：1, due to 3- mercaptopropyl trimethoxysilanes costly, be it is material modified most
Main cost, accounts for more than the 90% of whole material modified preparation cost.Therefore, it is necessary to by drafting raw material again, adjust
Whole technological parameter substantially reduces the bentonitic cost of sulfhydrylation to reduce amount of modifier.
The content of the invention
Present invention solves the technical problem that be to provide a kind of bentonite sulfhydrylation method with low cost and low cost
Sulfhydrylation bentonite.
Technical scheme：The sulfhydrylation bentonite of restoration of soil polluted by heavy metal, by bentonite, sulfhydryl compound
Reaction is mixed with sodium metasilicate to be made；Wherein, the weight proportion of bentonite, sulfhydryl compound and sodium metasilicate is：1:0.05~0.2:
0.06~0.10.
Wherein, sulfhydryl compound is soluble in ethanol, is added and used in the form of ethanol solution.Generally it is dissolved as body
Fraction is 1~5% ethanol solution.Sulfhydryl compound can also dissolve in methyl alcohol, and being added in the form of methanol solution makes
With.
Sodium metasilicate is dissolved in water, and can in form of an aqueous solutions be added and be used.Generally it is dissolved as mass percent concentration
For 6~10% aqueous solution.Sodium metasilicate can also be first added, is added water.
It is preferred that, the weight proportion of bentonite, sulfhydryl compound and sodium metasilicate is 1:0.05~0.1:0.06~0.08, more
Preferably, the weight proportion of bentonite, sulfhydryl compound and sodium metasilicate is 1:0.05:0.06.
Wherein, sulfhydryl compound can be 3- mercaptopropyl trimethoxysilanes, or 3- mercapto propyl-triethoxysilicanes
Alkane.
The invention solves the problems that second technical problem be to provide a kind of above-mentioned sulfhydrylation preparation method for bentonite：Will
Bentonite, the ethanol solution of sulfhydryl compound, sodium metasilicate and water mixing, are made into after mixed liquor, stirring reaction, scrubbed, filtering,
Dry obtained sulfhydrylation bentonite；Wherein, the ethanol solution of sulfhydryl compound is that sulfhydryl compound is dissolved in ethanol to prepare
Form, the ethanol solution of sulfhydryl compound is 1 by volume by sulfhydryl compound and ethanol:19~99 prepare；Due to the present invention
Seldom, preferably sulfhydryl compound is 1 by volume with ethanol to the mercapto reagent used:99 prepare.
Wherein, bentonite can be calcium-base bentonite.
Further, it is characterised in that the liquid-solid ratio of mixed liquor is 15~25mL:1g；It is preferred that liquid-solid ratio is 20mL:1g,
That is (volume of the volume of sulfhydryl compound+absolute ethyl alcohol volume+water):(quality of bentonitic weight+sodium metasilicate)=15~
25mL:1g；Preferably, (quality of bentonitic quality+sodium metasilicate):(the volume of sulfhydryl compound+absolute ethyl alcohol volume+water
Volume)=1g:20mL.Wherein, the usual density of 3- mercaptopropyl trimethoxysilanes is 1.057g/mL (room temperature).
Further, mixed liquor pH value is adjusted to 8~10；It is preferred that pH is 9.5~10.
Further, mixing time is at least 6h；It is preferred that 6h.
The invention solves the problems that the 3rd technical problem be obtained restoration of soil polluted by heavy metal sulfhydrylation bentonite
Application in heavy metal adsorption.
Beneficial effects of the present invention：
1st, the sulfhydrylation bentonite cost of restoration of soil polluted by heavy metal produced by the present invention is low, and cost performance is high.By adding
Plus auxiliary modifier sodium metasilicate, and regulation technological parameter, it is only that previous invention is special in 3- mercaptopropyl trimethoxysilane consumptions
In the case of 1/5th of profit, it can reach suitable to cadmium saturated adsorption capacity.
2nd, sulfhydrylation bentonite produced by the present invention is high to the adsorption rate of cadmium, in 0.1mol/L KNO3In the presence of, to cadmium
Saturated adsorption capacity reach more than 38mg/g, and acid solution is low to its desorption efficiency, and the material also has selectivity well.
3rd, method of modifying of the present invention is carried out on bentonite original soil, it is not necessary to acidifying in advance, is simplified preparation technology, is saved
The cost of acid, will not also produce waste liquor contamination environment.
