CN108637005A

CN108637005A - It is a kind of to repair polycyclic aromatic hydrocarbons contaminated composite material, preparation method and the usage

Info

Publication number: CN108637005A
Application number: CN201810458107.9A
Authority: CN
Inventors: 顾万建; 王莹; 吴晔; 蒋超; 方超
Original assignee: Jiangsu Jinhuan Environmental Protection Equipment Co Ltd
Current assignee: Jiangsu Jinhuan Environmental Protection Equipment Co Ltd
Priority date: 2018-05-14
Filing date: 2018-05-14
Publication date: 2018-10-12

Abstract

The invention belongs to technical field of environmental science, and in particular to a kind of rapidly and efficiently to repair polycyclic aromatic hydrocarbons contaminated composite material, preparation method and the usage.The mass ratio of the polycyclic aromatic hydrocarbons contaminated composite material of the reparation, including carbon dots modification zinc oxide and Fenton reagent, carbon dots modification zinc oxide and Fenton reagent is (1~10)：(10~1).The present invention also provides preparation method and uses.The present invention organically combines photocatalytic degradation and oxidative degradation process, and the two, which acts synergistically, realizes the fast degradation of polycyclic aromatic hydrocarbon, can also provide the heavy metal pollution information of environment.

Description

Composite material for repairing polycyclic aromatic hydrocarbon pollution, preparation method and application thereof

Technical Field

The invention belongs to the technical field of environmental science, and particularly relates to a composite material for repairing polycyclic aromatic hydrocarbon pollution, and a preparation method and application thereof.

Background

Regarding the removal of polycyclic aromatic hydrocarbon pollutants in the environment, the following processes are mainly adopted:

