CN112222177B - Method for improving efficiency of sodium persulfate in degrading organic pollutants - Google Patents
Method for improving efficiency of sodium persulfate in degrading organic pollutants Download PDFInfo
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- CN112222177B CN112222177B CN202011014853.2A CN202011014853A CN112222177B CN 112222177 B CN112222177 B CN 112222177B CN 202011014853 A CN202011014853 A CN 202011014853A CN 112222177 B CN112222177 B CN 112222177B
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- sodium persulfate
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- organic pollutants
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 title claims abstract description 26
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 title claims abstract description 26
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 12
- 230000000593 degrading effect Effects 0.000 title claims abstract description 8
- 239000002689 soil Substances 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 10
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- 230000001965 increasing effect Effects 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000012216 screening Methods 0.000 claims abstract description 5
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 239000011268 mixed slurry Substances 0.000 claims abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 7
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 4
- 239000003209 petroleum derivative Substances 0.000 claims description 4
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 239000003802 soil pollutant Substances 0.000 claims description 2
- 230000004913 activation Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 230000003381 solubilizing effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 229920004890 Triton X-100 Polymers 0.000 abstract description 3
- 239000013504 Triton X-100 Substances 0.000 abstract description 3
- -1 isooctylphenyl Chemical group 0.000 abstract description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 abstract description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 abstract description 3
- 238000001994 activation Methods 0.000 description 13
- 230000006872 improvement Effects 0.000 description 8
- 239000003814 drug Substances 0.000 description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000007725 thermal activation Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Classifications
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- 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
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for improving the efficiency of sodium persulfate in degrading organic pollutants, which comprises the following steps: step one, screening and crushing the collected organic contaminated soil for multiple times to obtain a pretreated soil sample with a small particle size; step two,Fully mixing the pretreated soil sample with a proper amount of distilled water, uniformly stirring, and preparing to obtain slurry; and step three, adding surfactant triton according to the soil quality, stirring uniformly, then adding a certain amount of sodium persulfate agent and mixed transition metal ions, mixing and stirring for a certain time to obtain mixed slurry, and maintaining under the dark condition. According to the invention, the activation effect of sodium persulfate is improved by introducing the transition metal ion combination, SO that the sodium persulfate is cracked to generate more sulfate radical free radicals SO4 ‑(ii) a And simultaneously, introducing surfactant Triton X-100 (isooctylphenyl polyoxyethylene ether) into the organic polluted soil to enhance the flow increasing and solubilizing effects of the organic pollutants, and further improving the degradation effect of the sodium persulfate oxidation agent on organic substances.
Description
Technical Field
The invention relates to the technical field of chemical oxidation agent preparation, in particular to a method for improving the efficiency of sodium persulfate in degrading organic pollutants.
Background
With the rapid development of socioeconomic performance in China, the urban industrial structure and spatial layout need to be further adjusted and reconstructed. Various chemical enterprises such as coking, batteries, pharmacy, printing and the like leave various polluted fields due to the factors of dismantling, moving and the like. The above sites have various types of pollutants and large concentration difference, and include various organic pollutants, such as petroleum (TPH), Polycyclic Aromatic Hydrocarbons (PAHs), chlorine-containing organic compounds (DDT), fluorine-containing organic compounds, and the like. When the high organic pollution content polluted soil in a field is treated, a persulfate oxidation system medicament is a better choice.
Since 2014, the research heat in the field of repairing organic polluted soil by using an oxidation medicament of an activated persulfate system is rapidly increased, but a single persulfate cannot achieve a good oxidative degradation effect,activation to generate sulfate radical SO is generally required4 -Can achieve better degradation effect, and therefore needs to be combined with an activating agent to obtain SO with strong oxidizing property4 -The common activation methods include thermal activation, alkali activation, transition metal ion activation, alkali activation, ultrasonic activation, and the like. The thermal activation mode has high energy consumption, the alkali activation puts higher requirements on equipment and environmental maintenance, and the ultrasonic activation needs further development of site repair equipment. In contrast, the transition metal ions can be activated at room temperature, and S can be activated without external energy supply2O8 2-Breaking of the double bond to form SO4 -To activate the persulfate. But the activation of single transition metal ion still has obvious defect, and the ferrous ion Fe widely used in soil remediation2+Is very easy to be oxidized into Fe3+And the addition amount and the addition rate need to be controlled, otherwise, Fe is caused2+With SO4 -Reaction and SO4 -A quenching effect is generated between.