4th, the sulfhydrylation bentonite of restoration of soil polluted by heavy metal produced by the present invention, is passivated with good soil and repairs
Effect, it is particularly possible to the content of soil available heavy metal such as cadmium is greatly reduced.Energy is fixed in absorption to heavy metal in soil
Power is good, and is difficult to be extracted.
5th, soil-repairing agent of the present invention is applied in crop growth period, can effectively reduces content of beary metal in crop.
Brief description of the drawings
Fig. 1 bentonites original soil (calcium base soil) and the bentonitic infrared spectrogram of sulfhydrylation, wherein MMT-SH is sulfhydrylation
Bentonite, MMT is calcium base soil.
XRD before and after Fig. 2 is bentonite modified, wherein MMT-SH are Modified soil, and MMT is calcium base soil.
Influence of Fig. 3 pH value of solution to modified effect.
Influence of Fig. 4 amount of sodium silicate to modified effect.
Influence of Fig. 5 liquid-solid ratioes to modified effect.
Influence of Fig. 6 reaction time to modified effect.
Fig. 7 sulfydryl bentonites are to Cd2+Saturated extent of adsorption.
Fig. 8 bentonite original soils are to Cd2+Saturated extent of adsorption.
Fig. 9 different amounts modifying agent sulfydryl bentonites are to Cd2+Saturated extent of adsorption：Bentonite original soil and 3- mercapto propyl group front threes
TMOS mass ratio is 1:0.05,1:0.1,1:0.2.
Embodiment
The invention solves the problems that first technical problem be to provide a kind of cheap restoration of soil polluted by heavy metal
Sulfhydrylation bentonite.
A kind of sulfhydrylation bentonite of restoration of soil polluted by heavy metal, is mixed by bentonite, sulfhydryl compound and sodium metasilicate
Reaction is made；Wherein, the weight proportion of bentonite, sulfhydryl compound and sodium metasilicate is：1:0.05~0.2:0.06~0.10.Plus
Entering the effect of sodium metasilicate has three：1st, sodium metasilicate is a kind of sodium agent, is removed after calcium base soil is changed into sodium base soil, sodium modification
Impurity between bentonite bed, cadmium ion is easier to react into interlayer, improves modified effect；2nd, the silicon in sodium metasilicate
Sulfonate groups are negatively charged, can neutralize bentonitic end face positive charge, cadmium cation is more easily by electrostatic attraction close to swollen
Profit soil reacts；3rd, sodium metasilicate is a kind of surfactant, also serves as a kind of dispersant, makes bentonite in modifying process,
Dispersiveness, suspension are more preferable.
If when preparing the sulfhydrylation bentonite of the present invention, sodium metasilicate is not added with, using only 3- mercapto propyl trimethoxy silicon
(bentonite is 1 with mercapto reagent amount ratio when alkane is individually modified：0.05), its adsorption rate is only 16.37%, and modified effect is not
Good, with the increase of sodium metasilicate addition, its adsorption rate gradually increases, when certain value is increased to, its adsorption rate with
The increase of amount of sodium silicate and be held essentially constant.When the consumption of sodium metasilicate is 6% with bentonitic amount ratio, its Modified soil
Adsorption rate to 10mg/L cadmium ions reaches 94.39%, and 4.77 times are improved than single modification, and desorption efficiency is low.Therefore, exist
In the case of considering properties of product and cost, it is preferably that the weight proportion of bentonite, sulfhydryl compound and sodium metasilicate is 1:0.05
~0.1:0.06~0.08, more preferably, bentonite:Sulfhydryl compound:Sodium metasilicate=1:0.05:0.06.
Above-mentioned sulfhydryl compound is one kind in 3- mercaptopropyl trimethoxysilanes or 3- mercaptopropyltriethoxysilanes.
The invention solves the problems that second technical problem be to provide a kind of above-mentioned sulfhydrylation preparation method for bentonite, this
The consumption of mercapto reagent is greatly reduced in sulfhydryl modified method, and modified effect is improved by adding auxiliary modifier sodium metasilicate.
Sulfhydrylation preparation method for bentonite：Bentonite, the ethanol solution of sulfhydryl compound, sodium metasilicate and water are mixed,
It is made into after mixed liquor, stirring reaction, scrubbed, filtering, dry obtained sulfhydrylation bentonite；Wherein, the ethanol of sulfhydryl compound
Solution is that sulfhydryl compound is dissolved in ethanol to be formulated, and the ethanol solution of sulfhydryl compound is by sulfhydryl compound and ethanol
It is 1 by volume:19~99 prepare；Because the mercapto reagent that the present invention is used is seldom, preferably sulfhydryl compound presses body with ethanol
Product is than being 1:99 prepare.
