CN107497845A - A kind of Cd-polluted farmland soil is passivated restorative procedure - Google Patents
A kind of Cd-polluted farmland soil is passivated restorative procedure Download PDFInfo
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- CN107497845A CN107497845A CN201710814684.2A CN201710814684A CN107497845A CN 107497845 A CN107497845 A CN 107497845A CN 201710814684 A CN201710814684 A CN 201710814684A CN 107497845 A CN107497845 A CN 107497845A
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- soil
- cadmium
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- agricultural land
- crown ether
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
Abstract
The present invention discloses a kind of Cd-polluted farmland soil in-situ passivation restorative procedure, belongs to agricultural land soil and repairs field；The present invention is used as passivator using CNT, humic acid and the calcium magnesium phosphate of crown ether modification, successively apply in agricultural land soil, and be passivated cadmium in soil by the means such as turning over, conserving, reduce available Cd content in agricultural land soil, while reduce absorbability of the crop to cadmium.Passivator cost of the present invention is low, to agricultural land soil and crop without negative effect, passivator can both be passivated cadmium in soil, the nutrient needed for crop can be discharged again, calcium ions and magnesium ions can reduce absorption of the crop to cadmium, passivator requires relatively low to the pH environment of soil simultaneously, has the effect for repairing cadmium ion well in the environment of meta-alkalescence.
Description
Technical field
The present invention relates to a kind of Cd-polluted farmland soil to be passivated restorative procedure, belongs to agricultural land soil and repairs field.
Background technology
Cadmium is mainly derived from mining, smelting, dirty filling, atmospheric sedimentation, fertilising etc. in agricultural land soil.Cadmium is not that plant growth must
The element needed, transfer ability of the cadmium in soil is very strong, is easily absorbed by plants, so as to influence plant physiology and biochemistry index, and
The yield and quality of crop are influenceed, plant has enrichment to cadmium, and cadmium enters human body by edible grain, and cadmium is a kind of carcinogenic
Material, toxic action can be produced to human body.China large area arable land is also happened occasionally by cadmium pollution, cadmium rice time, therefore, cadmium
The repairing and treating for polluting arable land is extremely urgent.
Conventional Cd-polluted farmland soil remediation method mainly has：
(1) Soil leaching technology：With the aqueous solution washed off soil of water, acid, surfactant, chelating agent etc., by soil
Cadmium be transferred in solution, then to elution also carry out harmlessness disposing.It is small that Soil leaching technology is applied to industrial pollution place
The a small amount of heavily contaminated soil of area, it is not suitable for large area largely light polluted farmland soil, meanwhile, Soil leaching technology is easily made
Into secondary pollution, therefore, farmland cadmium pollution soil reparation does not use Soil leaching technology typically.
(2) phytoremediation technology：Phytoremediation is mainly to pass through the cadmium in Cd-hyperaccumulator Root Absorption soil, and rich
Collection after plant growth certain time, gathers in plant and carries out harmlessness disposing.The technology can be by cadmium from soil
Remove, but the phytoremediation time is longer, and planting needs land occupation, influences the normal use in soil.
(3) electro reclamation：This method is that electrode is set in cadmium pollution soil, and addition addition is lived in contaminated soil
Agent, cadmium under the function of current to movable cathode, so as to which cadmium be removed from soil.Electrode current is made in electro reclamation soil
It is shorter with distance, small area pollution is applied in general to, and agricultural land soil is pollution in wide area, processing cost is of a relatively high.
(4) soil deep tillage method：Deep turning method is to plough deeply soil to make the pollutant for being gathered in top layer be distributed to depth of soils, is applicable
In the dilution of contaminated soil and from handling, this method total amount of pollutant does not change, and form does not also change.
(5) in-situ passivation method：This method is that passivator is added in cadmium pollution soil, passes through redox, precipitation, suction
It is attached, complexing etc. principle by the cadmium in soil be converted into low transfer ability, low biological effectiveness material, to reduce cadmium in soil
Environmental risk.This method have the characteristics that cost it is low, it is quick, do not influence soil normal use.
It can be seen that in-situ passivation method repair farmland cadmium pollution can large area implement, cost is relatively low, quick, while does not influence
The features such as soil normal use and accepted extensively by people.
The content of the invention
The invention provides a kind of Cd-polluted farmland soil to be passivated restorative procedure, overcome conventionally employed humic acid repair cadmium from
Requirement of the son to soil environment pH value, can effectively reduce available Cd content in agricultural land soil in the environment of meta-alkalescence, and then
Reduce the environmental risk of cadmium pollution soil.
Technical scheme is as follows：
A kind of Cd-polluted farmland soil is passivated restorative procedure, comprises the following steps：
The first step, humic acid is stirred with calcium magnesium phosphate in proportion together with, be configured to Mixed Surfactant System；
Second step, farmland is tentatively turned over using Cultivator, ploughed depth is mainly farming operation region；
3rd step, the CNT that the crown ether of preparation is modified uniformly is sowed in plowed soils using planting machine, and
Turned over repeatedly with Cultivator, the CNT of crown ether modification and agricultural land soil are sufficiently mixed, conserved 2~4 days；
4th step, the Mixed Surfactant System of preparation is uniformly sowed in plowed soils using the machine of sending out, with Cultivator repeatedly
Turn over, Mixed Surfactant System and soil are sufficiently mixed；
5th step, after the completion of turning over, to passivation restoring area soil sprinkler irrigation water to saturation, and conserve 15~20
My god, normal use is completed in maintenance.
