CN115368903A - Composition with functions of solubilizing and degrading organic pollutants and application thereof - Google Patents
Composition with functions of solubilizing and degrading organic pollutants and application thereof Download PDFInfo
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- CN115368903A CN115368903A CN202110541971.7A CN202110541971A CN115368903A CN 115368903 A CN115368903 A CN 115368903A CN 202110541971 A CN202110541971 A CN 202110541971A CN 115368903 A CN115368903 A CN 115368903A
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- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 16
- 230000000593 degrading effect Effects 0.000 title claims abstract description 12
- 230000003381 solubilizing effect Effects 0.000 title claims abstract description 11
- 239000002689 soil Substances 0.000 claims abstract description 107
- 150000002978 peroxides Chemical class 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 30
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 18
- 238000005067 remediation Methods 0.000 claims abstract description 14
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 4
- 238000002604 ultrasonography Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 239000000356 contaminant Substances 0.000 claims description 29
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 20
- 239000004343 Calcium peroxide Substances 0.000 claims description 19
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 19
- 235000019402 calcium peroxide Nutrition 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000002738 chelating agent Substances 0.000 claims description 11
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 11
- 239000011790 ferrous sulphate Substances 0.000 claims description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 11
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 11
- 229920000136 polysorbate Polymers 0.000 claims description 11
- 239000003209 petroleum derivative Substances 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 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
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- -1 sorbitan ester Chemical class 0.000 claims description 4
- 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
- TXVHTIQJNYSSKO-UHFFFAOYSA-N BeP Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-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
- 229960004995 magnesium peroxide Drugs 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 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 17
- 239000000243 solution Substances 0.000 description 16
- 235000015165 citric acid Nutrition 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 231100000719 pollutant Toxicity 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
- 230000010355 oscillation Effects 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000012028 Fenton's reagent Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 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
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012954 risk control 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
- NKFNBVMJTSYZDV-UHFFFAOYSA-N 2-[dodecyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCCCCCCCCCN(CCO)CCO NKFNBVMJTSYZDV-UHFFFAOYSA-N 0.000 description 1
- 241000254032 Acrididae Species 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 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
- 231100000315 carcinogenic Toxicity 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
- 239000007789 gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 208000007578 phototoxic dermatitis Diseases 0.000 description 1
- 231100000018 phototoxicity Toxicity 0.000 description 1
- 229910021646 siderite Inorganic materials 0.000 description 1
- 239000010414 supernatant solution 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
-
- 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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of soil remediation, and discloses a composition with functions of solubilizing and degrading organic pollutants and application thereof. The composition comprises a ferrous complex, a solubilizer and an independent solid peroxide, wherein the solubilizer is a non-ionic surfactant, and the mass ratio of the solid peroxide to the solubilizer is 1:0.2-3. The invention also provides a kit with the functions of solubilizing and degrading organic pollutants, which comprises the composition and an ultrasonic generator. The invention also provides a method for restoring the polluted soil, which comprises the following steps: (1) Under the conditions of a solvent and ultrasound, carrying out first mixing on a solubilizer and a ferrous complex and polluted soil; (2) And secondly mixing the product obtained by the first mixing and the solid peroxide. The invention improves the degradation rate of organic pollutants (especially polycyclic aromatic hydrocarbons) in soil and can maintain the pH value of the soil.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a composition with functions of solubilizing and 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 carcinogens found at the earliest and in the greatest number, and over 400 carcinogenic polycyclic aromatic hydrocarbons and their derivatives have been found to date. 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 for nearly 100-150 years, the concentrations of PAHs in soils (particularly in soils in urban areas) have increased, and that soils have 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 the industrialization process and the combined influence of the characteristics of persistent organic pollution and the global distillation effect and the grasshopper effect, the PAHs become environmental pollutants 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 is carried out, and the reaction is carried out,a reagent capable of producing highly reactive OH. In 1894, french scientist h.j.h, fenton, discovered in a scientific study that malic acid can be efficiently oxidized in an acidic aqueous solution when ferrous ions and hydrogen peroxide coexist. This study provides a new method for the analysis of reducing organics and selective oxidation of organics. The scientists who commemorate this great place later will 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 applied advanced oxidation method, and has unique advantages in treating general oxidized and nonbiodegradable toxic organic matters. However, the Fenton reagent needs to be acidic in 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).
