CN115368904A - Composition with function of degrading organic pollutants and application thereof - Google Patents
Composition with function of degrading organic pollutants and application thereof Download PDFInfo
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- CN115368904A CN115368904A CN202110541972.1A CN202110541972A CN115368904A CN 115368904 A CN115368904 A CN 115368904A CN 202110541972 A CN202110541972 A CN 202110541972A CN 115368904 A CN115368904 A CN 115368904A
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- ferrous
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- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 16
- 230000000593 degrading effect Effects 0.000 title claims abstract description 12
- 239000002689 soil Substances 0.000 claims abstract description 133
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 28
- 150000002978 peroxides Chemical class 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 27
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 24
- 238000005067 remediation Methods 0.000 claims abstract description 19
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 16
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 44
- 239000000356 contaminant Substances 0.000 claims description 34
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 17
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 14
- 239000011790 ferrous sulphate Substances 0.000 claims description 14
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 14
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000002738 chelating agent Substances 0.000 claims description 10
- 239000004343 Calcium peroxide Substances 0.000 claims description 8
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 8
- 235000019402 calcium peroxide Nutrition 0.000 claims description 8
- 239000003209 petroleum derivative Substances 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
- 239000003344 environmental pollutant 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
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 229910000015 iron(II) carbonate Inorganic materials 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 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
- 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
- 229960004995 magnesium peroxide Drugs 0.000 claims description 2
- 231100000719 pollutant Toxicity 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 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 230000002829 reductive effect Effects 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 12
- 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
- 230000010355 oscillation Effects 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 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
- 239000012028 Fenton's reagent Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012216 screening Methods 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-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
- 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
- 238000012954 risk control Methods 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 239000010414 supernatant solution Substances 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
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 238000004821 distillation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 239000007800 oxidant agent 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
- 230000001737 promoting effect Effects 0.000 description 1
- 229910021646 siderite Inorganic materials 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (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 a function of degrading organic pollutants and application thereof. The composition comprises solid peroxide, a ferrous complex and an independent reductive inorganic acid, wherein the molar ratio of the reductive inorganic acid to the ferrous complex calculated by ferrous ions is 0.1-0.75:1. the invention also provides a method for repairing the polluted soil, which comprises the following steps: (1) First mixing the solid peroxide, the ferrous complex and the contaminated soil in the presence of a solvent; (2) And carrying out second mixing on the product obtained by the first mixing and reducing inorganic acid. The invention improves the degradation rate of soil organic pollutants (especially polycyclic aromatic hydrocarbons) 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 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 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 the concentrations of PAHs in soils (particularly in soils in urban areas) have increased over the last 100 to 150 years.
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. 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 analyzed reduction for humansOrganic compounds and selectively oxidized organic compounds provide a new process. 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 (2).
However, when the solid peroxide and the ferrous complex in the prior art are used for degrading organic pollutants in soil, the ferrous complex can be quickly inactivated, so that the solid peroxide can not release OH, and the degradation rate of organic matters in the soil is low.
Disclosure of Invention
The invention aims to overcome the technical problems in the prior art and provide a composition with the function of degrading organic pollutants and application thereof.
The inventors of the present invention found that the use of a reducing inorganic acid in combination with a solid peroxide and a ferrous complex appears to increase Fe 2+ The utilization rate of the organic fertilizer is improved, the continuous release of OH of the solid peroxide is promoted, and the degradation rate of the organic matters in the soil is further improved.
In order to achieve the above objects, the present invention provides in a first aspect a composition having a function of degrading organic pollutants, which comprises a solid peroxide, a ferrous complex and a reducing inorganic acid independently present, wherein the molar ratio of the reducing inorganic acid to the ferrous complex calculated on a ferrous ion basis is 0.1 to 0.75:1.
in a second aspect, the invention provides the use of the composition as described above in the remediation of contaminated soil.
In a third aspect, the present invention provides a method for remediating contaminated soil, comprising the steps of:
(1) First mixing the solid peroxide, the ferrous complex and the contaminated soil in the presence of a solvent;
(2) And carrying out second mixing on the product obtained by the first mixing and reducing inorganic acid.
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. The method greatly reduces the consumption of the ferrous complex when the organic pollutants of unit mass are degraded.
