CN111892117A - Microemulsion for solubilizing chlorinated hydrocarbon pollutants in underground environment and preparation method thereof - Google Patents
Microemulsion for solubilizing chlorinated hydrocarbon pollutants in underground environment and preparation method thereof Download PDFInfo
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- CN111892117A CN111892117A CN202010786101.1A CN202010786101A CN111892117A CN 111892117 A CN111892117 A CN 111892117A CN 202010786101 A CN202010786101 A CN 202010786101A CN 111892117 A CN111892117 A CN 111892117A
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- 239000004530 micro-emulsion Substances 0.000 title claims abstract description 62
- 230000003381 solubilizing effect Effects 0.000 title claims abstract description 24
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 title claims abstract description 20
- 239000003344 environmental pollutant Substances 0.000 title abstract description 15
- 231100000719 pollutant Toxicity 0.000 title abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 34
- 239000011780 sodium chloride Substances 0.000 claims abstract description 17
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 10
- 239000012498 ultrapure water Substances 0.000 claims abstract description 10
- 239000004064 cosurfactant Substances 0.000 claims abstract description 7
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 5
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 17
- 229920000053 polysorbate 80 Polymers 0.000 claims description 17
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 10
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000356 contaminant Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 abstract description 9
- 238000005406 washing Methods 0.000 abstract description 3
- 229920000136 polysorbate Polymers 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 18
- 239000000693 micelle Substances 0.000 description 10
- 238000005063 solubilization Methods 0.000 description 9
- 230000007928 solubilization Effects 0.000 description 9
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Colloid Chemistry (AREA)
Abstract
The invention relates to a microemulsion for solubilizing chlorinated hydrocarbon pollutants in underground environment and a preparation method thereof. The microemulsion consists of an oil phase and a water phase in a mass ratio of 1:1, wherein the water phase comprises the following components in percentage by mass: non-ionic surfactant Tween 8010-16%, co-surfactant isopropanol 10-24%, sodium chloride 8-12%, and the balance ultrapure water, and the oil phase is PCE. The preparation method comprises the steps of fully dissolving the surfactant, the cosurfactant and the inorganic salt in water to obtain a water phase, then adding the PCE into the uniformly mixed water phase, slightly shaking and standing to obtain the microemulsion. The microemulsion system has good thermodynamic stability, low interfacial tension between the microemulsion and the oil phase and good solubilizing effect on the chlorohydrocarbon, and the solubilizing effect can be improved by 1900 times compared with that of clear water; can be used for washing residual chlorinated hydrocarbon pollutants in an aquifer and has wide application.
Description
Technical Field
The invention belongs to the technical field of environmental engineering, and particularly relates to a microemulsion with solubilizing capability on chlorinated hydrocarbon pollutants in underground environment and a preparation method thereof.
Background
Groundwater is an indispensable environmental factor and plays an important role in human life throughout the life. With the rapid development of the chemical industry, chlorinated hydrocarbons are widely used as a degreasing agent, a cleaning agent and a common raw material in chemical synthesis, and have extremely high detection rate in underground water. Most chlorinated hydrocarbons, such as tetrachloroethylene (PCE), which are denser than water, are heavy non-aqueous liquids (DNAPLs), have low solubility in water, are toxic, and are not easily degraded. Since DNAPLs are denser than water, contamination occurs by the action of gravity that migrates downward all the way, while they are hydrophobic and become trapped in the aqueous medium during migration, in the form of a residual phase.
Common techniques for remediating aquifers contaminated with DNAPLs include pump-out (P & T) and multi-phase extraction (MPE), with increasing amounts of contaminating contaminants pumped out, the extent of contamination is gradually reduced and the degree of contamination is reduced. However, due to the low water solubility and high interfacial tension with water of DNAPLs, the phenomenon of "tailing" and "bouncing back" often occurs after a period of pumping.
