CN113637480A - Repairing agent for residual pesticide contaminated soil and treatment method - Google Patents
Repairing agent for residual pesticide contaminated soil and treatment method Download PDFInfo
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- CN113637480A CN113637480A CN202110718167.1A CN202110718167A CN113637480A CN 113637480 A CN113637480 A CN 113637480A CN 202110718167 A CN202110718167 A CN 202110718167A CN 113637480 A CN113637480 A CN 113637480A
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- titanium dioxide
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- hydroxyapatite
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- 239000000575 pesticide Substances 0.000 title claims abstract description 47
- 239000002689 soil Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 39
- -1 Ca2+ ions Chemical class 0.000 claims abstract description 38
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000002791 soaking Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 230000001699 photocatalysis Effects 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000005507 spraying Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000004576 sand Substances 0.000 claims description 15
- 239000011164 primary particle Substances 0.000 claims description 12
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 3
- 229940085991 phosphate ion Drugs 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 abstract description 14
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 6
- ZBMRKNMTMPPMMK-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid;azane Chemical compound [NH4+].CP(O)(=O)CCC(N)C([O-])=O ZBMRKNMTMPPMMK-UHFFFAOYSA-N 0.000 description 5
- 239000005906 Imidacloprid Substances 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- 239000005820 Prochloraz Substances 0.000 description 5
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 description 5
- 229950001327 dichlorvos Drugs 0.000 description 5
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 5
- 229940056881 imidacloprid Drugs 0.000 description 5
- ATROHALUCMTWTB-OWBHPGMISA-N phoxim Chemical compound CCOP(=S)(OCC)O\N=C(\C#N)C1=CC=CC=C1 ATROHALUCMTWTB-OWBHPGMISA-N 0.000 description 5
- 229950001664 phoxim Drugs 0.000 description 5
- TVLSRXXIMLFWEO-UHFFFAOYSA-N prochloraz Chemical compound C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl TVLSRXXIMLFWEO-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 239000000447 pesticide residue Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000037358 bacterial metabolism Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 230000006806 disease prevention Effects 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field, in particular to a repairing agent for residual pesticide contaminated soil and a treatment method thereof, which are used for solving the defects in the prior art and comprise the repairing agent, wherein the repairing agent is prepared by mixing, stirring, sanding and dispersing a photocatalytic material, a dispersing agent and pure water, the photocatalytic material is prepared by sequentially soaking TiO2 particles in a solution containing Ca2+ ions and a solution containing phosphate ions, and filtering, cleaning and drying the solution. The titanium dioxide dispersion treatment liquid modified by the hydroxyapatite can be used for treating the soil polluted by the residual pesticide in a simple repeated spraying, lighting and turning manner, and can effectively carry out harmless treatment on the residual pesticide in the soil.
Description
Technical Field
The invention relates to the technical field of contaminated soil remediation, in particular to a remediation agent for soil contaminated by residual pesticide and a treatment method.
Background
In the cultivation of crops, various agricultural chemicals are sometimes scattered in order to achieve high yield, disease prevention, and insect repelling. Many pesticides are organic compounds, and contain a characteristic chemical structure in a molecule that determines their action characteristics. Many agricultural chemicals have strong toxicity to human bodies in addition to pests, viruses, and the like. In addition, pesticides have a strong influence on the ecological environment of farmlands and the surrounding, and sometimes destroy the ecological environment. From the viewpoint of safety to the human body and the like, a problem to be solved in the agricultural field at present is to minimize the land waste and environmental pollution problems caused by excessive application of various chemicals for increasing the yield of grains.
The existing methods for treating pesticide residues in soil mainly comprise a biological decomposition method, a physical treatment method, a chemical treatment method, an oxidative decomposition method and the like; the existing action mechanism of the biological decomposition method is mainly a bacterial metabolism mode, the essence of the bacterial pesticide degradation is an enzymatic reaction, the working principle is that a compound enters a bacterial body in a certain mode, and then the pesticide is completely degraded or decomposed into a nontoxic or less toxic compound with a smaller molecular weight through a series of physiological and biochemical reactions under the action of various enzymes, but the degrading enzyme is easily inactivated by the actions of non-biological denaturation, soil adsorption and the like in soil, the degradation activity is difficult to maintain for a long time, and the mobility of the enzyme in the soil is poor, so that the application of the biological treatment method in the treatment of the residual pesticide in the soil is limited; the physical treatment method can be divided into an extraction method and an adsorption method, the extraction method is also called a liquid-liquid extraction method and is a separation technology for extracting, separating and enriching useful substances from an aqueous solution, the adsorption method adopts different adsorbents, the common adsorption capacity of diatomite, gelatin, activated carbon, resin and the like is transferred from soil, the principle of the physical method is to transfer pesticide pollutants from the water phase of the soil aqueous solution to other phases, the pesticide treatment is not realized, and the environment is still damaged; the chemical treatment method adopts the methods of adding alkali, adding chlorine, adding hypochlorite and the like to react with the pesticide to destroy and decompose the pesticide, but some pesticides have stable properties and are refractory compounds which are not easy to biodegrade, the types of the pesticide treated by the method are limited, and the adopted chemical reagent can generate byproducts polluting the environment while decomposing the pesticide to destroy the environment; the oxidative decomposition method mainly adopts an ozone oxidation mode, because ozone has strong oxidizing property, the ozone can generate oxidation reduction reaction with most pesticides to oxidize and decompose toxic pesticides into nontoxic compounds, and the ozone is decomposed into oxygen, so that the environment is not damaged, but the problems that the solubility of the ozone in water is very low, specific ultraviolet irradiation is needed, the oxidation efficiency is low and the like exist.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a repairing agent for soil polluted by residual pesticide and a treatment method.
