Compound surfactant, repairing material and method for repairing chlorinated hydrocarbon pollutants

Abstract

The invention relates to a compound surfactant, a repairing material and a method for repairing chlorinated hydrocarbon pollutants. The compound surfactant is simple in component, good in solubilizing effect, green and low in toxicity, can effectively reduce the surface tension of an aqueous solution when being dissolved in water, and has relatively high low-temperature water solubility. The repairing material has a good solubilizing effect on hydrophobic chlorinated hydrocarbon, and when the repairing material is used for repairing the chlorinated hydrocarbon pollutants, the problems that in the prior art, a surfactant is poor in solubilizing effect on the chlorinated hydrocarbon pollutants in the underground water environment, cannot be suitable for the underground low-temperature application environment, has secondary pollution and the like are effectively solved.

Description

Technical Field

[0001] This disclosure relates to the field of environmental remediation technology, and more specifically, to a compound surfactant, remediation materials, and a method for remediating chlorinated hydrocarbon pollutants. Background Technology

[0002] Chlorinated hydrocarbons are common chemical raw materials with strong thermal and chemical stability. They are widely used in industry and agriculture as solvents, herbicides, dyes, degreasers, detergents, and flame retardants. However, due to improper industrial operations or accidental leaks, large amounts of chlorinated hydrocarbons are released into the environment and circulate into water bodies, ultimately becoming a major source of pollution in groundwater. Common chlorinated hydrocarbons include tetrachloroethylene (PCE) and trichloroethylene (TCE), which are mostly colorless liquids that are volatile at room temperature, have a density higher than water, and are poorly soluble in water. In groundwater environments, they migrate and infiltrate downwards, belonging to heavy, non-aqueous liquids that are difficult to completely remove, posing a threat to human health and ecological safety.

[0003] Groundwater chlorinated hydrocarbon remediation technologies can be categorized into several types, including monitored natural decay technology, gas-phase extraction technology, thermal treatment enhancement technology, multiphase extraction technology, in-situ chemical oxidation technology, permeable reactive barrier technology, and surfactant-enhanced extraction treatment technology. Among these, surfactant leaching remediation technology, by injecting surfactants into the underground aquifer, significantly enhances the solubility of residual chlorinated hydrocarbons in the aquifer medium and has attracted widespread attention due to its advantages such as strong operational adaptability and controllable secondary pollution.

[0004] Currently, commonly used surfactants are mainly anionic and nonionic. However, even after successfully applying surfactant-enhanced extraction technology to actual site remediation, several problems remain, based on real-world remediation cases. For example, nonionic surfactants (such as Tween 80 and Triton 100) have excellent solubilizing effects, but they are easily adsorbed and remain by clay minerals and organic matter in the soil, causing adsorption loss and secondary pollution. Anionic surfactants (such as sodium dodecyl sulfate) have less adsorption loss in the formation, but their high critical micelle concentration leads to a large dosage. High concentrations of surfactants are prone to precipitation in the low-temperature underground environment, weakening their solubilizing effect. Therefore, the solubilizing ability of a single nonionic or anionic surfactant as a solubilizing material for chlorinated hydrocarbons is limited.

[0005] Combining nonionic and anionic surfactants in a certain ratio can enhance the solubility of chlorinated hydrocarbons while inhibiting the adsorption of the surfactant system onto underground aquifers. Patent CN116102093A discloses a composite solubilizing material based on a synthesized anionic nonionic polyoxyethylene sulfonate-based gemini surfactant (GEO3S-12), achieving solubilization of chlorinated hydrocarbons. However, the synthesis of GEO3S-12 involves numerous and complex steps, and its high concentration poses a risk of secondary environmental pollution. Patent CN115505405A prepares an emulsion material by combining kitchen waste cooking oil, rhamnose glycolipids, and Triton 100, exhibiting high solubilization capacity for trichloroethylene. However, the complex composition of kitchen waste cooking oil and the addition of large amounts of it also pose new threats to groundwater safety. Summary of the Invention

[0006] The purpose of this disclosure is to provide a compound surfactant, a remediation material, and a method for remediating chlorinated hydrocarbon pollutants. The compound surfactant has simple components, good solubilizing effect, is environmentally friendly and low in toxicity, effectively reduces the surface tension of aqueous solutions when dissolved in water, and exhibits high low-temperature water solubility. The remediation material of this disclosure has a good solubilizing effect on hydrophobic chlorinated hydrocarbons. When used to remediate chlorinated hydrocarbon pollutants, it effectively overcomes the problems of existing technologies, such as poor solubilizing effect of surfactants on chlorinated hydrocarbon pollutants in groundwater environments, inapplicability to low-temperature underground applications, and secondary pollution.

[0007] To achieve the above objectives, a first aspect of this disclosure provides a compound surfactant comprising a nonionic surfactant and an anionic surfactant, wherein the nonionic surfactant is selected from sophorolipids and / or oligomeric modified sophorolipids, and the anionic surfactant is selected from alkylphenol polyoxyethylene ether salts; the sophorolipid is selected from acidic sophorolipids and / or lactone-type sophorolipids; and the oligomeric modified sophorolipid has a structure as shown in formula (1) or formula (2):

[0008]

[0009] Among them, X1 to X2 are selected from -(CH2). m -, m represents the number of CH2, where m is any integer from 0 to 12;

[0010] Z1 to Z5 are each independently selected from disaccharides, and R1 to R5 are each independently selected from -CH(CH3)-Y-COOH, wherein Y is selected from saturated or unsaturated straight-chain alkyl groups with 9 to 19 carbon atoms.

[0011] Optionally, the acidic sophorolipid comprises one or more compounds having the following structures:

[0012] Optionally, the lactone-type sophorolipid comprises one or more compounds having the following structures:

[0013]

[0014] Optionally, Z1 to Z4 are each independently selected from the following groups: in This represents the chemical bonds connecting Z1 to Z4 and R1 to R4; Indicates Z1~Z4 and or Connecting chemical bonds.

[0015] Optionally, Z5 is selected from in This indicates the chemical bond connecting Z5 and R5; Indicates Z5 and Connecting chemical bonds.

[0016] Optionally, m is selected from any integer from 0 to 10, preferably from any integer from 0 to 3; Y is selected from -(CH2)9-, -(CH2)6CH=CH(CH2)7- or -(CH2)3CH=CHCH2CH=CH(CH2)7-.

[0017] Optionally, the oligomeric modified sophorolipid comprises one or more compounds having the following structures:

[0018]

[0019] Optionally, the alkylphenol polyoxyethylene ether salt has the structure shown in formula (5):

[0020]

[0021] Wherein, R6 is selected from alkyl groups having 7 to 18 carbon atoms, preferably from alkyl groups having 8 to 16 carbon atoms; n is selected from any integer from 2 to 100, preferably from any integer from 2 to 80; M is sodium sulfate, potassium sulfate, sodium phosphate, potassium phosphate, sodium sulfonate, potassium sulfonate, sodium carboxylate, or potassium carboxylate.

