CN116102093A - Composite solubilizing material for repairing chlorinated hydrocarbon pollution in aquifer and preparation and application methods thereof - Google Patents
Composite solubilizing material for repairing chlorinated hydrocarbon pollution in aquifer and preparation and application methods thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 113
- 230000003381 solubilizing effect Effects 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 57
- 239000000243 solution Substances 0.000 claims abstract description 44
- 238000002347 injection Methods 0.000 claims abstract description 20
- 239000007924 injection Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001868 water Inorganic materials 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- -1 polyoxyethylene Polymers 0.000 claims abstract description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 8
- 125000000129 anionic group Chemical group 0.000 claims abstract description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012043 crude product Substances 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
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- 229910017053 inorganic salt Inorganic materials 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
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- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
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- 230000035484 reaction time Effects 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005067 remediation Methods 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 230000007928 solubilization Effects 0.000 abstract description 38
- 238000005063 solubilization Methods 0.000 abstract description 38
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 26
- 239000000693 micelle Substances 0.000 abstract description 15
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract description 13
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- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 8
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- 230000007613 environmental effect Effects 0.000 abstract description 2
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- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 10
- 229920000053 polysorbate 80 Polymers 0.000 description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
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- 239000011734 sodium Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
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- 229950011008 tetrachloroethylene Drugs 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
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- 230000015784 hyperosmotic salinity response Effects 0.000 description 2
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
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Images
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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/04—Surfactants, used as part of a formulation or alone
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
Abstract
The invention discloses a composite solubilizing material for repairing chlorinated hydrocarbon pollution in an aquifer and a preparation and application method thereof, belonging to the technical field of environmental engineering. The composite solubilizing material is synthesized into anionic and nonionic polyoxyethylene sulfonic gemini surfactant (GEO) 3 S-12) is used as a main material, and is mixed with calcium chloride or magnesium chloride and water in proportion to prepare micelle solution, and large-particle-size micelles in the solution provide solubilization sites for chlorinated hydrocarbon to increase the solubility of the chlorinated hydrocarbon in water, so that compared with the traditional surfactant, the chlorinated hydrocarbon has more excellent solubilization, low temperature resistance, medium adsorption resistance and salt resistance; optimal injection flow rate calculated by mathematical model between in-situ parameters (injection flow rate, medium particle size, residual saturation of contaminants) and solubilization removal of chlorinated hydrocarbons for composite solubilization materialThe in situ injection of the aqueous layer achieves solubilization and repair of chlorinated hydrocarbon. The invention can be used for solubilizing and repairing chlorinated hydrocarbon pollution of the aquifer by SEAR technology and has wide application.
Description
Technical Field
The invention belongs to the technical field of environmental engineering, and particularly relates to a composite solubilizing material for repairing chlorinated hydrocarbon pollution in an aquifer and a preparation method and an application method thereof.
Background
Chlorinated hydrocarbon is a common organic chlorine solvent, is widely used as a metal degreasing agent, a dry cleaning agent, a refrigerant and the like in social production and life, but is often leaked due to improper disposal or unreasonable discharge, and then migrates downwards to infiltrate into an underground aquifer to cause groundwater pollution, thereby seriously threatening the health of human beings. Chlorinated hydrocarbon contaminated groundwater is widely available worldwide, and statistics show that chlorinated hydrocarbon contamination is found in more than 3000 sites in the U.S. department of defense and in super-fund sites in about 80% of contaminated groundwater. Meanwhile, most chlorinated hydrocarbons are not easy to degrade naturally, and can cause damage to the liver, central nervous system, skin and digestive system of human body, and the decomposition products of the chlorinated hydrocarbons also have biotoxicity, so the chlorinated hydrocarbons are widely recognized as harmful organic pollutants needing to be controlled preferentially. Most chlorinated hydrocarbons belong to DNAPL, have the characteristics of higher density than water and low solubility, and the higher O/W interfacial tension is easy to stay in medium pores and difficult to remove, so that the problems of long time consumption, low efficiency, high cost and the like of the pollution repair of the chlorinated hydrocarbons in the aquifer are caused. The surfactant-enhanced aquifer repair (surfactant enhanced aquifer remediation, SEAR) technology can effectively shorten the extraction-treatment time, and mainly utilizes the solubilization of the surfactant, namely the solubilization material, on hydrophobic organic matters to improve the solubility and fluidity of chlorinated hydrocarbon in water, so that pollutants are extracted along with the water phase, and the influence of tailing and rebound effects is reduced to a certain extent, so that the SEAR technology is a practical technology for effectively repairing chlorinated hydrocarbon polluted sites. While the particular environment of the aquifer, such as medium, low temperature and high salt, tends to cause absorption and precipitation losses of the solubilising material, reducing the efficiency of the repair and secondary pollution, it is necessary to optimise the solubilising material so that it retains its solubilising capacity while adapting to the conditions of the underground environment.