firstly, microorganism removal method: application number CN201610440052.X belongs to the technical field of soil remediation, and specifically relates to a polycyclic aromatic hydrocarbon contaminated soil remediation agent. The soil remediation agent polluted by polycyclic aromatic hydrocarbons comprises the following components: chitin, zeolite powder, green algae, humic acid, shell powder, needle mushroom bran, corncobs, fly ash, tea seed shells, grass carbon ash, areca nut wood chips, palm wood chips, a complex enzyme preparation and a complex microbial agent. By adopting the soil remediation agent, mild enzymes and microbial strains are adopted to treat soil without introducing other chemical solvents, so that secondary pollution is avoided, and the action conditions are mild. Application number CN201610438092.0 discloses a polycyclic aromatic hydrocarbon contaminated soil remediation material, which comprises the following components: chitin, zeolite powder, green algae, humic acid, shell powder, needle mushroom bran, corncobs, rice bran, tea seed shells, grass carbon ash, areca nut wood chips, palm wood chips, a complex enzyme preparation and a complex microbial agent. The soil remediation material provided by the invention is adopted, mild enzymes and microbial strains are adopted to treat soil without introducing other chemical solvents, no new pollution is caused, the action conditions are mild, the strains not only degrade or adsorb polycyclic aromatic hydrocarbons, but also have a relatively obvious effect on improving the soil texture conditions of the soil. Application number CN201410744163.0 discloses a combined remediation method of polycyclic aromatic hydrocarbon contaminated soil, which comprises the following steps: (1) placing the polycyclic aromatic hydrocarbon polluted soil in a bioreactor, adding water at room temperature, and stirring; (2) adding subtilisin into the bioreactor, wherein the addition amount of the subtilisin is 5-30U/g soil, and stirring after adding, wherein the stirring speed is 30 rpm; (3) during stirring, adding sodium palmitate and methyl palmitate into the bioreactor, wherein the adding amount of the sodium palmitate is 3.5-5 wt% of the weight of the soil, and the adding amount of the methyl palmitate is 0.8-1.6 wt% of the weight of the soil, and continuously stirring after adding; (4) adding cotton straw powder into the bioreactor, wherein the adding amount of the cotton straw powder is 1.5-4.5 wt%, continuing stirring for 2 hours after adding, and separating and drying the soil and water after standing to obtain the repaired soil. Application number CN201310625720.2 discloses a method for restoring farmland soil polluted by polycyclic aromatic hydrocarbon by using anion-non mixed surfactant to strengthen ryegrass and rhizosphere microorganisms, belonging to the technical field of restoration of polluted soil. The invention comprises the following steps: (1) applying a low-concentration (30-150 mg/kg) anion-nonionic mixed surfactant on the surface layer of the PAHs polluted soil; (2) planting ryegrass, growing for 40-60 days, harvesting plant bodies, drying in the sun, transferring, and then burning intensively; (3) by repeating the operation, PAHs in the polluted soil can be removed until the environmental safety standard is reached. The method has the advantages that the PAHs adsorbed on the soil are solubilized and eluted by adopting the low-dose anionic-nonionic mixed surfactant, so that the degradation of the PAHs by rhizosphere microorganisms can be promoted, the absorption and accumulation of the PAHs by plants can be improved, and the repair efficiency of the PAHs is improved. Application number CN201310174080.8 discloses a Rhodospirillum strain, which is H1, and the preservation number is CGMCC No. 6869. The invention also provides a biological pure culture of the bacterial strain, which has all the identification characteristics of the rhodospirillum strain H1 with the preservation number of CGMCC No. 6869. The invention also provides a polycyclic aromatic hydrocarbon degradation reagent, which comprises rhodospirillum strain or biological pure culture. The invention also provides a soil remediation agent, which comprises the rhodospirillum strain or the biological pure culture. The rhodospirillum strain provided by the invention can effectively degrade polycyclic aromatic hydrocarbons in the environment, and the range of microorganisms capable of degrading polycyclic aromatic hydrocarbons is expanded. Application number CN201210387958.1 discloses Klebsiella pneumoniae (Klebsiella pneumoniae tzyx1) for degrading polycyclic aromatic hydrocarbons and application thereof in remediation of composite contaminated soil. The strain is Klebsiella pneumoniae (Klebsiella pneumoniae) Tzyx1, has a preservation number of CCTCC M2012239 in the China center for type culture Collection, and has the capacity of degrading polycyclic aromatic hydrocarbons. The strain can be applied to the treatment of polycyclic aromatic hydrocarbon and heavy metal contaminated soil. Application number CN201610668012.0 discloses a strain capable of degrading polycyclic aromatic hydrocarbon and application thereof, belonging to the technical field of biological engineering. The strain is Citrobacter freundil 2-14, and the preservation number in the China center for type culture collection is CCTCC NO: m2016371; and the strain is used for repairing soil polluted by polycyclic aromatic hydrocarbon. The strain capable of degrading the polycyclic aromatic hydrocarbon has the capability of growing by taking the polycyclic aromatic hydrocarbon as a carbon source and an energy source, can realize the effect of quickly degrading the polycyclic aromatic hydrocarbon pollution, and has the advantages of wide substrate degradation range and high degradation rate. Application number CN201610325152.8 discloses a Pantoea (Pantoea sp.) PYR16 for degrading polycyclic aromatic hydrocarbon organic pollutants, which belongs to the field of microorganism and environmental organic pollutant remediation and treatment, and the strain is preserved in China center for type culture Collection with the preservation number as follows: CCTCC NO: m2016227. The strain disclosed by the invention can efficiently degrade various polycyclic aromatic hydrocarbons, has wide environmental adaptation and heavy metal resistance, and can be planted in a severe environment to repair soil or water body which is compositely polluted by heavy metals and polycyclic aromatic hydrocarbons. Application number CN201610137138.5 discloses a combined remediation method of DDT-PAHs (dichloro-diphenyl-trichloroethane) -PAHs (polycyclic aromatic hydrocarbons) combined contaminated soil, and relates to a remediation method of contaminated soil. The combined remediation of the DDT-polycyclic aromatic hydrocarbon combined contaminated soil by the degrading bacteria and the biosurfactant rhamnolipid has the unique advantages of low remediation cost, large-area application, safety, simplicity, no secondary pollution and the like, can realize the remediation while production, and has wide application prospect. Application number CN201610129260.8 discloses a method for repairing DDT and polycyclic aromatic hydrocarbon composite contaminated soil, and relates to a method for repairing contaminated soil, wherein the method adopts an in-situ repairing mode for DDT and polycyclic aromatic hydrocarbon composite contaminated soil, and applies mixed surfactant into 0-20 cm surface soil of the contaminated soil; using 70-100 mg/kg of soil, uniformly mixing, and then inoculating 500ml/m2 of Bacillus methylotrophicus (Bacillus methylotrophicus) bacterial liquid; keeping the field water retention rate at 50-60%, regularly monitoring the contents of the dichlorodiphenyl trichloroethane and the polycyclic aromatic hydrocarbon in the soil, and repeating the operation according to the monitoring result after 1 month until the contents of the dichlorodiphenyl trichloroethane and the polycyclic aromatic hydrocarbon in the soil reach the soil environment safety standard; the method has important significance for preventing and treating soil dichlorodiphenyl trichloroethane and polycyclic aromatic hydrocarbon pollution, safely producing agricultural products and treating and repairing the soil. Application number CN201610018231.4 discloses a high-efficiency microbial film inoculant for degrading polycyclic aromatic hydrocarbon in polluted soil and a preparation method thereof. The invention adopts humin as a carrier, attaches microorganisms and forms a microbial film to obtain a microbial film microbial inoculum. The microbial film inoculant disclosed by the invention has the characteristics of simple preparation method, convenience in operation, short fermentation period, high growth speed, high enzyme activity and the like, has the characteristics of efficiently utilizing and degrading polycyclic aromatic hydrocarbons, and is a biological technology for efficiently removing polycyclic aromatic hydrocarbons in polluted environments. Application No. cn201510571244.x discloses a polycyclic aromatic hydrocarbon pollution repair microcapsule material, a preparation method and an application thereof, comprising the following steps: (1) culturing the mycobacterium flavum CP13 in a bacterial culture solution to obtain a bacterial solution; the mycobacterium flavum CP13 is preserved in the common microorganism center of China general microbiological culture Collection center in 2013, 7 and 22 months, and the preservation number is CGMCC No. 7963; (2) and (3) embedding the bacterial liquid into a microcapsule by layer-by-layer self-assembly by using calcium alginate and chitosan to prepare the polycyclic aromatic hydrocarbon pollution repairing microcapsule material. The microcapsule material with microbial activity is prepared by layer-by-layer self-assembly, and has super-strong environment adaptability and good removal capability on polycyclic aromatic hydrocarbon pollution. The microcapsule material can be used for biological treatment of industrial wastewater containing polycyclic aromatic hydrocarbon and biological remediation of soil polluted by polycyclic aromatic hydrocarbon. Application number CN201510066008.2 discloses a method for in-situ remediation of polycyclic aromatic hydrocarbon contaminated site by surfactant-enhanced microorganisms, and the polycyclic aromatic hydrocarbon PAHs in the contaminated site are subjected to in-situ degradation by the surfactant-enhanced indigenous microorganisms; the invention adopts the low-dose surfactant, changes the microbial community structure in the soil, promotes the enrichment of bacteria, and improves the activity of degrading bacteria, thereby enhancing the efficiency of in-situ restoration of PAHs polluted site/soil by microorganisms; the method has the advantages of simple technical process, low cost, short period, practicality and safety, and can be used for repairing organic polluted sites/soils such as PAHs and the like on a large scale. Application number CN201310479232.5 discloses a Mycobacterium flavum and application thereof in degrading petroleum component polycyclic aromatic hydrocarbon, wherein the Mycobacterium flavum is Mycobacterium flavum (Mycobacterium gilvum) CP13, is preserved in China general microbiological culture Collection center (CGMCC) in 7-22 months in 2013, and is called CGMCC for short, and the preservation number is CGMCC No. 7963. The strain is subjected to shake culture for 7 days at the pH of 7.0-10.0 and the temperature of 30-35 ℃ at a speed of 150r/min, and the degradation rate of the strain on pyrene with the initial concentration of 50mg/L can reach more than 88%. The strain also has strong degradation capability on fluoranthene, phenanthrene, anthracene, fluorene, acenaphthene, naphthalene and other polycyclic aromatic hydrocarbons, and can be used for bioremediation of petroleum-polluted water bodies and soil and biological treatment of industrial wastewater containing polycyclic aromatic hydrocarbons. Application number CN201310174080.8 discloses a Rhodospirillum strain, which is H1, and the preservation number is CGMCC No. 6869. The invention also provides a biological pure culture of the bacterial strain, which has all the identification characteristics of the rhodospirillum strain H1 with the preservation number of CGMCC No. 6869. The invention also provides a polycyclic aromatic hydrocarbon degradation reagent, which comprises rhodospirillum strain or biological pure culture. The invention also provides a soil remediation agent, which comprises the rhodospirillum strain or the biological pure culture. The rhodospirillum strain provided by the invention can effectively degrade polycyclic aromatic hydrocarbons in the environment, and the range of microorganisms capable of degrading polycyclic aromatic hydrocarbons is expanded. Application number CN201210380304.6 discloses a Mycobacterium (Mycobacterium sp.)16F for efficiently degrading polycyclic aromatic hydrocarbons and benzene organic matters, and the preservation number is CGMCC No. 6367. The mycobacterium 16F can efficiently, safely and quickly degrade polycyclic aromatic hydrocarbons and monocyclic benzene compounds, can grow and degrade by taking fluorene, naphthalene, anthracene, acenaphthene, phenanthrene, pyrene and benzopyrene as unique carbon sources and energy sources under aerobic conditions, and can also utilize benzene, m-xylene, toluene, salicylic acid, catechol and other various aromatic organic matters. The composite material is sensitive to antibiotics such as streptomycin, rifampicin, tetracycline and kanamycin, has a good degradation effect on mixed polycyclic aromatic hydrocarbons in aged soil and monocyclic benzene organic matters in water, can be used for repairing and purifying soil environment polluted by organic compounds of aromatic hydrocarbons, has an important significance for promoting sustainable development, and has a wide application prospect. Application number CN201210364057.0 discloses a microbial composition for degrading chlorine-containing polycyclic aromatic hydrocarbon in oil sludge and a treatment method thereof, wherein the microbial composition comprises the following microorganisms in percentage by weight: sphingomonas paucimobilis: sphingomonas bacteria: the oligotrophic decyclizing bacterium is 1: 0.5-1.5: 0.5-1.5. The invention also provides a method for treating the polluted soil by using the microbial composition for degrading the chlorine-containing polycyclic aromatic hydrocarbon in the oil sludge, which comprises the step of adding a microbial agent and a nutrient solution into the oil-containing sludge until the oil content is less than 0.5 percent after treatment. The invention starts from degrading polycyclic aromatic hydrocarbon and heterocyclic substances, separates and cultures three microorganisms which have obvious effect on the environmental toxic substances, researches necessary nutrient components required by the microorganisms to exert degradation activity, and improves the degradation effect of the microorganisms on the polycyclic aromatic hydrocarbon and the heterocyclic substances. Application number CN201110302755.3 discloses a polycyclic aromatic hydrocarbon degrading bacterium suitable for electric field conditions and application thereof. The polycyclic aromatic hydrocarbon degrading bacteria are pseudomonas fluorescens PB4, which are preserved in China center for type culture Collection in 7-19.2011, and the preservation registration numbers are CCTCC No: m2011260. The pseudomonas fluorescens PB4 is used for repairing contaminated soil. The strain obtained by separation has higher activity under the action of an electric field, and the degradation capability of single polycyclic aromatic hydrocarbon and mixed polycyclic aromatic hydrocarbon can be improved. After an electric field of 0.5-2.0V/cm is applied, the degradation activity of the pseudomonas fluorescens is enhanced, and the removal rates of single polycyclic aromatic hydrocarbon and mixed polycyclic aromatic hydrocarbon are respectively increased by 12.46-30.62% and 8.11-20.20% after 28 days. Application number CN201110052105.8 discloses a novel process and a technology for strengthening electric bioremediation of polycyclic aromatic hydrocarbon contaminated soil by using a surfactant, and provides a process and parameters for strengthening electric bioremediation of polycyclic aromatic hydrocarbon contaminated soil by using the surfactant, so that the efficiency of bioremediation of insoluble organic pollutants is effectively improved, and the research of electric remediation and in-situ bioremediation is promoted. The process comprises the steps of mixing and circulating two-electrode electrolyte, adding a surfactant and microorganisms into the electrolyte for electric injection, and performing a surfactant-enhanced electric bioremediation test when the voltage gradient is 1V/cm, the electrolyte is bacterial suspension (containing nutrient salts) and a surfactant, the pH value is 7.3, and the flow rate of the circulating electrolyte is 800 ml/h. Test results show that the novel surfactant-enhanced electric bioremediation process can effectively improve the degradation speed of phenanthrene in the polluted soil, improve the degradation rate of pyrene and benzopyrene, and solve the problem that pH of the soil is easy to change in acid and alkali in the traditional electric bioremediation process. Application number CN201010598120.8 discloses a sphingosine sagittifolia strain and application thereof in degrading polycyclic aromatic hydrocarbons. The sphingosine bacillus sagittiformis (Sphingobium yanoikuyae) provided by the invention is named as LD29, and the preservation number of the strain is CGMCC No. 4400. The sphingosine bacillus sagittifolia LD29 can grow and propagate by respectively using phenanthrene, anthracene, fluoranthene and pyrene as unique carbon source and energy source under aerobic condition, and can be degraded at the same time. In addition, the sphingosine bacterium cornus LD29 has a degradation effect on the mixed polycyclic aromatic hydrocarbons, and particularly has a degradation effect on pentacyclic benzo [ a ] pyrene in the mixed polycyclic aromatic hydrocarbons. The method can be used for repairing the soil polluted by the polycyclic aromatic hydrocarbon and repairing the water body polluted by the polycyclic aromatic hydrocarbon, reduces the content of the polycyclic aromatic hydrocarbon in the environment, has the advantages of rapidness, convenience and environmental protection, provides a new microbial resource for bioremediation polluted by the polycyclic aromatic hydrocarbon, has great value for environmental management, and has considerable economic benefit and good social benefit. Application number CN201010596211.8 discloses a polycyclic aromatic hydrocarbon degrading microbial agent, which consists of 2 strains of mycobacterium basophilus P6, oligoacidophilic oligotrophomonas P56 and the like. The microbial inoculum provided by the invention has the capability of degrading various polycyclic aromatic hydrocarbons in soil and sewage, has an obvious effect of repairing polycyclic aromatic hydrocarbon polluted soil, has the capability of degrading (pyrene and fluoranthene) polycyclic aromatic hydrocarbons in a solution of more than 90%, and has a good application prospect. Application No. CN200510038453.4 discloses a dual-inoculation biological method for reducing polychlorinated biphenyl and polycyclic aromatic hydrocarbon in contaminated soil, comprising the following steps: and (3) inoculating rhizobium and arbuscular mycorrhizal fungi while planting the leguminous plants on the polluted soil until the growth cycle of the leguminous plants is finished. The leguminous plants in the optimized scheme adopt perennial leguminous herbaceous plants, and alfalfa (Medicago sativa) is preferred; the arbuscular mycorrhizal fungus is preferably Glomus scovittae (Glomus calledonium). Before the double inoculation, a step of preparing the arbuscular mycorrhizal fungi preparation can be added. The method can obviously improve the degradation rate of POPs in the soil to be tested, particularly remarkably promotes the degradation capability of polychlorinated biphenyl and polycyclic aromatic hydrocarbon in the soil of the alfalfa root zone by double inoculation of mycorrhizal fungi and rhizobia, and is an ideal biological repair method. Application number CN200810011865.2 discloses a preparation method of a sludge microbial inoculum for repairing polycyclic aromatic hydrocarbon-polluted soil, which comprises the following steps: 1. collecting the dried sludge with the water content of 72-82% after dehydration, and airing for 48-72 hours; 2. adding sawdust accounting for 15-25% of the weight of the dry sludge, and uniformly stirring; placing the mixture of the dry sludge and the sawdust in a naturally ventilated room for stacking, keeping the indoor temperature at 25-32 ℃, and performing aerobic fermentation; piling for 5-7 days to obtain solid fermentation product; 3. uniformly spreading the solid fermentation product, wherein the average thickness is 5-10 cm, and uniformly spraying a bacterial culture solution accounting for 3% -5% of the weight of the solid fermentation product on the solid fermentation product; 4. covering plastic on the surface of the solid fermentation product sprayed with the bacterial culture solution, compacting the periphery, culturing for 48-72 hours, and adsorbing bacteria on the surface layer and the inner pores of the solid fermentation product to prepare the sludge microbial inoculum for repairing the polycyclic aromatic hydrocarbon polluted soil. The invention has the characteristics of low cost, convenient implementation of in-situ remediation and no secondary pollution. Application number CN200810162554.6 discloses a method for degrading polycyclic aromatic hydrocarbon pyrene in soil by using a new microbial strain, belonging to the technical field of microbial application. The invention screens a new pseudomonas putida strain PL2, CCTCC No. M207114 capable of degrading polycyclic aromatic hydrocarbons from soil; further provides a method for degrading polycyclic aromatic hydrocarbon pyrene in soil by using the strain, which comprises the steps of preparing a culture medium; activating and culturing strains; fermenting and culturing strains, inoculating strains to soil, degrading, measuring the residual quantity of polycyclic aromatic hydrocarbon pyrene in soil samples and the like. The method has the characteristics of rapidness, high efficiency, simplicity, practicality and the like, and the degradation rate of the polycyclic aromatic hydrocarbon (pyrene) can reach 50% -70% within 3-10 days under better process conditions. Can be popularized and applied in degradation treatment of soil areas polluted by polycyclic aromatic hydrocarbon. Application No. CN200510038453.4 discloses a dual-inoculation biological method for reducing polychlorinated biphenyl and polycyclic aromatic hydrocarbon in contaminated soil, comprising the following steps: and (3) inoculating rhizobium and arbuscular mycorrhizal fungi while planting the leguminous plants on the polluted soil until the growth cycle of the leguminous plants is finished. The leguminous plants in the optimized scheme adopt perennial leguminous herbaceous plants, and alfalfa (Medicago sativa) is preferred; the arbuscular mycorrhizal fungus is preferably Glomus scovittae (Glomus calledonium). Before the double inoculation, a step of preparing the arbuscular mycorrhizal fungi preparation can be added. The method can obviously improve the degradation rate of POPs in the soil to be tested, particularly remarkably promotes the degradation capability of polychlorinated biphenyl and polycyclic aromatic hydrocarbon in the soil of the alfalfa root zone by double inoculation of mycorrhizal fungi and rhizobia, and is an ideal biological repair method. Application number CN200510047472.3 discloses a preparation method of immobilized particles for repairing polycyclic aromatic hydrocarbon contaminated soil, which takes corn cobs as a main carrier material, mixes fresh, dried, crushed or ground corn cobs with 1.5-2 cm, and auxiliary materials including cottonseed cakes, bran, bean cake powder, rice chaff and/or wheat bran according to weight percentage, wherein the corn cobs account for 70-85%, and the auxiliary materials account for 15-30%; adjusting the water content to 40-55% by weight, adjusting the pH to 6.3-6.5, autoclaving, inoculating the stock full of fungal spores, and performing enrichment culture to obtain the required immobilized particles. The invention has the advantages that: the method has the advantages of low cost, high immobilization efficiency, simplicity and feasibility, and is suitable for large-scale in-situ soil remediation. The application number CN03101920.X discloses a Rhodococcus ruber (Rhodococcus ruber) Em CGMCC No.0868 strain, and growing cells, cell suspension and immobilized cells of the strain can degrade alkane such as hexadecane and polycyclic aromatic hydrocarbon such as anthracene, phenanthrene and pyrene; the strain can grow by taking alkane or polycyclic aromatic hydrocarbon as a unique carbon source and energy source, and simultaneously generates a lipid biological emulsifier; the emulsifier can obviously reduce the surface tension of an aqueous solution, has strong emulsifying capacity of grease substances, improves the solubility of alkane and polycyclic aromatic hydrocarbon in water, and obviously promotes the degradation of active strains on the alkane and polycyclic aromatic hydrocarbon. The strain and the biological emulsifier produced by the strain are suitable for biological treatment of oily wastewater and biological remediation (bioremediation) of petroleum-polluted soil.