Wherein, bentonite can be calcium-base bentonite.
Because mixed liquor liquid-solid ratio is bigger, modified effect can be more bad, and its desorption efficiency is also bigger, i.e., easier to be solved
Suction is got off, it is preferred, therefore, that the liquid-solid ratio of mixed liquor is 15~25mL:1g；Preferred mixed liquor liquid-solid ratio is 20mL:1g.
It is 20mL in liquid-solid ratio:1g, its modified effect is best, and its desorption efficiency is also very low.
In addition, when pH of mixed is less than 8, pH is bigger, and its adsorption effect to cadmium ion is also become better and better, but as its pH
Value is increased to after 10.00, and the adsorption rate of cadmium ion is reduced with the increase of pH value；When pH value is between 8-10, it is inhaled
Attached rate can reach more than 94%；Adsorption effect is not fine under the conditions of original solution pH value (about 11.57).Therefore, one is entered
Step, mixed liquor pH value is adjusted to 8~10, the experiment condition of comprehensive each side, the pH value of modified alta-mud is adjusted to 9.50-
10.00 between it is best.
Because the mixed liquor stirring reaction time is longer, its adsorption effect is also better, is also less susceptible to be desorbed.When
Between in 4 to 5 hours when, although its degree of modification all reaches more than 98%, but its desorption efficiency is relatively large, therefore mixing time
Preferably at least 6h；For cost-effective, preferably 6h.
The invention solves the problems that the 3rd technical problem be obtained restoration of soil polluted by heavy metal sulfhydrylation bentonite
Application in heavy metal adsorption.Particularly in the case where actual environment has various interference, cadmium pollution soil repair is passivated
Application.
The optimization preparation technology of sodium metasilicate of the present invention and sulfhydryl compound composite modified bentonite is：Using bentonite origin
Soil, 3- mercaptopropyl trimethoxysilanes and sodium metasilicate are composite modifier, bentonite original soil and 3- mercaptopropyl trimethoxysilanes
Weight proportion is 1:0.05, sodium metasilicate is 6% with bentonitic mass ratio；Reaction liquid-solid ratio is 20mL:1g；Modified suspension
Optimal pH is 9.50-10.00；Modification time is 6h.When solution cadmium initial concentration content is 10mg/L, sulfydryl bentonite is to cadmium
Adsorption rate can be up to more than 98%, acid rain desorption efficiency is below 1%；(the i.e. 0.1mol/L in the environment with the presence of competing ions
KNO3Solution), the saturated adsorption capacity to cadmium is 20.86mg/g (room temperature), is 20 times of original soil saturated adsorption capacity or so.
The embodiment of the present invention is further described with reference to embodiment, not therefore by present invention limit
System is among described scope of embodiments.
In following examples, the percentage composition of 3- mercaptopropyl trimethoxysilane ethanol solutions refers both to volume ratio.
The sulfhydrylation of embodiment 1 is bentonitic to prepare (1#), bentonite original soil and 3- mercaptopropyl trimethoxysilane mass ratioes
For 1:0.05.
2.00g bentonites original soil is weighed in 100mL small beakers, 10mL 1% 3- mercaptopropyl trimethoxysilanes are added
Ethanol solution and 0.12g sodium metasilicate powder, adding a certain amount of distilled water makes the solid-to-liquid ratio of system be 1g:20mL, is mixed, regulation
PH value of solution is 9.50~10.00, at room temperature after stirring reaction 6h, is washed with distilled water to neutrality, suction filtration, 40 DEG C of drying, grinding
80 mesh sieves are crossed, sulfhydrylation bentonite is made.