In the field restoration, a surfactant is added at the later stage of extraction, and the solubilization of the surfactant on the hydrophobic chlorohydrocarbon is utilized to improve the extraction efficiency. But the solubilizing effect of the surfactant is limited, the solubilizing capability of most of the surfactants to the chlorohydrocarbon can be improved by one order of magnitude compared with that of clear water, and the microemulsion has good solubilizing effect to hydrophobic organic matters, and has ultralow interfacial tension, superstrong emulsifying capability and good surface wetting capability. Thus, microemulsion flushing techniques can be used for residual chlorinated hydrocarbon contaminants in subterranean aquifers after pump-out techniques are used in the field.
The microemulsion is a transparent or semitransparent, thermodynamically stable and optically isotropic system formed by components such as a surfactant, water, oil, a cosurfactant and the like in a certain proportion. Shinoda and Friberg consider that the microemulsion is a swollen micelle, when the concentration of the surfactant in the aqueous solution is greater than the critical micelle concentration, the micelle is formed, at this time, a certain amount of oil (or a mixed solution of a certain amount of oil and a cosurfactant) is added, the oil enters the micelle to be solubilized, and the micelle swells to form the microemulsion along with the increase of the oil amount entering the micelle, so that the microemulsion is called a micelle emulsion. The swollen micelles can provide a larger storage space for the hydrophobic chlorohydrocarbons, thereby improving the solubility of the chlorohydrocarbons in water and forming super solubilization. Microemulsion "supersolubilization" is an extension of the concept of micellar solubilization, where the solubilizing power of these swollen micelles is an order of magnitude higher than that of normal micelles, and can be increased by two to three orders of magnitude compared to clear water solubilization.
The microemulsion is mainly used for washing and solubilizing various water-insoluble pollutants in underground environments such as soil and the like. At present, the used microemulsion is prepared by taking light organic solvents such as n-octane, n-hexane and the like as oil phases and then solubilizing the pollutants difficult to dissolve in water, and the solubilizing capability can be improved by two orders of magnitude compared with the solubilizing capability of clear water.
Disclosure of Invention
The invention provides a microemulsion for super solubilizing a chlorinated hydrocarbon pollutant by taking a chlorinated hydrocarbon pollutant as an oil phase and a preparation method of the microemulsion, which overcomes the defects that the conventional microemulsion has poor solubilizing effect and cannot avoid the use of a light organic solvent.
The purpose of the invention is realized by the following technical scheme:
a microemulsion for solubilizing chlorinated hydrocarbon pollutants in underground environment consists of an oil phase and an aqueous phase, wherein the aqueous phase comprises the following components in percentage by mass: 8-16% of nonionic surfactant, 8-24% of cosurfactant, 8-12% of inorganic salt and the balance of ultrapure water; the mass ratio of the oil phase to the ultrapure water is as follows: 1: 1;
the oil phase is tetrachloroethylene; the nonionic surfactant is Tween 80; the co-surfactant is biodegradable isopropyl alcohol (IPA); the inorganic salt is sodium chloride.
Further, the Tween80 was 12%, isopropanol was 12%, and sodium chloride was 12%.
Further, the Tween80 was 14%, isopropanol 12%, sodium chloride 8%.
The preparation method of the microemulsion for solubilizing the chlorinated hydrocarbon pollutants in the underground environment comprises the following steps:
A. weighing 8-16% of Tween80, 8-24% of isopropanol and 8-12% of sodium chloride according to the mass percentage of each component in the microemulsion, dissolving the components in ultrapure water, and uniformly mixing to obtain a water phase;
B. and D, adding tetrachloroethylene with the mass ratio of 1:1 to the water phase obtained in the step A into the obtained water phase, uniformly mixing, and standing for 10 hours to obtain the microemulsion.