In order to achieve the purpose, the invention adopts the following technical scheme:
the utility model provides a repairing agent for remaining pesticide pollutes soil, includes the repairing agent, the repairing agent is mixed the stirring and the sanding dispersion by photocatalysis material, dispersant and pure water and is made, the photocatalysis material is soaked in solution and the phosphate radical ion solution that contains Ca2+ ion in proper order by TiO2 granule, is made through filtering, washing, drying, the primary particle size of TiO2 granule is 10 ~ 400 nm.
A restoration treatment method for residual pesticide contaminated soil comprises the following steps:
s1, selecting TiO2 particles with the primary particle size of 10-400 nm;
step S2, sequentially soaking TiO2 particles in a solution containing Ca2+ ions and a solution containing phosphate ions, filtering, cleaning and drying to obtain hydroxyapatite modified titanium dioxide;
step S3, mixing and stirring the hydroxyapatite modified titanium dioxide obtained in the step S2, a dispersing agent and pure water, wherein the mass of the dispersing agent is 5-80 wt% of that of hydroxyapatite modified titanium dioxide particles, performing sand grinding dispersion by using a sand grinder, and obtaining uniformly dispersed dispersion treatment liquid by sand grinding;
and S4, spraying the dispersion treatment solution obtained in the step S3 into the soil polluted by the residual pesticide, and treating in a repeated spraying, illumination and ploughing mode, wherein the use amount of the hydroxyapatite modified titanium dioxide dispersion solution is adjusted according to the pollution degree.
Preferably, the primary particle size of the TiO2 particles is 10-100 nm.
Preferably, the phosphate ion-containing solution is one of a PO 43-solution, a HPO 42-solution or a H2PO 4-solution.
Preferably, the content of the hydroxyapatite-modified titanium dioxide in the dispersion treatment liquid is 0.5 to 30wt%,
preferably, the mass of the dispersing agent is 15-40 wt% of the hydroxyapatite modified titanium dioxide particles.
Preferably, in the step S3, the dispersing and sanding time is 10 to 1200 min.
Preferably, in the step S4, the depth of plowing is 300 to 500 mm.
The invention has the beneficial effects that: the titanium dioxide dispersion treatment solution modified by hydroxyapatite is adopted, the soil polluted by residual pesticide can be treated by simple repeated spraying, illumination and ploughing modes, and the method can effectively carry out harmless treatment on the residual pesticide in the soil, has the characteristics of low cost, high treatment efficiency and the like, effectively solves the technical defects of limited activity, poor stability and easy generation of secondary pollution in the existing method, solves the technical problem of residual pesticide treatment on the soil of agricultural cultivated land, and can prevent underground water pollution.
Drawings
FIG. 1 is a schematic view of a specific hydroxyapatite modification model of titanium dioxide according to the present invention;
FIG. 2 is an SEM image of titanium dioxide before and after modification according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Referring to fig. 1-2, a repairing agent for residual pesticide contaminated soil comprises a repairing agent, wherein the repairing agent is prepared by mixing, stirring, sanding and dispersing a photocatalytic material, a dispersing agent and pure water, the photocatalytic material is prepared by sequentially soaking TiO2 particles in a solution containing Ca2+ ions and a solution containing phosphate ions, and the TiO2 particles are prepared by filtering, cleaning and drying, and the primary particle size of the TiO2 particles is 10-400 nm.