Sulfhydrylation bentonite is shown in Fig. 1 with the native infrared spectrogram of bentonite calcium base.As seen from Figure 1, with calcium-base bentonite
(MMT) compare, sulfhydrylation bentonite (MMT-SH) occurs in that C-H stretching vibration peaks 2900, occur in that S-H's is flexible 2560
Vibration peak.The change of bentonitic infared spectrum shows bentonite surface by successfully organic functional after before modified, in grafting
(CH3O)3(CH2)3SH。
Bentonite calcium base soil is shown in Fig. 2 with sulfhydrylation bentonite XRD.It can be learnt by Fig. 2：Modified sulfhydrylation bentonite
XRD (MMT-SH) compared with the XRD (MMT) of calcium-base bentonite, without new in one 70 ° of whole range of diffraction of the angle of diffraction 5 °
Diffraction maximum occur, illustrate that modified sulfhydrylation bentonite has remained in that the crystalline phase of bentonite original soil is constituted, without new crystal
Compound is generated.The interlamellar spacing d of other modified alta-mud has reduced compared with original soil, it may be possible to sodium metasilicate is added in sample, and
Part divalent ion between the replaceable bentonite bed of sodium ion, such as Ca2+Deng.The hydrated radius of 1 valency sodium ion is smaller than divalent ion, makes
Its spacing diminishes.Therefore interlamellar spacing is modified has reduced, meet sodium modification feature.
The sulfhydrylation of embodiment 2 is bentonitic to prepare (2#), bentonite original soil and 3- mercaptopropyl trimethoxysilane mass ratioes
For 1:0.1.
2.00g bentonites original soil is weighed in 100mL small beakers, 10mL 2% 3- mercaptopropyl trimethoxysilanes are added
Ethanol solution and 0.12g sodium metasilicate powder, adding a certain amount of distilled water makes the solid-to-liquid ratio of system be 1g:20mL, is mixed, regulation
PH value of solution is 9.50~10.00, at room temperature after stirring reaction 6h, is washed with distilled water to neutrality, suction filtration, 40 DEG C of drying, grinding
80 mesh sieves are crossed, sulfhydrylation bentonite is made.
The sulfhydrylation of embodiment 3 is bentonitic to prepare (3#).Bentonite original soil and 3- mercaptopropyl trimethoxysilane mass ratioes
For 1:0.2.
2.00g bentonites original soil is weighed in 100mL small beakers, 10mL 4% 3- mercaptopropyl trimethoxysilanes are added
Ethanol solution and 0.12g sodium metasilicate powder, adding a certain amount of distilled water makes the solid-to-liquid ratio of system be 1g:20mL, is mixed, regulation
PH value of solution is 9.50~10.00, at room temperature after stirring reaction 6h, is washed with distilled water to neutrality, suction filtration, 40 DEG C of drying, grinding
80 mesh sieves are crossed, sulfhydrylation bentonite is made.
The sulfhydrylation of embodiment 4 is bentonitic to prepare (4#)
2.00g bentonites original soil is weighed in 100mL small beakers, 10mL 2% 3- mercaptopropyltriethoxysilanes are added
Methanol solution and 0.16g sodium metasilicate powder, adding a certain amount of distilled water makes the solid-to-liquid ratio of system be 1g:20mL, is mixed, regulation
PH value of solution is 9.50~10.00, at room temperature after stirring reaction 6h, is washed with distilled water to neutrality, suction filtration, 40 DEG C of drying, grinding
80 mesh sieves are crossed, sulfhydrylation bentonite is made.
Embodiment 5~8 be under different condition the sulfhydrylation bentonite for preparing to Cd2+Adsorption rate and Simulated Acid Rain desorption
As a result test.
The pH of embodiment 5 influence
2.00g bentonite original soils are weighed in beaker, the ethanol of 10mL 1% 3- mercaptopropyl trimethoxysilanes is added
Solution and 0.12g sodium metasilicate, adding distilled water makes the solid-to-liquid ratio of reaction system be 1g:20mL, stirs, and adjusts pH value of solution
Respectively 4.00,6.00,8.00,10.00,11.57 (not adjusting), 13.00, are stirred at room temperature reaction 6h, are washed with distillation
Wash to neutrality, suction filtration, sulfhydrylation bentonite is made in 40 DEG C of drying, ground 80 mesh sieve.
Obtained sulfhydrylation bentonite is to Cd2+Absorption and the desorption result of Simulated Acid Rain see Fig. 3.
As seen from Figure 3, during pH=8, adsorption rate is 94.684%, and desorption efficiency is 0.036%,；During pH=10, absorption
Rate is 97.498%, and desorption efficiency is 0.047%.
When pH value is between 8-10, its adsorption rate can reach more than 94%；When pH value is 9.50-10.00, change
Property bentonite adsorption rate be more than 98%.
