CN113248003A - Method for degrading chlordane in cyclodextrin solution by Schwerner mineral catalysis heterogeneous photo-Fenton reaction - Google Patents
Method for degrading chlordane in cyclodextrin solution by Schwerner mineral catalysis heterogeneous photo-Fenton reaction Download PDFInfo
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- BIWJNBZANLAXMG-YQELWRJZSA-N chloordaan Chemical compound ClC1=C(Cl)[C@@]2(Cl)C3CC(Cl)C(Cl)C3[C@]1(Cl)C2(Cl)Cl BIWJNBZANLAXMG-YQELWRJZSA-N 0.000 title claims abstract description 114
- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 89
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 67
- 239000011707 mineral Substances 0.000 title claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000000593 degrading effect Effects 0.000 title claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 title claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006731 degradation reaction Methods 0.000 claims abstract description 56
- 230000001699 photocatalysis Effects 0.000 claims abstract description 11
- 230000005855 radiation Effects 0.000 claims abstract description 4
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052742 iron Inorganic materials 0.000 abstract description 15
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 45
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 230000000694 effects Effects 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 12
- 239000002689 soil Substances 0.000 description 11
- 238000010828 elution Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000000356 contaminant Substances 0.000 description 8
- 229910052598 goethite Inorganic materials 0.000 description 8
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003480 eluent Substances 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- -1 iron ions Chemical class 0.000 description 6
- 239000003993 organochlorine pesticide Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 238000005067 remediation Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- GWHRPSOIZQENQQ-UHFFFAOYSA-N 5-chlorocyclopenta-1,3-diene Chemical group ClC1C=CC=C1 GWHRPSOIZQENQQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YVGGHNCTFXOJCH-UHFFFAOYSA-N DDT Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(Cl)C=C1 YVGGHNCTFXOJCH-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241000256602 Isoptera Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 229910001608 iron mineral Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229960002809 lindane Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- GVYLCNUFSHDAAW-UHFFFAOYSA-N mirex Chemical compound ClC12C(Cl)(Cl)C3(Cl)C4(Cl)C1(Cl)C1(Cl)C2(Cl)C3(Cl)C4(Cl)C1(Cl)Cl GVYLCNUFSHDAAW-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical group OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a method for degrading chlordane in a cyclodextrin solution by a Schwerner mineral catalytic heterogeneous photo-Fenton reaction, which comprises the steps of adjusting the concentration of the cyclodextrin in the cyclodextrin solution containing the chlordane to 0.4-1.5g/L, adding the Schwerner mineral, adjusting the pH value of the cyclodextrin solution to be neutral or acidic, adding hydrogen peroxide, carrying out ultraviolet radiation in a photocatalytic reactor, and carrying out degradation treatment at room temperature. Preferably, the pH range of the cyclodextrin solution is 3-5, the concentration of the Schneider mineral is 11.5-300mg/L, and the concentration of the hydrogen peroxide is 50-100 mmol/L. The method utilizes the synergistic effect of the schwertmannite on the adsorption of the chlordane and the efficient decomposition of hydrogen peroxide to generate hydroxyl free radicals, can realize the efficient degradation of the chlordane within the range of pH3-5, and has the chlordane degradation rate of more than 80 percent; meanwhile, the reaction time is short, no iron mud is generated, and no secondary pollution is caused to the environment.
Description
Technical Field
The invention belongs to the technical field of persistent organic pollutant treatment in environmental protection, and relates to a method for degrading chlordane in a cyclodextrin solution by using a Schwerer mineral to catalyze a heterogeneous photo-Fenton reaction.