However, polycyclic aromatic hydrocarbon has low solubility and large molecular weight, and is easy to be adsorbed on soil particles, so that solid peroxide is difficult to be in full contact with pollutants, and thus the polycyclic aromatic hydrocarbon is difficult to be in full reaction with polycyclic aromatic hydrocarbon in soil.
Disclosure of Invention
The invention aims to overcome the problem of low degradation rate of organic pollutants in soil in the prior art, and provides a composition with functions of compatibilization and degradation of organic pollutants and application thereof.
In order to achieve the above object, the present invention provides, in a first aspect, a composition having a function of solubilizing and degrading organic pollutants, the composition comprising a ferrous complex, a solubilizing agent and a solid peroxide, wherein the solubilizing agent is a nonionic surfactant, and the solid peroxide and the solubilizing agent are present independently in a mass ratio of 1:0.2-3.
The second aspect of the present invention provides a kit having the functions of solubilizing and degrading organic contaminants, which comprises the composition described above and an ultrasonic generator.
In a third aspect, the invention provides the use of the composition as described above in the remediation of contaminated soil.
In a fourth aspect, the present invention provides a method for remediating contaminated soil, comprising the steps of:
(1) Under the conditions of a solvent and ultrasound, carrying out first mixing on a solubilizer and a ferrous complex and polluted soil;
(2) And secondly mixing the product obtained by the first mixing and the solid peroxide. 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 such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a composition with the function of solubilizing and degrading organic pollutants, which comprises a ferrous complex, a solubilizer and an independent solid peroxide, wherein the solubilizer is a non-ionic surfactant, and the mass ratio of the solid peroxide to the solubilizer is 1:0.2-3.
According to the present invention, in order to further increase the degradation rate of the composition for degrading organic pollutants, the mass ratio of the solid peroxide to the solubilizing agent is preferably 1:0.5-1.
According to the present invention, preferably, the solubilizer is a sorbitan ester, preferably tween and/or span.
According to the present invention, the ferrous complex is obtained by a method not particularly limited, and is preferably 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 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.
The amounts of the solid peroxide, ferrous catalyst and chelating agent may be selected within a wide range according to the present invention. Preferably, the ferrous catalyst and the chelating agent are used in such amounts that the molar ratio of the solid peroxide to the ferrous catalyst to the chelating agent is 1:0.15-0.6:0.5-1.2, preferably 1:0.4-0.5:0.9-1.
According to the present invention, the kind of the chelating agent is not particularly limited, 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.
According to a preferred embodiment of the invention, the composition consists only of the above-mentioned ingredients.
The second aspect of the present invention provides a kit having the function of solubilizing and degrading organic pollutants, which comprises the composition described above and an ultrasonic generator.
According to the present invention, it is preferable that the intensity of the ultrasonic wave generated by the ultrasonic generator is 30 to 60kHz.
In a third aspect, the invention provides the use of the composition as described above in the remediation of contaminated soil.
The inventor of the invention finds that the degradation rate of organic matters in the soil is lower by directly contacting the solubilizer, the ferrous complex and the solid peroxide with the polluted soil; under the ultrasonic condition, after the solubilizer and the ferrous complex are contacted with the polluted soil for a period of time, the solid peroxide is added, so that the degradation rate of organic matters in the soil can be obviously improved. Accordingly, in a fourth aspect, the present invention provides a method of remediating contaminated soil comprising the steps of:
(1) Under the conditions of a solvent and ultrasound, carrying out first mixing on a solubilizer and a ferrous complex and polluted soil;
(2) And carrying out second mixing on the product obtained by the first mixing and the solid peroxide.