[0022] Optionally, the alkylphenol polyoxyethylene ether salt is selected from sodium octylphenol polyoxyethylene ether sulfate, sodium octylphenol polyoxyethylene ether sulfonate, potassium octylphenol polyoxyethylene ether phosphate, potassium octylphenol polyoxyethylene ether carboxylate, sodium nonylphenol polyoxyethylene ether sulfate, sodium nonylphenol polyoxyethylene ether sulfonate, potassium nonylphenol polyoxyethylene ether phosphate, potassium nonylphenol polyoxyethylene ether carboxylate, sodium dodecylphenol polyoxyethylene ether sulfate, sodium dodecylphenol polyoxyethylene ether sulfonate, potassium dodecylphenol polyoxyethylene ether phosphate, potassium dodecylphenol polyoxyethylene ether carboxylate, sodium tetradecylphenol polyoxyethylene ether sulfate, sodium tetradecylphenol polyoxyethylene ether sulfonate, potassium tetradecylphenol polyoxyethylene ether phosphate, and potassium tetradecylphenol polyoxyethylene ether carboxylate; preferably, the sodium octylphenol polyoxyethylene ether sulfate, sodium octylphenol polyoxyethylene ether sulfonate, sodium tetradecylphenol polyoxyethylene ether sulfonate, sodium tetradecylphenol polyoxyethylene ether phosphate, potassium tetradecylphenol polyoxyethylene ether carboxylate, and potassium tetradecylphenol polyoxyethylene ether carboxylate are selected from sodium octylphenol polyoxyethylene ether sulfate, sodium tetradecylphenol polyoxyethylene ether sulfonate, sodium tetradecylphenol polyoxyethylene ether sulfonate, sodium tetradecylphenol polyoxyethylene ether phosphate, and potassium tetradecylphenol polyoxyethylene ether carboxylate. The degree of polymerization of sodium octylphenol polyoxyethylene ether phosphate, potassium octylphenol polyoxyethylene ether carboxylate, and potassium octylphenol polyoxyethylene ether carboxylate is 10-80, preferably 80; the degree of polymerization of sodium nonylphenol polyoxyethylene ether sulfate, sodium nonylphenol polyoxyethylene ether sulfonate, potassium nonylphenol polyoxyethylene ether phosphate, and potassium nonylphenol polyoxyethylene ether carboxylate is 30-75, preferably 50; the degree of polymerization of sodium dodecylphenol polyoxyethylene ether sulfate, sodium dodecylphenol polyoxyethylene ether sulfonate, potassium dodecylphenol polyoxyethylene ether phosphate, and potassium dodecylphenol polyoxyethylene ether carboxylate is 2-70, preferably 5; and the degree of polymerization of sodium tetradecylphenol polyoxyethylene ether sulfate, sodium tetradecylphenol polyoxyethylene ether sulfonate, potassium tetradecylphenol polyoxyethylene ether phosphate, and potassium tetradecylphenol polyoxyethylene ether carboxylate is 10-80, preferably 30.

[0023] A second aspect of this disclosure provides a repair material comprising the compound surfactant described in the first aspect of this disclosure, wherein, based on the total weight of the compound surfactant in the repair material, the content of the nonionic surfactant is 70-95% by weight, and the content of the anionic surfactant is 5-30% by weight.

[0024] A third aspect of this disclosure provides a method for remediating chlorinated hydrocarbon contaminants, the method comprising: contacting the remediation material described in the second aspect of this disclosure with the chlorinated hydrocarbon contaminants in the presence of water.

[0025] Optionally, the method further includes: dissolving the remediation material in water to form an aqueous solution of the remediation material; mixing the aqueous solution of the remediation material with the chlorinated hydrocarbon contaminant and shaking; wherein the concentration of the remediation material in the aqueous solution of the remediation material is 30-100 g / L, and the volume ratio of the aqueous solution of the remediation material to the chlorinated hydrocarbon contaminant is (5-20):1.

[0026] Optionally, the oscillation temperature is 10–40°C, the rotation speed is 120–200 rpm, and the time is 20–40 h; the chlorinated hydrocarbon pollutants include chlorinated hydrocarbon polluted water, preferably chlorinated hydrocarbon polluted groundwater.

[0027] Through the above technical solutions, this disclosure provides a compound surfactant, a remediation material, and a method for remediating chlorinated hydrocarbon pollutants. The compound surfactant includes a nonionic surfactant and anionic surfactant. The nonionic surfactant is a sophorolipid or oligomeric modified sophorolipid with low toxicity, easy biodegradability, high emulsifying activity, and solubilizing properties. The anionic surfactant is an amphiphilic alkylphenol polyoxyethylene ether salt with hydrophobic alkyl chains and hydrophilic charges. Combining these two surfactants and dissolving them in water effectively reduces the surface tension of the aqueous solution and provides good thermodynamic stability. It does not precipitate at low temperatures, avoiding the problem of easy precipitation of single anionic surfactants at low temperatures and reducing the adsorption loss of single nonionic surfactants. The remediation material of this disclosure contains the above-mentioned compound surfactant, resulting in a low critical micelle concentration and excellent low-temperature water solubility in the aqueous solution. It forms negatively charged micelles in water, which increase the solubility of hydrophobic chlorinated hydrocarbons in water, providing a good solubilizing effect on hydrophobic chlorinated hydrocarbons. Furthermore, it is not easily adsorbed onto the medium, avoiding secondary pollution and making it suitable for underground environments. When used to remediate chlorinated hydrocarbon pollutants in groundwater environments, its solubilizing ability for chlorinated hydrocarbons is significantly better than that of a single surfactant of the same mass concentration, and it ensures the stability of the system in low-temperature groundwater environments, achieving highly efficient solubilization of chlorinated hydrocarbons.

[0028] Other features and advantages of this disclosure will be described in detail in the following detailed description section. Attached Figure Description

[0029] The accompanying drawings are provided to further illustrate the present disclosure and form part of the specification. They are used together with the following detailed description to explain the present disclosure, but do not constitute a limitation thereof. In the drawings:

[0030] Figure 1 This is the mass spectrum of the oligomodified sophoroliposide OSL-C1 prepared in Preparation Example 1 of this disclosure;

[0031] Figure 2 This is a graph showing the surface tension changes of aqueous solutions with concentrations of A1 to A4 in Test Example 1 of this disclosure;

[0032] Figure 3 This is a diagram showing the precipitation of aqueous solutions B1 to B4 and sodium dodecyl sulfate in Test Example 2 of this disclosure at a low temperature of 5°C. Detailed Implementation

[0033] The specific embodiments of this disclosure will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit this disclosure.

[0034] The first aspect of this disclosure provides a compound surfactant, the compound surfactant comprising a nonionic surfactant and an anionic surfactant, wherein the nonionic surfactant is selected from sophorolipids and / or oligomeric modified sophorolipids, and the anionic surfactant is selected from alkylphenol polyoxyethylene ether salts; the sophorolipid is selected from acidic sophorolipids and / or lactone-type sophorolipids; and the oligomeric modified sophorolipid has a structure as shown in formula (1) or formula (2):

[0035]

[0036] Among them, X1 to X2 are selected from -(CH2). m -, m represents the number of CH2 atoms, where m is any integer from 0 to 12; when m is 0 in X1 and X2, it means that X1 and X2 are single bonds.