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 degrading organic pollutants, which comprises solid peroxide, a ferrous complex and a reducing inorganic acid independently existing, wherein the molar ratio of the reducing inorganic acid to the ferrous complex calculated by ferrous ions is 0.1-0.75:1.
according to the present invention, in order to further increase the degradation rate of the composition for degrading organic pollutants, it is preferable that the molar ratio of the reducing inorganic acid to the ferrous complex calculated as ferrous ion is 0.25 to 0.5:1.
according to the present invention, the reducing inorganic acid may be an inorganic acid capable of promoting the reduction of iron ions to ferrous ions. In order to further increase the degradation rate, preferably, the reducing inorganic acid is a reducing dibasic inorganic acid, preferably sulfurous acid and/or phosphorous acid.
According to the present invention, the kind 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 ferrous complex is obtained by a method not particularly limited, and is preferably prepared from a ferrous catalyst and a chelating agent.
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 amounts such that the molar ratio of the solid peroxide to the ferrous catalyst to the chelating agent is 1:0.1-0.5:0.1 to 0.3, preferably 1:0.15-0.3:0.2-0.25.
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.
In a second 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 reducing inorganic acid, the solid peroxide and the ferrous complex with the polluted soil; when the solid peroxide and the ferrous complex are contacted with the polluted soil for a period of time, the degradation rate of organic matters in the soil can be obviously improved by adding the reducing inorganic acid. Accordingly, in a third aspect the present invention provides a method of remediating contaminated soil comprising the steps of:
(1) First mixing solid peroxide and a ferrous complex with contaminated soil in the presence of a solvent;
(2) And carrying out second mixing on the product obtained by the first mixing and reducing inorganic acid.
According to the invention, the time of the first mixing and the second mixing can be chosen within wide limits, preferably the sum of the times of the first mixing and the second mixing is between 6 and 48h, preferably between 12 and 24h.
According to the invention, the time of the first mixing is preferably 1/3 to 2/3 of the sum of the times of the first and second mixing.
According to the invention, preferably, the time of the first mixing is 6-12h; the time of the second mixing is 6-12h.
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 100-20000mg per kg of the contaminated soil.
According to the invention, the amount of the solid peroxide can be selected within a wide range. Preferably, the solid peroxide is used in an amount of 15 to 30g 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 to 3kg per kg of the contaminated soil.
According to the present invention, preferably, the solvent is water.
In the present invention, the specific kinds and amounts of the solid peroxide, the ferrous complex and the reducing inorganic acid are as described above and will not be 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 naphthalene, phenanthrene and benzo (a) pyrene. The composition and the method are particularly suitable for degrading the polycyclic aromatic hydrocarbon, and have particularly obvious effect of repairing the soil polluted by the polycyclic aromatic hydrocarbon.
The present invention will be described in detail below by way of examples.
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 naphthalene contaminant is 1000mg/kg Contaminated soil The pH of the contaminated soil was 6.5. Respectively adding 0.2g of calcium peroxide into 4 centrifugal tubes, and simultaneously adding a solution prepared from ferrous sulfate, citric acid and water (the mass ratio of water to contaminated soil is 2: 0.3:0.25. 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 3h, 6h, 12h and 24h respectively.
(2) And respectively adding sulfurous acid into the 4 centrifugal tubes, wherein the molar ratio of the sulfurous acid to the ferrous sulfate added in the step (1) is 0.5:1. and (3) carrying out vortex mixing for 30s by using a vortex mixing instrument again, putting the centrifugal tubes on a reverse mixer to carry out reverse oscillation reaction, wherein the reaction time of 4 centrifugal tubes is 3h, 6h, 12h and 24h respectively. 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 naphthalene concentration in the soil was determined by gas chromatography. The pH of the remediated soil was 6.5 and the results of the stop concentration and contaminant removal rate are shown in Table 1.
Example 2
(1) Taking 10g of contaminated soil, wherein the naphthalene concentration is 200mg/kg Contaminated soil The contaminated soil, having a pH of 6.5, was added to the centrifuge tube. Adding 0.2g 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 2: 0.15:0.2. 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 6h.
