Composite solubilizer, remediation preparation and remediation method for petroleum hydrocarbon contaminated soil remediation

Abstract

The present invention discloses a composite solubilizer, a remediation preparation and a remediation method for petroleum hydrocarbon contaminated soil. The composite solubilizer is composed of alkylphenol polyoxyethylene dibasic acid ester, alkyl polyoxyethylene polyoxypropylene ether and polyoxyethylene polyoxypropylene siloxane. The remediation preparation is sprayed into the soil contaminated by petroleum hydrocarbons. During the spraying process, the soil is continuously stirred so that it is evenly mixed with the remediation preparation. After the spraying of the remediation preparation is completed, the biological preparation is sprayed. At the same time, the soil is stirred evenly and a soil solubilization-biopile is built. The built soil solubilization-biopile is regularly maintained. The three components of the composite solubilizer of the present invention are similar to the structures of different types of petroleum hydrocarbons. According to the principle of like dissolves like, it has good solubility for petroleum hydrocarbons, so that pollutants are easily dissolved from the soil into the solubilizer, thereby making the soil more biodegradable. Moreover, the solubilizer is non-toxic and easily degradable, so as to facilitate the subsequent microbial treatment of the petroleum hydrocarbon contaminated soil.

Description

Technical Field

[0001] The present invention relates to the technical field of petroleum hydrocarbon contaminated soil remediation, and in particular to a composite solubilizer, a remediation preparation and a remediation method for petroleum hydrocarbon contaminated soil remediation. Background Art

[0002] With the continued rapid development of the domestic economy, the demand for oil has also increased rapidly. However, during the extraction, storage, processing, and storage, transportation, and use of oil products, large amounts of unused petroleum hydrocarbons are generated due to leakage and other factors. These petroleum hydrocarbons often flow unused and untreated onto the soil surface, then penetrate into the soil and further into the groundwater, causing petroleum hydrocarbon contamination of soil and groundwater. Therefore, how to quickly and efficiently remove petroleum hydrocarbon contaminants from soil while maintaining the original biological activity of the soil has become a key issue in the development of soil remediation technologies required by oil fields, refineries, and petrochemical processing companies. Among the various petroleum hydrocarbon-contaminated soil remediation technologies, the application of solubilizers allows pollutants adsorbed in the soil to be rapidly dissolved to the soil surface by the solubilizer. Further degradation by microorganisms reduces the petroleum hydrocarbon concentration in the soil to the required standard, thereby restoring the soil's activity and original use to the greatest extent possible.

[0003] The main component of a solubilizer is a surfactant, which contains both hydrophilic and lipophilic groups within its molecules. Based on the type and molecular composition of the petroleum hydrocarbons in the contaminated soil, a surfactant with a suitable molecular structure is identified and synthesized. It is designed to effectively dissolve and solubilize different types of petroleum hydrocarbons, while being non-toxic to the microorganisms being further treated. Ideally, it should serve as a nutrient for the microorganisms and not reduce the organic matter content in the soil.

[0004] Patent Document 1: Chinese Patent Document No. CN111346909A

[0005] Patent Document 1 proposes a foam-enhanced in-situ remediation method for petroleum hydrocarbon contamination. The claim involves adding a foamed solubilizer, oxidant, activator, and the like through an injection well. The solubilizer is polyoxyethylene sorbitan ester (Tween-80), and the oxidant is sodium percarbonate. Apparently, the solubilizer Tween-80, due to its weak lipophilicity, is only suitable for contaminated soils with low petroleum hydrocarbon content (no more than 1%), and its leaching and solubilization effect is very limited. The oxidant, sodium percarbonate, possesses a strong oxidizing property, which also has a strong bactericidal effect on microorganisms in subsequent biological treatment processes, rendering the solubilized soil unsuitable for biological treatment.

[0006] Patent Document 2: Chinese Patent Document No. CN112742855A

[0007] Patent document 2 proposes a modified eluent, the component of which is a sophorolipid sulfonate surfactant. The properties of this component are similar to those of the aforementioned Tween-80, and its lipophilicity is weak. Although it is a biosurfactant and has good biodegradability, its elution and solubilization effect on petroleum hydrocarbon pollution is poor and the cost is high.

[0008] Patent Document 3: Chinese Patent Document No. CN112724981A

[0009] Patent Document 3 proposes a petroleum-contaminated soil eluent composition, the main components of which are a nonionic surfactant, alkylphenol polyoxyethylene ether, and an amphoteric surfactant. This composition has a good elution effect on petroleum hydrocarbons in contaminated soil and can be used as a soil remediation eluent. However, its solubilization and dispersion properties are poor, making it unsuitable for use in soil remediation through a coupled solubilization and microbial degradation method. Summary of the Invention

[0010] The purpose of the present invention is to solve the technical problem that existing solubilizers have poor leaching and solubilization effects on petroleum hydrocarbon pollution and are not suitable for use in soil remediation through a coupled solubilization and microbial degradation method, and to provide a composite solubilizer, remediation preparation and remediation method for petroleum hydrocarbon contaminated soil.