[0037] Z1 to Z5 are each independently selected from disaccharide subunits, and R1 to R5 are each independently selected from -CH(CH3)-Y-COOH, wherein Y is selected from saturated or unsaturated straight-chain alkyl groups with 9 to 19 carbon atoms. Those skilled in the art will understand that a disaccharide subunit refers to a subunit formed by the loss of two or more H atoms from a disaccharide.

[0038] The disclosed sophorolipid is a surface-active glycolipid compound produced by microbial fermentation. Its molecule consists of two glucose molecules linked by a glycosidic bond, exhibiting high safety, low toxicity, and easy biodegradability, thus avoiding secondary pollution during use. Furthermore, compared to chemically synthesized surfactants, sophorolipid is less affected by factors such as temperature and pH, demonstrates good stability in groundwater environments, and effectively reduces the surface tension of aqueous solutions even at low concentrations, exhibiting excellent solubilizing properties. The sophorolipid can be prepared using commercially available chemical reagents or methods known in the art.

[0039] The oligomeric modified sophorolipid disclosed herein is a dimer or trimer of sophorolipid, formed by chemically linking the hydroxyl groups of sophorolipid to the aldehyde groups of an aldehyde crosslinking agent. This oligomeric modified sophorolipid exhibits better surface activity and solubilizing properties, while also possessing the excellent properties of sophorolipid such as stability, low toxicity, and easy biodegradability.

[0040] The compound surfactants provided in this disclosure include nonionic surfactants and anionic surfactants. The nonionic surfactant is sophorolipid or oligomodified sophorolipid, which has low toxicity, easy biodegradability, high emulsifying activity and solubilizing properties. The anionic surfactant is an amphiphilic alkylphenol polyoxyethylene ether salt with hydrophobic alkyl chain and hydrophilic charge. Combining these two surfactants and dissolving them in water can effectively reduce the surface tension of the aqueous solution and has good thermodynamic stability. It will not precipitate at low temperatures, which avoids the problem of easy precipitation of single anionic surfactants at low temperatures and reduces the adsorption loss of single nonionic surfactants.

[0041] In one embodiment of this disclosure, the acidic sophorolipid comprises one or more compounds having the following structures:

[0042]

[0043] In another embodiment, the lactone-type sophorolipid comprises one or more compounds having the following structures:

[0044] In one embodiment of this disclosure, Z1 to Z4 are each independently selected from the following groups: in This represents the chemical bonds connecting Z1 to Z4 and R1 to R4; Indicates Z1~Z4 and or Connecting chemical bonds. In the above embodiments, " The meaning of "representing the chemical bonds connecting Z1~Z4 and R1~R4" includes: This indicates the chemical bond connecting Z1 and R1. The chemical bond connecting Z2 and R2 This indicates the chemical bond connecting Z3 and R3. This indicates the chemical bond connecting Z4 and R4. Indicates Z1~Z4 and or The meaning of "connected chemical bonds" includes Indicates Z1 and Connected chemical bonds, Indicates Z2 and Connected chemical bonds, Indicates Z3 and Connected chemical bonds, Indicates Z4 and Connecting chemical bonds.

[0045] In one embodiment of this disclosure, Z5 is selected from... in This indicates the chemical bond connecting Z5 and R5; Indicates Z5 and Connecting chemical bonds.

[0046] In one embodiment of this disclosure, m is selected from any integer from 0 to 10, for example, m can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. When m is 0, X1 or X2 is a single bond. Specifically, when X1 is a single bond, the two carbon atoms on -CHOH- in formula (1) are directly connected by a single bond, that is, the structural formula of formula (1) is... When X2 is a single bond, the two carbon atoms on the -CH- bonds in equation (2) are directly connected by a single bond, that is, the structural formula of equation (2) is: Preferably, m is selected from any integer from 0 to 3, for example, m can be 0, 1, 2 or 3.

[0047] The types of R1 to R5 are not limited depending on the fatty acid chain to which the sophorolipid is attached. In one embodiment, Y in R1 to R5 is selected from -(CH2)9-, -(CH2)6CH=CH(CH2)7-, or -(CH2)3CH=CHCH2CH=CH(CH2)7-.

[0048] In one embodiment of this disclosure, the oligomeric modified sophorolipid comprises one or more compounds having the following structures:

[0049]

[0050] In the above embodiments, oligomeric modified sophorolipids have a branched spatial structure and intramolecular sugar ring steric hindrance, thus exhibiting lower surface tension and higher wettability.

[0051] In one embodiment of this disclosure, the method for preparing the oligomeric modified sophoroliposide includes:

[0052] (1) Prepare a sophorolipid aqueous solution by adjusting the pH of the sophorolipid aqueous solution to 1.0-5.0, preferably 2.0-4.0, with acid, and perform a first stirring to obtain a first solution;

[0053] (2) The first solution is brought into contact with the aldehyde crosslinking agent to obtain the second solution; the pH of the second solution is adjusted to 7.0-8.5, preferably 7.0-7.5, using an alkali, and then stirred for the second time;

[0054] The sophorolipids include acidic sophorolipids and / or lactone-type sophorolipids, wherein the acidic sophorolipids have the structure shown in Formula 3 below: The lactone-type sophorolipid has the structure shown in Formula 4: Wherein RZ- is selected from R1-Z1-, R2-Z2-, R3-Z3-, R4-Z4-, or R5-Z5-, and Z' and Z1 to Z5 are each independently selected from disaccharides; R1 to R5 are each independently selected from -CH(CH3)-Y-COOH, where Y is selected from saturated or unsaturated straight-chain alkyl groups with 9 to 19 carbon atoms; the aldehyde crosslinking agent is selected from CHO-X1-CHO or CHO-X2-CHO, where X1 to X2 are selected from -(CH2) m -, m represents the number of CH2, and m is selected from any integer from 0 to 12.

[0055] In a preferred embodiment, Z1 to Z4 and Z' are each independently selected from the following groups: Alternatively, Z5 and Z' can be selected independently. m is selected from any integer from 0 to 10, preferably from any integer from 0 to 3; Y is selected from -(CH2)9-, -(CH2)6CH=CH(CH2)7- or -(CH2)3CH=CHCH2CH=CH(CH2)7-.

[0056] In one embodiment of this disclosure, in step (1), the acidic sophorolipid is selected from one or more compounds having the following structure:

[0057]

[0058] In another embodiment, the lactone-type sophorolipid described in step (1) is selected from one or more compounds having the following structures:

[0059]

[0060] In one embodiment, based on the total weight of the sophorolipid aqueous solution, the content of sophorolipid in the sophorolipid aqueous solution is 5-30% by weight; the water used to prepare the sophorolipid aqueous solution is selected from one or more of deionized water, distilled water, and ultrapure water; the acid is selected from one or more of hydrochloric acid, sulfuric acid, and phosphoric acid; the temperature of the first stirring is 10-40°C, and the time is 20-120 min. In the above embodiment, the preferred sophorolipid is selected, which can produce oligomeric modified sophorolipid with better wetting, emulsifying, and solubilizing properties. The sophorolipid can be a commercially available chemical reagent or prepared according to methods known in the art.