(2) And adding sulfurous acid into the centrifugal pipe, wherein the molar ratio of the sulfurous acid to the ferrous sulfate added in the step (1) is 0.5:1. and (3) carrying out vortex mixing for 30s by using a vortex mixing instrument again, and then placing the centrifugal tube on a reverse mixing instrument for reverse oscillation reaction for 6h. 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 naphthalene concentration in the soil was determined by gas chromatography. 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.
Example 3
Soil remediation was carried out in accordance with the method of example 2, except that the naphthalene concentration was replaced with 300mg/kg Contaminated soil And the pH value of the polluted soil is 6.5. 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.
Example 4
Soil remediation was carried out in accordance with the method of example 2, except that the naphthalene concentration was replaced with 400mg/kg Contaminated soil And the pH value of the polluted soil is 6.5. 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.
Example 5
Soil remediation was carried out in accordance with the method of example 2, except that "naphthalene concentration was 200mg/kg Contaminated soil The concentration of "alternative" phenanthrene is 300mg/kg Contaminated soil ", and the pH of the contaminated soil was 6.5. The pH of the remediated soil was 6.5 and the results of the stop concentration and contaminant removal rate are shown in Table 1.
Example 6
Soil remediation was carried out in accordance with the method of example 2, except that "naphthalene concentration was set to 200mg/kg Contaminated soil The concentration of benzo (a) pyrene is 200mg/kg Contaminated soil ", and the pH of the contaminated soil was 6.5. The pH of the remediated soil was 6.5 and the results of the stop concentration and contaminant removal rate are shown in Table 1.
Example 7
Soil remediation was carried out according to the method of example 2 except that the contaminated soil wasReplacing soil with naphthalene contaminated soil collected from a coking plant, and detecting to obtain a naphthalene concentration of 200mg/kg Contaminated soil The concentration of the "alternative" naphthalene contaminant was 314mg/kg Contaminated soil ", and the pH of the contaminated soil was 6.5. The pH of the remediated soil was 6.5 and the results of the stop concentration and contaminant removal rate are shown in Table 1.
Example 8
(1) Taking 10g of contaminated soil, wherein the naphthalene concentration is 200mg/kg Contaminated soil The contaminated soil, having a pH of 6.5, was added to the centrifuge tube. Adding 0.3g 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 contaminated soil is 1:0.1:0.1. and then vortex mixing is carried out for 30s by using a vortex mixer, and the centrifugal tube is placed on a reverse mixer to carry out reverse oscillation reaction for 24h.
(2) And (2) adding phosphorous acid into the centrifugal tube, wherein the molar ratio of the sulfurous acid to the ferrous chloride added in the step (1) is 0.5:1. And (3) carrying out vortex mixing for 30s by using a vortex mixing instrument again, and then placing the centrifugal tube on a reverse mixer to carry out reverse oscillation reaction for 12h. 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 naphthalene concentration in the soil was determined by gas chromatography. 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.
Example 9
(1) Taking 10g of contaminated soil, wherein the naphthalene concentration is 200mg/kg Contaminated soil The contaminated soil, having a pH of 6.5, 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 water to contaminated soil is 3: 0.5:0.3. then vortex for 30s by using a vortex blending instrumentMixing, placing the centrifuge tube on a reverse mixer for reverse oscillation reaction for 3h.
(2) And adding sulfurous acid into the centrifugal pipe, wherein the molar ratio of the sulfurous acid to the ferrous sulfate added in the step (1) is 0.25:1. and (3) carrying out vortex mixing for 30s by using a vortex mixing instrument again, and then placing the centrifugal tube on a reverse mixer to carry out reverse oscillation reaction for 6h. 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 naphthalene concentration in the soil was determined by gas chromatography. 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.
Example 10
Soil remediation was carried out as in example 2, except that "the molar ratio of sulfurous acid to ferrous sulfate added in step (1) was 0.5:1 "instead" the molar ratio of sulfurous acid to ferrous sulfate added in step (1) was 0.1:1". The pH of the remediated soil was 6.5 and the results of the stop concentration and contaminant removal rate are shown in Table 1.
