CN115368902A - Kit with function of degrading organic pollutants and application thereof - Google Patents
Kit with function of degrading organic pollutants and application thereof Download PDFInfo
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- CN115368902A CN115368902A CN202110540724.5A CN202110540724A CN115368902A CN 115368902 A CN115368902 A CN 115368902A CN 202110540724 A CN202110540724 A CN 202110540724A CN 115368902 A CN115368902 A CN 115368902A
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- ferrous
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- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 17
- 230000000593 degrading effect Effects 0.000 title claims abstract description 12
- 239000002689 soil Substances 0.000 claims abstract description 117
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 22
- 150000002978 peroxides Chemical class 0.000 claims abstract description 21
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 18
- 238000005067 remediation Methods 0.000 claims abstract description 16
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 11
- 231100000719 pollutant Toxicity 0.000 claims abstract description 10
- 239000003209 petroleum derivative Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 34
- 239000000356 contaminant Substances 0.000 claims description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002738 chelating agent Substances 0.000 claims description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 12
- 229910052753 mercury Inorganic materials 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000004343 Calcium peroxide Substances 0.000 claims description 10
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 10
- 235000019402 calcium peroxide Nutrition 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 8
- 239000011790 ferrous sulphate Substances 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 8
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 claims description 6
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- TXVHTIQJNYSSKO-UHFFFAOYSA-N BeP Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004277 Ferrous carbonate Substances 0.000 claims description 3
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 3
- 229960004652 ferrous carbonate Drugs 0.000 claims description 3
- 235000019268 ferrous carbonate Nutrition 0.000 claims description 3
- 229910000015 iron(II) carbonate Inorganic materials 0.000 claims description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 claims description 2
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 229960004995 magnesium peroxide Drugs 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 229940105296 zinc peroxide Drugs 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 235000015165 citric acid Nutrition 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 4
- 239000000391 magnesium silicate Substances 0.000 description 4
- 229910052919 magnesium silicate Inorganic materials 0.000 description 4
- 235000019792 magnesium silicate Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010414 supernatant solution Substances 0.000 description 4
- 239000012028 Fenton's reagent Substances 0.000 description 3
- 230000000711 cancerogenic effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 206010007269 Carcinogenicity Diseases 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 231100000260 carcinogenicity Toxicity 0.000 description 2
- 230000007670 carcinogenicity Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012954 risk control Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 241000254032 Acrididae Species 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 208000007578 phototoxic dermatitis Diseases 0.000 description 1
- 231100000018 phototoxicity Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910021646 siderite Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- 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
-
- 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
- C09K2101/00—Agricultural use
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 of soil remediation, and discloses a kit with a function of degrading organic pollutants and application thereof. The kit comprises solid peroxide, a ferrous complex and an ultraviolet light source. The invention also provides a method for restoring the polluted soil, which comprises the following steps: in the presence of a solvent, the solid peroxide, ferrous complex and contaminated soil are mixed and then irradiated with an ultraviolet light source. The kit with the function of degrading organic pollutants can degrade various organic pollutants, particularly polycyclic aromatic hydrocarbon and petroleum hydrocarbon with complex structures, and has high degradation rate, and the removal rate of the pollutants can reach more than 90 percent at most.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a kit with a function of degrading organic pollutants and application thereof.
Background
Polycyclic Aromatic Hydrocarbons (PAHs) are compounds in which two or more benzene rings are linked together, and are classified into biphenyls, polyphenylaliphenyls, and polycyclic aromatic hydrocarbons according to the manner in which the benzene rings are linked. Polycyclic aromatic hydrocarbons are carcinogenic substances which are found at the earliest and in the largest quantity, and more than 400 carcinogenic polycyclic aromatic hydrocarbons and derivatives thereof have been found at present. Due to their toxicity and carcinogenicity, the USEPA has blacklisted 16 PAHs as priority toxic organic pollutants (priority pollutants) as early as 1976. Research in industrially developed countries has shown that, in recent 100-150 years, the concentration of PAHs in soil (especially in soil in urban areas) has increased, and soil has become an important sink for PAHs.