Background
The organochlorine pesticide is a kind of persistent organic pollutant with environmental persistence, biological accumulation, semi-volatility and high toxicity, and has been widely used in agricultural production. Organochlorine pesticides are classified into two major classes according to molecular structure differences: one is chlorobenzene and derivatives thereof, including dichlorodiphenyl trichloroethane, hexachloro cyclohexane and the like; the other is chloro cyclopentadiene including chlordane, mirex, etc. Since the effective and successful achievement of the stockholm convention in China, agricultural and pharmaceutical factories in China are moved and closed in succession, and a large number of organochlorine pesticide-polluted sites appear. If the fields are developed and utilized without treatment or under treatment, the human health can be greatly harmed. Therefore, the rapid remediation of organochlorine pesticide contaminated site soil is imminent.
The organic pollutant soil remediation technology mainly comprises the following steps: bioremediation technology, physical remediation technology, chemical oxidation/reduction technology and soil synergism elution technology. Among the polluted soil remediation technologies which are applied more at home and abroad, the elution technology is widely concerned by researchers due to the characteristics of high speed, high efficiency, low cost and the like. The soil elution technology is to wash polluted soil by adopting an eluant (an organic solvent, a surfactant, cyclodextrin and the like) and transfer pollutants in the soil into an eluent, so that the removal of the organic pollutants is realized. Further treatment of the contaminants in the eluent is required since the contaminants are not degraded or eliminated during the elution process. At present, most researches on elution technology are focused on screening, condition optimization and elution effect evaluation of an eluent, and the researches on the post-treatment technology of the eluent are less, wherein the researches on the post-treatment technology of the eluent, such as organic solvent extraction, activated carbon adsorption, air stripping, membrane separation and the like, only realize the transfer of pollutants, and the pollutants still exist and possibly harm the ecological environment. Therefore, there is a need to find a method for degrading organochlorine pesticides in an elution solution.
The homogeneous photo-Fenton reaction refers to Fe under the action of ultraviolet light2+/Fe3+Reacts with hydrogen peroxide to generate hydroxyl free radicals with strong oxidizing property. Free of hydroxyl groupsThe organic matter can be effectively degraded. However, the reaction requires a very narrow pH range (pH between 2.5 and 3), and iron-containing sludge is generated during the reaction, which increases the difficulty of treatment and disposal and limits the post-biochemical treatment of wastewater. Compared with a homogeneous system, the heterogeneous photo-Fenton reaction mostly adopts an iron oxide solid-phase catalyst, iron ions exist in the solid-phase catalyst in the process, the iron hydroxide precipitation cannot be caused, and the catalytic reaction keeps high efficiency in a wider pH range. In addition, studies have shown that adsorption of the catalyst to contaminants has a significant effect on the degradation of the contaminants, and adsorption of the contaminants on the catalyst surface accelerates the reaction rate. Therefore, the heterogeneous photo-fenton reaction has potential advantages for the degradation of organic contaminants.
Many studies at home and abroad take goethite as a catalyst to efficiently degrade various organic pollutants by utilizing heterogeneous light Fenton reaction. Although goethite shows good activity in the heterogeneous photo-Fenton reaction, the valence state of iron in the goethite is mostly trivalent, and trivalent iron ions need to consume a part of hydrogen peroxide to be reduced into divalent iron ions, so that the utilization rate of the hydrogen peroxide is reduced.
Relevant researches show that the dichlorodiphenyl trichloroethane (chlorobenzene organochlorine pesticide) in the soil eluent can be effectively degraded by utilizing the Fenton technology. However, non-aromatic compounds are more difficult to oxidize by hydroxyl radicals than chlorobenzene-based contaminants. The degradation of chloro cyclopentadiene organic chlorine pesticides is rarely reported.
Chlordane is an organochlorine pesticide using cyclopentadiene as raw material. About 70000 tons of industrial chlordane are produced globally in 1948-1988, and about 15000 tons of chlordane still remain in the environment at present. Nearly 20 chlordane production enterprises are shared in history of China, and the yield of the chlordane reaches 465 tons in 1974. In 1997-2001, the difference of the amount of chlordane used in different provinces is large due to different termite damage degrees, and 18 provinces, cities and autonomous regions in 19 provinces, cities and autonomous regions which have developed termite control have used chlordane.