The influence of the amount of sodium silicate of embodiment 6
2.00g bentonite original soils are weighed in beaker, the ethanol of 10mL 1% 3- mercaptopropyl trimethoxysilanes is added
Solution and sodium metasilicate, adding distilled water makes the solid-to-liquid ratio of reaction system be 1g:20mL, changes amount of sodium silicate (to bentonite
The percentage by weight of original soil), respectively 2%, 4%, 6%, 7%, 8%, 9%, 10%, 12.5%, stir, adjust solution
PH is 9.50-10.00, and reaction 6h is stirred at room temperature, and is washed with distilled water to neutrality, suction filtration, 40 DEG C of drying, ground 80 mesh
Sieve, is made sulfhydrylation bentonite.
Obtained Modified soil is to Cd2+Absorption and the desorption result of Simulated Acid Rain see Fig. 4.
As seen from Figure 4, the Modified soil for not adding sodium metasilicate is only 16.3% to the adsorption rate of 10mg/L cadmium ions,
When the consumption of sodium metasilicate is 6% with bentonitic amount ratio, its Modified soil reaches to the adsorption rate of 10mg/L cadmium ions
94.39%.When the consumption of sodium metasilicate is 8% with bentonitic amount ratio, adsorption rate reaches 98.6%, and as sodium metasilicate is used
The increase of amount, adsorption rate also increases.
Embodiment 7 reacts the influence of liquid-solid ratio
2.00g bentonite original soils are weighed in beaker, the ethanol of 10mL 1% 3- mercaptopropyl trimethoxysilanes is added
Solution and 0.12g sodium metasilicate, adding distilled water makes the solid-to-liquid ratio of reaction system be 1g:20mL, 1g:30mL, 1g:40mL, 1g:
50mL, 1g:60mL, stirs, and regulation pH value of solution is 9.50-10.00, and reaction 6h is stirred at room temperature, with distillation water washing
To neutral, suction filtration, 40 DEG C of drying, sulfhydrylation bentonite is made in ground 80 mesh sieve.
Obtained Modified soil is to Cd2+Absorption and the desorption result of Simulated Acid Rain see Fig. 5.
As seen from Figure 5, it is 20mL in liquid-solid ratio:1g, when ie in solution volume is 40mL, its modified effect preferably, is inhaled
Attached rate is 98.4%, and its desorption efficiency is also very low, less than 0.09%.
The influence of the modification time of embodiment 8
2.00g bentonite original soils are weighed in beaker, the ethanol of 10mL 1% 3- mercaptopropyl trimethoxysilanes is added
Solution and 0.12g sodium metasilicate, adding distilled water makes the solid-to-liquid ratio of reaction system be 1g:20mL, stirs, and adjusts pH value of solution
For 9.50-10.00, stirring reaction 4h, 5h, 6h respectively, is washed with distilled water to neutrality, suction filtration, 40 DEG C of drying are ground at room temperature
Honed 80 mesh sieve, is made sulfhydrylation bentonite.
Obtained Modified soil is to Cd2+Absorption and the desorption result of Simulated Acid Rain see Fig. 6.
As seen from Figure 6, when the time is in 4 to 5 hours, adsorption rate all reaches more than 98%, but its desorption efficiency
It is relatively large；When being more than 6 hours the time, adsorption rate is more than 99.4%, and desorption efficiency is about 0.1%, and the reaction time is longer, and it is inhaled
Attached effect is also better, is also less susceptible to be desorbed.
Saturated adsorption capacity (the 0.1mol/L KNO of the sulfhydrylation bentonite of embodiment 9 and bentonite original soil to cadmium3In the presence of
Under)
0.1250g sulfhydrylations bentonite accurately is weighed in the conical flask that 50mL is dried, and adds deionized water and 1.0mol/
LKNO3, make the KNO of solution3Concentration is 0.10mol/L, and regulation pH value of solution is 6.0, then is separately added into a series of different containing cadmium concentration
Solution, composite sample solution final total volume be 25mL.At room temperature after constant temperature oscillation adsorption reaction 60min, constant temperature is static
16h, is transferred in centrifuge tube, 3500r/min centrifugation 10min, takes supernatant liquor atomic absorption spectroscopy determination cadmium to put down
Weigh concentration.Similarly, the saturation to cadmium for doing original soil is adsorbed.
1# sulfhydrylations bentonite is shown in Fig. 7 Fig. 8 with bentonite original soil absorption result.
1#, 2#, 3# modified alta-mud made from embodiment 1~3 are tested to the saturated adsorption capacity of cadmium, and adsorbance is shown in Fig. 9.