Secondly, the application number CN201310058795.7 of the plant removal method discloses the application of indoleacetic acid in the reinforced remediation of polycyclic aromatic hydrocarbon-polluted soil. Planting gramineae plants in soil polluted by polycyclic aromatic hydrocarbon, and spraying methanol water solution of indoleacetic acid on the soil surface in the plant growth process; after 80-90 days of growth, harvesting the plant bodies, drying at low temperature and carrying out centralized treatment. The method has the advantages of simple process, low cost, in-situ remediation, no influence or damage to the surrounding environment, good remediation effect on the soil polluted by organic matters such as polycyclic aromatic hydrocarbon and the like, and suitability for remediation of the soil polluted by organic matters. Application number CN201610020606.0 discloses a method for repairing soil heavily polluted by polycyclic aromatic hydrocarbon by adopting plants, which comprises the following steps: planting plant seedlings on the soil polluted by the high-concentration polycyclic aromatic hydrocarbon, spraying a sodium selenite solution with a certain concentration on the leaf surfaces of the plant seedlings every 10-15 days for 2-3 months, removing the plants when the plants grow to the mature period, performing harmless treatment, and repeating the steps until the polycyclic aromatic hydrocarbon content of the soil reaches the environmental safety standard. The invention can improve the tolerance of plants to the pollution of high-concentration polycyclic aromatic hydrocarbon in soil, promote the absorption of the plants to the polycyclic aromatic hydrocarbon, has short restoration time and improves the restoration effect of plants. Because the industrial sodium selenite is cheap, the cost for treating the soil polluted by the high-concentration polycyclic aromatic hydrocarbon is low, and the method has high practical application value. Application number CN201510661029.9 discloses a method for repairing polycyclic aromatic hydrocarbon contaminated soil by alfalfa in cooperation with a complex microbial inoculant. Through the pretreatment of the alfalfa seeds, the germination period of the plants is shortened by 2-3 days, the tolerance of the plants to PAHs soil is enhanced, and the soil restoration capability of the plants is improved. And in the alfalfa-trichoderma-rhizobium combined remediation system, the degradation of PAHs in the polluted soil by the alfalfa is promoted by utilizing the synergistic effect generated between the trichoderma and the rhizobium. Meanwhile, the physiological profile of the microbial population level of the alfalfa rhizosphere soil is changed, the diversity and the stability of the ecological functions of the soil microbes are recovered, the growth environment of crops is improved, the quality and the yield of the crops are improved, and the method has a wide market application prospect. Application number CN201510159230.7 discloses Acinetobacter (Acinetobacter sp.) W145, which is deposited in the chinese type culture collection with the collection number: CCTCC NO: m2014192, the strain disclosed by the invention has high-efficiency and rapid degradation capability on phenanthrene, fluoranthene, pyrene and naphthalene, and is an excellent material for bioremediation of soil or environment. Application number CN201310625720.2 discloses a method for restoring farmland soil polluted by polycyclic aromatic hydrocarbon by using anion-non mixed surfactant to strengthen ryegrass and rhizosphere microorganisms, belonging to the technical field of restoration of polluted soil. The invention comprises the following steps: (1) applying a low-concentration (30-150 mg/kg) anion-nonionic mixed surfactant on the surface layer of the PAHs polluted soil; (2) planting ryegrass, growing for 40-60 days, harvesting plant bodies, drying in the sun, transferring, and then burning intensively; (3) by repeating the operation, PAHs in the polluted soil can be removed until the environmental safety standard is reached. The method has the advantages that the PAHs adsorbed on the soil are solubilized and eluted by adopting the low-dose anionic-nonionic mixed surfactant, so that the degradation of the PAHs by rhizosphere microorganisms can be promoted, the absorption and accumulation of the PAHs by plants can be improved, and the repair efficiency of the PAHs is improved. Application number CN201310408166.2 discloses a method for improving polycyclic aromatic hydrocarbon degradation capacity by using transgenic plants, which comprises the following specific steps: constructing a bivalent gene plant expression vector by using the modified P450 monooxygenase gene and the synthesized grape glutathione S-transferase (GST) gene, and then transforming the bivalent gene expression vector into a plant through agrobacterium mediation. By using the method, the tolerance and the degradation capability of the obtained transgenic plant to the polycyclic aromatic hydrocarbon are improved, and the cultivation of the transgenic plant is beneficial to repairing the soil environment polluted by the polycyclic aromatic hydrocarbon. Application number CN201210405609.8 discloses a method for remediating polycyclic aromatic hydrocarbon contaminated soil by using gramineous plant fire phoenix. The method is characterized in that gramineous plant fire phoenix is planted in PAHs polluted soil, so that the PAHs in the soil are degraded, removed or remarkably reduced through the combined action of the growth process of the plant and the secretion substances of the root system of the plant in the processes of germination, growth and maturation of the plant. According to the method, the fire phoenix is planted in the polycyclic aromatic hydrocarbon polluted soil, and the ornamental plant fire phoenix is adopted to restore the polycyclic aromatic hydrocarbon polluted soil. Compared with the traditional contaminated soil treatment method, the method has the advantages of low investment, small engineering quantity, low technical requirement and the like. Meanwhile, as an ornamental and economic plant, the fire phoenix planting can not only effectively degrade the polycyclic aromatic hydrocarbon pollution in the environmental soil, but also avoid the polluted plant from entering a food chain, and reduce the ecological risk brought by the treatment to the maximum extent. Application number CN201110261645.7 discloses a natural eluent for repairing polycyclic aromatic hydrocarbon contaminated soil and a repairing method thereof. The eluent is the extract of natural plant soapberry fruit; the specific extraction method comprises the following steps: ultrasonic extracting natural plant fructus Sapindi Mukouossi with 75% ethanol water solution for 30min, decolorizing the extractive solution with active carbon, concentrating, and vacuum drying. The repairing method comprises the following steps: 1) adding polycyclic aromatic hydrocarbon polluted soil and a natural eluting agent with a solid-liquid ratio of 1 g: 10-20 ml, oscillating for 12-24 hours at room temperature, and separating soil and supernate; 2) adding organic bentonite with a solid-liquid ratio of 0.02 g/10-20 ml and supernatant, oscillating for 6-12 hours at room temperature, and performing centrifugal separation to obtain supernatant, namely the recovered natural eluent. The natural eluting agent used in the invention has wide source, easy acquisition, high restoration efficiency, is a biodegradable substance, is environment-friendly and has no secondary pollution, thereby reducing the environmental risk of the eluting agent after the polluted soil is eluted and restored; the eluting agent can be recycled, so that the repair cost is reduced. Application number CN201010581595.6 discloses a method for treating and repairing Polycyclic Aromatic Hydrocarbons (PAHs) polluted soil by using Echinacea purpurea (Echinacea). Planting plants in soil polluted by polycyclic aromatic hydrocarbon to promote the plants to degrade, remove or remarkably reduce PAHs in the soil through the combined action of enzymes, small molecular organic acids and rhizosphere microorganisms secreted by the growth process and the root system of the plants in the processes of growing, blooming or maturing, wherein the plants are as follows: echinacea purpurea belongs to Compositae. Experiments prove that the echinacea purpurea effectively degrades the content of the polycyclic aromatic hydrocarbon in the polluted soil by utilizing the joint action of developed root systems and root system microorganisms. The invention can solve the problems of high technical difficulty, high cost, large engineering quantity, easy secondary pollution and the like in the prior art. The method has the advantages of strong operability, low cost, no damage to the physicochemical property of the soil, and purification and beautification of the environment. Application number CN201010547623.2 discloses a combined remediation method of polycyclic aromatic hydrocarbon contaminated soil, which comprises the following remediation steps: planting perennial bean plant alfalfa in polycyclic aromatic hydrocarbon polluted soil, inoculating arbuscular mycorrhizal fungi and a mixed bacterial agent consisting of bacillus and flavobacterium, and simultaneously adding a biological surfactant, wherein the biological surfactant is rhamnolipid. The rhizosphere effect generated by the plant root secretion improves the number and metabolic activity of soil microorganisms. By inoculating arbuscular mycorrhizal fungi, the growth of plants and the increase of root exudates are promoted, and further, the accumulation of organic pollutants at roots and the quantity of microorganisms in rhizosphere soil are increased. The inoculated high-efficiency polycyclic aromatic hydrocarbon degrading bacteria can also grow and propagate quickly by taking root exudates of plants as a carbon source and an energy source. And the polycyclic aromatic hydrocarbon is desorbed from the soil particles through the biosurfactant, so that the bioavailability and the degradability of the organic pollutants are improved. The application number CN201010508787.4 is a method for repairing the farmland soil polluted by polycyclic aromatic hydrocarbon by interplanting ganoderma and corn: the pH value is neutral or the pH value is slightly acidic, and the PAHs pollute the farmland; designing a combined ridge of 3 ridges of large ridge, small ridge and large ridge; planting corn on large ridges; and (3) growing the corn seedlings to 0.75-1 m, and applying urea to adjust the soil C/N to be 10: 1-15: 1; ditching the small ridges, spraying copper sulfate at the bottoms of the ditches, and inoculating 2 rows of ganoderma lucidum fungus sticks side by side; collecting spores after the ganoderma lucidum grows for 40 to 50 days; harvesting the corns after the corns are ripe; meanwhile, harvesting the lucid ganoderma sporocarp; and (4) measuring the content of PAHs in the soil by liquid chromatography. The invention can effectively promote the degradation rate of PAHs organic pollutants in soil, and has the advantages of environmental protection, no secondary pollution, economy and strong operability. The degradation rate of the combined action of the plants and the lucid ganoderma planted by the method reaches 36.5-45.9 percent, and the efficiency is improved by 107.39-141.21 percent compared with the efficiency of single plant repair. Application number CN200910184526.9 discloses a chemical strengthening phytoremediation method for polycyclic aromatic hydrocarbon-cadmium combined polluted soil, belonging to the field of soil pollution treatment. The method comprises the following steps: (A) measuring the content of cadmium, polycyclic aromatic hydrocarbon phenanthrene and pyrene in soil, and performing willow seed insertion; (B) after the willow is planted for four months, a chemical enhancer consisting of ethyl lactate and ethylene diamine tetraacetic acid is added. The willow is golden weeping willow J1011, and the planting density of the willow is 4-6 plants per square meter of phenanthrene, pyrene and cadmium in 5, 50 and 6mg/kg of soil respectively. The invention avoids the defects of plant restoration such as short plant, slow growth speed, small biomass on the overground part and the like; the environmental risk of heavy metal cadmium in the soil for plant extraction and remediation is reduced; the addition of the chemical reinforcing agents improves the repair efficiency of repairing heavy metals by independently using organic ligands as chelating extraction agents, simultaneously enhances the repair effect of polycyclic aromatic hydrocarbons of organic pollutants in soil, and realizes the simultaneous repair of cadmium and polycyclic aromatic hydrocarbon combined pollution in soil. The application number CN200910013169.X discloses a strengthening repairing agent for super-enriching repairing plant solanum nigrum, which comprises malic acid, glutamic acid and cysteine in a molar ratio of 0.1-1.0: 0.1-1.0. In the cadmium-polycyclic aromatic hydrocarbon combined polluted potting soil transplanted with the black nightshade, malic acid, glutamic acid and cysteine are mixed and poured into the potting soil in the form of water mixed liquor according to the content of 0.1-1.0mmol/kg, the mixture is poured once every 15 days for 3 times, and when the black nightshade is mature, plants and soil samples are harvested. Compared with a control without adding amino acid, the treatment effect of the mixed solution of the malic acid, the glutamic acid and the cysteine with low dosage is optimal, the Cd content on the overground part of the black nightshade is increased by 2.26 times, meanwhile, the removal rate of the total amount of the polycyclic aromatic hydrocarbon in the soil can reach 34.5 percent, and the repair efficiency of the black nightshade on the cadmium and the polycyclic aromatic hydrocarbon is obviously improved. Application number CN200910107989.5 discloses that polyhydroxyalkanoate, which is a completely biodegradable material, is combined with organic and inorganic nutrients to prepare a slow release fertilizer with the effect of soil remediation, and through slowly releasing the organic and inorganic nutrients, the slow release fertilizer can promote the propagation of microorganisms and the continuous and rapid growth of plants, accelerate the bioactivity and water solubility of polycyclic aromatic hydrocarbons, and simultaneously can avoid the loss of fertilizers and the defects of repeated fertilization, save the cost and improve the soil remediation efficiency. The invention also discloses a soil pollution remediation method by using the slow release fertilizer, plants with remediation efficacy are planted in the soil applied with the slow release fertilizer, and the microorganism-plant remediation technology can be used for realizing efficient, environment-friendly and continuous remediation of Polycyclic Aromatic Hydrocarbon (PAHs) polluted soil. Application number CN200410017631.0 discloses a method for phytoremediation of polycyclic aromatic hydrocarbon contaminated soil by using a surfactant to enhance efficiency. The method comprises the following steps: 1) planting ryegrass or red clover plants in the soil polluted by the polycyclic aromatic hydrocarbon, wherein the planting density of the ryegrass or the red clover plants is 200-250 plants per square meter; 2) when the plant grows to 10-12 cm of plant height, applying 15-150 g of nonionic surfactant polyoxyethylene (20) sorbitan monooleate or lauryl polyoxyethylene (23) ether solution to the soil, wherein the application amount of the nonionic surfactant in each square meter of soil is 15-150 g; 3) after the plants grow for 50-60 days, the plants are harvested, dried in the sun, and transferred to other places to be burned in a centralized manner. The invention has the advantages that the easily degradable nonionic surfactant is adopted as the synergistic agent, thereby avoiding the pollution of exogenous chemical reagents to soil; the technical process is simple and the cost is low; the remediation effect on the soil polluted by organic matters such as polycyclic aromatic hydrocarbon is good; is suitable for treating large-area organic contaminated soil.