The existing common method for reducing the loss of the solubilizing material mainly comprises the steps of comparing and screening the solubilizing material, wherein the comparing and screening of the solubilizing material takes a certain characteristic of the solubilizing material as a screening index according to the use environment condition so as to ignore other defects, preferably a desired material, and most solubilizing materials have respective advantages and disadvantages in different characteristics, such as an anionic surfactant Sodium Dodecyl Sulfate (SDS) commonly used for site repair has the advantage of low medium absorption, but is easy to cause salting out or low-temperature precipitation; the nonionic surfactant Tween80 has the advantage of low temperature resistance, but the formed micelle is uncharged and can be adsorbed on an aqueous layer medium in a large amount, so that the surfactant screened by material comparison cannot completely achieve all aspects of characteristics and is suitable for underground environment. The solubilization material is compounded by adding other surfactants or short-chain alcohols complementary to the main surfactant to form a composite material, so that the surfactant material can improve and supplement the short plates of the main surfactant while maintaining the advantages of the main surfactant, but the additional alcohols can increase the risk of secondary pollution, and the essence of the surfactant is not changed under the method. Therefore, the development of a novel solubilizing material which has excellent self-solubilizing capability, is not easy to be adsorbed by a medium and is resistant to underground low-temperature and high-salt environment is of great significance from the molecular structure.
Gemini surfactants are a class of solubilising materials of special structure that chemically bond two pairs of amphiphilic molecules, i.e. every two surfactant molecules are "grouped" by a linking group, forming a new surfactant monomer. Conventional surfactant molecules have limited ability to reduce surface tension because they repel each other between like groups, making their alignment less tight in the interface or agglomerate. The two monomers in the gemini surfactant molecule are close to each other, and the repulsive force between the two monomer molecules is weakened, so that the gemini surfactant can ensure that the two single chains in the same group are close to each other no matter in the form of the monomers arranged on the surface or clustered together, thereby obtaining more compact arrangement, and therefore, compared with the traditional single chain surfactant, the gemini surfactant has higher surface activity and solubilization potential. In addition, the addition of nonionic groups to the anionic surfactant molecular structure can change the Krafft point of the surfactant so that the surfactant has low-temperature resistance while having low medium adsorption loss, thereby essentially optimizing the performance of the solubilizing material. Therefore, combining functional groups with different properties and functions into one molecule from the molecular level and controlling the structure of the functional groups to be a gemini design to synthesize a new solubilizing material has great significance for promoting the SEAR technology to solubilize and repair chlorinated hydrocarbon polluted aquifer.
Besides the solubilization effectiveness of the solubilization material itself, in-situ application parameters such as material injection flow rate, medium particle size and residual saturation of pollutants in actual engineering can influence the solubilization efficiency by changing the contact area and time of the micelles with solubilization effect and pollutants in the solubilization material, but the influence of these factors on the solubilization efficiency and the specific relationship between the factors and the solubilization efficiency are not clear, so that reliable basis cannot be provided for actual engineering. Therefore, the solubilizing material which is suitable for the low-temperature high-salt condition of the aquifer is designed and prepared for removing chlorinated hydrocarbon of the aquifer, and meanwhile three factors of injection flow rate of the material, medium particle size and residual saturation of pollutants affect the solubilizing efficiency, a mathematical model of the three factors and the solubilizing efficiency is built, so that the solubilizing material has great reference value for repairing chlorinated hydrocarbon pollution of the aquifer by SEAR technology.
Disclosure of Invention
The invention aims to provide a composite solubilizing material for repairing chlorinated hydrocarbon pollution in an aquifer, which overcomes the defects that the existing solubilizing material is easy to be adsorbed by a medium in the aquifer and is not resistant to low temperature and high salt so as to reduce the solubilizing efficiency. Also provides a preparation and application method of the composite solubilizing material for repairing chlorinated hydrocarbon pollution in the aquifer, wherein the composite solubilizing material is an anionic nonionic polyoxyethylene sulfonic gemini surfactant (GEO) 3 S-12), calcium chloride (CaCl) 2 ) Or magnesium chloride (MgCl) 2 ) The micelle solution mixed with water according to a certain proportion forms large-particle-size micelle which provides solubilization sites for chlorinated hydrocarbon, so that the solubility of the chlorinated hydrocarbon in water is improved, and the composite solubilization material is injected into an aquifer to improve the solubilization and repair efficiency of the chlorinated hydrocarbon; the optimal in-situ injection flow rate of the material is calculated according to the mathematical model of in-situ parameters (injection flow rate, medium particle size and residual saturation of pollutants) and the solubilization capacity of the chlorinated hydrocarbon, so that the optimal solubilization removal capacity of the chlorinated hydrocarbon is obtained.