With the continuous rise of cadmium initial concentration it can be seen from Fig. 7, Fig. 8, sulfydryl bentonite and bentonite original soil are to cadmium
Adsorption capacity all gradually increase, finally tend to balance, reach saturation state.Contrast two kinds of bentonites, 1# sulfydryl bentonites pair
The saturated extent of adsorption of cadmium be 20.86mg/g, original soil only 1mg/g, bentonite through mercapto reagent and sodium metasilicate it is composite modified after
Adsorption capacity to cadmium is greatly improved, and saturated adsorption capacity is than high 20 times.
Fig. 9 can be seen that 1# sulfhydrylations bentonite is 20.42mg/g, 2# sulfhydrylation bentonites pair to the saturated extent of adsorption of cadmium
The saturated extent of adsorption of cadmium is 31.20mg/g；3# sulfhydrylations bentonite is 37.96mg/g to the saturated extent of adsorption of cadmium.
In addition, 4# sulfhydrylations bentonite is 30.98mg/g to the saturated extent of adsorption of cadmium, with 2# sulfhydrylation bentonites to cadmium
Saturated extent of adsorption is basically identical, therefore does not represent on the diagram.
Sulfydryl-montmorillonite made from the original scheme of comparative example 1 (i.e. the Chinese patent of Application No. 201210139593.0)
Complex material is tested to the saturated adsorption capacity of cadmium.
2 parts of sulfydryls as made from original scheme-montmorillonite Complex material 0.1250g accurately is weighed, D1, D2 examination is designated as
Sample, D1 samples are measured in the solution for do not interfere with ion, KNOs of the D2 in 0.1mol/L3In the presence of be measured.
In the conical flask that 0.125g D1 samples are placed in 50mL dryings, deionized water is added, regulation pH value of solution is 6.0, then
A series of different solution containing cadmium concentration are separately added into, composite sample solution final total volume is 25mL.Constant temperature shakes at room temperature
Swing after adsorption reaction 60min, the static 16h of constant temperature is transferred in centrifuge tube, 3500r/min centrifugation 10min take supernatant liquor to use
Atomic absorption spectroscopy determination cadmium equilibrium concentration.After measured, D1 samples sulfydryl-montmorillonite Complex material is to Cd2+It is full
It is 67.9mg/g with adsorbance, it is consistent with the saturated extent of adsorption of original record.
In the conical flask that 0.125g D2 samples are placed in 50mL dryings, deionized water and 1.0mol/L KNO are added3, make
The KNO of solution3Concentration is 0.10mol/L, and regulation pH value of solution is 6.0, then is separately added into a series of different solution containing cadmium concentration,
Composite sample solution final total volume is 25mL.At room temperature after constant temperature oscillation adsorption reaction 60min, the static 16h of constant temperature, transfer
Into centrifuge tube, 3500r/min centrifugation 10min take supernatant liquor atomic absorption spectroscopy determination cadmium equilibrium concentration.Through
Determine, D1 samples sulfydryl-montmorillonite Complex material is to Cd2+Saturated extent of adsorption be 37.82mg/g.
The experiment of comparative example 1 is it is known that due to KNO in solution3Presence, the saturation of composite can be influenceed to adsorb
Amount.KNO of sulfydryl made from the original scheme-montmorillonite Complex material in 0.1mol/L3In the presence of in the environment of, it is to Cd2+'s
Saturated extent of adsorption is 37.82mg/g.
By embodiment 9 and comparative example 1 test it can be seen from 3- mercapto propyl trimethoxy silicon used in 1# sulfhydrylation bentonites
Alkane consumption is 1st/20th of original scheme, and consumption reduces 95%, but its saturated adsorption capacity to cadmium is only than original
There is scheme to reduce 46%, greatly save cost, cost performance is high.In addition, experiment shows to increase amount of modifier, make bentonite
It is 1 with the ratio between modifying agent：When 0.2 (i.e. 3# sulfhydrylations bentonite), i.e. amount of modifier are 1/5th of original scheme, saturation
Adsorption capacity is material modified suitable with original scheme, and saturated extent of adsorption is 37.96mg/g.
Reparation application of the embodiment 10 in cadmium pollution soil and lead cadmium combined pollution soil
First, experiment prepares：Soil collection is near Chengdu University of Technology dove tree garden, and through XRF measuring, it is led
Want composition as shown in table 1.