Preferably：The mass ratio of two kinds of compositions of the Mixed Surfactant System of the preparation is：Humic acid: calcium magnesium phosphate 1~5:
1。
Preferably：Mixed Surfactant System addition is the 1~10% of agricultural land soil amount in the agricultural land soil.
The dosage for the CNT that crown ether is modified is 0.3%~0.5% in the agricultural land soil.
The preparation method of the CNT of crown ether modification is specially：
The first step, the acidifying of CNT, 5g multi-walled carbon nanotubes are often taken to be placed in 50ml hydrochloric acid and sulfuric acid mixed system
In, the volume ratio of hydrochloric acid and sulfuric acid is 2: 1, hydrochloric acid using 37% concentrated hydrochloric acid, sulfuric acid using 98% the concentrated sulfuric acid,
Ultrasound environments are shaken, and multi-walled carbon nanotube is uniformly dispersed in nitration mixture, are heated to 40 DEG C of stirring reactions 4 hours, are cooled to room
Temperature, add the deionized water dilute solution of 5 times of nitration mixture volumes, filter, the CNT after acidifying is cleaned 3 times with deionized water, gone out
Remove acid remaining in CNT, product 70 DEG C of dryings 24 hours under 0.1Mpa vacuum environments, obtain the smooth solid in surface；
Second step, the 10g coronal ether compounds prepared are dissolved in DMF 70ml, ultrasonic oscillation
25 minutes, fully dissolving, filtering, obtain yellow solution, the multi-walled carbon nanotube of 8g acidifyings prepared by the first step are added, at 35 DEG C
Under the conditions of ultrasonic vibration 1 hour, dissolve CNT, obtain the CNT of homogeneous phase solution, as organic decoration.
The preparation method of crown ether is as follows：
The first step, by 1mol 2, double (methylol) phenol of 6- are dissolved in 50ml dichloromethanes with 1mol 2,2- dimethylpropanes
In alkane solution, triflate catalyst 0.05mol is added, reaction 2 hours, filtering is stirred at room temperature, solution steams in rotation
Concentrated on hair instrument, obtain solid fraction compound 1, i.e. (2,2,6- trimethyl -4H-1,3- benzo dioxin -8- methyl) methanol；
Second step, 1mol (2,2,6- trimethyl -4H-1, the 3- benzo dioxin -8- methyl) methanol for taking the first step to obtain
It is dissolved in 40ml dichloromethane solutions, adds 1mol pyridine chlorochromates and carry out acetalation, it is small that reaction 1.5 is stirred at room temperature
When, filtering, solution concentrates on a rotary evaporator, obtains solid fraction compound 2, i.e. (2,2,6- trimethyl -4H-1,3- benzos two
Dislike English -8- methyl) formaldehyde；
3rd step, (2,2,6- trimethyl -4H-1,3- benzo dioxin -8- methyl) formaldehyde prepared by 1mol second steps
It is dissolved in 65ml n-hexanes, leads to bromination hydrogen, minute ventilation volume 80ml, realize deprotection and Benzylphosphonium Bromide, filter, it is molten
Liquid concentrates on a rotary evaporator, obtains solid fraction compound 3, i.e. 3- (bromomethyl) -2- hydroxyl -5- benzaldehydes；
4th step, 1mol O are taken, O '-bis- (2- hydroxy ethoxies) benzene, are dissolved in 50ml tetrahydrofuran solutions, then added
2.2mol3- (bromomethyl) -2- hydroxyl -5- benzaldehydes and 0.05mol sodium hydrides, it is stirred at room temperature 30 minutes, filters, it is molten
Liquid concentrates on a rotary evaporator, and acquisition solid fraction compound 4, i.e., 3,3 '-((((1,2- phenylene two (oxo)) two (ethane -2,
1- diyls)) two (oxos)) two (methylene)) two (2- hydroxy-5-methyl base benzene (first) aldehyde)；
5th step, the compound 4 for taking the steps of 1mol the 4th to prepare are dissolved in 110ml ethanol, then add 2.5mol 1- pyrenes
Methylamine hydrochloride, it is heated to 60 DEG C and stirs 1 hour, be down to room temperature, 0 DEG C static 2 hours, and filtering, solution is on a rotary evaporator
Concentration, obtain solid fraction compound 5, i.e. 2- ((E)-(((3a1,5a1- dihydropyrene -1- bases) methyl) imino group) methyl) -6- ((2-
(2- (2- ((2- hydroxy-5-methyl bases -3- ((E)-((pyrene -1- ylmethyls) imino group) methyl) benzyl) oxo) ethyoxyl) benzene
Epoxide) ethyoxyl) methyl) -4- methylphenols.
The present invention has the characteristics that compared with prior art：
(1) CNT that the present invention is modified with crown ether is mixed with soil in advance, utilizes the hat on CNT
Shape ether is easier to be combined with divalent cadmium ion in slight alkali environment, prevents cadmium ion from forming hydroxyl cadmium in alkaline annular
Ion, and the combination later stage between crown ether and divalent cadmium ion is substituted by humic acid, so as in more preferable rehabilitating soil
Cadmium ion；
(2) for the present invention using humic acid as a kind of passivator, humic acid is a kind of complicated natural high molecular polymer,
Being added in soil will not adversely affect to soil, and the principle such as humic acid is by adsorbing, being complexed, chelating, reduction is blunt
Change cadmium in agricultural land soil, while humic acid is not easy to decompose for Institute of Micro-biology, cadmium is not easy to be discharged by microbiological effect after passivation；
(3) for the present invention using calcium magnesium phosphate as a kind of passivator, calcium magnesium phosphate is a kind of slow-release fertilizer, and nutrient is thrown at it
Slowly release after adding, reduces influence of the nutrient to environment, the phosphate radical of calcium magnesium phosphate release can be formed with cadmium solubility product compared with
Small compound, is passivated cadmium, meanwhile, calcium magnesium element is contained in calcium magnesium phosphate, there is antagonism to absorption of the crop to cadmium,
Reduce uptake of the plant to cadmium；
(4) present invention is used in mixed way with humic acid and calcium magnesium phosphate, and humic acid and calcium magnesium phosphate in itself all can be as cadmiums
Passivator, while humic acid and calcium magnesium phosphate mix and apply and nutrient can be promoted to discharge, and can both strengthen the passivation effect to cadmium,
Nutrient can be provided to crop by having.