Third, elution application No. CN200910011728.3 discloses an eluent for removing polycyclic aromatic hydrocarbon pollutants in soil and a preparation method thereof. The eluent is fatty acid methyl ester. Preparation: adding methanol into soybean oil, wherein the molar ratio of the methanol to the soybean oil is 3: 1, adding n-hexane, uniformly mixing the substances, adding immobilized enzyme, and culturing on a shaker at 38 ℃ and 160r/min to obtain fatty acid methyl ester; the methanol is added in 3 times, and the first time is started; the second time is added after 10 hours of reaction; adding after 13h for the third time, namely adding after 23h after the reaction starts; and the addition amount is the same each time. The selected fatty acid methyl ester has the advantages of biodegradability, low viscosity, no toxicity, low exhaust emission and the like; the eluent can repair the soil polluted by high-concentration polycyclic aromatic hydrocarbon and does not cause secondary pollution to the environment. Application No. CN200810110573.4 discloses a cyclic regeneration method of cyclodextrin eluent. The glass column is filled with high molecular resin adsorbent to prepare an adsorption column, a liquid inlet is arranged below the adsorption column, and a liquid outlet is arranged above the adsorption column. And (3) introducing cyclodextrin eluent in the process of repairing the polycyclic aromatic hydrocarbon-polluted soil into an adsorption column through a metering pump, periodically measuring the concentration of the polycyclic aromatic hydrocarbon in an inlet solution and an outlet solution of the adsorption column, and collecting the cyclodextrin solution of which the concentration of the polycyclic aromatic hydrocarbon in the outlet solution is less than 10% of that of the polycyclic aromatic hydrocarbon in the inlet solution, namely the recovered recyclable cyclodextrin solution. When the concentration of the polycyclic aromatic hydrocarbon in the outlet solution is more than 10 percent of that of the polycyclic aromatic hydrocarbon in the inlet solution, the adsorption column needs to be regenerated by using organic solvent elution. The invention has the advantages of simple process, high speed, high practicability, high regeneration efficiency and the like. Application number CN200810019385.0 discloses an eluent for remedying soil polycyclic aromatic hydrocarbon-copper composite pollution and a method thereof. The eluent consists of two reagents A and B, wherein A is lactate or lactate aqueous solution with weight percentage more than 30%, B is ethylenediamine organic ligand or ethylenediamine organic ligand aqueous solution with weight percentage more than 25%, and the two reagents A and B are packaged separately. The method for remedying the polycyclic aromatic hydrocarbon-copper combined pollution of the soil comprises the steps of firstly analyzing the content of polycyclic aromatic hydrocarbon and heavy metal in the soil and the basic physicochemical property of the soil; then preparing an eluting agent; adding eluting agent to elute soil for more than 12h, and separating soil and supernatant. The method has good repairing effect, and provides a method for simultaneously repairing the heavy metal-organic matter combined pollution of the soil; the lactate has wide sources and easy acquisition, improves the repair efficiency of independently using the organic ligand as the eluent, and has lower repair cost; both lactate and the organic ligand are biodegradable substances, so that the environmental risk after leaching and repairing is reduced.