The dove tree Orchard Soil main component of table 1
| Project | Na2O (%) | MgO (%) | Al2O3(%) | SiO2(%) | K2O (%) | CaO (%) | Fe2O3(%) | MnO (%) |
| Numerical value | 0.65 | 1.45 | 19.55 | 68.02 | 2.45 | 1.27 | 5.35 | 0.095 |
| Project | P2O5(%) | TiO2(%) | Cr2O3(%) | SO3(%) | ZrO2(%) | Rb2O (%) | ZnO (%) | SrO (%) |
| Numerical value | 0.12 | 0.88 | 0.047 | 0.045 | 0.034 | 0.016 | 0.014 | 0.013 |
(1) preparation of cadmium pollution soil
After soil collection, natural air drying is milled, and crosses 20 mesh sieves, standby.To analyze pure Cd (NO3)2·4H2O prepares water-soluble
Liquid, weighs 50g soil, be separately added into soil cadmium solution make in soil cadmium content be 0,0.5,1,2,5mg/kg, solid-to-liquid ratio
For 1g:1mL, is fully mixed, and is cultivated at 8-10 DEG C 2 months, is made external source because of the moisture content of evaporation loss with weighing method supplement weekly
Cadmium reaches stable equilibrium with soil interaction.
(2) preparation of lead cadmium combined pollution soil
Cadmium solution and lead solution are sequentially added in soil, make in soil cadmium content be, 0,0.5,1,2,5mg/kg, lead contains
Amount is respectively 0,50,200,500,1000mg/kg, fully mix, remaining preparation method with cadmium pollution soil.
2nd, repairing test
Series 1：In the simulation cadmium pollution of different cadmium concentrations and the soil of lead cadmium combined pollution respectively plus 0.5g is 1% to change
Property bentonite the 1# sulfhydrylations bentonite of embodiment 1 (this experiment using), fully mix, supplement evaporation loss with weighing method weekly
Moisture, at 8-10 DEG C cultivate 1 month, air-dry, cross 60 mesh sieves, the available Cd content of sampling analysis each sample.
Series 2：Add 1% bentonite origin respectively in the simulation cadmium pollution of different cadmium concentrations and the soil of lead cadmium combined pollution
Soil, remaining homologous series 1.
Series 3：Any material is not added with the simulation cadmium pollution of different cadmium concentrations and the soil of lead cadmium combined pollution, remaining
Homologous series 1.
3rd, in soil cadmium extracting method
Mixing extractant is 0.005mol/L DTPA+0.01mol/L CaC12+0.1mo/L TEA.Weigh 1.967g
DTPA is dissolved in 14.92g (13.3mL) TEA and a small amount of water, then by 1.11g CaC12It is soluble in water, 1000mL appearances are transferred in the lump
In measuring bottle, about 950mL is added water to, pH to 7.3 is adjusted with 6mol/L HC1, finally uses distilled water constant volume, be stored in plastic bottle.
2g pedotheques are weighed, 20mL extractants are added, 25 DEG C of vibration 60min are transferred in centrifuge tube, 2500r/min
30min is centrifuged, cadmium concentration in extract solution is determined with ICP-MS.The extraction cadmium amount mg/ of every gram of contaminated soil is calculated according to cadmium concentration
kg。
4th, result
It is as shown in table 2 that single cadmium pollution soil cadmium extracts result
Table 2. mixes extraction result of the extractant to the cadmium in cadmium pollution soil
As shown in Table 2, the stronger mixing extractant of (1) extractability can extract the cadmium in three serial pedotheques
Go out a part, and with the cadmium amount increase of addition, the cadmium amount of extraction also increases.(2) it is not added with material modified and adds bentonite origin
In the cultivate soil of soil, the cadmium amount that different cadmium additions are extracted is substantially suitable, illustrates that bentonite original soil does not have soil blunt
Change performance.(3) cadmium concentration extracted in the cadmium pollution soil for having added MMT-SH, which is far below, have been added bentonite original soil and not to have had
Plus the soil sample of any material, when adding identical cadmium amount, plus bentonite original soil and without the extraction in the soil for adding any material
Cadmium amount is very big, is add sulfhydryl modified bentonite soil extract amount 10-50 times.