Brief description of the drawings
Fig. 1 is ultraviolet-absorbable spectrogram of the CNT of crown ether modification；
Fig. 2 is the transmission electron microscope figure of the CNT before crown ether modification；
Fig. 3 is the transmission electron microscope figure of the CNT after crown ether modification.
Embodiment
The present invention provides a kind of Cd-polluted farmland soil passivation restorative procedure, comprises the following steps：
The first step, humic acid is stirred with calcium magnesium phosphate in proportion together with, be configured to Mixed Surfactant System；
Second step, farmland is tentatively turned over using Cultivator, ploughed depth is mainly farming operation region；
3rd step, the CNT that the crown ether of preparation is modified uniformly is sowed in plowed soils using planting machine, and
Turned over repeatedly with Cultivator, the CNT of crown ether modification and agricultural land soil are sufficiently mixed, conserved 2~4 days；
4th step, the Mixed Surfactant System of preparation is uniformly sowed in plowed soils using the machine of sending out, with Cultivator repeatedly
Turn over, Mixed Surfactant System and soil are sufficiently mixed；
5th step, after the completion of turning over, to passivation restoring area soil sprinkler irrigation water to saturation, and conserve 15~20
My god, normal use is completed in maintenance.
Preferably：The mass ratio of two kinds of compositions of the Mixed Surfactant System of the preparation is：Humic acid: calcium magnesium phosphate 1~5:
1。
Preferably：Mixed Surfactant System addition is the 1~10% of agricultural land soil amount in the agricultural land soil.
The dosage for the CNT that crown ether is modified is 0.3%~0.5% in the agricultural land soil.
Added Cadmium enters soil, can be changed into other forms, absorption of the soil to cadmium and the organic nothing of soil by adsorption by soil
The factors such as machine component, soil aciditiy are closely related.Natural organic substance humic acid (also known as humic acid) is a kind of absorption well
Into the material of the heavy metal cadmium ion in soil, humic acid is complicated, containing a variety of functional groups, is dissolved in alkaline solution,
But insoluble in acid solution.Because humic acid has multiple functions group, various active is showed in soil, is handed over by ion
Change, the complexing to metal ion and oxidation-reduction reaction, the heavy metal cadmium ion in soil of degrading, especially humic acid conduct
A kind of weak acid, its carboxyl are complexed with cadmium ion, form Coordinative Chemistry key, and stable presence, reduces soil in a manner of complex
The cadmium ion of free state in earth, make the presence stable in a manner of organic complex of most of cadmium ion, formed insoluble or moved
Dynamic property is poor, the material of small toxicity, so as to the cadmium ion in rehabilitating soil, reduces biological effectiveness of the cadmium ion in soil, subtracts
Few its migrates into water body, plant and other environment units.
But humic acid is hydrophilic gel, the moisture run into soil easily expands, and causes to be partly dissolved, makes itself
And the combination exchange capacity of cadmium ion weakens.
In addition, cadmium ion tends to hydrolyze in soil, hydroxyl cadmium ion (CdOH is formed+), this hydroxyl
Cadmium ion is caused in soil to be adsorbed than heavy metal cadmium ion (Cd2+) in soil it is caused absorption it is even more serious, and with
PH rising, divalence heavy metal cadmium ion further forms hydroxide precipitation, and this reduces humic acid and heavy metal cadmium
The complexing of ion, the simple heavy metal cadmium ion used in humic acid rehabilitating soil, high is required to the pH value of soil environment, generally
In acid stronger soil, generally in pH value below 5, the absorption combination of humic acid heavy metal cadmium ion is stronger, and difficult
With desorption, with the continuous enhancing of pH alkalescence, cadmium ion is prior to being hydrolyzed into hydroxyl cadmium ion (CdOH+), it is suppressed that humic acid
Ion coordination complexing.
CNT is also a kind of renovation agent of heavy metal ion in rehabilitating soil well, and CNT has very high
Mechanical property, unique Electronic Performance, big draw ratio, high chemical stability and larger reference area, existing scholar adopt
The heavy metal cadmium ion in water is eliminated with CNT, but in acid condition, H in solution+Excessive concentration, occupy absorption
The absorption of agent is located at cadmium ion and forms competitive Adsorption, causes absorption of the CNT to cadmium ion.Present inventor is in morning
Found in the research of phase, CNT is modified, modified by organo-functional group, one is formed in carbon nano tube surface
A little highly delocalized pi-electrons, reduce H caused by sour environment+Adsorbance on the carbon nanotubes, at the same heavy metal ion and this
Highly delocalized pi-electron forms π-π non-covalent bond effects and is combined a bit, obtains the CNT of functionalization, this organic decoration
Method will not cause structure to destroy CNT in itself, obtain structure-preserved functional carbon nanotubes.