Cyclodextrin is used as a soil eluent and is widely applied to the remediation of the soil polluted by chlordane. However, the degradation of chlordane in cyclodextrin solutions has not been reported.
Disclosure of Invention
1. Technical problem
Aiming at the problems that chlordane in a cyclodextrin solution generated in the process of eluting and repairing the chlordane-polluted soil by cyclodextrin is difficult to effectively degrade, the pH requirement of Fenton reaction is strict, iron mud is easy to generate and the like, the invention aims to provide a method for degrading chlordane in the cyclodextrin solution by using Schwerer mineral to catalyze heterogeneous light Fenton reaction, so that the chlordane in the cyclodextrin solution can be efficiently and quickly degraded, and no secondary pollution is generated.
2. Technical scheme
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for degrading chlordane in a cyclodextrin solution by using Schwerner minerals to catalyze heterogeneous photo-Fenton reaction is characterized in that the method takes the Schwerner minerals as catalysts to catalyze and degrade the chlordane in the cyclodextrin solution under the irradiation of ultraviolet light, and comprises the following steps:
(1) adjusting the concentration of cyclodextrin in cyclodextrin solution containing chlordane to 0.4-1.5g/L, adding Schneider mineral, and adjusting pH of cyclodextrin solution to neutral or acidic;
(2) adding hydrogen peroxide into the cyclodextrin solution in the step (1), wherein the concentration of the hydrogen peroxide is more than 20 mmol/L;
(3) and (3) in a photocatalytic reactor, carrying out ultraviolet radiation on the cyclodextrin solution under the stirring condition, and carrying out degradation reaction at room temperature.
Preferably, in the step (1), the concentration of the cyclodextrin is 0.8-1.0 g/L.
Preferably, in step (1), the pH is adjusted to a range of 3 to 7, more preferably 3 to 5.
Preferably, in the step (1), the addition concentration of the schlerian mineral is 11.5-300mg/L based on the volume of the cyclodextrin solution; more preferably, the amount of Schwerner mineral is in the range of 11.5-150 mg/L.
In the step (2), the hydrogen peroxide is an aqueous solution with the mass percentage of 30%.
Preferably, in the step (2), the volume of the cyclodextrin solution is taken as a reference, and the concentration of hydrogen peroxide is 50-100 mmol/L.
Preferably, in the step (3), the wavelength of ultraviolet light is less than or equal to 365 nm.
Preferably, in the step (3), the reaction time is 12 to 24 hours.
The schlerian mineral is a metastable secondary hydroxyl sulfate high-iron mineral with poor crystallinity and special appearance, and the basic chemical formula of the schlerian mineral is Fe8O8(OH)8-2x(SO4)xAnd x is between 1 and 1.75. The valence state of iron ions in the Schwerner minerals is the coexistence of divalent and trivalent, and the catalytic decomposition capability to hydrogen peroxide is strong. Meanwhile, the Schneider minerals have higher specific surface area and good adsorption capacity on organic matters. According to the method, a small amount of schlerren mineral is added into the cyclodextrin solution, meanwhile, low-concentration hydrogen peroxide is added, and under the ultraviolet radiation, the chlordane in the cyclodextrin solution is degraded by utilizing the synergistic effect of the schlerren mineral on the chlordane and the hydroxyl free radical generated by efficiently decomposing the hydrogen peroxide.
3. Advantageous effects
The invention has the following beneficial effects:
(1) the method utilizes the adsorption effect of schlempe mineral on chlordane and the synergistic effect of efficiently decomposing hydrogen peroxide to generate hydroxyl free radicals, forms a system with stronger oxidability, can efficiently degrade chlordane in cyclodextrin solution, and has short reaction time and high processing speed.