[0061] In one embodiment of this disclosure, in step (2), the molar ratio of the aldehyde crosslinking agent to the sophorolipid in the first solution is 1:(2-4), preferably 1:(2-3); the aldehyde crosslinking agent is selected from alkyl dialdehydes, which are selected from glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, adipaldehyde, or heptaaldehyde, preferably glyoxal, succinaldehyde, or glutaraldehyde; the alkali is selected from one or more of sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate; the second stirring temperature is 10-40°C, and the time is 3-6 hours. In the above embodiments, the aldehyde crosslinking agent can be a pure product or an aqueous solution of any mass fraction, for example, a 25% or 50% aqueous solution.

[0062] In one embodiment of this disclosure, the alkylphenol polyoxyethylene ether salt has the structure shown in formula (5): Wherein, R6 is selected from alkyl groups having 7 to 18 carbon atoms, preferably from alkyl groups having 8 to 16 carbon atoms; n represents the degree of polymerization, and n is selected from any integer from 2 to 100, preferably from any integer from 2 to 80; M is sodium sulfate, potassium sulfate, sodium phosphate, potassium phosphate, sodium sulfonate, potassium sulfonate, sodium carboxylate, or potassium carboxylate. It will be understood in the art that when M is selected from the above categories, the compound of formula (5) is selected from one or more of the corresponding alkylphenol polyoxyethylene ether sulfate, alkylphenol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether sulfonate, and alkylphenol polyoxyethylene ether carboxylic acid salts, forming a potassium or sodium salt. For example, M being sodium sulfate means that the compound of formula (5) is a sodium salt of alkylphenol polyoxyethylene ether sulfate.

[0063] In the above embodiments of sulfate esters, the alkylphenol polyoxyethylene ether salt has a hydrophobic alkyl chain and a hydrophilic charge, which is beneficial to improving the adsorption capacity of hydrophobic chlorinated hydrocarbons and realizing the solubilization of chlorinated hydrocarbons.

[0064] In one embodiment of this disclosure, the alkylphenol polyoxyethylene ether salt is selected from sodium octylphenol polyoxyethylene ether sulfate, sodium octylphenol polyoxyethylene ether sulfonate, potassium octylphenol polyoxyethylene ether phosphate, potassium octylphenol polyoxyethylene ether carboxylate, sodium nonylphenol polyoxyethylene ether sulfate, sodium nonylphenol polyoxyethylene ether sulfonate, potassium nonylphenol polyoxyethylene ether phosphate, potassium nonylphenol polyoxyethylene ether carboxylate, sodium dodecylphenol polyoxyethylene ether sulfate, sodium dodecylphenol polyoxyethylene ether sulfonate, potassium dodecylphenol polyoxyethylene ether phosphate, potassium dodecylphenol polyoxyethylene ether carboxylate, sodium tetradecylphenol polyoxyethylene ether sulfate, sodium tetradecylphenol polyoxyethylene ether sulfonate, potassium tetradecylphenol polyoxyethylene ether phosphate, and potassium tetradecylphenol polyoxyethylene ether carboxylate.

[0065] In a preferred embodiment, the degree of polymerization of sodium octylphenol polyoxyethylene ether sulfate, sodium octylphenol polyoxyethylene ether sulfonate, potassium octylphenol polyoxyethylene ether phosphate, and potassium octylphenol polyoxyethylene ether carboxylate is 10-80, preferably 80; the degree of polymerization of sodium nonylphenol polyoxyethylene ether sulfate, sodium nonylphenol polyoxyethylene ether sulfonate, potassium nonylphenol polyoxyethylene ether phosphate, and potassium nonylphenol polyoxyethylene ether carboxylate is 30-75, preferably 50; the degree of polymerization of sodium dodecylphenol polyoxyethylene ether sulfate, sodium dodecylphenol polyoxyethylene ether sulfonate, potassium dodecylphenol polyoxyethylene ether phosphate, and potassium dodecylphenol polyoxyethylene ether carboxylate is 2-70, preferably 5; and the degree of polymerization of sodium tetradecylphenol polyoxyethylene ether sulfate, sodium tetradecylphenol polyoxyethylene ether sulfonate, potassium tetradecylphenol polyoxyethylene ether phosphate, and potassium tetradecylphenol polyoxyethylene ether carboxylate is 10-80, preferably 30. In the above embodiments, the degree of polymerization, i.e. the value of n in formula (5), represents the average number of repeating units contained in the molecular chain of alkylphenol polyoxyethylene ether salt. For example, a degree of polymerization of 80 for sodium octylphenol polyoxyethylene ether sulfate means that the average number of repeating units CH2CH2O contained in the molecular chain of sodium octylphenol polyoxyethylene ether sulfate is 80.

[0066] A second aspect of this disclosure provides a repair material comprising the compound surfactant described in the first aspect of this disclosure. Based on the total weight of the compound surfactant in the repair material, the content of the nonionic surfactant is 70-95% by weight, preferably 75-95% by weight; and the content of the anionic surfactant is 5-30% by weight, preferably 5-25% by weight. In a preferred embodiment, the weight ratio of the nonionic surfactant to the anionic surfactant is (2.5-19):1, preferably (3-19):1.

[0067] The remediation material disclosed herein contains the aforementioned compound surfactant with a specific composition, which results in the remediation material aqueous solution having a low critical micelle concentration and excellent low-temperature water solubility, and forming negatively charged micelles in water. These micelles can increase the solubility of hydrophobic chlorinated hydrocarbons in water, have a good solubilizing effect on hydrophobic chlorinated hydrocarbons, and are not easily adsorbed onto the medium, thus avoiding secondary pollution and making them suitable for underground environments.

[0068] A third aspect of this disclosure provides a method for remediating chlorinated hydrocarbon contaminants, the method comprising: contacting the remediation material described in the second aspect of this disclosure with the chlorinated hydrocarbon contaminants in the presence of water.

[0069] When the above-mentioned remediation material is used to remediate chlorinated hydrocarbon pollutants, the solubilization capacity of chlorinated hydrocarbons is significantly better than that of a single surfactant of the same mass concentration, and the stability of the system is ensured in the low-temperature environment of groundwater, thus achieving efficient solubilization of chlorinated hydrocarbons.

[0070] In one embodiment of this disclosure, the method further includes: dissolving the remediation material in water to form an aqueous solution of the remediation material; mixing the aqueous solution of the remediation material with the chlorinated hydrocarbon contaminant and agitating; the concentration of the remediation material in the aqueous solution of the remediation material can be 1–100 g / L, preferably 5–100 g / L, more preferably 5–80 g / L, for example 10 g / L, 15 g / L, 20 g / L, 25 g / L, 30 g / L, 35 g / L, 40 g / L, 45 g / L, 50 g / L, 60 g / L, 70 g / L, or any value between these two, for example 10–60 g / L, 20–55 g / L, or 30–50 g / L; the volume ratio of the aqueous solution of the remediation material to the chlorinated hydrocarbon contaminant is (5–20):1, preferably (7–15):1. The source of the water is not limited, for example, it can be deionized water, tap water, or groundwater.