In research process, it has been found that the big pi-electron conjugated system of CNT makes it easily assemble bunchy, it is difficult to shape
Into homogeneous film, acidifying modification is carried out to CNT, prevents it from assembling bunchy, turns into homogeneous film, make to repair to greatest extent
The organic matter of decorations can fully be combined with divalent cadmium ion.Acidifying modification is carried out to CNT here, is formed homogeneous
Film, also further reduce the H in the sour environment of outer rim+Introducing to modification of the CNT to cadmium ion.
Inventor's mirror crown compound of the prior art, a kind of crown compound is found by studying, it is to trivalent chromium
Ion has stable chelation, forms stable compound, is further applied to the divalent cadmium ion of the application, also
There is stable complex role well.In the present invention, the crown compound prepared by double (methylol) phenol of 2,6- is formed surely
Fixed closed loop parcel divalent cadmium ion, forms stable compound, is advantageous to the absorption of divalent cadmium ion.
The preparation method of the CNT of the crown ether modification is as follows：
The first step, the acidifying of CNT, 5g multi-walled carbon nanotubes are often taken to be placed in 50ml hydrochloric acid and sulfuric acid mixed system
In, the volume ratio of hydrochloric acid and sulfuric acid is 2: 1, hydrochloric acid using 37% concentrated hydrochloric acid, sulfuric acid using 98% the concentrated sulfuric acid,
Ultrasound environments are shaken, and multi-walled carbon nanotube is uniformly dispersed in nitration mixture, are heated to 40 DEG C of stirring reactions 4 hours, are cooled to room
Temperature, add the deionized water dilute solution of 5 times of nitration mixture volumes, filter, the CNT after acidifying is cleaned 3 times with deionized water, gone out
Remove acid remaining in CNT, product 70 DEG C of dryings 24 hours under 0.1Mpa vacuum environments, obtain the smooth solid in surface；
Second step, the 10g coronal ether compounds prepared are dissolved in DMF 70ml, ultrasonic oscillation
25 minutes, fully dissolving, filtering, obtain yellow solution, the multi-walled carbon nanotube of 8g acidifyings prepared by the first step are added, at 35 DEG C
Under the conditions of ultrasonic vibration 1 hour, dissolve CNT, obtain the CNT of homogeneous phase solution, as organic decoration.
The preparation method of crown ether is as follows：
The first step, by 1mol 2, double (methylol) phenol of 6- are dissolved in 50ml dichloromethanes with 1mol 2,2- dimethylpropanes
In alkane solution, triflate catalyst 0.05mol is added, reaction 2 hours, filtering is stirred at room temperature, solution steams in rotation
Concentrated on hair instrument, obtain solid fraction compound 1, i.e. (2,2,6- trimethyl -4H-1,3- benzo dioxin -8- methyl) methanol；
Second step, 1mol (2,2,6- trimethyl -4H-1, the 3- benzo dioxin -8- methyl) methanol for taking the first step to obtain
It is dissolved in 40ml dichloromethane solutions, adds 1mol pyridine chlorochromates and carry out acetalation, it is small that reaction 1.5 is stirred at room temperature
When, filtering, solution concentrates on a rotary evaporator, obtains solid fraction compound 2, i.e. (2,2,6- trimethyl -4H-1,3- benzos two
Dislike English -8- methyl) formaldehyde；
3rd step, (2,2,6- trimethyl -4H-1,3- benzo dioxin -8- methyl) formaldehyde prepared by 1mol second steps
It is dissolved in 65ml n-hexanes, leads to bromination hydrogen, minute ventilation volume 80ml, realize deprotection and Benzylphosphonium Bromide, filter, it is molten
Liquid concentrates on a rotary evaporator, obtains solid fraction compound 3, i.e. 3- (bromomethyl) -2- hydroxyl -5- benzaldehydes；
4th step, 1mol O are taken, O '-bis- (2- hydroxy ethoxies) benzene, are dissolved in 50ml tetrahydrofuran solutions, then added
2.2mol3- (bromomethyl) -2- hydroxyl -5- benzaldehydes and 0.05mol sodium hydrides, it is stirred at room temperature 30 minutes, filters, it is molten
Liquid concentrates on a rotary evaporator, and acquisition solid fraction compound 4, i.e., 3,3 '-((((1,2- phenylene two (oxo)) two (ethane -2,
1- diyls)) two (oxos)) two (methylene)) two (2- hydroxy-5-methyl base benzene (first) aldehyde)；
5th step, the compound 4 for taking the steps of 1mol the 4th to prepare are dissolved in 110ml ethanol, then add 2.5mol 1- pyrenes
Methylamine hydrochloride, it is heated to 60 DEG C and stirs 1 hour, be down to room temperature, 0 DEG C static 2 hours, and filtering, solution is on a rotary evaporator
Concentration, obtain solid fraction compound 5, i.e. 2- ((E)-(((3a1,5a1- dihydropyrene -1- bases) methyl) imino group) methyl) -6- ((2-
(2- (2- ((2- hydroxy-5-methyl bases -3- ((E)-((pyrene -1- ylmethyls) imino group) methyl) benzyl) oxo) ethyoxyl) benzene
Epoxide) ethyoxyl) methyl) -4- methylphenols.