According to the invention, the time of the first mixing can be selected within a wide range, preferably from 10 to 30min.
According to the invention, the time of the second mixing can be chosen within a wide range, preferably from 6 to 48h.
According to the present invention, the content of the contaminant in the contaminated soil is not particularly limited. Preferably, the content of the contaminant in the contaminated soil is 200-15000mg per kg of the contaminated soil.
The amount of the solid peroxide used according to the invention can be chosen within a wide range. Preferably, the solid peroxide is used in an amount of 10-27g 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 the 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, the ferrous complex and the solubilizer, and the ultrasonic frequency 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 naphthalene,
At least one of phenanthrene and benzo (a) pyrene.
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 explanation, 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 naphthalene contaminant is 1000mg/kg Contaminated soil The pH of the contaminated soil was 7.5. Preparing a solution (the mass ratio of water to the polluted soil is 1.5) from tween 40, ferrous sulfate, citric acid and water, adding the solution into 4 centrifugal tubes respectively, mixing the solution in a vortex manner for 30s, and performing ultrasonic treatment on the 4 centrifugal tubes in an ultrasonic cleaner at room temperature for 15min, wherein the ultrasonic intensity is 40kHz.
(2) And respectively adding 0.2g of calcium peroxide into 4 centrifugal tubes, wherein the molar ratio of the calcium peroxide to the ferrous sulfate and the citric acid added in the step (1) is 1:0.4:0.9, the mass ratio of the calcium peroxide to the tween 40 added in the step (1) is 1:0.5. and then vortex mixing is carried out for 30s by using a vortex mixer, the centrifugal tube is placed on a counter-rotating mixer to carry out counter-rotating oscillation reaction, and the reaction time of 4 centrifugal tubes is 6h, 12h, 24h and 48h respectively.
(3) 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 upper solution was filtered through a magnesium silicate column. After filtration, the anthracene concentration in the soil was determined by gas chromatography. The pH of the remediated soil was 7.5 and the results for the stopping concentration and contaminant removal rate are shown in Table 1.
Example 2
(1) Taking 10g of polluted soil, wherein the concentration of naphthalene pollutants is 1000mg/kg Contaminated soil The contaminated soil, which had a pH of 7.5, was added to the centrifuge tube. Preparing a solution (the mass ratio of water to polluted soil is 2:1) from Tween 40, ferrous sulfate, citric acid and water, adding the solution into a centrifugal tube, carrying out vortex mixing for 30s, and carrying out ultrasonic treatment on the centrifugal tube in an ultrasonic cleaner at room temperature for 15min with the ultrasonic intensity of 40kHz.
(2) And adding 0.2g of calcium peroxide into the centrifuge tube, wherein the molar ratio of the calcium peroxide to the ferrous sulfate and the citric acid added in the step (1) is 1: 0.5:1, the mass ratio of the calcium peroxide to the tween 40 added in the step (1) is 1:0.5. and then, carrying out vortex mixing for 30s by using a vortex mixer, and then placing the centrifugal tube on a reverse mixer to carry out reverse oscillation reaction for 12h.
(3) 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 upper solution was filtered through a magnesium silicate column. After filtration, the anthracene concentration in the soil was determined by gas chromatography. The pH of the remediated soil was 7.5 and the results of the stop concentration and contaminant removal rate are shown in Table 1.
Examples 3 to 7
Soil remediation was carried out according to the method of example 2, except that the type and concentration of the contaminants and the reaction time were as shown in Table 1. The pH of the contaminated soil was 7.5. The pH value of the soil after remediation is 7.5. The results of the stop concentration and contaminant removal rate are shown in Table 1.