PAHs mainly come from human production activities and energy utilization processes, and production processes of petroleum and petrochemical products, and are ubiquitous in the environment. Polycyclic aromatic hydrocarbon belongs to indirect carcinogen, and the toxicity mainly comprises the processes and effects of chemical carcinogenicity, phototoxicity effect, inhibition on microorganisms and the like. With the advance of industrialization process and the combined influence of the characteristics of persistent organic pollution and global distillation effect and grasshopper effect, the PAHs become environmental pollutants which are widely distributed all over the world nowadays.
The advanced oxidation technique is also called deep oxidation technique, and mainly refers to that an oxidizing agent is decomposed in the presence of other substances to generate OH, so that radical type reaction is generated. In this case, the contaminant may be directly or indirectly "mineralized" to CO 2 And H 2 And O. Compared with the common chemical oxidation technology, the advanced oxidation technology has the main characteristics that OH with high reaction activity is generated in a system, and the activity of free radicals is fully utilized to quickly and thoroughly oxidize organic pollutants in soil. The Fenton reagent refers to the compound which is added with H when ferrous ions are naturally or artificially added 2 O 2 The reaction takes place, and a highly reactive OH reagent can be produced. The acidic water-soluble was found in a scientific study by french scientist h.j.h, fenton in 1894When ferrous ions and hydrogen peroxide coexist in the liquid, the malic acid can be effectively oxidized. This study provides a new method for the analysis of reducing organics and selective oxidation of organics. The scientist who commemorates this great place of later men would be Fe 2+ /H 2 O 2 Named Feton reagent, the reaction using this reagent is called the Fenton reaction. It is an efficient and widely used advanced oxidation method, and has unique advantages in treating common oxidative and nonbiodegradable toxic organic matters. However, the Fenton reagent needs acidity as reaction conditions, so that the Fenton reagent has high influence on soil after reaction. So that the solid peroxide is used as H 2 O 2 A substitute for (1).
CN106493162A discloses a method for repairing phthalate-contaminated soil by using microwave-enhanced calcium peroxide. According to the method, the phthalate polluted soil is prepared into a slurry soil mixed solution according to a certain liquid-solid ratio, a certain amount of citric acid, ferrous sulfate and calcium peroxide are added into the solution, and after microwave treatment and standing, the degradation rate of the phthalate in the soil reaches over 80 percent. The method has the advantages of simple process conditions, low operation requirements, high treatment efficiency, less oxidant waste and the like, and is suitable for repairing the phthalate-polluted soil.
However, the above method still has the problems of simple pollutant structure and low concentration, so that the soil remediation agent capable of degrading the pollutants with complex structure and high concentration in the soil is urgently needed.
Disclosure of Invention
The invention aims to overcome the technical problems in the prior art and provide a kit with a function of degrading organic pollutants and application thereof.
The inventor of the invention finds that when the organic matters in the soil are degraded by the solid peroxide and the ferrous complex, the organic matters with complex structures and high concentration in the soil can be degraded by increasing the irradiation of the ultraviolet light source.
In order to achieve the above object, the present invention provides, in a first aspect, a kit having a function of degrading organic pollutants, the kit comprising a solid peroxide, a ferrous complex, and an ultraviolet light source.
The invention also provides application of the kit in contaminated soil remediation.
In a third aspect, the present invention provides a method for remediating contaminated soil, comprising: in the presence of a solvent, mixing the solid peroxide and the ferrous complex with the contaminated soil, and then irradiating with an ultraviolet light source.
Through the technical scheme, the invention improves the degradation rate of soil organic pollutants (especially polycyclic aromatic hydrocarbons) and can maintain the pH value of soil.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a kit with the function of degrading organic pollutants, which comprises solid peroxide, a ferrous complex and an ultraviolet light source.
According to the present invention, the wavelength of the ultraviolet light emitted from the ultraviolet light source is not particularly limited, and in order to increase the degradation rate of the organic pollutants, the wavelength of the ultraviolet light emitted from the ultraviolet light source is preferably 230 to 260nm, and more preferably 250 to 255nm.