(2) The method utilizes the Schwerner mineral to catalyze the heterogeneous photo-Fenton reaction to degrade the chlordane in the cyclodextrin solution, can realize the high-efficiency degradation of the chlordane within 12-24 hours, and the degradation rate of the chlordane can reach more than 80-85%.
(3) The method utilizes the Schneider mineral to catalyze the heterogeneous light Fenton reaction to degrade the chlordane in the cyclodextrin solution, can realize the high-efficiency degradation of the chlordane within the range of pH3-7, and has the chlordane degradation rate of more than 80 percent below pH 5; in the application process of the method, the iron leaching amount is less, and no iron mud is generated, so that secondary pollution to the environment is avoided.
(4) The method has the advantages of simple operation, easy process control and low treatment cost. Moreover, the Schlemn's mineral is abundant in nature and has the characteristic of environmental friendliness, so that the Schlemn's mineral has a wide application prospect.
Drawings
FIG. 1 shows the schlerian mineral, goethite and Fe in example 1 of the present invention2+Respectively catalyzing the photo-Fenton reaction to degrade chlordane in the cyclodextrin solution;
FIG. 2 is a graph showing the effect of degrading chlordane by photocatalytic heterogeneous Fenton reaction at different addition amounts of Schneider minerals in example 2 of the present invention;
FIG. 3 is a graph showing the effect of Schneider mineral catalysis heterogeneous light Fenton reaction on the degradation of chlordane under different hydrogen peroxide concentrations in example 3 of the present invention;
FIG. 4 is a graph showing the effect of Schneider mineral catalyzing the heterogeneous photo-Fenton reaction to degrade chlordane at different initial pH values in example 4 of the present invention;
FIG. 5 is a graph showing the effect of Schwerer mineral catalyzing heterogeneous photo-Fenton reaction to degrade chlordane at different cyclodextrin concentrations in example 5 of the present invention;
FIG. 6 is a graph showing the iron elution content of the Schneider mineral in the process of degrading chlordane in example 6 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. It is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.
Example 1
A method for degrading chlordane in a cyclodextrin solution by a Schwerner mineral catalytic heterogeneous photo-Fenton reaction comprises the following specific steps:
the first step is as follows: taking 2.5mL of chlordane mother liquor (solvent is n-hexane) with concentration of 200mg/L into a 1000mL triangular flask, adding 500mL of cyclodextrin solution with concentration of 0.8g/L after the n-hexane is volatilized, placing on a magnetic stirrer of 180r/min, stirring for 1h to fully dissolve chlordane, and using HClO4Adjusting the pH value of the mixed solution to 3 with NaOH;
the second step is that: weighing 0.575mg of Schneider minerals, putting the Schneider minerals into a 50mL light reaction bottle, adding 50mL of the mixed solution obtained in the first step as a target water body (the concentration of chlordane is 1mg/L, the concentration of cyclodextrin is 0.8g/L), and adding 250 mu L of hydrogen peroxide with the mass fraction of 30%; moving to a quartz glass photocatalytic reactor, turning on an ultraviolet lamp (with the wavelength of 365mn), stirring at the rotating speed of 180r/min, and performing degradation reaction at room temperature (25 +/-2 ℃);
the third step: taking out 1mL of degradation samples at 0h, 2h, 4h, 8h, 12h, 24h, 36h and 48h respectively, carrying out pretreatment, and then analyzing by GC/ECD.
As shown in figure 1, a small amount of Schneider mineral and hydrogen peroxide are added into the cyclodextrin solution, under the irradiation of ultraviolet light, the chlordane in the cyclodextrin solution can be effectively degraded through heterogeneous light Fenton reaction, the chlordane degradation tends to be stable after 12 hours, the chlordane degradation is basically finished after 24 hours, and the chlordane degradation rate is about 83 percent.