Wherein, the contaminated soil in example 7 was naphthalene contaminated soil collected from a coking plant, and the naphthalene concentration was found to be 216mg/kg Contaminated soil 。
Example 8
(1) Taking 10g of polluted soil, wherein the concentration of naphthalene pollutants is 1000mg/kg Contaminated soil The contaminated soil, having a pH of 7.5, was added to the centrifuge tube. Preparing span 60, ferrous sulfate, citric acid and water into an aqueous solution (the mass ratio of the water to the polluted soil is 2:1), adding the aqueous solution into a centrifugal tube, carrying out vortex mixing for 30s, and carrying out ultrasonic treatment on the centrifugal tube in an ultrasonic cleaner at room temperature for 10min with the ultrasonic intensity of 50kHz.
(2) And adding 0.27g of calcium peroxide into the centrifuge tube, wherein the molar ratio of the calcium peroxide to the ferrous sulfate and the citric acid added in the step (1) is 1: 0.6: 1.2, and the mass ratio of the calcium peroxide to the span 60 added in the step (1) is 1: 0.52. And then, carrying out vortex mixing for 30s by using a vortex mixer, and then placing the centrifugal tube on a reverse mixer to carry out reverse oscillation reaction for 12h.
(3) 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 upper solution was filtered through a magnesium silicate column. After filtration, the anthracene concentration in the soil was determined by gas chromatography. The pH of the remediated soil was 7.5 and the results for the stopping concentration and contaminant removal rate are shown in Table 1.
Example 9
(1) Taking 10g of polluted soil, wherein the concentration of naphthalene pollutants is 1000mg/kg Contaminated soil The contaminated soil, which had a pH of 7.5, was added to the centrifuge tube. Preparing Tween 80, ferrous sulfate, citric acid and water into a solution (the mass ratio of water to contaminated soil is 3: 1), adding into a centrifugal tube, mixing by vortex for 30s, and performing ultrasonic treatment at room temperature for 30min in an ultrasonic cleaner for 30kHz.
(2) And adding 0.1g of calcium peroxide into the centrifuge tube, wherein the molar ratio of the calcium peroxide to the ferrous sulfate and the citric acid added in the step (1) is 1: 0.15:0.5, wherein the mass ratio of the calcium peroxide to the Tween 80 added in the step (1) is 1:1.2. and then, carrying out vortex mixing for 30s by using a vortex mixer, and then placing the centrifugal tube on a reverse mixer to carry out reverse oscillation reaction for 12h.
(3) 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 anthracene concentration in the soil was determined by gas chromatography. The pH of the remediated soil was 7.5 and the results for the stopping concentration and contaminant removal rate are shown in Table 1.
Example 10
Soil remediation was carried out according to the method of example 2, except that the mass ratio of "calcium peroxide to tween 40 added in step (1) was 1: 0.5' instead of the method, the mass ratio of the calcium peroxide to the Tween 40 added in the step (1) is 1:2.5". The pH of the remediated soil was 7.5 and the results for the stopping concentration and contaminant removal rate are shown in Table 1.
Example 11
Soil remediation was carried out in accordance with the method of example 2, except that "Tween 40" was replaced with "lauryl diethanol amine". The pH of the remediated soil was 7.5 and the results for the stopping concentration and contaminant removal rate are shown in Table 1.
Example 12
Soil remediation was carried out in the same manner as in example 2, except that "sonication for 15min in a centrifugal tube sonicator at a sonication intensity of 40kHz" was replaced with "sonication for 5min in a centrifugal tube sonicator at a sonication intensity of 20kHz". The pH of the remediated soil was 7.5 and the results for the stopping concentration and contaminant removal rate are shown in Table 1.
Example 13
Soil remediation was performed according to the method of example 2, except that "a solution prepared from tween 40, ferrous sulfate, citric acid and water" was added to the centrifuge tube at the same time as "calcium peroxide" in step (1), and "calcium peroxide" was not added in step (2). The pH of the remediated soil was 8 and the results of the stopping concentration and contaminant removal rate are shown in Table 1.
Comparative example 1
Soil remediation was carried out according to the method of example 2, except that tween 40 in step (1) was replaced with calcium peroxide. The pH of the remediated soil was 8 and the results of the stopping concentration and contaminant removal rate are shown in Table 1.