Therefore, the search for a more efficient activation mode has practical significance on persulfate oxidation technology. In addition, part of organic pollutants are tightly combined with the polluted soil, the solubilizing capability of the organic pollutants in the soil is improved, and the organic pollutants are further reacted with an oxidant, so that the oxidative degradation effect of an oxidation medicament on the organic matters can be further exerted.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide a method for improving the efficiency of sodium persulfate in degrading organic pollutants, and overcomes the defect of single transition metal ion Fe by introducing the combination of transition metal ions2+The rate of activation of sodium persulfate is difficult to control and the quenching effect is problematic. Meanwhile, the surfactant Triton is added to assist the organic matters to overflow in the polluted soil, so that the effective degradation efficiency of sodium persulfate on organic pollutants can be remarkably improved.
In order to solve the technical problems, the invention is realized by the following technical scheme: a method for improving the efficiency of degrading organic pollutants by sodium persulfate comprises the following steps:
step one, screening and crushing the collected organic contaminated soil for multiple times to obtain a pretreated soil sample with a small particle size;
step two, fully mixing the pretreated soil sample with distilled water, uniformly stirring, and preparing to obtain slurry;
and step three, adding surfactant triton according to the soil quality, stirring uniformly, then adding a certain amount of sodium persulfate agent and mixed transition metal ions, mixing and stirring for a certain time to obtain mixed slurry, and maintaining under the dark condition.
As an improvement of the technical scheme, in the first step, the organic polluted soil pollutant is mainly total petroleum hydrocarbon.
As an improvement of the technical scheme, in the first step, the screening and crushing times are 3-5 times, and the polluted soil with the particle size range of 2-5mm is obtained.
As an improvement of the technical scheme, in the second step, the mud obtained after uniform mixing and stirring has the water content of about 1:1-1:1.5 and the stirring time is within 24-48 h.
As an improvement of the technical scheme, in the third step, the surfactant triton added according to the soil mass is 0.8-2.5% of the soil mass.
As an improvement of the technical scheme, in the third step, the addition amount of the sodium persulfate medicament is 2-5% of the mass of the soil.
In the third step, the mixed transition metal ions are made of cobalt ions (Co)2+) Copper ion (Cu)2+) And ferrous ion (Fe)2+) And (3) combining the components.
Further, in the third step, Fe is added according to the soil quality2+About 0.15 to about 0.3mmol/g, Cu2+About 0.1 to about 0.2mmol/g, Co2+About 0.08 to about 0.15 mmol/g.
As an improvement of the technical scheme, in the third step, the time for mixing and stirring the surfactant and the medicament is within 30-48 h.
As an improvement of the technical scheme, in the third step, the curing temperature is 15-25 ℃, and the curing time is 7-15 days.
Use of a method as described above for increasing the efficiency of sodium persulfate to degrade organic contaminants, for the oxidative degradation of total petroleum hydrocarbons in contaminated soil.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the particle size of the polluted soil treated by the method is within 2-5mm, the particle size is smaller, and the polluted soil has a higher specific surface area to react with an oxidizing agent. The water-soil ratio of the slurry obtained after uniform mixing is kept between 1:1 and 1:1.5, and the surfactant triton, the mixed transition metal ions and the sodium persulfate can be effectively dispersed, so that the medicament added into the dispersion liquid is ensured to be in proper concentration.
The added surfactant triton can obviously enhance the flow increasing and solubilizing effects of organic pollutants in the polluted soil, so that the organic matters overflow to a greater extent, and the oxidative degradation effect of sodium persulfate on the organic pollutants is improved. The mixed transition metal ions can overcome the defect of single transition metal ions Fe2+The activation is easy to be oxidized by air, the adding rate is difficult to control, the quenching effect is good, and the like.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the contents of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following detailed description is given in conjunction with the preferred embodiments.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 is a graph showing the effect of sodium persulfate on oxidative degradation of total petroleum hydrocarbons in comparison to the present example.