The extraction of lead cadmium combined pollution Cadmium in Soil the results are shown in Table 3
Table 3 mixes extraction result of the extractant to the cadmium in lead cadmium pollution soil
As shown in Table 3, the result one that the experimental result that cadmium lead combined contamination soil is obtained is obtained with single cadmium pollution soil
Cause.The cadmium amount that simply each series is extracted is more some larger than the cadmium amount that single cadmium pollution is extracted, and this is probably because lead is by sticking
It is fixed on modified alta-mud, have impact on the fixation of cadmium.(1) the stronger mixing extractant of extractability can be by three series soil
Cadmium in earth sample extracts a part, and with the cadmium amount increase of addition, the cadmium amount of extraction also increases.(2) it is not added with being modified material
In the cultivate soil of material and addition bentonite original soil, the cadmium amount that different cadmium additions are extracted is substantially suitable, illustrates bentonite origin
Soil does not have soil inactivating performance.(3) cadmium concentration extracted in the cadmium pollution soil for having added MMT-SH, which is far below, to be added
Bentonite original soil and without plus any material soil sample, add identical cadmium amount when, plus bentonite original soil and without plus any material
Soil extract solution in cadmium amount it is very big, be plus 10-20 times of sulfhydryl modified bentonite soil extract amount.
Mixing extractant is generally used for evaluating Heavy Metals in Contaminated Soils bioactivity, with stronger extractability,
It is the extractant for available heavy metal commonly used in the world at present.This research have selected the stronger mixing of extractability and extract
Agent carries out extraction experiment, the repairing effect to evaluate sulfhydrylation montmorillonite heavy metal contaminated soil.Test result indicates that：This
The sulfhydryl modified bentonite of invention is good to the absorption crystallized ability of cadmium in soil, and is difficult to be extracted, in the soil of actual cadmium pollution
Earth passivation is repaired to be expected to obtain good effect in application.
Claims (10)
1. the sulfhydrylation bentonite of restoration of soil polluted by heavy metal, it is characterised in that by bentonite, sulfhydryl compound and sodium metasilicate
Reaction is mixed to be made；Wherein, the weight proportion of bentonite, sulfhydryl compound and sodium metasilicate is：1:0.05~0.2:0.06~
0.10。
2. the sulfhydrylation bentonite of restoration of soil polluted by heavy metal according to claim 1, it is characterised in that bentonite,
The weight proportion of sulfhydryl compound and sodium metasilicate is 1:0.05~0.1:0.06~0.08, it is preferable that bentonite, sulfhydryl compound and
The weight proportion of sodium metasilicate is 1:0.05:0.06.
3. the sulfhydrylation bentonite of restoration of soil polluted by heavy metal according to claim 1 or 2, it is characterised in that sulfydryl
Compound is one kind in 3- mercaptopropyl trimethoxysilanes or 3- mercaptopropyltriethoxysilanes.
4. the sulfhydrylation preparation method for bentonite of the restoration of soil polluted by heavy metal described in any one of claims 1 to 3, it is special
Levy and be, bentonite, the ethanol solution of sulfhydryl compound, sodium metasilicate and water are mixed, are made into after mixed liquor, stirring reaction, pass through
Washing, filtering, dry obtained sulfhydrylation bentonite；Wherein, the ethanol solution of sulfhydryl compound is to be dissolved in sulfhydryl compound
It is formulated in ethanol.
5. the sulfhydrylation preparation method for bentonite of restoration of soil polluted by heavy metal according to claim 4, its feature exists
In, sulfhydryl compound ethanol solution by sulfhydryl compound and ethanol by volume 1:19~99 are formulated；It is preferred that sulfhydrylation
Compound is 1 by volume with ethanol:99 prepare.
6. the sulfhydrylation preparation method for bentonite of the restoration of soil polluted by heavy metal according to claim 4 or 5, its feature
It is, bentonite is calcium-base bentonite.
7. the sulfhydrylation preparation method for bentonite of the restoration of soil polluted by heavy metal according to any one of claim 4~6,
Characterized in that, the liquid-solid ratio of mixed liquor is 15~25mL:1g；It is preferred that liquid-solid ratio is 20mL:1g.
8. the sulfhydrylation preparation method for bentonite of the restoration of soil polluted by heavy metal according to any one of claim 4~7,
Characterized in that, mixed liquor pH value is adjusted into 8~10；It is preferred that pH is 9.5~10.
9. the sulfhydrylation preparation method for bentonite of the restoration of soil polluted by heavy metal according to any one of claim 4~8,
Characterized in that, mixing time is at least 6h；It is preferred that 6h.
10. the sulfhydrylation bentonite of the restoration of soil polluted by heavy metal described in any one of claims 1 to 3 is in heavy metal adsorption
Application.
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