The apparatus for providing an ultraviolet light source according to the present invention may be an apparatus commonly used in the art, and preferably, the ultraviolet light source is a low pressure mercury lamp.
According to the present invention, the type of the solid peroxide is not particularly limited, and preferably, the solid peroxide is an alkaline solid peroxide, and is preferably at least one of calcium peroxide, magnesium peroxide, and zinc peroxide.
According to the present invention, the manner of obtaining the ferrous complex is not particularly limited, and preferably, the ferrous complex is prepared from a ferrous catalyst and a chelating agent. It is understood that the solution of reacting the ferrous catalyst and the chelating agent in situ to form the ferrous complex is also within the scope of the present application.
According to the present invention, the amounts of the solid peroxide, the ferrous catalyst and the chelating agent can be selected within a wide range, and in order to further increase the degradation rate of the organic pollutants, it is preferable that the ferrous catalyst and the chelating agent are used in such an amount that the molar ratio of the solid peroxide to the ferrous catalyst to the chelating agent is 1:0.2-0.54:0.3 to 1.2, preferably 1:0.25-0.5:0.5-1.
According to the present invention, the chelating agent may be a chelating agent commonly used in the art, and preferably, the chelating agent is at least one of citric acid, tartaric acid, ethylenediaminetetraacetic acid, gluconic acid, N-hydroxyethylethylenediaminetriacetic acid, and N, N-dihydroxyethylglycine.
According to the present invention, the kind of the ferrous catalyst is not particularly limited, and various materials capable of providing ferrous ions, such as ferrous salts and/or ferrous oxides, may be used. Preferably, the ferrous catalyst is at least one of ferrous sulfate, ferrous chloride, ferrous oxide, and ferrous carbonate. Wherein the ferrous carbonate can be provided by siderite.
The invention provides an application of the kit in contaminated soil remediation in a second aspect.
In a third aspect, the present invention provides a method for remediating contaminated soil, comprising: in the presence of a solvent, the solid peroxide, ferrous complex and contaminated soil are mixed and then irradiated with an ultraviolet light source.
According to the present invention, the irradiation time is not particularly limited, and in order to increase the degradation rate of organic contaminants, it is preferable that the irradiation time is 6 to 48 hours.
According to the present invention, it is preferable that the content of the contaminant in the contaminated soil is 100 to 20000mg per kg of the contaminated soil.
According to the present invention, it is preferred that the solid peroxide is used in an amount of 10 to 25g per kg of contaminated soil in terms of contaminants.
According to the present invention, it is preferable that the solvent is used in an amount of 1.5 to 3kg per kg of contaminated soil.
According to the present invention, preferably, the solvent is water.
In the present invention, the specific types and amounts of the solid peroxide and the ferrous complex, and the ultraviolet light source are as described above, and are not described herein again.
According to the present invention, preferably the contaminant in the contaminated soil is an organic contaminant, preferably a polycyclic aromatic hydrocarbon and/or a petroleum hydrocarbon, more preferably at least one of pyrene, phenanthrene and benzo (a) pyrene. The kit and the method are particularly suitable for degrading the polycyclic aromatic hydrocarbon, and have particularly obvious effect on repairing the soil polluted by the polycyclic aromatic hydrocarbon.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
the contaminated soil is, without specific description, a contaminated soil homemade in a laboratory. The self-making method comprises the following steps: the soil without contaminants was dried at room temperature, sieved through a 10 mesh sieve and finally the contaminants were added.