Compared with the prior art, the invention has the beneficial effects that:
1. the microemulsion formed by the invention has simple and easily obtained components, low cost, biodegradability and safe and simple operation;
2. the oil used for forming the microemulsion is the chlorinated hydrocarbon to be treated in a polluted site, so that the resource utilization of pollutants is realized;
3. the microemulsion formed by the invention has better thermodynamic stability, and the appearance of the microemulsion has no obvious change after being placed for 95 days, namely, no obvious layering and sedimentation phenomena.
4. The microemulsion formed by the invention has good solubilization effect on the hydrophobic chlorinated hydrocarbon, and the solubilization effect is improved by 1900 times compared with that of clear water;
5. the microemulsion formed by the invention can be used for washing residual hydrochloric ether pollutants in an aquifer, and has wide application;
6. the invention provides a preparation method of microemulsion, which ensures that the finally prepared microemulsion has excellent property and transparent or semitransparent liquid appearance by reasonably controlling the dosage of each component in the microemulsion.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a graph showing the microemulsion particle size in the microemulsion formed in group 10 of example 2 according to the present invention;
FIG. 2a is a schematic diagram showing the appearance of the microemulsion of example 5 before standing;
FIG. 2b is a schematic representation of the appearance of the microemulsion of example 5 after standing for 95 days.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification.
Example 1
A microemulsion for solubilizing chlorinated hydrocarbon pollutant in underground environment is composed of oil phase and water phase, the oil phase is tetrachloroethylene. The water phase comprises the following components in percentage by mass: nonionic surfactant Tween80 (8-16%), cosurfactant isopropanol (8-24%), sodium chloride (8-12%) and ultrapure water as the rest; the mass ratio of the oil phase to the ultrapure water is as follows: 1:1.
The microemulsion for super solubilization of chlorinated hydrocarbon pollutants in underground environment is prepared by the following method:
A. weighing Tween80, isopropanol and sodium chloride according to the mass percentage of each component in the microemulsion, dissolving in ultrapure water, and uniformly mixing to obtain a water phase;
B. and (4) adding the water phase obtained in the step (A) into the PCE, slightly shaking and uniformly mixing, and standing for 10 hours to obtain the microemulsion.
Example 2
The microemulsions of example 1 were tested for their ability to solubilize tetrachloroethylene. 10 μ L of the configuration in example 1 was takenThe concentration of tetrachloroethylene in the sample was measured by Agilent 1100 hplc. And calculating the solubilization times of the microemulsion on tetrachloroethylene compared with clear water. As shown in Table 1, the microemulsion formed by the multiple formulations can solubilize tetrachloroethylene in an amount of 10 of that of the PCE dissolved in clear water3Wherein the combination ratio of 10 th to 17 th can reach 1900 times.
TABLE 1 Tween80 microemulsion static solubilization orthogonal experimental results
Example 3
The microemulsion particle size was measured in the microemulsions formed in group 10 of example 2 (Tween 80: isopropanol: sodium chloride: 14%: 12%: 8%).
Filtering the sample with 0.45 micron film, setting the sample in a colorimetric dish, and measuring the grain size and grain size dispersion coefficient (PDI) of the microemulsion by using a nanometer grain size and Zeta potentiometer, wherein the measuring temperature is 25 ℃. As shown in fig. 1, it can be seen from fig. 1 that the average particle size of the microemulsions in group 10 (Tween 80: isopropanol: sodium chloride: 14%: 12%: 8%) in example 2 is 42.84 ± 0.94nm, and PDI is 0.328 ± 0.044, indicating that the microemulsion has uniform particle size distribution and good dispersibility.
Example 4
The interfacial tension between the microemulsion formed in group 10 of example 2 (Tween 80: isopropanol: sodium chloride: 14%: 12%: 8%) and the PCE phase was determined.
And measuring the interfacial tension between the microemulsion and the PCE by using a rotary drop interfacial tension meter, wherein the measured interfacial tension is 0.032 mN/m.