Detailed Description
Other aspects, features and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
Example one
A method for improving the efficiency of degrading organic pollutants by sodium persulfate comprises the following steps:
step one, screening and crushing 8g of collected organic contaminated soil for 5 times to obtain a pretreated soil sample with the particle size of 3 mm;
step two, fully mixing the pretreated soil sample with 8g of distilled water, stirring for 36 hours until the slurry is uniform, and preparing a mixture with a water-soil ratio of 1:1 of a slurry;
step three, adding 1.5 percent of surfactant Triton X-100 (isooctylphenyl polyoxyethylene ether) according to the mass of soil, mixing and stirring for 30 hours until the slurry is uniform, adding 2.5 percent of sodium persulfate again, and adding 0.25mmol/g of Fe2+0.2mmol/g Cu2+And 0.15mmol/g Co2+Mixing and stirring for 48h to obtain uniform slurry, and maintaining for 7 days at 25 ℃ in the dark.
And (3) pumping and filtering the slurry after the reaction by using a vacuum pump, naturally drying the soil obtained by filtering at room temperature, and finally analyzing the residual total petroleum hydrocarbon amount of the soil.
Two groups of experiments of a blank group and a control group are set, wherein the activator added in the blank group is only single transition heavy metal ion Fe2+And the rest experimental conditions are the same as those of the first embodiment, and the experimental conditions of the control group are the same as those of the first embodiment. Two sets of experimental results were obtained as shown in figure 1:
as can be seen from figure 1, after the surfactant triton and the mixed transition metal ions are added, the oxidative degradation efficiency of the total petroleum hydrocarbon in the polluted soil is improved by 11.7%, and the improvement effect is obvious.
According to the invention, the activation effect of sodium persulfate is improved by introducing the transition metal ion combination, SO that the sodium persulfate is cracked to generate more sulfate radical free radicals SO4 -H, performing; and simultaneously, introducing surfactant Triton X-100 (isooctylphenyl polyoxyethylene ether) into the organic polluted soil to enhance the flow increasing and solubilizing effects of the organic pollutants, and further improving the degradation effect of the sodium persulfate oxidation agent on organic substances.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (2)
1. A method for improving the efficiency of degrading organic pollutants by sodium persulfate is characterized by comprising the following steps:
step one, screening and crushing the collected organic contaminated soil for 3-5 times to obtain a pretreated soil sample with the particle size range of 2-5 mm;
the organic polluted soil pollutants are mainly total petroleum hydrocarbon;
step two, fully mixing the pretreated soil sample with a proper amount of distilled water, uniformly stirring, and preparing slurry, wherein the water content of the slurry is 1:1-1:1.5, and the stirring time is within 24-48 h;
step three, adding surfactant triton according to the mass of soil, wherein the content of the triton is 0.8-2.5% of the mass of the soil, uniformly stirring, then adding 2-5% of sodium persulfate agent and mixed transition metal ions formed by combining cobalt ions, copper ions and ferrous ions, mixing and stirring for a certain time to obtain mixed slurry, and maintaining under the dark condition;
mixing and stirring for 30-48h, maintaining at 15-25 deg.C for 7-15 days;
added Fe2+0.15-0.3mmol/g, Cu2+0.1-0.2mmol/g, Co2+Is 0.08-0.15 mmol/g.
2. Use of the method for increasing the efficiency of sodium persulfate to degrade organic pollutants as claimed in claim 1 for the oxidative degradation of total petroleum hydrocarbons in contaminated soil.
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Address after: Building 10, New Factory High tech Industrial Park, No. 28 Fengshuo Road, Qiaokou District, Wuhan City, Hubei Province 430000 Patentee after: Gezhouba Ecological Governance (Hubei) Co.,Ltd. Country or region after: China Address before: Building 1, No. 6, 4th Road, Wuhan University Science Park, Donghu Development Zone, Wuhan City, Hubei Province 430079 Patentee before: GEZHOUBA ZHONGGU TECHNOLOGY CO.,LTD. Country or region before: China |