The invention aims at realizing the following technical scheme:
a composite solubilizing material for repairing chlorinated hydrocarbon pollution in an aquifer, comprising the following components: GEO (GEO) n S-m, inorganic salt and water.
The GEO is provided with n S-m is an anionic nonionic polyoxyethylene sulfonic gemini surfactant, and has the structural formula:
the preparation method of the composite solubilizing material for repairing chlorinated hydrocarbon pollution in the aquifer comprises the following steps:
A. anionic nonionic polyoxyethylene sulfonic gemini surfactant (GEO n S-m, n=3, 5,7; m=10, 12): (1) the ethylene glycol and the maleic anhydride are catalyzed by p-toluenesulfonic acid under the condition of acetone solvent and nitrogen to generate a monoesterification product, wherein the mol ratio of the ethylene glycol to the maleic anhydride is 1:2, the mass of the p-toluenesulfonic acid is 1% of the total mass of reactants, the reaction temperature is 70 ℃, and the reaction time is 1 hour. (2) Fatty alcohol polyoxyethylene ether (AEOnL-m, n=3, 5,7; m=10, 12) is added into the monoesterification product, and p-toluenesulfonic acid is used for catalyzing under the vacuum and nitrogen conditions to generate a double esterification product, wherein the mol ratio of AEOnL-m to maleic anhydride is 1:1.15, the mass of the p-toluenesulfonic acid is 1 percent of the total mass of reactants, the reaction temperature is 120 ℃, and the reaction time is 3 hours. (3) Adding sodium hydroxide solution to neutralize the catalyst, adding sodium bisulphite solution to react to obtain crude product solution, and drying to obtain crude product, wherein the molar ratio of sodium hydroxide to p-toluenesulfonic acid is 1:1, the mass concentration of sodium hydroxide solution is 10%, the molar ratio of sodium bisulphite to maleic anhydride is 1:1.05, the mass concentration of sodium bisulphite solution is 35%, the reaction temperature is 110 ℃, the reaction time is 16 hours, and the drying temperature is 105 ℃. (4) Dissolving the crude product with anhydrous ethanol, filtering insoluble substances (unreacted salts and salts generated during the reaction), and evaporating solvent ethanol under reduced pressure to obtain yellow viscous liquid GEO n S-m, the mass ratio of the absolute ethyl alcohol to the crude product is 15:1, and the rotary evaporation temperature is 70 ℃.
B. And B, synthesizing the anionic and nonionic polyoxyethylene sulfonic gemini surfactant GEO in the step A n S-m, mixing with inorganic salt and water according to a certain mass fraction to obtain the composite solubilizing material.
Further, step B, the GEO n S-m is GEO 3 S-12, inorganic salt is CaCl 2 Or MgCl 2 。
Further, the steps ofAnd step B, the mass fraction is as follows: GEO (GEO) 3 S-12 accounts for 4.0 percent, caCl 2 Accounting for 0.11 percent or MgCl 2 0.095% and the balance water.
The application method of the composite solubilizing material for repairing chlorinated hydrocarbon pollution in the aquifer comprises the steps of bringing the aquifer parameter medium particle size B (unit: mm) and chlorinated hydrocarbon residual saturation C (unit: percent) of the previous field investigation into a quadratic model relation between chlorinated hydrocarbon solubilizing removal y (unit: g) and the injection flow rate A (unit: m/d) of the composite solubilizing material, and obtaining the injection flow rate of the composite solubilizing material when the chlorinated hydrocarbon solubilizing removal is measured to an optimal value.