[0071] In one embodiment of this disclosure, the oscillation temperature is 10–40°C, the rotation speed is 120–200 rpm, and the time is 20–40 h; the chlorinated hydrocarbon pollutants include chlorinated hydrocarbon polluted water, preferably chlorinated hydrocarbon polluted groundwater.

[0072] The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereto. Unless otherwise specified, all raw materials used in the examples and comparative examples of the present disclosure are commercially available and are pure reagents.

[0073] The mass spectrometer used in the examples and comparative examples was a Bruker UltrafleXtreme. The detection conditions for mass spectrometry were as follows: ionization source in MALDI-TOF positive ion mode; sheath gas flow rate of 45 arb, auxiliary gas flow rate of 10 arb, capillary voltage of 3300 V, and capillary temperature of 350 °C.

[0074] Preparation Example 1

[0075] This preparation example illustrates the preparation method of oligomeric modified sophorolipid OSL-C1:

[0076] (1) Weigh 12.4 g (10 mmol) of lactone-type sophorolipid (SL, purchased from Shandong Qilu Biotechnology Co., Ltd., with a mass content of 50% and a structural formula of...). Add 50g of distilled water to a round-bottom flask and stir magnetically at room temperature (25±2℃) until homogeneous to obtain a sophorolipid aqueous solution containing 20% ​​by weight. Then slowly add hydrochloric acid while stirring for the first time to adjust the pH of the system to 3.0. Continue stirring magnetically at room temperature (25±2℃) for 30 minutes to obtain the first solution.

[0077] (2) Slowly add 0.8 g of 50 wt% glutaraldehyde aqueous solution (aldehyde crosslinking agent, 4 mmol, purchased from Inokai) to the first solution, wherein the molar ratio of glutaraldehyde to sophorolipid in the first solution is 1:2.5; continue stirring at room temperature (25±2℃) for 4 h, then stop the reaction to obtain the second solution. Slowly add 10 wt% sodium hydroxide aqueous solution to the second solution while stirring for a second time, and adjust the pH of the system to 7.0 to obtain oligomeric modified sophorolipid, denoted as OSL-C1. Mass spectrometry analysis shows that OSL-C1 comprises a mixture with the following structure:

[0078]

[0079] X1~X2 are -(CH2)3-, R1~R5 are -CH(CH3)-Y-COOH, Y is -(CH2)6CH=CH(CH2)7-, and its mass fraction is 10.4%.

[0080] Mass spectrometry analysis of the oligomodified sophorolipid was performed, and the MALDI-TOF mass spectrum is shown below. Figure 1 As shown, the mass spectrum peak with a mass-to-charge ratio of 1367.745 corresponds to the molecular ion peak ([M+Na)) after the addition of one sodium ion to the disosophorolipid. + Mass spectrometry results showed that the active substance obtained from the reaction was mainly disosophorolipid, while trisophorolipid was present in smaller amounts and had a large molecular weight, making it difficult for it to precipitate. Therefore, the peak intensity of trisophorolipid in the mass spectrometry was very low.

[0081] Preparation Example 2

[0082] This preparation example illustrates the preparation method of oligomeric modified sophorolipid OSL-C2:

[0083] The method of Preparation Example 1 was used, with the only difference being that in step (1), 12.4 g (10 mmol) of lactone-type sophorolipid was added to 10 g of distilled water, and the content of sophorolipid in the resulting sophorolipid aqueous solution was 55% by weight; in step (2), 0.29 g of 40 wt% glyoxal aqueous solution (5 mmol) was slowly added to the first solution, wherein the molar ratio of glyoxal to sophorolipid in the first solution was 1:2. Finally, oligomeric modified sophorolipid was obtained, denoted as OSL-C2. OSL-C2 comprises a mixture having the structures shown in formulas (I) to (VI), wherein X1 to X2 are single bonds (-(CH2)0-), R1 to R5 are -CH(CH3)-Y-COOH, Y is -(CH2)6CH=CH(CH2)7-, and its mass fraction is 27.8%.

[0084] Example 1

[0085] This example illustrates the preparation method of aqueous solutions of repair materials A1 to A4:

[0086] Preparation method of A1 aqueous solution: Weigh 400 mg of lactone-type sophorolipid (SL, nonionic surfactant, structural formula as shown in Preparation Example 1) and 100 mg of sodium octylphenol polyoxyethylene ether sulfate (OPE) with a degree of polymerization of 80. 80 S has the structure shown in equation (5). R6 (octyl, n=80, anionic surfactant, purchased from Beijing Xingpu New Product Development Center) was formulated into repair material A1. Based on the total weight of nonionic and anionic surfactants, A1 contained 80% by weight of nonionic surfactant and 20% by weight of anionic surfactant, with a nonionic surfactant to anionic surfactant weight ratio of 4:1. A1 was dissolved in distilled water to prepare a 10 g / L aqueous solution, thus obtaining the A1 aqueous solution.

[0087] The preparation method for aqueous solution A2 is the same as that for aqueous solution A1, the only difference being: 400 mg of oligomeric modified sophoroliposide ester (OSL-C1) prepared in Example 1 and 100 mg of sodium octylphenol polyoxyethylene ether sulfonate (OPE) with a degree of polymerization of 80 are weighed. 80 SO), and prepare an A2 aqueous solution with a concentration of 10 g / L.

[0088] The preparation method for aqueous solution A3 is the same as that for aqueous solution A1, except that: 400 mg of oligomeric modified sophoroliposide (OSL-C2) prepared in Preparation Example 2 and 100 mg of potassium octylphenol polyoxyethylene ether phosphate (OPE) with a degree of polymerization of 80 are weighed. 80 P), prepare an A3 aqueous solution with a concentration of 10 g / L.

[0089] The preparation method for A4 aqueous solution is the same as that for A1 aqueous solution, the only difference being: weigh 400 mg of lactone-type sophorolipid (SL) and 100 mg of potassium octylphenol polyoxyethylene ether carboxylate (OPE) with a degree of polymerization of 80. 80 C) Prepare an A4 aqueous solution with a concentration of 10 g / L.

[0090] Example 2

[0091] This example illustrates the preparation method of aqueous solutions of repair materials B1 to B4:

[0092] Preparation method of B1 aqueous solution: Weigh 1900 mg of lactone-type sophorolipid (SL) and 100 mg of sodium nonylphenol polyoxyethylene ether sulfate (NPE) with a degree of polymerization of 50. 50 S has the structure shown in equation (5). R6 (nonyl, n=50, purchased from Beijing Xingpu New Product Development Center) was formulated into repair material B1. Based on the total weight of nonionic and anionic surfactants, B1 contained 95% by weight of nonionic surfactant and 5% by weight of anionic surfactant, with a nonionic surfactant to anionic surfactant weight ratio of 19:1. B1 was dissolved in distilled water to prepare a 40 g / L aqueous solution, yielding the B1 aqueous solution.