Example 1
(1) Adding 10g of contaminated soil into 4 centrifugal tubes respectively, wherein the concentration of pyrene contaminants is 1000mg/kg Contaminated soil The pH of the contaminated soil was 6. Then 0.25g of calcium peroxide is added into 4 centrifugal tubes, and a solution prepared from ferrous sulfate, citric acid and water (the mass ratio of the water to the polluted soil is 2: 0.5:1. and then carrying out vortex mixing for 30s by using a vortex mixer, then placing the conical flask under a light source of a low-pressure mercury lamp for irradiation, wherein the wavelength of ultraviolet light emitted by the low-pressure mercury lamp is 253nm, taking the conical flask out of the vortex mixer every 3 hours for 1min, and carrying out vortex mixing on the conical flask by using 4 centrifugal tubes for 6 hours, 12 hours, 24 hours and 48 hours respectively.
(2) And after the reaction is finished, taking down the centrifugal tube, centrifuging for 3min at the rotating speed of 5000r/min, and pouring out the upper-layer solution after centrifugation. Adding 30mL of n-hexane, mixing for 30s in a vortex manner, and reversely oscillating the centrifugal tube for 2h for extraction. After extraction, the supernatant solution was filtered through a magnesium silicate column. After filtration, the pyrene concentration in the soil was determined by gas chromatography. The pH of the remediated soil was 6 and the results of the stopping concentration and contaminant removal rate are shown in Table 1.
Example 2
(1) Taking 10g of contaminated soil, wherein the concentration of pyrene contaminants is 200mg/kg Contaminated soil The contaminated soil, having a pH of 6, was added to the centrifuge tube. Adding 0.15g of calcium peroxide into a centrifugal tube, and simultaneously adding a solution prepared from ferrous sulfate, citric acid and water (the mass ratio of the water to the polluted soil is 1.5): 0.25:0.5. and then carrying out vortex mixing for 30s by using a vortex mixer, then placing the conical flask under a light source of a low-pressure mercury lamp for irradiation, taking the conical flask out of the vortex mixer every 3 hours to carry out vortex mixing for 1min, wherein the wavelength of ultraviolet light emitted by the low-pressure mercury lamp is 254nm, and the reaction time is 12 hours.
(2) And after the reaction is finished, taking down the centrifugal tube, centrifuging for 3min at the rotating speed of 5000r/min, and pouring out the upper-layer solution after centrifugation. Adding 30mL of n-hexane, mixing for 30s in a vortex manner, and reversely oscillating the centrifugal tube for 2h for extraction. After extraction, the supernatant solution was filtered through a magnesium silicate column. After filtration, the pyrene concentration in the soil was determined by gas chromatography. The pH of the remediated soil was 6 and the results of the stopping concentration and contaminant removal rate are shown in Table 1.
Example 3
Soil remediation was conducted in accordance with the method of example 2, except that the pyrene concentration was replaced with 300mg/kg Contaminated soil And the pH value of the polluted soil is 6. The pH of the remediated soil was 6 and the results of the stopping concentration and contaminant removal rate are shown in Table 1.
Example 4
Soil remediation was conducted in accordance with the method of example 2, except that the pyrene concentration was replaced with 400mg/kg Contaminated soil And the pH value of the polluted soil is 6. The pH of the remediated soil was 6 and the results of the stopping concentration and contaminant removal rate are shown in Table 1.
Example 5
Soil remediation was carried out in accordance with the method of example 2, except that "pyrene pollutant concentration was set to 200mg/kg Contaminated soil The concentration of the phenanthrene is 300mg/kg Contaminated soil "and the pH value of the contaminated soil is 6. The pH of the remediated soil was 6 and the results of the stopping concentration and contaminant removal rate are shown in Table 1.
Example 6
Soil remediation was performed in accordance with the method of example 2, except that "pyrene contaminant concentration was set to 200mg/kg Contaminated soil "substituted" with benzo (a) pyrene concentration of 200mg/kg Contaminated soil "and the pH value of the contaminated soil is 6. The pH of the remediated soil was 6 and the results of the stop concentration and contaminant removal rate are shown in Table 1.
Example 7
Soil remediation was carried out in accordance with the method of example 2, except that the contaminated soil was replaced with pyrene-contaminated soil collected from a certain coking plant, and the pyrene concentration was detected to be replaced with 174mg/kg Contaminated soil And the pH value of the polluted soil is 6. The pH of the remediated soil was 6 and the results of the stopping concentration and contaminant removal rate are shown in Table 1.