A restoration treatment method for residual pesticide contaminated soil comprises the following steps: s1, selecting TiO2 particles with the primary particle size of 10-400 nm; step S2, sequentially soaking TiO2 particles in a solution containing Ca2+ ions and a solution containing phosphate ions, wherein the solution containing phosphate ions is one of a PO 43-solution, a HPO 42-solution or a H2PO 4-solution, and filtering, cleaning and drying to obtain hydroxyapatite modified titanium dioxide; step S3, mixing and stirring the hydroxyapatite modified titanium dioxide obtained in the step S2, a dispersing agent and pure water, wherein the mass of the dispersing agent is 5-80 wt% of that of hydroxyapatite modified titanium dioxide particles, performing sanding dispersion by using a sand mill, and obtaining uniformly dispersed dispersion treatment liquid by sanding, the content of the hydroxyapatite modified titanium dioxide in the dispersion treatment liquid is 0.5-30 wt%, the mass of the dispersing agent is 15-40 wt% of that of the hydroxyapatite modified titanium dioxide particles, and the dispersion sanding time is 10-1200 min; and S4, spraying the dispersion treatment solution obtained in the step S3 into the soil polluted by the residual pesticide, and treating in a repeated spraying, lighting and turning mode, wherein the turning depth is 300-500 mm, and the using amount of the hydroxyapatite modified titanium dioxide dispersion solution is adjusted according to the pollution degree.
The first embodiment is as follows:
the titanium dioxide used in this example was a commercially available product (Shiyuan TTO-55) having a primary particle size of 20 nm; modifying hydroxyapatite: selecting 100g of titanium dioxide, soaking in 0.2 molar CaCl2 solution (200 ml), filtering, cleaning and drying after 20min of soaking, soaking in 0.2 molar Na2HPO4 solution again, filtering, cleaning and drying after 20min of soaking to obtain hydroxyapatite-modified titanium dioxide, wherein SEM pictures of the titanium dioxide before and after modification are shown in figure 2;
it can be clearly seen from the figure that a layer of modifier is attached to the surface of the titanium dioxide, and the layer of the modifier is hydroxyapatite which is clearly determined by X-ray analysis;
preparing a hydroxyapatite modified titanium dioxide dispersion treatment solution: mixing (100 g) hydroxyapatite modified titanium dioxide, 4700g pure water and 200g dispersing agent, dispersing by a sand mill, wherein the dispersing treatment can be performed by a stirrer in advance before the dispersing treatment is performed by the sand mill, and the dispersing time is 2 hours, so as to obtain 2wt% hydroxyapatite modified titanium dioxide dispersing treatment liquid;
treating the soil polluted by residual pesticide by using hydroxyapatite modified titanium dioxide dispersion treatment liquid, repeatedly ploughing for 5 times, analyzing the contents of pesticides such as imidacloprid, prochloraz, glufosinate-ammonium, dichlorvos, paraquat, phoxim and the like in the soil, and controlling the ploughing depth to be 300 mm.
Example two:
the titanium dioxide used in this example was a commercially available product (Shiyuan TTO-55) having a primary particle size of 30nm, modified with hydroxyapatite: soaking 100g of titanium dioxide in a 0.05 molar calcium acetate solution (200 ml), filtering, cleaning and drying after 20min, soaking in a 0.2 molar NaH2PO4 solution for 20min, filtering, cleaning and drying to obtain hydroxyapatite modified titanium dioxide;
the layer is hydroxyapatite which is confirmed by SEM observation and X-ray analysis;
preparing a hydroxyapatite modified titanium dioxide dispersion liquid: mixing (100 g) hydroxyapatite modified titanium dioxide, 4700g pure water and 200g dispersing agent, dispersing by a sand mill, wherein the dispersing treatment can be performed by a stirrer in advance before the dispersing treatment is performed by the sand mill, and the dispersing time is 2 hours, so as to obtain 2wt% hydroxyapatite modified titanium dioxide dispersing treatment liquid;
treating the soil polluted by residual pesticide by using hydroxyapatite modified titanium dioxide dispersion treatment liquid, repeatedly ploughing for 5 times, analyzing the contents of pesticides such as imidacloprid, prochloraz, glufosinate-ammonium, dichlorvos, paraquat, phoxim and the like in the soil, and controlling the ploughing depth to be 400 mm.
Example three:
the titanium dioxide used in this example was a commercially available product (Shiyuan TTO-55) having a primary particle size of 50nm, modified with hydroxyapatite: soaking 100g of titanium dioxide in 200ml of 0.1 molar calcium nitrate solution for 20min, filtering, cleaning and drying, soaking in 0.1 molar Na3PO4 solution for 20min, filtering, cleaning and drying to obtain hydroxyapatite modified titanium dioxide;
the layer is hydroxyapatite which is confirmed by SEM observation and X-ray analysis;
preparing a hydroxyapatite modified titanium dioxide dispersion liquid: hydroxyapatite-modified titanium dioxide (100 g), purified water (4700 g) and a dispersing agent (200 g) were mixed and dispersed by a sand mill, and the mixture was preliminarily dispersed by a stirrer before dispersion by the sand mill for 2 hours to obtain a 2wt% hydroxyapatite-modified titanium dioxide dispersion treatment solution.