It is found through experiments that in the range of the same soil environment of pH value 5~10, the carbon nanometer modified using crown ether
Pipe is more preferable to the adsorption effect of divalent cadmium ion than humic acid, and the divalent cadmium ion being free in soil is less, and consideration is probably
Because crown ether organic group is easier to combine with divalent cadmium ion, cadmium ion is prevented to form hydroxyl cadmium ion (CdOH+)。
Because crown ether organic group and divalent cadmium ion form π-π non-covalent bonds, and divalent cadmium ion and humic acid
Carboxyl is complexed with cadmium ion, forms Coordinative Chemistry key, first adds the CNT of a small amount of crown ether modification in this application, with
After add substantial amounts of humic acid, handled, to the repairing effect of divalent cadmium ion clearly, consider may the reason for be
The Coordinative Chemistry key that the carboxyl of humic acid is formed to divalent cadmium ion is non-compared with crown ether organic group and divalent cadmium ion formation π-π
Covalent bond is more stable, thus, it is only required to which good soil remediation effect can be achieved in the CNT for wanting a small amount of crown ether to modify.
And the CNT modified using the crown ether of the application, also can well ensure soil among the environment of meta-alkalescence
The repairing effect of divalent cadmium ion in earth, using method provided by the invention, not only repairing effect is good, and cost is cheap.
The present invention is described in further detail with reference to embodiment, but protection scope of the present invention and unlimited
In the content.
The preparation of the crown ether of embodiment 1
By 1mol 2, double (methylol) phenol of 6- are dissolved in 50ml dichloromethane solutions with 1mol 2,2- dimethylpropanes
In, triflate catalyst 0.05mol is added, reaction 2 hours is stirred at room temperature, filtering, solution is on a rotary evaporator
Concentration, obtain (2,2,6- trimethyl -4H-1,3- benzo dioxin -8- methyl) methanol；Take 1mol (2,2, the 6- front threes of acquisition
Base -4H-1,3- benzo dioxin -8- methyl) methanol is dissolved in 40ml dichloromethane solutions, and add 1mol pyridine chlorochromates and enter
Row acetalation, reaction 1.5 hours, filtering is stirred at room temperature, solution concentrates on a rotary evaporator, obtains (2,2,6- front threes
Base -4H-1,3- benzo dioxin -8- methyl) formaldehyde；By 1mol (2,2,6- trimethyl -4H-1,3- benzo dioxin -8- first
Base) formaldehyde is dissolved in 65ml n-hexanes, and lead to bromination hydrogen, minute ventilation volume 80ml, realize deprotection and Benzylphosphonium Bromide,
Filtering, solution concentrate on a rotary evaporator, obtain 3- (bromomethyl) -2- hydroxyl -5- benzaldehydes；Take 1mol O, O '-bis- (2-
Hydroxy ethoxy) benzene, it is dissolved in 50ml tetrahydrofuran solutions, then adds 2.2mol3- (bromomethyl) -2- hydroxyl -5- benzaldehydes
And 0.05mol sodium hydrides, it is stirred at room temperature 30 minutes, filters, solution concentrates on a rotary evaporator, acquisition 3,3 '-
((((1,2- phenylene two (oxo)) two (ethane -2,1- diyls)) two (oxos)) two (methylene)) two (2- hydroxy-5-methyl bases
Benzene (first) aldehyde)；Take 1mol 3,3 '-((((1,2- phenylene two (oxo)) two (ethane -2,1- diyls)) two (oxos)) two
(methylene)) two (2- hydroxy-5-methyl base benzene (first) aldehyde) are dissolved in 110ml ethanol, then add 2.5mol 1- pyrene methylamine salts
Hydrochlorate, it is heated to 60 DEG C and stirs 1 hour, be down to room temperature, 0 DEG C is static 2 hours, filtering, concentrates on a rotary evaporator, consolidate
Body product, 2- ((E)-(((3a1,5a1- dihydropyrene -1- bases) methyl) imino group) methyl) -6- ((2- (2- (2- ((2- hydroxyls -
5- methyl -3- ((E)-((pyrene -1- ylmethyls) imino group) methyl) benzyl) oxo) ethyoxyl) phenoxy group) ethyoxyl) first
Base) -4- methylphenols.
The compound1H NMR datas are as follows：
1H-NMR (300MHz, DMSO) δ 8.80-8.71 (m, 2H), 8.31 (m, 1H), 8.23 (m, 1H), 8.13-8.03
(m, 2H), 8.04 (m, 1H), 7.78 (m, 1H), 7.70 (m, 1H), 7.62 (m, 1H), 7.54 (m, 1H), 7.22 (m, 1H),
7.09 (m, 1H), 7.05 (m, 1H), 6.99-6.83 (m, 4H), 6.78-6.68 (m, 2H), 6.57 (s, 1H), 6.09 (s, 1H),
5.84 (s, 2H), 5.80 (s, 1H), 5.31 (s, 4H), 4.80 (s, 4H), 4.31 (t, J=8.4Hz, 4H), 3.77 (t, J=
8.4Hz, 4H), 3.66 (s, 2H), 2.63 (s, 2H), 2.36 (s, 3H)；ES-LCMS m/z 923.4(M+H).
The CNT of the crown ether of embodiment 2 modification
5g multi-walled carbon nanotubes are taken to be placed in 50ml hydrochloric acid and sulfuric acid mixed system, the volume ratio of hydrochloric acid and sulfuric acid is 2:
1, hydrochloric acid using 37% concentrated hydrochloric acid, sulfuric acid using 98% the concentrated sulfuric acid, ultrasound environments concussion, make multi-wall carbon nano-tube
Pipe is uniformly dispersed in nitration mixture, is heated to 40 DEG C of stirring reactions 4 hours, is cooled to room temperature, adds the deionized water of 5 times of nitration mixture volumes
Dilute solution, filtering, the CNT after acidifying are cleaned 3 times with deionized water, and remaining acid, product exist in CNT of going out
The lower 70 DEG C of dryings of 0.1Mpa vacuum environments 24 hours, obtain the smooth solid in surface；Coronal etherificate prepared by 10g embodiments 1
Compound is dissolved in DMF 70ml, ultrasonic oscillation 25 minutes, fully dissolving, filtering, it is molten to obtain yellow
Liquid, the multi-walled carbon nanotube of 8g acidifyings prepared by the first step is added, ultrasonic vibration 1 hour, makes CNT under the conditions of 35 DEG C
Dissolving, obtains the CNT of homogeneous phase solution, as organic decoration.