Example 8
(1) Taking 10g of contaminated soil, wherein the concentration of pyrene contaminants is 200mg/kg Contaminated soil The contaminated soil, having a pH of 6, was added to the centrifuge tube. Adding 0.1g of calcium peroxide into a centrifugal tube, and simultaneously adding a solution prepared from ferrous sulfate, citric acid and water (the mass ratio of the water to the polluted soil is 1.5): 0.21:0.3. and then vortex mixing is carried out for 30s by using a vortex mixer, then the conical flask is placed under a light source of a low-pressure mercury lamp for irradiation, the wavelength of ultraviolet light emitted by the low-pressure mercury lamp is 243nm, the conical flask is taken out from the vortex mixer every 3 hours for vortex mixing for 1min, and the reaction time is 12 hours.
(2) And after the reaction is finished, taking down the centrifugal tube, centrifuging for 3min at the rotating speed of 5000r/min, and pouring out the upper-layer solution after centrifugation. Adding 30mL of n-hexane, mixing for 30s in a vortex manner, and reversely oscillating the centrifugal tube for 2h for extraction. After extraction, the supernatant solution was filtered through a magnesium silicate column. After filtration, the pyrene concentration in the soil was determined by gas chromatography. The pH of the remediated soil was 6 and the results of the stopping concentration and contaminant removal rate are shown in Table 1.
Example 9
(1) Taking 10g of contaminated soil, wherein the concentration of pyrene contaminants is 200mg/kg Contaminated soil The contaminated soil, having a pH of 6, was added to the centrifuge tube. Adding 0.25g of calcium peroxide into a centrifugal tube, and simultaneously adding a solution prepared from ferrous sulfate, citric acid and water (the mass ratio of water to the polluted soil is 3: 0.54:1.2. and then carrying out vortex mixing for 30s by using a vortex mixer, then placing the conical flask under a light source of a low-pressure mercury lamp for irradiation, wherein the wavelength of ultraviolet light emitted by the low-pressure mercury lamp is 256nm, taking out the conical flask on the vortex mixer every 3 hours for 1min, and carrying out vortex mixing for 12h.
(2) And after the reaction is finished, taking down the centrifugal tube, centrifuging for 3min at the rotating speed of 5000r/min, and pouring out the upper-layer solution after centrifugation. 30mL of n-hexane was added and mixed by swirling for 30 seconds, and the centrifuge tube was then inverted and shaken for 2 hours to extract. After extraction, the supernatant solution was filtered through a magnesium silicate column. After filtration, the pyrene concentration in the soil was determined by gas chromatography. The pH of the remediated soil was 6 and the results of the stop concentration and contaminant removal rate are shown in Table 1.
Example 10
Soil remediation was carried out as in example 2, except that the mass of calcium peroxide added in step (1) was 0.05g, wherein the molar ratio of calcium peroxide, ferrous sulfate and citric acid was 1:0.6:1.25, the mass ratio of water to the polluted soil is 3.5:1. the pH of the remediated soil was 5 and the results of the stop concentration and contaminant removal rate are shown in Table 1.
Example 11
Soil remediation was carried out as in example 2, except that the low-pressure mercury lamp emitted ultraviolet light at a wavelength of 270nm. The pH of the remediated soil was 6.5 and the results of the stopping concentration and contaminant removal rate are shown in Table 1.
Comparative example 1
Soil remediation was carried out as in example 1, except that only one set of experiments was carried out, and "irradiation of the erlenmeyer flask under a low pressure mercury lamp light source" was replaced with "putting the erlenmeyer flask in the dark". The pH of the remediated soil was 7 and the results of the stopping concentration and contaminant removal rate are shown in Table 1.