Fourth, wetland restoration method application number CN201010509762.6 discloses a method for restoring polycyclic aromatic hydrocarbon contaminated soil by using artificial wetland, which is characterized by comprising the following steps: (1) isolating a remediation area of the polycyclic aromatic hydrocarbon-polluted soil from the surrounding environment by using a ditch, and arranging a water tank communicated with the ditch on the polycyclic aromatic hydrocarbon-polluted soil; (2) leveling the surface of the polycyclic aromatic hydrocarbon polluted soil, planting restoration plants on the surface of the soil, and installing a water supply device at a higher position of the terrain; periodically supplying water to the repair plants through a water supply device to maintain the growth of the repair plants, and recycling water flow into the water supply device from a ditch or a water tank; (3) and harvesting and transferring the overground part of the plant after the repairing plant is mature, and determining whether to continue repairing according to the repairing condition of the polluted soil. The method is safe and efficient, has no secondary pollution, can beautify the environment and relieve the greenhouse effect, and has the advantages of low treatment cost, energy conservation, good effect and the like.

And fifthly, application number CN201210492831.6 of catalytic degradation discloses a method for repairing soil polluted by polycyclic aromatic hydrocarbon by combining a photocatalysis technology and an electrostatic spinning technology. The specific operation steps comprise preparing spinning solution by tetrabutyl titanate, bismuth nitrate and other substances, covering the surface of the polluted soil to be repaired with an electro-spun fiber membrane with photocatalytic activity by a high-voltage electro-spinning technology, and driving polycyclic aromatic hydrocarbon to migrate to the surface of the photocatalytic electro-spun fiber membrane by the action of water vapor transpiration under the sun exposure and be degraded by photocatalysis. The invention has the advantages of overcoming the obstacle of photocatalysis technology in the field of soil remediation, realizing full utilization of solar energy, effectively protecting the soil structure and fertility system, blocking natural precipitation and volatilization of polycyclic aromatic hydrocarbon, limiting the grasshopper effect of polycyclic aromatic hydrocarbon and playing a role in positive origin clearingThe function of (1). Application number CN200610134208.8 discloses ultraviolet nano TiO of polycyclic aromatic hydrocarbon polluted soil₂Catalytic degradation method for mixing polluted soil with nano TiO₂The mixture of (A) and (B) is paved in a vessel, and the nano TiO₂The weight ratio of the added amount of the organic fertilizer to the contaminated soil is 0.2-5%, the organic fertilizer is placed in an ultraviolet illumination box for illumination degradation, and the illumination conditions in the illumination box are as follows: the ultraviolet irradiation wavelength is 210-365nm, the sample is 5-20cm away from the light source, and the irradiation intensity is 500-10000 mu w/cm²The temperature is 25-35 ℃, the humidity in the ventilation control box is 30-50%, and the illumination time is 2-14 days. The invention has the advantages that: the method has the advantages of high pollutant removal speed, high efficiency, easy operation and no secondary pollution.

The method comprises the steps of (1) preparing soil particles, firstly air-drying and grinding the polluted site soil, (2) setting a repair system, namely adding methyl β cyclodextrin leacheate into a stirrer, (3) adjusting the reaction temperature to 50 +/-2 ℃ (4) simultaneously adjusting an ultrasonic emitter: 35kHz ultrasonic for 30min, (5) continuously leaching and repairing for 3 times, (6) deeply repairing degrading bacteria, namely inoculating polycyclic aromatic hydrocarbon degrading bacteria to the continuously leached and repaired soil, adjusting N/P to 10:1, continuously degrading for 90-140 days, and applying the edible fungus chaff and the biological surfactant to repair the polycyclic aromatic hydrocarbon and heavy metal polluted site soil, wherein the application No. CN201010135665.5 utilizes the edible fungus chaff and the biological surfactant to jointly reinforce the plant to repair the aromatic hydrocarbon polluted soil, and has the prospect of improving the utilization rate of the polycyclic aromatic hydrocarbon polluted soil by the application No. CN 35-60 mg, and improving the utilization rate of the polycyclic aromatic hydrocarbon and the biological surfactant, namely the plant soil by the plant degrading bacteria and the degrading the polycyclic aromatic hydrocarbon and the organic hydrocarbon and improving the utilization rate of the polycyclic aromatic hydrocarbon polluted soil by the polycyclic aromatic hydrocarbon by the organic hydrocarbon and the organic fertilizer produced by the plant, and the polycyclic aromatic hydrocarbon by the plant, and the degrading bacteria, and the organic fertilizer, and the soil produced by the plant, and the soil produced by the plant, and the polycyclic aromatic hydrocarbon, and the plant, and the organic fertilizer, and the polycyclic aromatic hydrocarbon are applied to be used for the soil, the soil are efficiently repaired soil, the soil can be recovered by the plant, the soil after the soil is prepared by the soil with the application No. 10-degrading bacteria, the plant, the soil is applied to be used for the soil, the soil with the application No. 10-degrading bacteria, the high efficiency of the soil is improved by the application No. 10-.

Seventhly, the application number CN201610853459.5 of a microwave remediation method discloses a microwave remediation method of a polycyclic aromatic hydrocarbon contaminated site, which comprises the steps of air-drying soil containing polycyclic aromatic hydrocarbon and total petroleum hydrocarbon under natural conditions, and ensuring the water content of the air-dried soil to be 10-25%; screening the air-dried soil, and removing large stones and concrete blocks to obtain soil to be treated; uniformly mixing a certain amount of the microwave absorbent with the soil to be treated; putting the soil to be treated mixed with the microwave adsorbent into a microwave treatment device, starting a microwave generator of the microwave treatment device to ensure that the temperature in the microwave treatment device reaches a preset temperature, and carrying out microwave treatment on the soil to be treated for a certain time. The method provided by the application is simple and easy to operate, short in operation time, high in treatment efficiency, movable, safe and environment-friendly, and mainly aims at small tail gas generation amount in the treatment stage and low purification cost, so that a new effective method is provided for thermal remediation of the polluted soil.