UV-Vis spectra is analyzed
The coronal ether compound and the compound-modified more wall carbon of the crown ether of embodiment 2 for weighing the preparation of embodiment 1 respectively are received
Mitron, tetrahydrofuran solution is dissolved in, ultrasonic vibration, obtains uniform solution, use the 330 of Japanese Hitachi companies
Spectrophotometer tests two tetrahydrofuran solutions and obtains uv-visible absorption spectroscopy respectively.
Fig. 1 shows crown ether organic compound and its ultraviolet-visible of CNT modified in tetrahydrofuran solution
Spectrum.
From figure as can be seen that a show embodiment 1 prepare coronal ether compound occur 430nm at significantly it is very wide
Characteristic absorption peak, this is the π-π of the compound*Electron transition, b show the compound-modified multi-walled carbon nanotube of crown ether after π-
π*The absworption peak of electron transition appears in 457nm, with crown ether compound phase ratio, moves 27nm, because coronal etherificate
Compound and CNT form conjugated system, and it is overlapping local electronics to be present, moves absworption peak.
Tem study
Weigh respectively crown ether modification prepared by a small amount of embodiment 2 CNT and it is commercially available it is unmodified before carbon receive
Mitron, it is dissolved in tetrahydrofuran solution, ultrasonic vibration, then drops on copper mesh, dries, use Japanese Hitachi companies
Microscopic pattern change between CNT after the modification of 8000 transmission electron microscope observations and the CNT before modification.
Analyze CNT electromicroscopic photograph Fig. 2 and Fig. 3 before and after the organic compound modified CNT of crown ether
As can be seen that the caliber of unmodified multi-walled carbon nanotube is small, tube wall is smooth, and after modification, the pipe of multi-walled carbon nanotube
Footpath substantially becomes big, and caliber is thickening, and due to there is the parcel of coronal ether compound to modify, appearance is uneven.
Cadmium in Soil reparative experiment：
Embodiment 3
The targeted Cd-polluted farmland soil of the present embodiment, test area 30m × 30m, cadmium concentration 10.23mg/kg, according to
《The measure diethylene triamine pentacetic acid (DTPA) extraction-inductively coupled plasma emission spectrography of 8 kinds of available state elements of soil》
(HJ804-016) the available Cd content of detection is 4.864mg/kg, and after testing, the pH value of soil is 9.
It is as follows to be passivated restoring cadmium polluted agricultural land soil key step：
The first step, the ratio of humic acid and calcium magnesium phosphate in mass ratio 2: 1 is uniformly mixed, obtains compounding passivation
Agent；
Second step, farmland is tentatively turned over using Cultivator, ploughed depth is mainly farming operation region；
3rd step, the CNT that crown ether prepared by embodiment 2 is modified uniformly is sowed using planting machine and is turning over soil
In earth, and turned over repeatedly with Cultivator, the CNT of crown ether modification and agricultural land soil are sufficiently mixed, conserved 4 days, institute
The addition for stating the CNT of crown ether modification is the 0.3% of soil weight；
4th step, Mixed Surfactant System prepared above is uniformly sowed in plowed soils using the machine of sending out, uses Cultivator
Turn over repeatedly, Mixed Surfactant System and soil are sufficiently mixed, the addition of the Mixed Surfactant System is agricultural land soil weight
1%；
5th step, after the completion of turning over, to passivation restoring area soil sprinkler irrigation water to saturation, and conserve 20 days, support
Shield completes normal use.
According to above-mentioned steps to Cd-polluted farmland soil passivation repair after, in agricultural land soil cadmium according to《8 kinds of available states of soil
Measure diethylene triamine pentacetic acid (DTPA) extraction-inductively coupled plasma emission spectrography of element》(HJ804-016) detection is effective
State cadmium content is reduced to 0.076mg/kg by 4.864mg/kg.
Comparative example 1
Soil environment in embodiment 3 carries out contrast test, test area 30m × 30m, cadmium concentration 10.23mg/
Kg, according to《The measure diethylene triamine pentacetic acid (DTPA) extraction-inductively coupled plasma atomic emission of 8 kinds of available state elements of soil
Method》(HJ804-016) the available Cd content of detection is 4.864mg/kg, and after testing, the pH value of soil is 9.
It is as follows to be passivated restoring cadmium polluted agricultural land soil key step；
The first step, the ratio of humic acid and calcium magnesium phosphate in mass ratio 2: 1 is uniformly mixed, obtains compounding passivation
Agent；
Second step, farmland is tentatively turned over using Cultivator, ploughed depth is mainly farming operation region；
3rd step, Mixed Surfactant System prepared above is uniformly sowed in plowed soils using the machine of sending out, uses Cultivator
Turn over repeatedly, Mixed Surfactant System and soil are sufficiently mixed, the addition of the Mixed Surfactant System is agricultural land soil weight
1%；
4th step, after the completion of turning over, to passivation restoring area soil sprinkler irrigation water to saturation, and conserve 24 days, support
Shield completes normal use.
According to above-mentioned steps to Cd-polluted farmland soil passivation repair after, in agricultural land soil cadmium according to《8 kinds of available states of soil
Measure diethylene triamine pentacetic acid (DTPA) extraction-inductively coupled plasma emission spectrography of element》(HJ804-016) detection is effective
State cadmium content is reduced to 2.639mg/kg by 4.864mg/kg.