[0093] The preparation method for aqueous solution B2 is the same as that for aqueous solution B1, the only difference being: weigh 1900 mg of oligomodified sophoroliposide (OSL-C1) and 100 mg of sodium nonylphenol polyoxyethylene ether sulfonate (NPE) with a degree of polymerization of 50. 50 SO), to prepare a B2 aqueous solution with a concentration of 40 g / L.

[0094] The preparation method for aqueous solution B3 is the same as that for aqueous solution B1, the only difference being: weigh 1900 mg of oligomodified sophoroliposide (OSL-C2) and 100 mg of potassium nonylphenol polyoxyethylene ether phosphate (NPE) with a degree of polymerization of 50. 50 P), prepare a B3 aqueous solution with a concentration of 40 g / L.

[0095] The preparation method for aqueous solution B4 is the same as that for aqueous solution B1, the only difference being: weigh 1900 mg of lactone-type sophorolipid (SL) and 100 mg of nonylphenol polyoxyethylene ether potassium carboxylate (NPE) with a degree of polymerization of 50. 50 C) Prepare a B4 aqueous solution with a concentration of 40 g / L.

[0096] Example 3

[0097] This example illustrates the preparation method of aqueous solutions of repair materials C1 to C4:

[0098] Preparation method of C1 aqueous solution: Weigh 900 mg of lactone-type sophorolipid (SL) and 100 mg of sodium dodecylphenol polyoxyethylene ether sulfate (DPE5S) with a degree of polymerization of 5, which has the structure shown in formula (5). R6 (dodecyl group, n=5, purchased from Beijing Xingpu New Product Development Center) was formulated into repair material C1. Based on the total weight of nonionic and anionic surfactants, C1 contained 90% by weight of nonionic surfactant and 10% by weight of anionic surfactant, with a nonionic surfactant to anionic surfactant weight ratio of 9:1. C1 was dissolved in distilled water to prepare a 20 g / L aqueous solution, yielding the C1 aqueous solution.

[0099] The preparation method of C2 aqueous solution is the same as that of C1 aqueous solution, except that: 900 mg of oligomodified sophoroliposide (OSL-C1) and 100 mg of sodium dodecylphenol polyoxyethylene ether sulfonate (DPE5SO) with a degree of polymerization of 5 are weighed to prepare a C2 aqueous solution with a concentration of 20 g / L.

[0100] The preparation method of C3 aqueous solution is the same as that of C1 aqueous solution, except that: 900 mg of oligomodified sophoroliposide (OSL-C2) and 100 mg of potassium dodecylphenol polyoxyethylene ether phosphate (DPE5P) with a degree of polymerization of 5 are weighed to prepare a C3 aqueous solution with a concentration of 20 g / L.

[0101] The preparation method for C4 aqueous solution is the same as that for C1 aqueous solution, except that: 900 mg of lactone-type sophorolipid (SL) and 100 mg of dodecylphenol polyoxyethylene ether potassium carboxylate (DPE5C) with a degree of polymerization of 5 are weighed to prepare a C4 aqueous solution with a concentration of 20 g / L.

[0102] Example 4

[0103] This example illustrates the preparation method of aqueous solutions for repair materials D1 to D4:

[0104] Preparation method of D1 aqueous solution: Weigh 2250 mg of lactone-type sophorolipid (SL) and 750 mg of sodium tetradecylphenol polyoxyethylene ether sulfate (TPE) with a degree of polymerization of 30. 30 S has the structure shown in equation (5). R6 (tetradecyl, n=30, purchased from Beijing Xingpu New Product Development Center) was formulated into repair material D1. Based on the total weight of nonionic and anionic surfactants, D1 contained 75% by weight of nonionic surfactant and 25% by weight of anionic surfactant, with a nonionic surfactant to anionic surfactant weight ratio of 3:1. D1 was dissolved in distilled water to prepare a 60 g / L aqueous solution, yielding the D1 aqueous solution.

[0105] The preparation method for the D2 aqueous solution is the same as that for the D1 aqueous solution, except that: 2250 mg of oligomodified sophoroliposide (OSL-C1) and 750 mg of sodium tetradecylphenol polyoxyethylene ether sulfonate (TPE) with a degree of polymerization of 30 are weighed out. 30 SO), to prepare a D2 aqueous solution with a concentration of 60 g / L.

[0106] The preparation method for the D3 aqueous solution is the same as that for the D1 aqueous solution, except that: 2250 mg of oligomeric modified sophoroliposide (OSL-C2) and 750 mg of tetradecylphenol polyoxyethylene ether phosphate potassium (TPE) with a degree of polymerization of 30 are weighed out. 30 P), prepare a D3 aqueous solution with a concentration of 60 g / L.

[0107] The preparation method for the D4 aqueous solution is the same as that for the D1 aqueous solution, the only difference being: weigh 2250 mg of lactone-type sophorolipid (SL) and 750 mg of tetradecylphenol polyoxyethylene ether potassium carboxylate (TPE) with a degree of polymerization of 30. 30 C) Prepare a D4 aqueous solution with a concentration of 60 g / L.

[0108] Example 5

[0109] This example illustrates the preparation method of aqueous solutions of repair materials E1 to E4:

[0110] The preparation method of E1 aqueous solution is the same as that of D1 aqueous solution, except that: the remediation material D1 is dissolved in the polluted groundwater (chlorinated hydrocarbon content is 3439 μg / L) to prepare an aqueous solution with a concentration of 60 g / L, thus obtaining E1 aqueous solution.

[0111] The preparation method of E2 aqueous solution is the same as that of D2 aqueous solution, the only difference being that: the remediation material D2 is dissolved in the polluted groundwater to prepare an aqueous solution with a concentration of 60g / L, thus obtaining E2 aqueous solution.

[0112] The preparation method of E3 aqueous solution is the same as that of D3 aqueous solution, the only difference being that: the remediation material D3 is dissolved in the polluted groundwater to prepare an aqueous solution with a concentration of 60g / L, thus obtaining E3 aqueous solution.

[0113] The preparation method of E4 aqueous solution is the same as that of D4 aqueous solution, the only difference being that: the remediation material D4 is dissolved in the polluted groundwater to prepare an aqueous solution with a concentration of 60g / L, thus obtaining E4 aqueous solution.