Eighthly, high-temperature roasting method application number CN201410294841.8 discloses a method for simultaneously restoring heavy metal and polycyclic aromatic hydrocarbon in soil by roasting, belonging to the technical field of polluted soil restoration. The method comprises the steps of taking a certain amount of heavy metal and PAHs composite polluted soil, placing the soil into a roasting furnace for roasting at 400-700 ℃ for 0.5-4 h, taking out a sample after roasting, and naturally cooling to room temperature. The method can melt heavy metals and minerals in the soil into vitrified substances through high-temperature roasting treatment to achieve a fixing effect, and simultaneously, PAHs in the soil are quickly volatilized and decomposed to be removed through the high-temperature roasting treatment, so that the risk of soil heavy metal-PAHs composite pollution is effectively eliminated, and the aim of repairing is fulfilled. The method is simple, convenient, rapid, high in efficiency and good in effect, and is suitable for repairing the heavy metal-organic pollutant composite contaminated site soil left after the enterprise is moved. Application number CN201410294841.8 discloses a method for simultaneously repairing heavy metals and polycyclic aromatic hydrocarbons in soil by roasting, belonging to the technical field of polluted soil repair. The method comprises the steps of taking a certain amount of heavy metal and PAHs composite polluted soil, placing the soil into a roasting furnace for roasting at 400-700 ℃ for 0.5-4 h, taking out a sample after roasting, and naturally cooling to room temperature. The method can melt heavy metals and minerals in the soil into vitrified substances through high-temperature roasting treatment to achieve a fixing effect, and simultaneously, PAHs in the soil are quickly volatilized and decomposed to be removed through the high-temperature roasting treatment, so that the risk of soil heavy metal-PAHs composite pollution is effectively eliminated, and the aim of repairing is fulfilled. The method is simple, convenient, rapid, high in efficiency and good in effect, and is suitable for repairing the heavy metal-organic pollutant composite contaminated site soil left after the enterprise is moved.

Ninth, application No. CN200710191318.2 of ultrasonic wave repairing method discloses a method for repairing polycyclic aromatic hydrocarbon polluted soil by ultrasonic wave, which is to treat polycyclic aromatic hydrocarbon polluted soil slurry with the humidity of 5% -95% and the polycyclic aromatic hydrocarbon concentration of 10-10000 mug/kg under the ultrasonic wave irradiation condition, and the ultrasonic frequency is 20 kHz-100 kHz; the ultrasonic output power is 100W-2.0 kw; the ultrasonic irradiation time is 5 min-4 h. The polycyclic aromatic hydrocarbon is 16 priority control polycyclic aromatic hydrocarbon compounds specified in the U.S. EPA 610. The method mainly utilizes the cavitation effect of ultrasonic waves to degrade or reduce the persistent organic pollutants such as polycyclic aromatic hydrocarbon and the like in the soil.

Ten, application No. CN200710157565.0 of ultraviolet light irradiation method discloses a method for degrading polycyclic aromatic hydrocarbon in soil by ultraviolet light, which comprises the steps of paving a mixture of polluted soil and humic acid in a vessel by taking humic acid as a sensitizing agent, placing the mixture in an ultraviolet illumination box for illumination degradation, wherein the thickness of a soil layer is 0.15-0.5 mm, the addition amount of the humic acid is 3-45 mg/kg of soil, and the illumination conditions in the illumination box are as follows: the ultraviolet irradiation wavelength is 210-365nm, the sample is 5-20cm away from the light source, and the irradiation intensity is 500-10000 mu w/cm²The temperature is 20-38 ℃, the relative humidity in the ventilation control box is 30-50%, and the illumination time is 2-18 days. The invention has the advantages of high speed, high efficiency, easy operation and no secondary pollution.

Eleven, oxidation removal method: application number CN201610813853.6 discloses a method for removing polycyclic aromatic hydrocarbons in soil by persulfate-calcium peroxide composite oxidation. Sieving the air-dried soil to be detected, mixing the sieved soil with calcium peroxide uniformly, adding distilled water to prepare slurry, adding oxalate ions, ferrous ions and persulfate ions in sequence, stirring uniformly to obtain a slurry reaction solution, standing the slurry reaction solution in a dark place, and removing the polycyclic aromatic hydrocarbon in the soil after the reaction is finished. The method can effectively remove naphthalene, acenaphthylene, phenanthrene, anthracene, fluoranthene, pyrene and benzo [ a ] in the complex environment of soil]Anthracene, benzo [ b ]]Fluoranthene, benzo [ a ]]Pyrene, dibenzo [ a, b ]]Anthracene, benzo [ ghi ]]Perylene, indeno [1,2,3-cd]Pyrene and polycyclic aromatic hydrocarbon are high in removal rate, neutral pH of soil can be kept, acidified soil is improved, and a catalyst and a chelating agent are adopted, so that the removal effect and the removal efficiency are improved. Application number CN201610207018.8 discloses a method for removing polycyclic aromatic hydrocarbons in soil by Fenton reagent package oxidation, belonging to the technical field of soil remediation. Mixing air-dried soil to be detected with distilled water to prepare slurry, adding an acidic reagent into the slurry to adjust the pH value of the slurry to 3-5 to obtain acidic slurry, adding a Fenton reagent bag into the acidic slurry and uniformly stirring to obtain a slurry reaction liquid, then standing the slurry reaction liquid for reaction, and removing the slurry reaction liquid after the reaction is finishedRemoving polycyclic aromatic hydrocarbons in soil; wherein the Fenton reagent package consists of FeSO₄、H₂O₂And K₂C₂O₄And (4) forming. The method can effectively remove naphthalene, acenaphthene, acenaphthylene, anthracene, fluorene and phenanthrene in the soil, shortens the treatment time compared with the traditional Fenton reagent, and improves the removal rate.

Twelve and other methods application No. CN10065739. X discloses the application of sulfonated graphene in repairing polycyclic aromatic hydrocarbon contaminated soil, adding sulfonated graphene eluent into soil according to a soil-liquid ratio of 2g (10-40) mL, placing the sulfonated graphene eluent in a centrifuge tube, placing the sulfonated graphene eluent on an oscillator after ultrasonic strengthening for 30 minutes, oscillating and leaching at room temperature of 150rpm for 24 hours, centrifuging the sulfonated graphene after oscillation is finished, and removing supernatant to complete repairing, the invention utilizes sulfonated graphene to effectively remove PAHs in the contaminated soil, so that the removal rate of PAHs is higher than 84%, under the same leaching conditions (eluent concentration, soil-liquid ratio, leaching times and the like), the removal rate of PAHs in SGO leached contaminated soil is 150% and more than 200% of the leaching addition rate of methyl- β -cyclodextrin (methyl- β -MCD) and polysorbate (TW80), the removal rate of PAHs is respectively, the application No. CN200710157565.0 discloses a method for degrading aromatic hydrocarbon in soil by ultraviolet light, the method for degrading aromatic hydrocarbon in soil by taking humic acid as a sensitizer, placing a mixture of contaminated soil in a box, the illumination light source, the illumination of 0.10000-500 cm, the illumination intensity of 0.5-500 cm, the illumination of a soil is 0.5-500 mg of a light source, the illumination of a soil layer, and the illumination of a soil is added in the illumination container, the illumination container is 365, the illumination of the soil is 365, the soil is added²The temperature is 20-38 ℃, the relative humidity in the ventilation control box is 30-50%, and the illumination time is 2-18 days. The invention has the advantages of high speed, high efficiency, easy operation and no secondary pollution. Application number CN200710195109.5 discloses a method for ectopically restoring polycyclic aromatic hydrocarbon polluted soil by using cyclodextrin, belonging to the technical field of polluted soil chemical treatment. And mixing the polycyclic aromatic hydrocarbon polluted soil subjected to air drying, grinding and sieving with a cyclodextrin solution, treating in a rotary oscillator, and separating in a centrifuge. Wherein the mass ratio of water to cyclodextrin is 100: 3-10, the mass ratio of soil to cyclodextrin solution is 1: 1-4, and the soil and cyclodextrin solution are treated in a rotary oscillatorThe time is 16-32 hours. The method has the advantages of simple and easy operation, rapidness, high efficiency and no secondary pollution. Application number CN200610134071.6 discloses an ultraviolet light degradation method for polycyclic aromatic hydrocarbon-contaminated soil, which uses an ultraviolet illumination device to treat polycyclic aromatic hydrocarbon-contaminated soil. The method specifically comprises the following steps: spreading the polluted soil in a vessel, placing the vessel in an ultraviolet illumination box for illumination degradation, wherein the illumination conditions in the illumination box are as follows: the ultraviolet irradiation wavelength is 210-365nm, the sample is 5-20cm away from the light source, and the irradiation intensity is 500-10000 mu w/cm²The temperature is 25-35 ℃, the humidity in the ventilation control box is 30-50%, and the illumination time is 2-50 days. The operation is easy. The method has the advantages of simple treatment for removing the polluted soil, low cost, high speed and high efficiency, and only needs simple treatment of air drying and screening the polluted soil, and then the device for spreading the polluted soil on a plane is placed under an ultraviolet light source for irradiation. The invention belongs to photochemical degradation, does not cause secondary pollution, and is an environment-friendly method for treating polluted soil.