By comparing embodiment 3 and comparative example 1 as can be seen that when pre- advanced without the CNT for adding crown ether modification
Row repair process, the cadmium content of the available state finally obtained is much higher compared with the content of the cadmium of available state after treatment, says
The effect that cadmium ion is repaired in the bright simple passivation using humic acid in slight alkali environment is poor, and this may be exactly because by adding
The CNT for adding crown ether to modify, the generation of hydroxyl cadmium ion is prevented in alkaline environment, contributes to later stage humic acid pair
The bonding passivation of cadmium ion.
Embodiment 4
The targeted Cd-polluted farmland soil of the present embodiment, cadmium concentration 5.23mg/kg, test area 30m × 30m, according to
《The measure diethylene triamine pentacetic acid (DTPA) extraction-inductively coupled plasma emission spectrography of 8 kinds of available state elements of soil》
(HJ804-016) the available Cd content of detection is 2.178mg/kg, and after testing, the pH value of soil is 7.
It is as follows that the present invention is passivated restoring cadmium polluted agricultural land soil key step：
The first step, the ratio of humic acid and calcium magnesium phosphate in mass ratio 1: 1 is uniformly mixed, obtains compounding passivation
Agent；
Second step, farmland is tentatively turned over using Cultivator, ploughed depth is mainly farming operation region；
3rd step, the CNT that crown ether prepared by embodiment 2 is modified uniformly is sowed using planting machine and is turning over soil
In earth, and turned over repeatedly with Cultivator, the CNT of crown ether modification and agricultural land soil are sufficiently mixed, conserved 3 days, institute
The addition for stating the CNT of crown ether modification is the 0.5% of soil weight；
4th step, Mixed Surfactant System prepared above is uniformly sowed in plowed soils using the machine of sending out, uses Cultivator
Turn over repeatedly, Mixed Surfactant System and soil are sufficiently mixed, the addition of the Mixed Surfactant System is agricultural land soil weight
2%；
5th step, after the completion of turning over, to passivation restoring area soil sprinkler irrigation water to saturation, and conserve 18 days, support
Shield completes normal use.
According to above-mentioned steps to Cd-polluted farmland soil passivation repair after, in agricultural land soil cadmium according to《8 kinds of available states of soil
Measure diethylene triamine pentacetic acid (DTPA) extraction-inductively coupled plasma emission spectrography of element》(HJ804-016) detection is effective
State cadmium content is reduced to below test limit by 2.178mg/kg.
Embodiment 5
The targeted Cd-polluted farmland soil of the present embodiment, cadmium concentration 2.89mg/kg, test area 30m × 30m, according to
《The measure diethylene triamine pentacetic acid (DTPA) extraction-inductively coupled plasma emission spectrography of 8 kinds of available state elements of soil》
(HJ804-016) the available Cd content of detection is 1.438mg/kg, and after testing, the pH value of soil is 4.
It is as follows that the present invention is passivated restoring cadmium polluted agricultural land soil key step：
The first step, the ratio of humic acid and calcium magnesium phosphate in mass ratio 2: 1 is uniformly mixed, obtains compounding passivation
Agent；
Second step, farmland is tentatively turned over using Cultivator, ploughed depth is mainly farming operation region；
3rd step, the CNT that crown ether prepared by embodiment 2 is modified uniformly is sowed using planting machine and is turning over soil
In earth, and turned over repeatedly with Cultivator, the CNT of crown ether modification and agricultural land soil are sufficiently mixed, conserved 3 days, institute
The addition for stating the CNT of crown ether modification is the 0.5% of soil weight；
4th step, Mixed Surfactant System prepared above is uniformly sowed in plowed soils using the machine of sending out, uses Cultivator
Turn over repeatedly, Mixed Surfactant System and soil are sufficiently mixed, the addition of the Mixed Surfactant System is agricultural land soil weight
8%；
5th step, after the completion of turning over, to passivation restoring area soil sprinkler irrigation water to saturation, and conserve 20 days, support
Shield completes normal use.
According to above-mentioned steps to Cd-polluted farmland soil passivation repair after, in agricultural land soil cadmium according to《8 kinds of available states of soil
Measure diethylene triamine pentacetic acid (DTPA) extraction-inductively coupled plasma emission spectrography of element》(HJ804-016) detection is effective
State cadmium content is reduced to 0.018mg/kg by 1.438mg/kg.
Comparative example 2
Soil environment in embodiment 5 carries out contrast test, test area 30m × 30m, cadmium concentration 2.89mg/
Kg, test area 30m × 30m, according to《The measure diethylene triamine pentacetic acid (DTPA) extraction-inductive of 8 kinds of available state elements of soil
Plasma emlssion spectrometry》(HJ804-016) the available Cd content of detection is 1.438mg/kg, after testing, the pH of soil
It is worth for 4.
It is as follows to be passivated restoring cadmium polluted agricultural land soil key step：
The first step, the ratio of humic acid and calcium magnesium phosphate in mass ratio 2: 1 is uniformly mixed, obtains compounding passivation
Agent；
Second step, farmland is tentatively turned over using Cultivator, ploughed depth is mainly farming operation region；
3rd step, Mixed Surfactant System prepared above is uniformly sowed in plowed soils using the machine of sending out, uses Cultivator
Turn over repeatedly, Mixed Surfactant System and soil are sufficiently mixed, the addition of the Mixed Surfactant System is agricultural land soil weight
8%；
4th step, after the completion of turning over, to passivation restoring area soil sprinkler irrigation water to saturation, and conserve 24 days, support
Shield completes normal use.