[0114] Test Example 1

[0115] The aqueous solutions of the repair materials A1-A4 prepared in Example 1, the nonionic surfactants SL, OSL-C1, OSL-C2, and the anionic surfactant OPE were respectively applied. 80 S, OPE 80 SO, OPE 80 P, OPE 80 C was prepared into aqueous solutions of the test sample with a mass concentration ranging from 0.01 mg / L to 50 mg / L. The surface tension values ​​of the aqueous solutions at different concentrations were measured using a KRUSS K100 surface tension meter (Germany). The test method was the hanging plate method (industry standard ASTM D1331-14), and the test temperature was 25℃. As the concentration of the aqueous solution increased, the surface tension value continuously decreased. After a certain critical concentration, the surface tension value remained essentially constant. This constant surface tension value is defined as γ. CAC The test results are shown in Table 1 and... Figure 2 :

[0116] Table 1

[0117] <![CDATA[γ CAC / (mN / m)]]> A1 aqueous solution 36.4 A2 aqueous solution 33.8 A3 aqueous solution 34.6 A4 aqueous solution 34.9 SL aqueous solution 38.2 OSL-C1 aqueous solution 36.1 OSL-C2 aqueous solution 37.0 <![CDATA[OPE 80 S aqueous solution]]> 38.1 <![CDATA[OPE 80 SO aqueous solution]]> 34.2 <![CDATA[OPE 80 P aqueous solution]]> 38.4 <![CDATA[OPE 80 C aqueous solution]]> 37.4

[0118] From Table 1 and Figure 2 It can be seen that the surface tension of the repair material A1 aqueous solution is lower than that of the single surfactants SL and OPE. 80 The surface tension of S,A2 aqueous solution is lower than that of single surfactants OSL-C1 and OPE. 80 SO, the surface tension of A3 aqueous solution is lower than that of single surfactants OSL-C2 and OPE. 80 The surface tension of P,A4 aqueous solution is lower than that of single surfactants SL and OPE. 80 C indicates that the repair materials A1 to A4 can effectively reduce the surface tension of the aqueous solution and have a higher solubilizing capacity.

[0119] Test Example 2

[0120] The aqueous solutions of repair materials B1-B4 prepared in Example 2 and the sodium dodecyl sulfate solution (concentration 40 g / L) were stored at 5°C for 48 h, and the precipitation of the system was observed. Figure 3 As shown, from left to right, the solutions are aqueous solutions of B1 to B4 and sodium dodecyl sulfate solution; the top and bottom rows are photographs of each system before and after 48 hours of storage.

[0121] Figure 3 It is evident that a large amount of sodium dodecyl sulfate solid precipitated out, while the aqueous solutions of repair materials B1 to B4 remained unchanged, indicating that the aqueous solutions of repair materials B1 to B4 have good thermal stability and good solubility at low temperatures.

[0122] Test Example 3

[0123] The aqueous solutions of the repair materials C1 to C4 prepared in Example 3 were taken and the Zeta potentials of the solutions were measured using a Zetasizer Nano ZS instrument. The results are shown in Table 2.

[0124] Table 2

[0125] C1 aqueous solution C2 aqueous solution C3 aqueous solution C4 aqueous solution ζ(mV) -48 -51 -37 -42

[0126] Table 2 shows that the Zeta potential of the C1 to C4 aqueous solutions of the remediation materials disclosed in this invention is negative, which is conducive to the formation of negatively charged micelles. These micelles can increase the solubility of hydrophobic chlorinated hydrocarbons in water, have a good solubilizing effect on hydrophobic chlorinated hydrocarbons, and are not easily adsorbed on the medium, thus avoiding secondary pollution and making them suitable for underground environments.

[0127] Test Example 4

[0128] The aqueous solutions of repair materials B1-B4 prepared in Example 2, nonionic surfactants SL, OSL-C1, OSL-C2, and anionic surfactant NPE were respectively applied. 50 S, NPE 50 SO, NPE 50 P, NPE 50 C was prepared into aqueous solutions with mass concentrations of 10 g / L, 20 g / L, 30 g / L, and 40 g / L. 15 mL of these aqueous solutions and 1 mL of tetrachloroethylene (PCE) were added to 20 mL glass bottles, respectively, to achieve a volume ratio of the remediation material aqueous solution to the chlorinated hydrocarbon contaminant of 15:1. The glass bottles were then placed in a 20°C constant-temperature water bath shaker and shaken at 150 rpm for 30 h. After centrifugation, the supernatant was collected and the concentration of tetrachloroethylene was determined to evaluate the solubilizing effect of the above aqueous solutions on tetrachloroethylene. The results are shown in Table 3.

[0129] Table 3

[0130]

[0131]

[0132] As shown in Table 3, under the same usage, the aqueous solutions of B1-B4 have a better solubilizing effect on tetrachloroethylene than a single surfactant. Furthermore, under the same solubilizing effect, the amount of the repair material used in this invention is smaller than that of a single surfactant. Moreover, the aqueous solutions of the repair materials B1-B4 disclosed in this invention exhibit better solubilizing effects on tetrachloroethylene at concentrations of 30-40 g / L. In particular, at a concentration of 40 g / L, the concentration of tetrachloroethylene in the supernatant is consistently higher than 14000 mg / L, indicating that the solubilizing performance of the aqueous solutions of the repair materials B1-B4 on tetrachloroethylene is superior to that of a single surfactant (including single nonionic surfactants and single anionic surfactants).

[0133] Test Example 5

[0134] Take the aqueous solutions of repair materials D1-D4 prepared in Example 4, as well as SL, OSL-C1, OSL-C2, and TPE. 30 S, TPE 30 SO, TPE 30 P, TPE 30C. Aqueous solutions with mass concentrations of 10 g / L, 20 g / L, 30 g / L, and 40 g / L were prepared. 10 mL of these aqueous solutions and 1 mL of tetrachloroethylene (PCE) were added to a 20 mL glass bottle, making the volume ratio of the remediation material aqueous solution to the chlorinated hydrocarbon contaminant 10:1. The glass bottle was then placed in a 20°C constant temperature water bath shaker and shaken at 180 rpm for 24 hours. After centrifugation, the supernatant was collected and the tetrachloroethylene concentration was determined to evaluate the solubilizing effect of the above aqueous solutions on tetrachloroethylene. The results are shown in Table 4.

[0135] Table 4

[0136]

[0137]

[0138] As shown in Table 4, under the same usage, the aqueous solutions of D1 to D4 have a better solubilizing effect on tetrachloroethylene than a single surfactant. Furthermore, under the same solubilizing effect, the amount of the remediation material of this invention required is less than that of a single surfactant. Moreover, the aqueous solutions of D1 to D4 at concentrations of 30–40 g / L exhibit even better solubilizing effects on tetrachloroethylene. Especially at a concentration of 40 g / L, the concentration of tetrachloroethylene in the supernatant is consistently higher than 13000 mg / L, indicating that the solubilizing performance of the aqueous solutions of D1 to D4 on tetrachloroethylene is superior to that of a single surfactant.

[0139] Test Example 6

[0140] Take the aqueous solutions of repair materials E1-E4 prepared in Example 5, as well as SL, OSL-C1, OSL-C2, and TPE. 30 S, TPE 30 SO, TPE 30 P, TPE 30 C. Using contaminated groundwater (chlorinated hydrocarbon content 3439 μg / L), aqueous solutions with mass concentrations of 10 g / L, 20 g / L, 30 g / L, and 40 g / L were prepared. 10 mL of these aqueous solutions and 1 mL of tetrachloroethylene (PCE) were added to 20 mL glass bottles, ensuring a volume ratio of the remediation material aqueous solution to the chlorinated hydrocarbon contaminant of approximately 10:1. The glass bottles were then placed in a 20°C constant-temperature water bath shaker and shaken at 180 rpm for 24 hours. After centrifugation, the supernatant was collected and the tetrachloroethylene concentration was determined to evaluate the solubilizing effect of the above aqueous solutions on tetrachloroethylene. The results are shown in Table 5.