Comparative example 1
The method for degrading chlordane in cyclodextrin solution by adopting photo-Fenton reaction comprises the following specific steps:
the first step is as follows: taking 2.5mL of chlordane mother liquor (solvent is n-hexane) with concentration of 200mg/L into a 1000mL triangular flask, adding 500mL of cyclodextrin solution with concentration of 0.8g/L after the n-hexane is volatilized, placing on a magnetic stirrer of 180r/min, stirring for 1h to fully dissolve chlordane, and using HClO4Adjusting the pH value of the mixed solution to 3 with NaOH;
the second step is that: 0.5mg goethite and 1.56mg FeSO were weighed out4·7H2Respectively putting the O into 50mL photoreaction bottles (the content of the Fe in the photoreaction bottles is the same as that in the photoreaction bottle in the embodiment 1), then adding 50mL of the mixed solution obtained in the first step as a target water body (the concentration of the chlordane is 1mg/L, the concentration of the cyclodextrin is 0.8g/L), and then adding 250 mu L of hydrogen peroxide with the mass fraction of 30%; moving to a quartz glass photocatalytic reactor, turning on an ultraviolet lamp (with the wavelength of 365mn), stirring at the rotating speed of 180r/min, and performing degradation reaction at room temperature (25 +/-2 ℃);
the third step: taking out 1mL of degradation samples at 0h, 2h, 4h, 8h, 12h, 24h, 36h and 48h respectively, carrying out pretreatment, and then analyzing by GC/ECD.
From the results shown in fig. 1, in the reaction systems of different catalysts, the chlordane degradation rate in the schwann mineral system tends to be stable within 12 hours and reaches about 80%; the degradation rate of the chlordane is less than 40 percent in a goethite system for 12 hours, and the chlordane is required to be stableAnd (7) 36 h. In Fe2+In a homogeneous photo-Fenton reaction system which is a catalyst, the degradation of chlordane is faster than that of Schneider minerals in the initial stage, but the degradation tends to be stable for 24 hours. In addition, the degradation effect of the photo-Fenton system composed of different catalysts on chlordane is as follows in sequence: scholar mineral>Fe2+>Goethite. For the degradation treatment of chlordane in cyclodextrin solution, the Schwerer mineral catalyzes heterogeneous photo-Fenton reaction ratio Fe2+The system and the goethite system have better effect, shorter time and better catalytic performance.
Example 2
The method for degrading chlordane in cyclodextrin solution by using Schwerer mineral to catalyze heterogeneous photo-Fenton reaction comprises the following specific steps:
the first step is as follows: taking 2.5mL of chlordane mother liquor (solvent is n-hexane) with concentration of 200mg/L into a 1000mL triangular flask, adding 500mL of cyclodextrin solution with concentration of 0.8g/L after the n-hexane is volatilized, placing on a magnetic stirrer of 180r/min, stirring for 1h to fully dissolve chlordane, and using HClO4Adjusting the pH value of the mixed solution to 3 with NaOH;
the second step is that: weighing 0mg, 0.05mg, 3mg, 7.5mg and 15mg of Schneider minerals, respectively putting into a 50mL light reaction bottle, then adding 50mL target water (the concentration of chlordane is 1mg/L, the concentration of cyclodextrin is 0.8g/L), and then adding 250 mu L hydrogen peroxide with the mass fraction of 30%; moving to a photocatalytic reactor, opening an ultraviolet lamp (with the wavelength of 365mn), stirring at the rotating speed of 180r/min, and performing degradation reaction at room temperature (25 +/-2 ℃);
the third step: and 1mL of degraded sample is taken out at 0h, 2h, 4h, 6h, 8h, 12h and 24h respectively, and is analyzed by GC/ECD after pretreatment.
As can be seen from FIG. 2, the chlordane degradation rate increases first and then decreases slightly as the addition of Schneider mineral increases. The best effect is achieved when the addition amount of the Schwerer mineral is 60mg/L, and the degradation rate of the chlordane is about 88 percent. When the addition amount of the Schneider mineral is 11.5-300mg/L, the degradation rate of the chlordane can reach more than 80%. A preferred range is 11.5-150 mg/L.