TABLE 1
Example 14
Soil remediation was carried out according to 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 detected12500mg/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) Contaminated soil ) The standard exceeding multiple is 2.78 times; wherein the concentration of naphthalene pollutant is 233mg/kg Contaminated soil Screening value of 70mg/kg for land exceeding the second type Contaminated soil (ii) a The pH value of the polluted soil is 7.5, and the polluted soil does not contain impurities such as stones, building residues, garbage and the like. The pH of the remediated soil was 7.5 and the results of the stopping concentration and contaminant removal rate are shown in Table 2.
Example 15
Soil remediation was carried out according to the method of example 2, except that the contaminated soil was collected from petroleum hydrocarbon contaminated soil at a certain petrol station in Beijing and the total petroleum hydrocarbon in the soil was found to be 10600mg/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) Contaminated soil ) The standard exceeding multiple is 2.36 times; wherein the concentration of naphthalene contaminant is 167mg/kg Contaminated soil Screening value of 70mg/kg for land exceeding the second type Contaminated soil (ii) a The pH value of the polluted soil is 7.5, and the polluted soil does not contain impurities such as stones, building residues, garbage and the like. The pH of the remediated soil was 7.5 and the results of the stop concentration and contaminant removal rate are shown in Table 3.
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 composition with the functions of solubilizing and degrading organic pollutants, which is characterized by comprising a ferrous complex, a solubilizer and an independent solid peroxide, wherein the solubilizer is a non-ionic surfactant, and the mass ratio of the solid peroxide to the solubilizer is 1:0.2-3.
2. The composition according to claim 1, wherein the mass ratio of the solid peroxide to the solubilizing agent is 1:0.5 to 1;
and/or, the solubilizer is sorbitan ester, preferably Tween and/or span.
3. The composition of claim 1 or 2, wherein the ferrous complex is prepared from a ferrous catalyst and a chelating agent;
and/or the solid peroxide is alkaline solid peroxide, preferably at least one of calcium peroxide, magnesium peroxide and zinc peroxide.
4. The composition of claim 3, wherein the ferrous catalyst and the chelating agent are used in amounts such that the molar ratio of the solid peroxide, ferrous catalyst and chelating agent is 1:0.15-0.6:0.5-1.2, preferably 1:0.4-0.5:0.9-1.
5. The composition of claim 3 or 4, 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.
6. A kit having a function of solubilizing and degrading organic contaminants, which comprises the composition of any one of claims 1 to 5 and an ultrasonic generator;
preferably, the intensity of the ultrasonic wave generated by the ultrasonic generator is 30-60kHz.
7. Use of a composition according to any one of claims 1 to 6 for the remediation of contaminated soil.
8. A method of remediating contaminated soil, comprising the steps of:
(1) Under the conditions of a solvent and ultrasound, carrying out first mixing on a solubilizer and a ferrous complex and polluted soil;
(2) And secondly mixing the product obtained by the first mixing and the solid peroxide.