Treating the soil polluted by residual pesticide by using hydroxyapatite modified titanium dioxide dispersion treatment liquid, repeatedly ploughing for 5 times, and analyzing the contents of pesticides such as imidacloprid, prochloraz, glufosinate-ammonium, dichlorvos, paraquat, phoxim and the like in the soil.
Comparative example:
the titanium dioxide used in the comparative example was a commercially available product (Shinylogen TTO-55) having a primary particle diameter of 50 nm;
preparation of titanium dioxide dispersion: mixing (100 g) hydroxyapatite modified titanium dioxide, 4700g pure water and 200g dispersing agent, dispersing by a sand mill, wherein the dispersing treatment can be performed by a stirrer in advance before the dispersing treatment is performed by the sand mill, and the dispersing time is 2 hours, so as to obtain 2wt% hydroxyapatite modified titanium dioxide dispersing treatment liquid;
treating the soil polluted by residual pesticide by using hydroxyapatite modified titanium dioxide dispersion treatment liquid, repeatedly ploughing for 5 times, analyzing the contents of pesticides such as imidacloprid, prochloraz, glufosinate-ammonium, dichlorvos, paraquat, phoxim and the like in the soil, and controlling the ploughing depth to be 400 mm.
The following is an analysis of the pesticide residue on virgin soil and soil treated with the photocatalytic treatment agents of the examples and comparative examples, and the data obtained are as follows:
| imidacloprid | Prochloraz | Glufosinate-ammonium | Dichlorvos | Paraquat (Paraquat) | Phoxim | Residual pesticide process Degree of rotation | |
| Original soil Sample (A) | 100% | 100% | 100% | 100% | 100% | 100% | Severe severity of disease |
| Example 1 | 2.5% | 4.6% | 1.4% | 3.5% | 2.7% | 5.3% | Almost decompose |
| Example 2 | 3.0% | 2.2% | 3.2% | 3.1% | 3.2% | 1.2% | Almost decompose |
| Example 3 | 2.4% | 2.5% | 1.0% | 2.7% | 3.5% | 3.2% | Almost decompose |
| Comparative example 1 | 45% | 53% | 60% | 93% | 58% | 75% | Is divided into half Right side |
From the results, it was found that the treatment of the residual pesticide-contaminated soil with the hydroxyapatite-modified titanium dioxide dispersion treatment liquid gave a good pesticide decomposition effect and that the soil improvement could be achieved at a low cost.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. The repairing agent for the residual pesticide contaminated soil is characterized by comprising a repairing agent, wherein the repairing agent is prepared by mixing, stirring and sanding a photocatalytic material, a dispersing agent and pure water, the photocatalytic material is prepared by sequentially soaking TiO2 particles in a solution containing Ca2+ ions and a solution containing phosphate ions, and the solution is prepared by filtering, cleaning and drying, and the primary particle size of the TiO2 particles is 10-400 nm.
2. A restoration treatment method for residual pesticide contaminated soil is characterized by comprising the following steps:
s1, selecting TiO2 particles with the primary particle size of 10-400 nm;
step S2, sequentially soaking TiO2 particles in a solution containing Ca2+ ions and a solution containing phosphate ions, filtering, cleaning and drying to obtain hydroxyapatite modified titanium dioxide;
step S3, mixing and stirring the hydroxyapatite modified titanium dioxide obtained in the step S2, a dispersing agent and pure water, wherein the mass of the dispersing agent is 5-80 wt% of that of hydroxyapatite modified titanium dioxide particles, performing sand grinding dispersion by using a sand grinder, and obtaining uniformly dispersed dispersion treatment liquid by sand grinding;
and S4, spraying the dispersion treatment solution obtained in the step S3 into the soil polluted by the residual pesticide, and treating in a repeated spraying, illumination and ploughing mode, wherein the use amount of the hydroxyapatite modified titanium dioxide dispersion solution is adjusted according to the pollution degree.
3. The method for repairing and treating the soil polluted by the residual pesticide is characterized in that the primary particle size of TiO2 particles is 10-100 nm.
4. The method as claimed in claim 2, wherein the phosphate ion-containing solution is one of a PO43-, HPO42-, or H2PO 4-solution.
5. The method for remediating soil contaminated with residual pesticides as claimed in claim 2, wherein the content of hydroxyapatite-modified titanium dioxide in the dispersion treatment liquid is 0.5-30 wt%,
the method for remediating the soil contaminated by the residual pesticide according to claim 2, wherein the dispersant accounts for 15-40 wt% of the hydroxyapatite-modified titanium dioxide particles.
6. The method for remediating soil contaminated with residual pesticides as claimed in claim 2, wherein the dispersing and sanding time in step S3 is 10-1200 min.
7. The method according to claim 2, wherein in the step S4, the depth of plowing is 300 to 500 mm.
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