Example 3
The method for degrading chlordane in cyclodextrin solution by using Schwerer mineral to catalyze heterogeneous photo-Fenton reaction comprises the following specific steps:
the first step is as follows: taking 2.5mL of chlordane mother liquor (solvent is n-hexane) with concentration of 200mg/L into a 1000mL triangular flask, adding 500mL of cyclodextrin solution with concentration of 0.8g/L after the n-hexane is volatilized, placing on a magnetic stirrer of 180r/min, stirring for 1h to fully dissolve chlordane, and using HClO4Adjusting the pH value of the mixed solution to 3 with NaOH;
the second step is that: respectively weighing 3mg of Schneider minerals, putting the Schneider minerals into 50mL of light reaction bottles, then adding 50mL of target water (the concentration of chlordane is 1mg/L, and the concentration of cyclodextrin is 0.8g/L), and respectively adding 10 mu L, 50 mu L, 100 mu L, 250 mu L and 500 mu L of hydrogen peroxide with the mass fraction of 30% into each reaction bottle; moving to a photocatalytic reactor, opening an ultraviolet lamp (with the wavelength of 365mn), stirring at the rotating speed of 180r/min, and performing degradation reaction at room temperature (25 +/-2 ℃);
the third step: and 1mL of degraded sample is taken out at 0h, 2h, 4h, 6h, 8h, 12h and 24h respectively, and is analyzed by GC/ECD after pretreatment.
As can be seen from FIG. 3, the degradation rate of chlordane increases with the increase of the concentration of hydrogen peroxide, and can reach more than 75% when the concentration of hydrogen peroxide reaches more than 20 mmol/L. When the concentration of the hydrogen peroxide is more than or equal to 50mmol/L, the degradation rate of the chlordane tends to be stable, and the degradation rate of the chlordane can reach 85 percent. The concentration of hydrogen peroxide is preferably 50-100mmol/L, and the degradation rate of chlordane reaches more than 80%.
Example 4
The method for degrading chlordane in cyclodextrin solution by using Schwerer mineral to catalyze heterogeneous photo-Fenton reaction comprises the following specific steps:
the first step is as follows: taking 2.5mL of chlordane mother liquor (the solvent is n-hexane) with the concentration of 200mg/L into a 1000mL triangular flask, adding 500mL of cyclodextrin solution with the concentration of 0.8g/L after the n-hexane is volatilized, and stirring for 1h on a magnetic stirrer of 180r/min to fully dissolve chlordane;
the second step is that: respectively weighing 3mg of Schneider minerals, placing into a 50mL light reaction bottle, adding 50mL target water (chlordane concentration is 1mg/L, cyclodextrin concentration is 0.8g/L), and using HClO4And NaOH are respectively used for adjusting the pH value of the mixed solution in each reaction bottle to 3, 5, 7,9 and 11; then 250 mul of hydrogen peroxide with the mass fraction of 30 percent is respectively added; moving to a photocatalytic reactor, opening an ultraviolet lamp (with the wavelength of 365mn), stirring at the rotating speed of 180r/min, and performing degradation reaction at room temperature (25 +/-2 ℃);
the third step: and 1mL of degraded sample is taken out at 0h, 2h, 4h, 6h, 8h, 12h and 24h respectively, and is analyzed by GC/ECD after pretreatment.
As can be seen from FIG. 4, the schrader mineral system has better chlordane degradation efficiency under acidic condition, and the chlordane degradation rate is reduced with the increase of the initial pH of the solution. When the pH value of the solution is less than or equal to 7, the degradation rate of the chlordane is about more than 70 percent, and the degradation rate is the highest when the pH value is 3, and the degradation rate of the chlordane is 88.5 percent. Under alkaline conditions, the degradation efficiency of chlordane is obviously reduced, and when the pH value is 9 and 11, the degradation rate of chlordane is respectively 50 percent and 12.4 percent. Preferably, the pH value of the solution is 3-5, and the degradation rate of the chlordane reaches more than about 80 percent.