9. The method of claim 8, wherein the time of the first mixing is 10-30min,
and/or the time of the second mixing is 6-48h;
and/or the content of contaminants in the contaminated soil is 200-15000mg per kg of contaminated soil;
and/or the amount of said solid peroxide is between 10 and 27g per kg of contaminated soil, calculated 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 naphthalene,
At least one of phenanthrene and benzo (a) pyrene.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195122A (en) * | 2007-12-18 | 2008-06-11 | 南京信息工程大学 | Method for renovating polycyclic aromatic hydrocarbon contaminated soil with ultrasound wave |
| CN103752601A (en) * | 2013-12-31 | 2014-04-30 | 北京高能时代环境技术股份有限公司 | Method for remedying organic compound pollution in soil and/or water |
| CN104936453A (en) * | 2012-11-29 | 2015-09-23 | 液体化肥系统有限公司 | Fermented soil additive |
| CN105834207A (en) * | 2016-05-20 | 2016-08-10 | 上海化工研究院 | Method for combined remediation of organic matter polluted soil |
| CN106040731A (en) * | 2016-08-16 | 2016-10-26 | 南京格洛特环境工程股份有限公司 | Organic pollution soil restoration method |
| CN106345800A (en) * | 2016-09-12 | 2017-01-25 | 南京农业大学 | Method for removing polycyclic aromatic hydrocarbons in soil by using persulfate-calcium peroxide through compound oxidation |
| CN106493162A (en) * | 2016-12-22 | 2017-03-15 | 常州大学 | A kind of method that PAEs contaminated soils repaired by microwave reinforced calper calcium peroxide |
| CN108380663A (en) * | 2018-04-25 | 2018-08-10 | 上海化工研究院有限公司 | The method that class Fenton oxidation method removes half volatile organic contaminant in soil |
| CN108568451A (en) * | 2018-03-15 | 2018-09-25 | 中国科学院南京土壤研究所 | A method of repairing polycyclic aromatic hydrocarbon pollution |
| CN109266359A (en) * | 2018-09-11 | 2019-01-25 | 四川长虹格润环保科技股份有限公司 | Petroleum hydrocarbon contaminated soil repairs medicament and its application method |
| CN109304363A (en) * | 2018-10-29 | 2019-02-05 | 东华大学 | A kind of chemical remediation medicament and its application method suitable for oil-polluted soils |
| CN111704226A (en) * | 2020-06-03 | 2020-09-25 | 中国电建集团中南勘测设计研究院有限公司 | Petroleum organic polluted underground water remediation process, remediation system and application |
-
2021
- 2021-05-18 CN CN202110541971.7A patent/CN115368903A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195122A (en) * | 2007-12-18 | 2008-06-11 | 南京信息工程大学 | Method for renovating polycyclic aromatic hydrocarbon contaminated soil with ultrasound wave |
| CN104936453A (en) * | 2012-11-29 | 2015-09-23 | 液体化肥系统有限公司 | Fermented soil additive |
| CN103752601A (en) * | 2013-12-31 | 2014-04-30 | 北京高能时代环境技术股份有限公司 | Method for remedying organic compound pollution in soil and/or water |
| CN105834207A (en) * | 2016-05-20 | 2016-08-10 | 上海化工研究院 | Method for combined remediation of organic matter polluted soil |
| CN106040731A (en) * | 2016-08-16 | 2016-10-26 | 南京格洛特环境工程股份有限公司 | Organic pollution soil restoration method |
| CN106345800A (en) * | 2016-09-12 | 2017-01-25 | 南京农业大学 | Method for removing polycyclic aromatic hydrocarbons in soil by using persulfate-calcium peroxide through compound oxidation |
| CN106493162A (en) * | 2016-12-22 | 2017-03-15 | 常州大学 | A kind of method that PAEs contaminated soils repaired by microwave reinforced calper calcium peroxide |
| CN108568451A (en) * | 2018-03-15 | 2018-09-25 | 中国科学院南京土壤研究所 | A method of repairing polycyclic aromatic hydrocarbon pollution |
| CN108380663A (en) * | 2018-04-25 | 2018-08-10 | 上海化工研究院有限公司 | The method that class Fenton oxidation method removes half volatile organic contaminant in soil |
| CN109266359A (en) * | 2018-09-11 | 2019-01-25 | 四川长虹格润环保科技股份有限公司 | Petroleum hydrocarbon contaminated soil repairs medicament and its application method |
| CN109304363A (en) * | 2018-10-29 | 2019-02-05 | 东华大学 | A kind of chemical remediation medicament and its application method suitable for oil-polluted soils |
| CN111704226A (en) * | 2020-06-03 | 2020-09-25 | 中国电建集团中南勘测设计研究院有限公司 | Petroleum organic polluted underground water remediation process, remediation system and application |
Non-Patent Citations (1)
| Title |
|---|
| 罗永明: "《中药化学成分提取分离技术与方法》", vol. 1, 上海科学技术出版社, pages: 69 * |
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