Further, the quadratic model relation between the solubilizing removal amount y of the chlorinated hydrocarbon and the injection flow rate A of the composite solubilizing material is as follows:
y＝0.99486-0.083547A-2.3554B+0.23669C-0.082025AB
-4.52879×10 -3 AC-0.037492BC+8.50091×10 -3 A 2
+2.03303B 2 -4.18417×10 -3 C 2 (R 2 ＝0.9923)。
compared with the prior art, the invention has the beneficial effects that:
1. main material GEO of the composite solubilizing material 3 The S-12 has the advantages of simple preparation method, no high-temperature and high-pressure condition, wide raw material sources, low price and easy industrial production;
2. main material GEO of the composite solubilizing material 3 The S-12 has good surface activity and better chlorinated hydrocarbon solubilizing capability than the traditional surfactant, and is more suitable for solubilizing and removing chlorinated hydrocarbon pollution by SEAR technology;
3. main material GEO of the composite solubilizing material 3 Compared with the traditional surfactant, the S-12 has more excellent low temperature resistance, salt resistance and medium adsorptivity resistance, and is suitable for underground environment;
4. the composite solubilizing material is simple in preparation, the solution is clear and transparent, the viscosity is low, all components are environment-friendly, and secondary pollution to the underground environment is avoided;
5. the size of the micelle playing a role in solubilization in the composite solubilizing material is larger than that of a single surfactant, the capability of solubilizing chlorinated hydrocarbon is stronger, and the solubility of tetrachloroethylene in water can be improved to 33g/L, which is 660 times that of clear water (10 ℃ and 50 mg/L) under the same condition;
6. the invention establishes a quadratic model relation between the injection flow rate of the composite solubilizing material and the parameters of the aquifer (the medium grain diameter and the residual saturation of the chlorinated hydrocarbon) and the solubilizing quality of the chlorinated hydrocarbon, can bring the aquifer parameters of the prior field investigation into the quadratic model relation, and obtains the injection flow rate of the composite solubilizing material when the solubilizing and removing quantity of the chlorinated hydrocarbon is the best value, thereby providing an important reference for removing the chlorinated hydrocarbon of the aquifer in the practical field application of the SEAR technology.
Drawings
FIG. 1 is a main material GEO of a composite solubilizing material n S-m (n=3, 5,7; m=10, 12) infrared spectrogram
FIG. 2 is a main material GEO of the composite solubilizing material n Nuclear magnetic resonance hydrogen spectrum of S-m (n=3, 5,7; m=10, 12)
FIG. 3 is a main material GEO of the composite solubilizing material n Nuclear magnetic resonance carbon spectrum of S-m (n=3, 5,7; m=10, 12)
FIG. 4 is a main material GEO of the composite solubilizing material n Biodegradability map of S-m (n=3, 5,7; m=10, 12)
FIG. 5 is a main material GEO of the composite solubilizing material n Surface tension variation of S-m (n=3, 5,7; m=10, 12) series concentration aqueous solutions
FIG. 6 is a main material GEO of the composite solubilizing material n Solute precipitation profile for S-m (n=3, 5,7; m=10, 12) and conventional surfactant solutions (40 g/L) at different temperatures
FIG. 7 is a main material GEO of the composite solubilizing material n Zeta potential and adsorption capacity patterns of S-m (n=3, 5,7; m=10, 12) and conventional surfactant solutions (40 g/L) on river sand of different particle sizes
FIG. 8 is a main material GEO of the composite solubilizing material n S-m (n=3, 5,7; m=10, 12) and solubilization capacity plots of conventional surfactant solutions (0-40 g/L) versus different chlorinated hydrocarbons
FIG. 9 is a composite incrementMain material GEO of soluble material 3 S-12 and solute precipitation profile under conventional surfactant solutions (40 g/L) containing different inorganic salt species and concentrations
FIG. 10 is a main material GEO of the composite solubilizing material 3 Solubilization capacity for tetrachloroethylene under conditions of S-12 and conventional surfactant solutions (40 g/L) containing different kinds and concentrations of inorganic salts and micelle particle size diagram under conditions of containing 50mM different kinds of inorganic salts
FIG. 11 is a main material GEO of the composite solubilizing material 3 S-12 (mass concentration 4%) solution viscosity map under the condition of containing different concentrations of calcium chloride or magnesium chloride
Detailed Description
The invention is described in further detail below in connection with specific embodiments:
example 1
Preparation of the Main Material GEO of the composite solubilised Material n S-m(n＝3，5，7；m＝10，12)