Example 5
The method for degrading chlordane in cyclodextrin solution by using Schwerer mineral to catalyze heterogeneous photo-Fenton reaction comprises the following specific steps:
the first step is as follows: taking 2.5mL of chlordane mother liquor (the solvent is n-hexane) with the concentration of 200mg/L into a 1000mL triangular flask, after the n-hexane is volatilized, respectively adding 500mL of cyclodextrin solutions with the concentrations of 0.4g/L, 0.8g/L, 1.5g/L and 5.0g/L, placing the cyclodextrin solutions on a magnetic stirrer of 180r/min, and stirring for 1 hour to fully dissolve chlordane;
the second step is that: respectively weighing 3mg of Schneider minerals, placing into a 50mL light reaction bottle, adding 50mL target water (with chlordane concentration of 1mg/L and cyclodextrin concentrations of 0.4g/L, 0.8g/L, 1.5g/L and 5.0g/L), and adding HClO4Respectively adjusting the pH value of the mixed solution in each reaction bottle to 3 with NaOH; then 250 mul of hydrogen peroxide with the mass fraction of 30 percent is respectively added; moving to a photocatalytic reactor, opening an ultraviolet lamp (with the wavelength of 365mn), stirring at the rotating speed of 180r/min, and performing degradation reaction at room temperature (25 +/-2 ℃);
the third step: and 1mL of degraded sample is taken out at 0h, 2h, 4h, 6h, 8h, 12h and 24h respectively, and is analyzed by GC/ECD after pretreatment.
As shown in FIG. 5, when the cyclodextrin was 0.4g/L, the degradation rate of chlordane was 73.3%. When the concentration of the cyclodextrin is 0.8g/L, the degradation rate of the chlordane is about 88.5 percent after 24 hours. When the concentration of the cyclodextrin is increased to 1.5g/L, the degradation rate of the chlordane is 70.9 percent, excessive cyclodextrin can inhibit the degradation of the chlordane, and when the concentration of the cyclodextrin is increased to 5g/L, the degradation rate of the chlordane is only 11.7 percent after 24 hours. Thus, a suitable cyclodextrin concentration range is 0.4-1.5g/L, with the most preferred range being 0.8-1.0 g/L.
Because the cyclodextrin has a low-polarity cavity structure with a certain size, molecules of the cyclodextrin can be adsorbed on the surface of the Schneider mineral, more active sites are provided, and the chlordane is wrapped to form a complex compound to promote the degradation of the chlordane; however, when the concentration of cyclodextrin is too high, a plurality of cyclodextrin molecules are complexed with chlordane together, the cyclodextrin cavity and branched chains are increased, the adsorption amount of minerals to the cyclodextrin is reduced, and active sites are reduced, so that the degradation rate of the chlordane is influenced. In addition, too much cyclodextrin competes with the contaminant for OH in the fenton system, which in turn results in a decrease in the rate of chlordane degradation.