[0141] Table 5

[0142]

[0143]

[0144]

[0145] Table 5 shows that in groundwater environments, the remediation materials E1-E4 aqueous solutions also exhibit excellent solubilizing effects on tetrachloroethylene. At the same dosage, the E1-E4 aqueous solutions show better solubilizing effects on tetrachloroethylene than single surfactants, and for the same solubilizing effect, the dosage of the remediation material of this invention is lower than that of a single surfactant. Furthermore, concentrations of E1-E4 at 30-40 g / L show even better solubilizing effects on tetrachloroethylene, especially at a concentration of 40 g / L, where the tetrachloroethylene concentration is consistently above 13000 mg / L, indicating that the solubilizing performance of the E1-E4 aqueous solutions on tetrachloroethylene is superior to that of single surfactants.

[0146] The preferred embodiments of this disclosure have been described in detail above with reference to the accompanying drawings. However, this disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this disclosure, various simple modifications can be made to the technical solutions of this disclosure, and these simple modifications all fall within the protection scope of this disclosure.

[0147] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, this disclosure will not describe the various possible combinations separately.

[0148] Furthermore, various different embodiments of this disclosure can be combined in any way, as long as they do not violate the spirit of this disclosure, they should also be regarded as the content disclosed in this disclosure.

Claims

1. A complexing surfactant characterized in that, The complex surfactant comprises a nonionic surfactant selected from sophorolipids and / or oligomodified sophorolipids and an anionic surfactant selected from alkylphenol polyoxyethylene ether salts; the sophorolipids are selected from acid sophorolipids and / or lactone sophorolipids; the oligomodified sophorolipids have a structure as shown in formula (1) or formula (2): wherein X1to X2are selected from -(CH2) m -, m represents the number of CH2, m is selected from any integer from 0 to 12; Z1-Z5 are each independently selected from a disaccharide radical, and R1-R5 are each independently selected from -CH(CH3)-Y-COOH, wherein Y is selected from a saturated or unsaturated linear alkyl group having 9-19 carbon atoms.

2. The complexing surfactant according to claim 1, characterized in that, The acid sophorolipids include one or more of the compounds having a structure as shown below:

3. The complexing surfactant of claim 1, wherein, The lactone sophorolipids include one or more of the compounds having a structure as shown below:

4. The complexing surfactant of claim 1, wherein, Z1to Z4are each independently selected from the following groups: wherein represents a chemical bond by which Z1to Z4are linked to R1to R4; * represents a chemical bond by which Z1to Z4are linked to or R1to R4.

5. The complexing surfactant of claim 1, wherein, Z5is selected from wherein represents a chemical bond by which Z5is attached to R5; * represents a chemical bond by which Z5is attached to R5.

6. The complexing surfactant of claim 1, wherein, m is selected from any integer between 0 and 10, preferably from any integer between 0 and 3; Y is selected from -(CH2)9-, -(CH2)6CH=CH(CH2)7- or -(CH2)3CH=CHCH2CH=CH(CH2)7-.

7. The complexing surfactant of claim 1, wherein, The oligomodified sophorolipids include one or more of the compounds having a structure as shown below:

8. The complexing surfactant of claim 1, wherein, The alkylphenol polyoxyethylene ether salts have a structure as shown in formula (5): wherein R6 is selected from an alkyl group having 7-18 carbon atoms, preferably from an alkyl group having 8-16 carbon atoms; n is selected from any integer between 2 and 100, preferably from any integer between 2 and 80; and M is sodium sulfate, potassium sulfate, sodium phosphate, potassium phosphate, sodium sulfonate, potassium sulfonate, sodium carboxylate or potassium carboxylate.

9. The complexing surfactant of claim 8, wherein, The alkylphenol polyoxyethylene ether salts are selected from sodium octylphenol polyoxyethylene ether sulfate, sodium octylphenol polyoxyethylene ether sulfonate, potassium octylphenol polyoxyethylene ether phosphate, potassium octylphenol polyoxyethylene ether carboxylate, sodium nonylphenol polyoxyethylene ether sulfate, sodium nonylphenol polyoxyethylene ether sulfonate, potassium nonylphenol polyoxyethylene ether phosphate, potassium nonylphenol polyoxyethylene ether carboxylate, sodium dodecylphenol polyoxyethylene ether sulfate, sodium dodecylphenol polyoxyethylene ether sulfonate, potassium dodecylphenol polyoxyethylene ether phosphate, potassium dodecylphenol polyoxyethylene ether carboxylate, sodium tetradecylphenol polyoxyethylene ether sulfate, sodium tetradecylphenol polyoxyethylene ether sulfonate, potassium tetradecylphenol polyoxyethylene ether phosphate, potassium tetradecylphenol polyoxyethylene ether carboxylate; Preferably, the degree of polymerization of the sodium octylphenol polyoxyethylene ether sulfate, sodium octylphenol polyoxyethylene ether sulfonate, potassium octylphenol polyoxyethylene ether phosphate, potassium octylphenol polyoxyethylene ether carboxylate is 10-80, preferably 80; the degree of polymerization of the sodium nonylphenol polyoxyethylene ether sulfate, sodium nonylphenol polyoxyethylene ether sulfonate, potassium nonylphenol polyoxyethylene ether phosphate, potassium nonylphenol polyoxyethylene ether carboxylate is 30-75, preferably 50; the degree of polymerization of the sodium dodecylphenol polyoxyethylene ether sulfate, sodium dodecylphenol polyoxyethylene ether sulfonate, potassium dodecylphenol polyoxyethylene ether phosphate, potassium dodecylphenol polyoxyethylene ether carboxylate is 2-70, preferably 5; the degree of polymerization of the sodium tetradecylphenol polyoxyethylene ether sulfate, sodium tetradecylphenol polyoxyethylene ether sulfonate, potassium tetradecylphenol polyoxyethylene ether phosphate, potassium tetradecylphenol polyoxyethylene ether carboxylate is 10-80, preferably 30.

10. A restorative material characterized by, The repair material comprises the complex surfactant according to any one of claims 1-9, and the content of the nonionic surfactant is 70-95% by weight, and the content of the anionic surfactant is 5-30% by weight, based on the total weight of the complex surfactant in the repair material.

11. A method of remediating a chlorinated hydrocarbon contaminant, characterized by, The method comprises: contacting the repair material according to claim 10 with a chlorinated hydrocarbon contaminant in the presence of water.

12. The method of claim 11, wherein, The method further comprises: dissolving the repair material in water to form a repair material aqueous solution; mixing and oscillating the repair material aqueous solution with the chlorinated hydrocarbon contaminant. The concentration of the repair material in the repair material aqueous solution is 30-100 g / L, and the volume ratio of the repair material aqueous solution to the chlorinated hydrocarbon contaminant is (5-20):

1.

13. The method of claim 12, wherein, The oscillation temperature is 10-40°C, the rotation speed is 120-200 rpm, and the time is 20-40 h; and the chlorinated hydrocarbon contaminant comprises chlorinated hydrocarbon contaminated water, preferably chlorinated hydrocarbon contaminated groundwater.

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