According to above-mentioned steps to Cd-polluted farmland soil passivation repair after, in agricultural land soil cadmium according to《8 kinds of available states of soil
Measure diethylene triamine pentacetic acid (DTPA) extraction-inductively coupled plasma emission spectrography of element》(HJ804-016) detection is effective
State cadmium content is reduced to 0.067mg/kg by 1.438mg/kg.
By comparing embodiment 5 and comparative example 2 as can be seen that in the environment of slant acidity, humic acid is in itself to cadmium ion
Passivation repairing effect it is very good, with addition crown ether be modified CNT effect difference it is little, illustrate in sour environment,
Cadmium ion is not easy to change into hydroxyl cadmium ion, and free state cadmium ion is more, humic acid can by most free state cadmium from
Son, which absorbs, to be repaired.
Comparative example 3
Tested in the soil environment of embodiment 3, test area 30m × 30m, cadmium concentration 10.23mg/kg, according to《Soil
The measure diethylene triamine pentacetic acid (DTPA) extraction-inductively coupled plasma emission spectrography of 8 kinds of available state elements of earth》 (HJ804-
016) the available Cd content of detection is 4.864mg/kg, and after testing, the pH value of soil is 9.
It is as follows to be passivated restoring cadmium polluted agricultural land soil key step：
The first step, the ratio of humic acid and calcium magnesium phosphate in mass ratio 2: 1 is uniformly mixed, obtains compounding passivation
Agent；
Second step, farmland is tentatively turned over using Cultivator, ploughed depth is mainly farming operation region；
3rd step, commercially available CNT is uniformly sowed in plowed soils using planting machine, and with Cultivator repeatedly
Turn over, CNT and agricultural land soil are sufficiently mixed, conserve 4 days, the addition of the CNT of the crown ether modification is
The 0.3% of soil weight；
4th step, Mixed Surfactant System prepared above is uniformly sowed in plowed soils using the machine of sending out, uses Cultivator
Turn over repeatedly, Mixed Surfactant System and soil are sufficiently mixed, the addition of the Mixed Surfactant System is agricultural land soil weight
1%；
5th step, after the completion of turning over, to passivation restoring area soil sprinkler irrigation water to saturation, and conserve 20 days, support
Shield completes normal use.
According to above-mentioned steps to Cd-polluted farmland soil passivation repair after, in agricultural land soil cadmium according to《8 kinds of available states of soil
Measure diethylene triamine pentacetic acid (DTPA) extraction-inductively coupled plasma emission spectrography of element》(HJ804-016) detection is effective
State cadmium content is reduced to 2.531mg/kg by 4.864mg/kg.
Comparing embodiment 3, comparative example 1 and comparative example 3, improve the reparation to the cadmium ion in slight alkali environment, it is necessary to adopt
The CNT modified with crown ether, for common CNT, does not almost work, comparative example 3 does not almost have with comparative example 1
There is difference, this is probably because of the delocalized pi-electron of height that crown ether organic group is formed, it is easier to formed with cadmium ion non-
Covalent bond, Adsorption of Cadmium.
All above-mentioned this intellectual properties of primarily implementation, the not this new product of implementation of setting limitation other forms
And/or new method.Those skilled in the art will utilize this important information, the above modification, to realize similar execution feelings
Condition.But all modifications or transformation belong to the right of reservation based on new product of the present invention.
The above described is only a preferred embodiment of the present invention, being not the limitation for making other forms to the present invention, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, the technical spirit according to the present invention is to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (4)
1. a kind of Cd-polluted farmland soil is passivated restorative procedure, it is characterised in that：Comprise the following steps：
The first step, humic acid is stirred with calcium magnesium phosphate in proportion together with, be configured to Mixed Surfactant System；
Second step, farmland is tentatively turned over using Cultivator, ploughed depth is mainly farming operation region；
3rd step, the CNT that the crown ether of preparation is modified uniformly is sowed in plowed soils using planting machine, and with turning over
Cultivated machine is turned over repeatedly, and the CNT of crown ether modification and agricultural land soil are sufficiently mixed, conserved 2~4 days；
4th step, the Mixed Surfactant System of preparation is uniformly sowed in plowed soils using the machine of sending out, turned over repeatedly with Cultivator,
Mixed Surfactant System and soil are sufficiently mixed；
5th step, after the completion of turning over, to passivation restoring area soil sprinkler irrigation water to saturation, and conserve 15~20 days.
2. Cd-polluted farmland soil as claimed in claim 1 is passivated restorative procedure, it is characterised in that：The compounding of the preparation is blunt
The mass ratio of two kinds of compositions of agent is：Humic acid: calcium magnesium phosphate 1~5: 1.
3. Cd-polluted farmland soil as claimed in claim 1 or 2 is passivated restorative procedure, it is characterised in that：The agricultural land soil
Middle Mixed Surfactant System addition is the 1~10% of agricultural land soil amount.
4. the Cd-polluted farmland soil passivation restorative procedure as described in claims 1 to 3, it is characterised in that：The agricultural land soil
The dosage of the CNT of middle crown ether modification is 0.3%~0.5%.
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| CN109122132A (en) * | 2018-09-06 | 2019-01-04 | 云南农业大学 | Utilize the method made between teasel root chrysanthemum and passivator couples reduction corn cadmium content |
| CN110000206A (en) * | 2019-04-30 | 2019-07-12 | 北京淖尔科技有限公司 | A kind of heavy metal pollution place fast hierarchical renovation technique and prosthetic device |
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