Example 6
The method is characterized in that the chlordane in the cyclodextrin solution is degraded by using a Schwerer mineral catalytic heterogeneous photo-Fenton reaction, and the dissolved iron content in the determination process comprises the following steps:
the first step is as follows: taking 2.5mL of chlordane mother liquor (solvent is n-hexane) with concentration of 200mg/L into a 1000mL triangular flask, adding 500mL of cyclodextrin solution with concentration of 0.8g/L after the n-hexane is volatilized, placing on a magnetic stirrer of 180r/min, stirring for 1h to fully dissolve chlordane, and using HClO4Adjusting the pH value of the mixed solution to 3 with NaOH;
the second step is that: weighing 3mg of Schneider minerals, putting the Schneider minerals into a 50mL light reaction bottle, and then adding 50mL of target water (the concentration of chlordane is 1mg/L, and the concentration of cyclodextrin is 0.8 g/L); adding 250 mu L of hydrogen peroxide with the mass fraction of 30%; moving to a photocatalytic reactor, opening an ultraviolet lamp (with the wavelength of 365mn), stirring at the rotating speed of 180r/min, and performing degradation reaction at room temperature (25 +/-2 ℃);
the third step: taking out the filtrate (1mL) of the sample to be tested in a 10mL colorimetric tube at 0h, 2h, 4h, 6h, 8h, 12h and 24h respectively, adding 0.2mL of hydroxylamine hydrochloride solution with the concentration of 100g/L, uniformly mixing, and standing for 2 min; respectively adding 0.8mL of 200g/L sodium acetate buffer solution and 1mL of 2g/L phenanthroline solution, diluting with water to scale mark, mixing, and standing for 10 min; the absorbance was measured at a wavelength of 510nm in an ultraviolet spectrophotometer.
As can be seen from FIG. 5, the degradation rate of chlordane is more than 85% after 24h, and the iron elution amount is only 1.2 mg/L. The result shows that the amount of dissolved iron is less, no iron mud is generated and no secondary pollution is generated to the environment in the process of degrading the chlordane by the Schwerner mineral catalyst.
Claims (8)
1. A method for degrading chlordane in a cyclodextrin solution by using Schwerner minerals to catalyze heterogeneous photo-Fenton reaction is characterized in that the method takes the Schwerner minerals as catalysts to catalyze and degrade the chlordane in the cyclodextrin solution under the irradiation of ultraviolet light, and comprises the following steps:
(1) adjusting the cyclodextrin concentration of the cyclodextrin solution containing chlordane to 0.4-1.5gAdding schlempe mineral and regulating pH value of cyclodextrin solution to neutral or acid;
(2) adding hydrogen peroxide into the cyclodextrin solution in the step (1), wherein the concentration of the hydrogen peroxide is more than 20 mmol/L;
(3) and (3) in a photocatalytic reactor, carrying out ultraviolet radiation on the cyclodextrin solution under the stirring condition, and carrying out degradation reaction at room temperature.
2. The method for degrading chlordane in a cyclodextrin solution by using Schneider mineral to catalyze heterogeneous photo-Fenton reaction according to claim 1, wherein the concentration of the cyclodextrin in the step (1) is 0.8-1.0 g/L.
3. The method for degrading chlordane in cyclodextrin solution by Schneider mineral catalysis heterogeneous photo-Fenton reaction according to claim 1, wherein in the step (1), the pH of the cyclodextrin solution is adjusted to be in the range of 3-7.
4. The method for degrading chlordane in cyclodextrin solution by Schneider mineral catalysis heterogeneous photo-Fenton reaction according to claim 3, wherein in the step (1), the pH of the cyclodextrin solution is adjusted to be in the range of 3-5.
5. The method for degrading chlordane in a cyclodextrin solution by using Schwerner mineral to catalyze heterogeneous photo-Fenton reaction according to claim 1, wherein in the step (1), the addition concentration of the Schwerner mineral is 11.5-300mg/L based on the volume of the cyclodextrin solution.
6. The method for degrading chlordane in cyclodextrin solution by Schwerner mineral catalysis heterogeneous photo-Fenton reaction according to claim 1, wherein in the step (2), the hydrogen peroxide concentration is 50-100mmol/L based on the volume of the cyclodextrin solution.
7. The method for degrading chlordane in cyclodextrin solution by Schwerner mineral catalysis heterogeneous photo-Fenton reaction according to claim 1, wherein in the step (3), the wavelength of ultraviolet light is less than or equal to 365 nm.
8. The method for degrading chlordane in cyclodextrin solution by Schneider mineral catalysis heterogeneous photo-Fenton reaction according to claim 1, wherein in the step (3), the reaction time is 12-24 hours.
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