Example 11
Soil remediation was performed according to the method of example 2, except that sulfurous acid was added when calcium peroxide and a solution prepared from ferrous sulfate, citric acid and water were added in step (1); and sulfurous acid is not added in the step (2). The pH of the remediated soil was 5.5 and the results of the stopping concentration and contaminant removal rate are shown in Table 1.
Example 12
Soil remediation was carried out in accordance with the method of example 2, except that the reaction time in step (1) was 1 hour and the reaction time in step (2) was 11 hours. The pH of the remediated soil was 6.9 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 2, except that the naphthalene contaminant concentration was 1000mg/kg Contaminated soil And in step (2)The sulfurous acid is replaced by calcium peroxide. The pH of the remediated soil was 8 and the results of the stop concentration and contaminant removal rate are shown in Table 1.
Comparative example 2
Soil remediation was carried out as in example 2, except that the naphthalene contaminant concentration was 1000mg/kg Contaminated soil The molar ratio of sulfurous acid to ferrous sulfate added in the step (1) is 0.5:1 "substituted by" the molar ratio of sulfurous acid to ferrous sulfate added in step (1) is 1:1". The pH of the remediated soil was 5.5 and the results of the stop concentration and contaminant removal rate are shown in Table 1.
Comparative example 3
Soil remediation was carried out as in example 2, except that the naphthalene contaminant concentration was 1000mg/kg Contaminated soil "sulfurous acid" was replaced by "dilute sulfuric acid". The pH of the remediated soil was 6 and the results of the stop concentration and contaminant removal rate are shown in Table 1.
TABLE 1
As can be seen from the results in Table 1, when the composition and the method of the invention are used for degrading organic pollutants, the reaction time is 12 hours, the highest degradation rate can reach 82%, and the pH value of the soil is not changed before and after remediation.
Example 14
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 of the soil was found to be 11200mg/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 2.49 times; wherein the naphthalene concentration is 245mg/kg Contaminated soil Over and aboveScreening value for second kind land of 70mg/kg Contaminated soil (ii) a The pH value of the polluted soil is 6.5, and the polluted soil does not contain impurities such as stones, building residues, garbage and the like. The pH of the remediated soil was 6.5 and the results of the stop concentration and contaminant removal rate are shown in Table 2.
TABLE 2
Example 15
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 gasoline station in Beijing and examined to determine the total petroleum hydrocarbon content of 14500mg/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 3.22 times; wherein the concentration of naphthalene contaminant is 203mg/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 6.5, and the polluted soil does not contain impurities such as stones, building residues, garbage and the like. The pH of the remediated soil was 6.5 and the results of the stop concentration and contaminant removal rate are shown in Table 3.
TABLE 3
As can be seen from the results in tables 2 and 3, the composition and method of the present invention are also applicable to the soil contaminated by petroleum hydrocarbon, and the degradation rate of petroleum hydrocarbon can reach more than 80%.
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 having a function of degrading organic pollutants, which comprises a solid peroxide, a ferrous complex and a reducing inorganic acid independently existing, wherein the molar ratio of the reducing inorganic acid to the ferrous complex calculated by ferrous ions is 0.1-0.75:1.
2. the composition of claim 1, wherein the molar ratio of the reducing inorganic acid to the ferrous complex, as ferrous ion, is from 0.25 to 0.5:1;
and/or the reducing inorganic acid is a reducing binary inorganic acid, preferably sulfurous acid and/or phosphorous acid.
3. The composition 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 composition of any one of claims 1-3, wherein the ferrous complex is prepared from a ferrous catalyst and a chelating agent.
5. The composition of claim 4, 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 1:0.1-0.5:0.1 to 0.3, preferably 1:0.15-0.3:0.2-0.25.
6. The composition of 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 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) First mixing solid peroxide and a ferrous complex with contaminated soil in the presence of a solvent;
(2) And carrying out second mixing on the product obtained by the first mixing and reducing inorganic acid.
9. The method of claim 8, wherein the sum of the times of the first and second mixing is 6-48h, wherein the time of the first mixing is 1/3-2/3 of the sum of the times of the first and second mixing;
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 between 15 and 30g per kg of contaminated soil, calculated as contaminants;
and/or the solvent is used in an amount of 1 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 naphthalene, phenanthrene and benzo (a) pyrene.
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