The research and discovery of the prior art show that the exploration of a novel efficient polycyclic aromatic hydrocarbon pollutant treatment process still has practical value and scientific challenge.

The invention creatively provides a novel material for a novel process for treating polycyclic aromatic hydrocarbon pollutants. The invention takes the carbon point modified zinc oxide composite catalyst as visible light catalytic activity, and then adds Fenton reagent as an oxidant to realize the rapid degradation of polycyclic aromatic hydrocarbon under the synergistic action of catalysis and oxidation.

The invention adopts a high-carbon organic matter combustion-supporting method to prepare the high-carbon deposition trace carbon modified zinc oxide visible-light-driven photocatalyst in a macroscopic quantity. The preparation principle is that the effective doping of carbon element in zinc oxide crystal and the mass deposition on the surface are realized by utilizing the combustion reaction heat of high-carbon organic matter at high temperature; meanwhile, a large amount of gas is generated in the reaction process, and the product can be effectively crushed, so that small-sized carbon dot modified zinc oxide nanoparticles are obtained, and the macroscopic preparation of the carbon dot modified zinc oxide-based visible-light-induced photocatalyst is realized.

Disclosure of Invention

The invention aims to provide a composite material for rapidly and efficiently repairing polycyclic aromatic hydrocarbon pollution for treating polycyclic aromatic hydrocarbon in soil and water.

The composite material comprises two parts, namely carbon-point modified zinc oxide and a Fenton reagent.

Specifically, one of the technical problems to be solved by the invention is to provide a composite material for repairing polycyclic aromatic hydrocarbon pollution, which comprises carbon-point modified zinc oxide and a fenton reagent, wherein the mass ratio of the carbon-point modified zinc oxide to the fenton reagent is (1-10): (10-1).

Wherein,

fenton reagent was from commercially available material.

The preparation process of the carbon point modified zinc oxide comprises the following steps:

(1) placing the high-carbon organic substance and a zinc source in a mortar, fully grinding until the system is viscous and transparent, transferring the system into a crucible, and drying until no gas is discharged to obtain a brown fluffy substance;

(2) and calcining the obtained brown fluffy substance, and cooling after the calcination is finished to obtain the carbon-point modified zinc oxide.

Wherein,

the high-carbon organic matter is one or more of malic acid, oxalic acid, citric acid and glucose;

the zinc source is one or more of zinc acetate and zinc nitrate;

the molar ratio of the high-carbon organic substance to the zinc source is (8-10): 1;

the drying temperature in the step (1) is 100-200 ℃, and the drying time is 1-8 h;

the calcining temperature in the step (2) is 500-600 ℃, and the calcining time is 1-4 h.

The cooling in the step (2) is natural cooling or rapid cooling; preferably, the rapid cooling is carried out, the cooling speed of the rapid cooling is 100-200 ℃/min, and the rapid cooling is carried out in an air cooling mode.

The second technical problem solved by the invention is to provide a preparation method of the composite material for repairing polycyclic aromatic hydrocarbon pollution, which comprises the following steps: performing carbon point modification on zinc oxide and a Fenton reagent according to the following steps of (1-10): (10-1) by mass ratio, stirring and compounding.

The invention solves the technical problem and provides the application of the composite material for repairing polycyclic aromatic hydrocarbon pollution in repairing polycyclic aromatic hydrocarbon polluted environment.

The polycyclic aromatic hydrocarbon-contaminated environment includes soil, water, and the like contaminated with polycyclic aromatic hydrocarbons.

The invention combines photocatalytic degradation with oxidation-reduction treatment, accelerates the treatment effect and remarkably improves the treatment effect; according to the invention, the carbon-doped zinc oxide and the Fenton reagent have a synergistic effect, a small amount of zinc ions generated in the reaction of the zinc oxide can accelerate the rate of oxidative degradation, and the dosage of ferrous sulfate in the Fenton reagent can be reduced; the carbon point modified zinc oxide can absorb ultraviolet light and visible light, and has the effects of improving the activity of the Fenton reagent and accelerating the reaction speed; the carbon on the surface of the zinc oxide modified by the carbon points exists in the form of the carbon points, so that the spectrum utilization range can be remarkably improved, and the catalytic activity is improved. At present, no report on the synergistic utilization of carbon-doped zinc oxide and Fenton reagent exists.

The invention solves the technical problem of providing the application of the composite material for repairing polycyclic aromatic hydrocarbon pollution in identifying whether the polluted environment contains heavy metal ions. The composite material for repairing polycyclic aromatic hydrocarbon pollution can give out the information of heavy metal ion pollution in the polluted environment through the mechanism that the carbon spots can generate fluorescence quenching when meeting the heavy metal ions.

The invention has the following advantages:

1. the photocatalytic degradation technology and the oxidative degradation technology of the polycyclic aromatic hydrocarbon are ingeniously combined, a novel composite material for repairing polycyclic aromatic hydrocarbon pollution is prepared for the first time, and a brand new material is provided for effective treatment of the polycyclic aromatic hydrocarbon.

2. The composite material can repair the soil polluted by the polycyclic aromatic hydrocarbon, and can give out the information that the polluted environment (such as polluted soil and the like) is polluted by the heavy metal ions through the mechanism that the carbon spots can generate fluorescence quenching when meeting the heavy metal ions.

3. The raw materials used in the invention have rich and cheap sources, the preparation process is simple, and no industrial pollution such as waste water, waste residue and the like is generated in the production process.

4. Compared with other technologies, the product prepared by the method has the advantages that the polycyclic aromatic hydrocarbon in soil and sewage can be enriched by the carbon-point modified zinc oxide, and catalytic degradation is carried out under the irradiation of light; the carbon point modified zinc oxide can also dissociate zinc ions, and has a further activation effect on hydrogen peroxide in a Fenton reagent;

5. the carbon dot modified zinc oxide catalyst material provided by the invention can be directly used as a light source by using sunlight, can quickly and efficiently degrade organic dye, and has high visible light utilization rate and large industrial application prospect.

6. By utilizing the carbon-point-modified zinc oxide/Fenton reagent composite material provided by the invention, the photocatalytic degradation function and the oxidative degradation function are synergistically complemented, so that the degradation efficiency is greatly improved, compared with the method of simply using a Fenton reagent, the degradation time can be saved by at least more than 50%, and the efficiency of treating polycyclic aromatic hydrocarbon is remarkably improved.

Detailed Description

The present invention will be further illustrated by the following specific examples.

The preparation method of the Fenton reagent in the embodiment and the comparative example of the invention comprises the following steps: the mol ratio of the ferrous sulfate to the hydrogen peroxide is 1: 10, regulating the pH value to be about 4 by using sulfuric acid.

Example 1

Weighing the raw materials according to the molar ratio of the high-carbon organic matter oxalic acid to the zinc acetate of 10:1, placing the raw materials in a mortar, fully grinding until the system is viscous and transparent, transferring the transparent liquid into a crucible, and drying for 1h at 200 ℃ until no gas is discharged. And finally calcining the obtained brown fluffy substance at 500 ℃ for 4h, and rapidly cooling (the cooling method is air cooling; the cooling speed is 100 ℃/min) to obtain light pink powder (namely the carbon dot modified zinc oxide). The particle size of the product is about 40nm through observation of a transmission electron microscope, and the product has good dispersibility.

1g of the carbon point modified zinc oxide is taken, 10g of Fenton reagent material is added and stirred to obtain the composite material for repairing polycyclic aromatic hydrocarbon pollution, and then the composite material is added into the sewage or soil polluted by polycyclic aromatic hydrocarbon to realize the catalytic-oxidation treatment of the polycyclic aromatic hydrocarbon.

Example 2

Weighing the raw materials according to the molar ratio of the high-carbon organic matter citric acid to the zinc nitrate of 10:1, placing the raw materials into a mortar, fully grinding until the system is viscous and transparent, transferring the transparent liquid into a crucible, and drying at 150 ℃ for 5 hours until no gas is discharged. And finally calcining the obtained brown fluffy substance at 600 ℃ for 2h, and rapidly cooling (the cooling method is air cooling; the cooling speed is 100 ℃/min) to obtain light pink powder (namely the carbon dot modified zinc oxide). The particle size of the product is about 55nm through observation of a transmission electron microscope, and the product has good dispersibility.

1g of the carbon point modified zinc oxide is taken, 1g of Fenton reagent material is added and stirred to obtain the composite material for repairing polycyclic aromatic hydrocarbon pollution, and then the composite material is added into the sewage or soil polluted by polycyclic aromatic hydrocarbon to realize the catalytic-oxidation treatment of the polycyclic aromatic hydrocarbon.

Example 3

Weighing the raw materials according to the molar ratio of the high-carbon organic matter citric acid to the zinc nitrate of 10:1, placing the raw materials into a mortar, fully grinding until the system is viscous and transparent, transferring the transparent liquid into a crucible, and drying at 200 ℃ for 6 hours until no gas is discharged. And finally calcining the obtained brown fluffy substance at 800 ℃ for 2h, and rapidly cooling (the cooling method is air cooling; the cooling speed is 200 ℃/min) to obtain light pink powder (namely the carbon dot modified zinc oxide). The particle size of the product is about 50nm through observation of a transmission electron microscope, and the product has good dispersibility.