Adding maleic anhydride into a three-neck flask with a condensing reflux pipe, adding an acetone solvent, dissolving, adding glycol and a catalyst p-toluenesulfonic acid, introducing nitrogen, heating to 70 ℃, and reacting for 1 hour to generate a monoesterification product; loading a water separator, vacuumizing, adding fatty alcohol polyoxyethylene ether (AEOnL-m, n=3, 5,7; m=10, 12) and catalyst p-toluenesulfonic acid into the monoesterified product, introducing nitrogen gas, heating to 120 ℃, and reacting for 3 hours to obtain a double esterified product; after the double-esterified product is cooled to room temperature, adding a sodium hydroxide solution with the mass concentration of 10% to neutralize the catalyst, adding a sodium bisulphite solution with the mass concentration of 35%, heating to 110 ℃, reacting for 16 hours to generate a crude product solution, and drying to obtain a crude product; adding absolute ethanol solution into the crude product, filtering insoluble substances (unreacted and salts generated in the reaction), and evaporating solvent ethanol under reduced pressure at 70deg.C to obtain yellow viscous liquid GEO as main material of final product composite solubilization material n S-m (n=3, 5,7; m=10, 12). Wherein the mol ratio of the glycol to the maleic anhydride is 1:2, the mass of the p-toluenesulfonic acid is 1% of the total mass of the reactants, the mol ratio of AEOnL-m to the maleic anhydride is 1:1.15, the mol ratio of the sodium hydroxide to the p-toluenesulfonic acid is 1:1,the molar ratio of the sodium bisulphite to the maleic anhydride is 1:1.05, and the mass ratio of the absolute ethyl alcohol to the crude product is 15 ∶ 1。
Example 2
Taking the main material GEO of the composite solubilizing material in example 1 n S-m (n=3, 5,7; m=10, 12), which was uniformly coated on the surface of potassium bromide tablet, and then subjected to infrared spectroscopic test using Thermo Fisher SCIENTIFIC infrared spectrometer, the result shows that 2854cm -1 at-CH 3 Symmetrical telescopic vibration peaks of (2); 2924cm -1 at-CH 2 -an antisymmetric stretching vibration peak; 1734cm -1 The stretching vibration peak of carbonyl C=O; 1245cm -1 The stretching vibration peak of-C-O-; 1112cm -1 The asymmetric stretching vibration peak of-C-O-C-; 1042cm -1 At the characteristic peak of O=S, each functional group accords with GEO n Structural features of S-m (n=3, 5,7; m=10, 12) are shown in fig. 1.
Example 3
Taking the main material GEO of the composite solubilizing material in example 1 n S-m (n=3, 5,7; m=10, 12), dissolved in tritium chloroform, was tested using a bruck (AVANCE 600) liquid nmr hydrogen, carbon spectrometer, and the results showed, 1 H-NMR：δppm＝3.63-3.66(24H，CH 2 CH 2 O，d)，3.43-3.46(4H，CH 2 -O，a)，2.34(2H，CH，c)，1.56-1.58(4H，O＝C-CH 2 ，b)，1.23-1.31(44H，CH 2 ，e)，0.87-0.89(6H，CH 3 ，f)； 13 C-NMR：δppm＝69.31-71.25(O-CH 2 CH 2 -O，a)，60.62-61.36(O-CH 2 -R，d)，31.73(S-CH-R，c)，22.29-29.62(C-CH 2 -R，b)，13.93(R-CH 3 and e) the following steps. The detected 6 hydrogen atoms and 5 carbon atoms are all identical to GEO n Hydrocarbon skeletons in the S-m molecules correspond to each other, proving GEO n S-m (n=3, 5,7; m=10, 12) was successfully synthesized as shown in fig. 2, 3.
Example 4
Taking the main material GEO of the composite solubilizing material in example 1 n S-m (n=3, 5,7; m=10, 12), according to the national standard GB/T15818-2018 surface active @ surface activeGEO is determined in the steps in experimental method of biological degradation degree of agent n S-m biodegradability (Primary biodegradability) at day 7, european and domestic legislation and standards for surfactants suggest that surfactant biodegradability exceeding 90% is readily biodegradable as an environmentally friendly surfactant [4 ]]. The results show that GEO n The primary degree of biodegradation of S-m is higher than 90%, wherein the preferred GEO of the invention 3 The highest primary biodegradation degree of S-12 is 93%, which accords with the standard of the environment-friendly surfactant, as shown in figure 4.
Example 5
Taking the main material GEO of the composite solubilizing material in example 1 n S-m (n=3, 5,7; m=10, 12) is configured as an aqueous solution with a mass concentration of 0.0003g/L to 0.04g/L, the surface tension is measured by using a QBZY-1 surface tensiometer, the surface tension is plotted on the abscissa, the surface tension is plotted on the ordinate, the solution concentration corresponding to the inflection point of the surface tension drop, namely, critical Micelle Concentration (CMC), and micelles with solubilization capacity are formed when the solution solubility is higher than CMC. The results show that GEO n The CMC of S-m increases with increasing number of polyoxyethylene groups and decreasing hydrophobic carbon chain length, wherein the preferred GEO of the invention 3 The CMC of S-12 is lowest, 2.14X10 -3 mM, compared with the conventional surfactants SDS (5.75 mM) and Tween80 (3.03X10) -2 mM) [5] 1-2 orders of magnitude lower, with higher solubilization potential, as shown in figure 5.