Example 5
The thermodynamic stability of the microemulsions formed in group 10 of example 2 (Tween 80: isopropanol: sodium chloride: 14%: 12%: 8%) was determined. And (3) considering the underground environment temperature, respectively placing the microemulsion in the environment of 10 ℃ and 25 ℃, and observing the layering, uniformity and transparency of the system. After standing for 95 days, the system is still uniform and transparent liquid without obvious change. Thus showing that the micro-emulsion has better thermodynamic stability.
It was found experimentally that the microemulsion consisted of the following concentrations of components: when the content of the Tween80 is 12%, the content of the isopropanol is 12%, the content of the sodium chloride is 12% or the content of the Tween80 is 14%, the content of the isopropanol is 12%, and the content of the sodium chloride is 8%, the microemulsion is stable in property, has a good solubilizing effect on hydrophobic chlorinated hydrocarbon, and the solubilizing effect can be improved by 1900 times compared with that of clear water.
Claims (4)
1. A microemulsion for solubilizing chlorinated hydrocarbon contaminants in a subterranean environment, characterized by: the oil-water composite material consists of an oil phase and a water phase in a mass ratio of 1:1, wherein the water phase comprises the following components in percentage by mass: 8-16% of nonionic surfactant, 8-24% of cosurfactant, 8-12% of inorganic salt and the balance of ultrapure water; the mass ratio of the oil phase to the ultrapure water is as follows: 1: 1;
the oil phase is tetrachloroethylene; the nonionic surfactant is Tween 80; the cosurfactant is biodegradable isopropanol; the inorganic salt is sodium chloride.
2. The microemulsion of claim 1 for solubilizing chlorinated hydrocarbon contaminants in a subterranean environment, wherein: the Tween80 content is 12%, the isopropanol content is 12%, and the sodium chloride content is 12%.
3. The microemulsion of claim 1 for solubilizing chlorinated hydrocarbon contaminants in a subterranean environment, wherein: the Tween80 is 14%, the isopropanol is 12%, and the sodium chloride is 8%.
4. The method of claim 1, comprising the steps of:
A. weighing 8-16% of Tween80, 8-24% of isopropanol and 8-12% of sodium chloride according to the mass percentage of each component in the microemulsion, dissolving the components in ultrapure water, and uniformly mixing to obtain a water phase;
B. and D, adding tetrachloroethylene with the mass ratio of 1:1 to the water phase obtained in the step A into the obtained water phase, uniformly mixing, and standing for 10 hours to obtain the microemulsion.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114314796A (en) * | 2021-12-29 | 2022-04-12 | 北京师范大学 | Material with double functions of activating persulfate and solubilizing chlorohydrocarbon |
| CN114632808A (en) * | 2022-03-07 | 2022-06-17 | 吉林大学 | Method for efficiently repairing chlorinated solvent polluted water-containing layer by using in-situ microemulsion |
| CN115505405A (en) * | 2022-10-13 | 2022-12-23 | 上海市环境科学研究院 | Chlorinated hydrocarbon solubilizing emulsion material based on waste grease and preparation method thereof |
| CN116102093A (en) * | 2022-11-23 | 2023-05-12 | 吉林大学 | Composite solubilizing material for repairing chlorinated hydrocarbon pollution in aquifer and preparation and application methods thereof |
| CN118062979A (en) * | 2024-03-11 | 2024-05-24 | 上海大学 | Method for degrading insoluble halogenated organic matters by surfactant synergistic Fenton-like advanced oxidation |
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Cited By (5)
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| CN116102093A (en) * | 2022-11-23 | 2023-05-12 | 吉林大学 | Composite solubilizing material for repairing chlorinated hydrocarbon pollution in aquifer and preparation and application methods thereof |
| CN118062979A (en) * | 2024-03-11 | 2024-05-24 | 上海大学 | Method for degrading insoluble halogenated organic matters by surfactant synergistic Fenton-like advanced oxidation |
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Application publication date: 20201106 |