TABLE 1
Example 12
Soil remediation was carried out in accordance with the method of example 2, except that the contaminated soil was collected from the petroleum hydrocarbon contaminated soil of a certain gas station in Beijing and the total petroleum hydrocarbon in the soil was detected to be 10100mg/kg Contaminated soil The screening value of the second type land exceeding the soil environmental quality construction land soil pollution risk control standard is (4500 mg/kg), and the standard exceeding multiple is 2.24 times; wherein the concentration of pyrene pollutant is 168mg/kg Contaminated soil (ii) a The pH value of the polluted soil is 6, and the polluted soil does not contain impurities such as stones, building residues, garbage and the like. The pH of the remediated soil was 6 and the results of the stop concentration and contaminant removal rate are shown in Table 2.
TABLE 2
Example 13
Soil remediation was performed as in example 2, except that the contaminated soil was collected from petroleum hydrocarbon contaminated soil of a gasoline station in Beijing and examined to determine the total petroleum hydrocarbon 12100mg/kg Contaminated soil The screening value of the second type of land exceeding the soil environmental quality construction land soil pollution risk control standard is (4500 mg/kg), and the standard exceeding multiple is 2.69 times; wherein the pyrene pollutant concentration is 193mg/kg Contaminated soil (ii) a The pH value of the polluted soil is 6, and the polluted soil does not contain impurities such as stones, building residues, garbage and the like. The pH value of the repaired soil is 6, the termination concentration and the pollutant removal rateThe results are shown in Table 3.
TABLE 3
The results in tables 1-3 show that the kit with the function of degrading organic pollutants can degrade various organic pollutants, particularly polycyclic aromatic hydrocarbons and petroleum hydrocarbons with complex structures, and has high degradation rate, and the removal rate of the pollutants can reach more than 90% at most.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A kit with a function of degrading organic pollutants is characterized by comprising solid peroxide, a ferrous complex and an ultraviolet light source.
2. The kit according to claim 1, wherein the ultraviolet light source emits ultraviolet light at a wavelength of 230 to 260nm, preferably 250 to 255nm, and the ultraviolet light source is a low-pressure mercury lamp.
3. The kit according to claim 1 or 2, wherein the solid peroxide is an alkaline solid peroxide, preferably at least one of calcium peroxide, magnesium peroxide and zinc peroxide.
4. The kit of any one of claims 1 to 3, wherein the ferrous complex is prepared from a ferrous catalyst and a chelating agent.
5. The kit of claim 4, wherein the ferrous catalyst and the chelating agent are used in amounts such that the molar ratio of the solid peroxide, the ferrous catalyst and the chelating agent is 1:0.2-0.54:0.3 to 1.2, preferably 1:0.25-0.5:0.5-1.
6. The kit according to claim 4 or 5, wherein the chelating agent is at least one of citric acid, tartaric acid, ethylenediaminetetraacetic acid, gluconic acid, N-hydroxyethylethylenediaminetriacetic acid and N, N-dihydroxyethylglycine;
and/or the ferrous catalyst is at least one of ferrous sulfate, ferrous chloride, ferrous oxide and ferrous carbonate.
7. Use of a kit according to any one of claims 1 to 6 for the remediation of contaminated soil.
8. A method of remediating contaminated soil, comprising: in the presence of a solvent, mixing the solid peroxide and the ferrous complex with the contaminated soil, and then irradiating with an ultraviolet light source.
9. The method of claim 8, wherein the irradiation time is 6-48h;
and/or the content of the pollutants in the polluted soil is 100-20000mg per kilogram of the polluted soil;
and/or the amount of said solid peroxide is 10-25g per kg of contaminated soil measured as contaminants;
and/or the solvent is used in an amount of 1.5 to 3kg per kg of contaminated soil.
10. The method according to claim 8 or 9, wherein the contaminant in the contaminated soil is an organic contaminant, preferably a polycyclic aromatic hydrocarbon and/or a petroleum hydrocarbon, more preferably at least one of pyrene, phenanthrene and benzo (a) pyrene.
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Cited By (1)
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| CN117778014A (en) * | 2023-12-22 | 2024-03-29 | 哈尔滨工业大学 | Application of active oxygen carrying oxidant in removing organic pollutants in soil |
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