Example 6
Taking the main material GEO of the composite solubilizing material in example 1 n S-m (n=3, 5,7; m=10, 12) and traditional surfactants SDS and Tween80 are respectively prepared into aqueous solutions with the mass concentration of 40g/L, the aqueous solutions are respectively placed in environments of 5 ℃, 10 ℃, 15 ℃, 20 ℃ and 25 ℃ for 24 hours, solute precipitation conditions of the solutions are observed, the solutions are centrifuged at corresponding preservation temperatures to obtain supernatant, and the concentration of the surfactants in the supernatant is measured according to the methods of annex A and B in the national standard GB/T15818-2018. The results showed that SDS precipitated below 10℃and GEO n S-m has no solute precipitation in the environment of 5-25 ℃, and has excellent low temperature resistance, as shown in figure 6.
Example 7
Taking the main material GEO of the composite solubilizing material in example 1 n S-m (n=3, 5,7; m=10, 12) and conventional surfactants SDS and Tween80 were prepared as aqueous solutions with mass concentrations of 40g/L, the Zeta potential of the micelle surface of the above solution was measured using a Malvern Nano-ZS 910Zeta potentiometer, while 5ml of the solution was put into a 20ml glass bottle, 10g of crude, neutralized fine river sand (particle sizes of 0.5-1.0mm, 0.25-0.5mm and 0.1-0.25mm, respectively) was added, and the solution was oscillated at 10℃for 24 hours at 150rpm, and the concentration of the surfactant in the solution was measured according to the methods of appendix A and B in national standard GB/T15818-2018. The results show that GEO n The maximum adsorption quantity of S-m on river sand increases with the decrease of the medium grain diameter, and GEO n The maximum adsorption quantity of S-m on river sand with different particle sizes is lower than that of the traditional surfactants SDS and Tween80, wherein the preferred GEO of the invention 3 S-12 has the highest electronegativity on the surface of the micelle and the highest electrostatic repulsive force between media, so that the adsorption quantity on river sand with each particle size is lowest, adsorption on coarse sand and medium sand does not occur, and the adsorption capacity of the medium is excellent, as shown in figure 7.
Example 8
Taking the main material GEO of the composite solubilizing material in example 1 n S-m (n=3, 5,7; m=10, 12) and conventional surfactants SDS and Tween80 were prepared as aqueous solutions having mass concentrations of 0g/L, 10g/L, 20g/L, 30g/L, 40g/L, respectively, 10ml of the surfactant solution and 0.25ml of tetrachloroethylene (PCE), 2.5ml of Carbon Tetrachloride (CT), 2.5ml of Trichloroethylene (TCE), 2Ml of Chlorobenzene (MCB) were placed in a 20ml headspace bottle, and oscillated at 10℃for 48 hours at 150rpm, the supernatant was centrifuged at 5000rpm for 20 minutes, and the concentration of the supernatant PCE was measured using an Agilent1260 high performance liquid chromatograph, and the concentrations of the supernatant CT, TCE and MCB were measured using a purge trap and high performance gas chromatograph. The results show that GEO n The S-m solubilizing capacity of PCE, CT, MCB is higher than that of the traditional surfactants SDS and Tween80, and the solubilizing capacity of TCE is equivalent to that of Tween 80. Among them, GEO preferred in the present invention 3 The solubilization capacity of S-12 to PCE, CT, TCE, MCB can reach 15.1g/L, 15.9g/L, 14.4g/L and 15.8g/L respectively, which is far superior to the traditional surfactant, as shown in figure 8As shown.
Example 9
Taking the main material GEO of the preferred composite solubilizing material of examples 6, 7, 8 3 S-12 and traditional surfactants SDS and Tween80 are respectively prepared into aqueous solutions with the mass concentration of 40g/L, and NaCl, KCl, caCl with certain mass is respectively added into the solutions 2 、MgCl 2 、NaHCO 3 、Na 2 CO 3 、NaHCO 3 And Na (Na) 2 SO 4 The concentration of the inorganic salt was set at 50mM, and the solution was observed for precipitation of solutes. The result shows that the SDS solution is prepared in KCl and CaCl 2 Severe precipitation occurs in the presence of GEO 3 The S-12 solution remained stable and had excellent salt tolerance as shown in FIG. 9.