10g of the carbon point modified zinc oxide is taken, 1g of Fenton reagent material is added and stirred to obtain the composite material for repairing polycyclic aromatic hydrocarbon pollution, and then the composite material is added into the sewage or soil polluted by polycyclic aromatic hydrocarbon to realize the catalytic-oxidation treatment of the polycyclic aromatic hydrocarbon.

Example 4

Weighing the raw materials according to the molar ratio of the high-carbon organic matter malic acid to the zinc acetate of 10:1, placing the raw materials in a mortar, fully grinding until the system is viscous and transparent, transferring the transparent liquid into a crucible, and drying at 200 ℃ for 6 hours until no gas is discharged. And finally, calcining the obtained brown fluffy substance at 600 ℃ for 1h, and quickly cooling (the cooling method is air cooling; the cooling speed is 100 ℃/min) to obtain light pink powder (namely the carbon dot modified zinc oxide). The particle size of the product is about 50nm through observation of a transmission electron microscope, and the product has good dispersibility.

And (3) taking 5g of the carbon point modified zinc oxide, adding 5g of Fenton reagent material, stirring to obtain a composite material for repairing polycyclic aromatic hydrocarbon pollution, and then adding the composite material into the polycyclic aromatic hydrocarbon polluted sewage or soil to realize the catalytic-oxidation treatment of the polycyclic aromatic hydrocarbon.

Example 5

Weighing the raw materials according to the molar ratio of the high-carbon organic matter glucose to the zinc nitrate of 10:1, placing the raw materials in a mortar, fully grinding until the system is viscous and transparent, transferring the transparent liquid into a crucible, and drying at 180 ℃ for 5 hours until no gas is discharged. And finally calcining the obtained brown fluffy substance at 600 ℃ for 2h, and rapidly cooling (the cooling method is air cooling; the cooling speed is 100 ℃/min) to obtain light pink powder (namely the carbon dot modified zinc oxide). The particle size of the product is about 60nm through observation of a transmission electron microscope, and the product has good dispersibility.

10g of the carbon point modified zinc oxide is taken, 20g of Fenton reagent material is added and stirred to obtain the composite material for repairing polycyclic aromatic hydrocarbon pollution, and then the composite material is added into the sewage or soil polluted by polycyclic aromatic hydrocarbon to realize the catalytic-oxidation treatment of the polycyclic aromatic hydrocarbon.

Comparative example 1

And stirring and compounding 10g of pure zinc oxide and 10g of Fenton reagent material to obtain the zinc oxide/Fenton reagent composite catalyst material.

Comparative example 2

And stirring and compounding 10g of pure zinc oxide and 20g of Fenton reagent material to obtain the zinc oxide/Fenton reagent composite catalyst material.

Comparative example 3

Placing glucose and zinc nitrate into a mortar according to a molar ratio of 10:1, fully grinding until the system is viscous and transparent, transferring the transparent liquid into a crucible, and drying at 180 ℃ for 5 hours until no gas is discharged. And finally calcining the obtained brown fluffy substance at 600 ℃ for 2h, and then rapidly cooling (the cooling method is air cooling; the cooling speed is 100 ℃/min) to obtain light pink powder, namely the carbon dot modified zinc oxide catalyst material. The particle size of the product is about 60nm through observation of a transmission electron microscope, and the product has good dispersibility.

Comparative example 4

100 wt% Fenton's reagent was used as the catalyst material.

Test example 1

The composite materials for repairing polycyclic aromatic hydrocarbon pollution of examples 1-5 and the catalyst materials of comparative examples 1-5 were subjected to a degradation performance test in the presence of sewage containing both polycyclic aromatic hydrocarbon naphthalene and polycyclic aromatic hydrocarbon anthracene under a test environment, and the amount of the composite material or the catalyst material added was 5g/L of sewage, and the degradation was carried out for 12 hours.

The method is carried out under the irradiation of visible light, characteristic peaks of naphthalene and anthracene are detected by an ultraviolet spectrophotometer, the content of polycyclic aromatic hydrocarbon anthracene and polycyclic aromatic hydrocarbon naphthalene is detected at the positions with wavelengths of 252nm and 275nm respectively, and the degradation rate is calculated.

Polycyclic aromatic hydrocarbon naphthalene degradation rate (%) - (content before degradation-content after degradation)/content before degradation × 100%

Polycyclic aromatic hydrocarbons anthracene degradation rate (%) (content before degradation-content after degradation)/content before degradation × 100%

TOC residual ratio (%) -content after degradation/content before degradation X100%

The test results are given in the following table:

	polycyclic aromatic Hydrocarbon naphthalene degradation Rate (%)	Anthracene degradation rate of polycyclic aromatic hydrocarbons (%)
			Example 1	99.5	98.5
Example 2	99.3	98.2
			Example 3	99.4	98.4
Example 4	99.4	98.4
			Example 5	99.2	98.1
Comparative example 1	42.3	40.1
			Comparative example 2	48.6	47.2
Comparative example 3	91.2	90.1
			Comparative example 4	40.1	39.2

The composite material for repairing polycyclic aromatic hydrocarbon pollution in the embodiments 1 to 5 of the invention can realize the complete degradation of polycyclic aromatic hydrocarbons such as naphthalene, anthracene and the like. The Total Organic Carbon (TOC) value after treatment was 0, which indicated complete degradation and no organic debris remained, as determined by a TOC analyzer.

In addition, the invention also tests that the polycyclic aromatic hydrocarbon can not be completely degraded by methods such as pure zinc oxide, pure Fenton reagent, pure hydrogen peroxide or pure ferrous ions, and a plurality of organic fragments are easy to remain in a partially degraded system. The composite material for repairing polycyclic aromatic hydrocarbon pollution is a carbon-point-modified zinc oxide/Fenton reagent composite material, the photocatalytic degradation function and the oxidative degradation function are synergistically complementary, the degradation efficiency is greatly improved, compared with the method of simply using a Fenton reagent, the degradation time can be saved by at least over 50%, and the efficiency of treating polycyclic aromatic hydrocarbon is obviously improved.

Test example 2

Simulating soil polluted by heavy metal, adding heavy metal ions (copper chloride, the adding amount of copper ions is 50mg/kg of soil)) into soil containing both polycyclic aromatic hydrocarbon naphthalene and polycyclic aromatic hydrocarbon anthracene, then adding the composite material for repairing polycyclic aromatic hydrocarbon pollution prepared in the examples 1-5, wherein the input amount of the composite material or catalyst material is 5g/kg of soil, and simultaneously setting a group of control groups without adding the composite material for repairing polycyclic aromatic hydrocarbon pollution. Then, each group was irradiated with ultraviolet light (wavelength of about 315nm), and the results showed that examples 1 to 5 exhibited fluorescence quenching after irradiation with ultraviolet light, because the carbon dots on the fluorescent zinc oxide exhibited fluorescence quenching, indicating that heavy metal ions were present in the soil, whereas the control group did not exhibit fluorescence quenching, and thus heavy metal ions were not identified.

Claims

1. A composite material for repairing polycyclic aromatic hydrocarbon pollution is characterized in that: the method comprises the following steps of preparing a carbon point modified zinc oxide and a Fenton reagent, wherein the mass ratio of the carbon point modified zinc oxide to the Fenton reagent is (1-10): (10-1).

2. The composite for remediation of polycyclic aromatic hydrocarbon contamination of claim 1, wherein: the preparation process of the carbon point modified zinc oxide comprises the following steps:

(2) and calcining the obtained brown fluffy substance, quickly cooling after the calcination is finished, and reserving more crystal defects to obtain the carbon-point-modified zinc oxide.

3. The composite for remediation of polycyclic aromatic hydrocarbon contamination of claim 2, wherein: the high-carbon organic matter is one or more of malic acid, oxalic acid, citric acid and glucose.

4. The composite for remediation of polycyclic aromatic hydrocarbon contamination of claim 2, wherein: the zinc source is one or more of zinc acetate and zinc nitrate.

5. The composite for remediation of polycyclic aromatic hydrocarbon contamination of claim 2, wherein: the molar ratio of the high-carbon organic substance to the zinc source is (8-10): 1.

6. the composite for remediation of polycyclic aromatic hydrocarbon contamination of claim 2, wherein: the drying temperature in the step (1) is 100-200 ℃, the drying time is 1-8 hours, the calcining temperature in the step (2) is 500-600 ℃, and the calcining time is 1-4 hours.

7. The composite for remediation of polycyclic aromatic hydrocarbon contamination of claim 2, wherein: the cooling in the step (2) is natural cooling or rapid cooling; preferably, the rapid cooling is carried out, and the cooling speed of the rapid cooling is 100-200 ℃/min.

8. The method for preparing the composite material for repairing polycyclic aromatic hydrocarbon pollution, which is disclosed by any one of claims 1 to 7, comprises the following steps: performing carbon point modification on zinc oxide and a Fenton reagent according to the following steps of (1-10): (10-1) by mass ratio, stirring and compounding.

9. Use of the composite material for repairing polycyclic aromatic hydrocarbon pollution, as defined in any one of claims 1 to 7, for repairing polycyclic aromatic hydrocarbon polluted environment.

10. Use of the composite material for repairing polycyclic aromatic hydrocarbon pollution, disclosed by any one of claims 1-7, for identifying whether a polluted environment contains heavy metal ions.