Example 10
Taking the main material GEO of the preferred composite solubilizing material of examples 6, 7, 8 3 S-12 and traditional surfactants SDS and Tween80 are respectively prepared into aqueous solutions with the mass concentration of 40g/L, and NaCl, KCl, caCl with certain mass is respectively added into the solutions 2 、MgCl 2 、NaHCO 3 、Na 2 CO 3 、NaHCO 3 And Na (Na) 2 SO 4 The inorganic salt concentration is set to be 0mM, 10mM, 20mM, 30mM, 40mM and 50mM, 10ml of solution and 0.25ml of PCE are respectively placed in a 20ml headspace bottle, the mixture is oscillated for 48 hours at 10 ℃ and 150rpm, the supernatant liquid is centrifuged at 5000rpm for 20 minutes, and the concentration of the supernatant PCE is measured by using an Agilent1260 high performance liquid chromatograph; the particle size of the micelles in the surfactant solution without inorganic salts and at a concentration of 50mM inorganic salts was also determined using a Malvern Nano-ZS particle size Analyzer. The results show that GEO 3 The solubilization capacity of S-12 is improved under the condition of containing inorganic salt, and the salt tolerance and the synergy with the inorganic salt are superior to those of the traditional surfactant; inorganic salts by increasing GEO 3 S-12 micelle particle size to expand the volume of contaminants within the micelle for solubilization, thereby promoting solubilization of PCE, particularly CaCl, which is preferred in the present invention 2 And MgCl 2 GEO as the concentration of the two inorganic salts increases 3 The amount of S-12 solubilizing PCE is increased first and then basically unchanged, and the preferable mass concentration of the invention is 0.11 percent CaCl 2 (10 mM) and 0.095% MgCl by mass 2 (10 mM) at the lowest addition level for achieving optimal solubilization capacity of the composite solubilizing material, 4% GEO of the composite solubilizing material of the present invention 3 S-12+0.11％CaCl 2 Or 0.095% MgCl 2 The solubilization capacity for PCE can reach 33mg/L, which is 660 times of that of clear water (50 mg/L) under the same conditions, as shown in FIG. 10.
Example 11
Example 10 contains 0mM, 10mM, 20mM, 30mM, 40mM, 50mM CaCl, respectively 2 And MgCl 2 GEO of (2) 3 S-12 (4% by mass) solution, 16ml of composite solubilising material, shear rate 12.23S using a Bowler-femto DV-2T viscometer -1 Viscosity of the solution under conditions, and the results show that the viscosity of the composite solubilizing material increases with increasing concentrations of the two inorganic salts, when CaCl 2 And MgCl 2 The viscosity of the composite solubilizing material is less than 2cP at concentrations below the preferred 0.11% and 0.095% of the present invention, near the water phase, and the injection pressure is low when used in situ, and the material is easily migrated in the aquifer, as shown in fig. 11.
Example 12
Taking the main material GEO of the preferred composite solubilizing material of examples 6, 7, 8 3 S-12, preparing an aqueous solution with the mass concentration of 40g/L, carrying out in-situ solubilization chlorohydrocarbon experiment by using a one-dimensional simulation column with the length of 13cm and the diameter of 2.5cm, filling river sand into the simulation column at the experimental environment temperature of 20 ℃, placing the simulation column vertically, filling deionized water into the simulation column from bottom to top by using a peristaltic pump at the flow rate of 0.3ml/min, fully saturating the column and measuring the Pore Volume (PV) of the column, injecting PCE (NAPL phase) from the upper port of the column, sealing to enable PCE to be distributed for 24 hours, inverting the column, and injecting GEO with the configuration of 10PV from bottom to top 3 S-12, wherein the combination of 3 parameters of surfactant solution injection flow rate (factor A), medium particle size (factor B) and residual saturation of pollutants (factor C) is designed by using a Box-Behnken (BBD) method, 17 groups of experiments are carried out, samples are collected from outlet timing to measure PCE concentration, and the PCE concentration in the samples is integrated to calculate the solubilization removal quality of PCE in each parameter combination experiment.
Example 13
The results of 17 experimental groups in all example 12 were analyzed and fitted using Design-Expert software. Software fitting results show that GEO 3 The solubilization removal of chlorinated hydrocarbons by S-12 (y) and 3 factors of surfactant solution injection flow rate (factor a), media particle size (factor B) and residual saturation of contaminants (factor C) satisfy a quadratic model relationship:
y＝0.99486-0.083547A-2.3554B+0.23669C-0.082025AB
-4.52879×10 -3 AC-0.037492BC+8.50091×10 -3 A 2
+2.03303B 2 -4.18417×10 -3 C 2 (R 2 = 0.9923); the secondary model relation is a unitary quadratic equation between the solubilization removal amount of chlorinated hydrocarbon and the material injection flow rate when in use, so that the results of the field investigation of the medium particle size and the residual saturation of the pollutants can be brought into the model relation of the invention to calculate the material injection flow rate corresponding to the best solubilization removal quality of chlorinated hydrocarbon.
Claims (6)
1. A composite solubilizing material for repairing chlorinated hydrocarbon pollution in an aquifer, characterized by being composed of the following components: GEO (GEO) n S-m, inorganic salt and water.
The GEO is provided with n S-m is an anionic nonionic polyoxyethylene sulfonic gemini surfactant, and has the structural formula:
2. according to claim 1A process for the preparation of a composite solubilising material for remediation of chlorinated hydrocarbon pollution in aquifers, characterized in that it comprises the following two steps a and B: A. anionic nonionic polyoxyethylene sulfonic gemini surfactant (GEO n S-m, n=3, 5,7; m=10, 12): (1) the ethylene glycol and the maleic anhydride are catalyzed by p-toluenesulfonic acid under the condition of acetone solvent and nitrogen to generate a monoesterification product, wherein the mol ratio of the ethylene glycol to the maleic anhydride is 1:2, the mass of the p-toluenesulfonic acid is 1% of the total mass of reactants, the reaction temperature is 70 ℃, and the reaction time is 1 hour. (2) Fatty alcohol polyoxyethylene ether (AEOnL-m, n=3, 5,7; m=10, 12) is added into the monoesterification product, and p-toluenesulfonic acid is used for catalyzing under the vacuum and nitrogen conditions to generate a double esterification product, wherein the mol ratio of AEOnL-m to maleic anhydride is 1:1.15, the mass of the p-toluenesulfonic acid is 1 percent of the total mass of reactants, the reaction temperature is 120 ℃, and the reaction time is 3 hours. (3) Adding sodium hydroxide solution to neutralize the catalyst, adding sodium bisulphite solution to react to obtain crude product solution, and drying to obtain crude product, wherein the molar ratio of sodium hydroxide to p-toluenesulfonic acid is 1:1, the mass concentration of sodium hydroxide solution is 10%, the molar ratio of sodium bisulphite to maleic anhydride is 1:1.05, the mass concentration of sodium bisulphite solution is 35%, the reaction temperature is 110 ℃, the reaction time is 16 hours, and the drying temperature is 105 ℃. (4) Dissolving the crude product with anhydrous ethanol, filtering insoluble substances (unreacted salts and salts generated during the reaction), and evaporating solvent ethanol under reduced pressure to obtain yellow viscous liquid GEO n S-m, the mass ratio of the absolute ethyl alcohol to the crude product is 15:1, and the rotary evaporation temperature is 70 ℃. B. And B, synthesizing the anionic and nonionic polyoxyethylene sulfonic gemini surfactant GEO in the step A n S-m, mixing with inorganic salt and water according to a certain mass fraction to obtain the composite solubilizing material.
3. The method of preparing a composite solubilizing material for repairing chlorinated hydrocarbon pollution in aqueous layer as claimed in claim 2, wherein in step B, said GEO n S-m is GEO 3 S-12, inorganic salt is CaCl 2 Or MgCl 2 。
4. The method for preparing a composite solubilizing material for repairing chlorinated hydrocarbon pollution in an aquifer according to claim 2, wherein the mass fraction of step B is: GEO (GEO) 3 S-12 accounts for 4.0 percent, caCl 2 Accounting for 0.11 percent or MgCl 2 0.095% and the balance water.
5. The method for repairing a complex solubilizing material contaminated with chlorinated hydrocarbons in an aquifer according to claim 1, wherein the parameters of the aquifer, such as the medium particle size B (unit: mm) and the residual saturation C (unit:%) of chlorinated hydrocarbons, are carried into a quadratic model relation between the amount y (unit: g) of chlorinated hydrocarbons to be solubilized and the injection flow rate A (unit: m/d) of the complex solubilizing material, and the injection flow rate of the complex solubilizing material is obtained when the optimal amount of chlorinated hydrocarbons to be solubilized and removed is measured.
6. The method of claim 5, wherein the quadratic model relation between the amount of the solubilizing and removing chlorinated hydrocarbon y and the injection flow rate of the composite solubilizing material A is:
y＝0.99486-0.083547A-2.3554B+0.23669C-0.082025AB
-4.52879×10 -3 AC-0.037492BC+8.50091×10 -3 A 2
+2.03303B 2 -4.18417×10 -3 C 2 (R 2 ＝0.9923)。
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