[0011] In order to solve the above-mentioned technical problems, the present invention adopts a technical solution: a composite solubilizer for remediation of petroleum hydrocarbon contaminated soil, comprising the following raw materials in the following weight percentages:

[0012] 10-98% alkylphenol polyoxyethylene dibasic acid ester;

[0013] 1-75% alkyl polyoxyethylene polyoxypropylene ether; and

[0014] 0.05-15% polyoxyethylene polyoxypropylene siloxane.

[0015] Alkylphenol polyoxyethylene dibasic acid ester and alkyl polyoxyethylene polyoxypropylene ether have the functions of solubilization, cleaning, dispersion and emulsification, and polyoxyethylene polyoxypropylene siloxane has the functions of dispersing, defoaming, solubilization and reducing surface tension; different types of surfactants can be applied to petroleum hydrocarbon contaminated soils with different compositions.

[0016] As a further optimization of the composite solubilizer for remediation of petroleum hydrocarbon contaminated soil of the present invention, the composite solubilizer is composed of the following raw materials in the following weight percentages:

[0017] 40-80% alkylphenol polyoxyethylene dibasic acid ester;

[0018] 15-50% alkyl polyoxyethylene polyoxypropylene ether; and

[0019] 1-10% polyoxyethylene polyoxypropylene siloxane.

[0020] As a further optimization of the composite solubilizer for remediation of petroleum hydrocarbon contaminated soil of the present invention: the molecular formula of the alkylphenol polyoxyethylene dicarboxylic acid ester is: R1-C6H5O-(-C2H4O-) m OOC-C n H 2。n -COO-(-C2H4O-) m -C6H5O-R1, where R1 is C1-C 36 Alkyl, m is any integer from 1 to 40, and n is any integer from 1 to 30.

[0021] As a further optimization of the composite solubilizer for remediation of petroleum hydrocarbon contaminated soil of the present invention: the R1 is C2-C 24 Alkyl, m is any integer from 2 to 30, and n is any integer from 2 to 24.

[0022] As a further optimization of the composite solubilizer for remediation of petroleum hydrocarbon contaminated soil of the present invention: the molecular formula of the alkyl polyoxyethylene polyoxypropylene ether is: R2-(-C2H4O-) p -(-CH2CH(CH3)O-) q -H, where R2 is C1-C 36 Alkyl, p is any integer from 1 to 36, and q is any integer from 1 to 36.

[0023] As a further optimization of the composite solubilizer for remediation of petroleum hydrocarbon contaminated soil of the present invention: the R2 is C2-C 24 Alkyl, p is any integer from 4 to 24, and q is any integer from 2 to 24.

[0024] As a further optimization of the composite solubilizer for remediation of petroleum hydrocarbon contaminated soil of the present invention: the molecular formula of the polyoxyethylene polyoxypropylene siloxane is: (C n H 2n+1 )3-Si-O-(-(C n H 2n+1 )2Si-O-) r -(-CH2CH2O-) s -(-CH2CH(CH3)O-) t -Si-(-C n H 2n+1 )3, wherein n is any integer from 1 to 20, s is any integer from 2 to 40, and t is any integer from 1 to 30.

[0025] As a further optimization of the composite solubilizer for remediation of petroleum hydrocarbon contaminated soil of the present invention: n is any integer from 1 to 12, s is any integer from 6 to 24, and t is any integer from 2 to 24.

[0026] A preparation for remediating petroleum hydrocarbon-contaminated soil comprises water and the composite solubilizer, wherein the concentration of the composite solubilizer is 0.1-20%.

[0027] A method for remediating petroleum hydrocarbon-contaminated soil comprises spraying a remediation agent into the petroleum hydrocarbon-contaminated soil, continuously stirring the soil during the spraying process to uniformly mix it with the remediation agent, spraying a biological agent after the spraying of the remediation agent is completed, and simultaneously stirring the soil to uniformly form a solubilization-biopile, and regularly maintaining the formed soil solubilization-biopile.

[0028] As a further optimization of the petroleum hydrocarbon contaminated soil remediation method of the present invention: the weight ratio of the remediation preparation to the petroleum hydrocarbon contaminated soil is 1 / 1-1 / 50.

[0029] The present invention has the following beneficial effects:

[0030] 1. The components of the composite solubilizer of the present invention are alkylphenol polyoxyethylene dibasic acid ester, alkyl polyoxyethylene polyoxypropylene ether and polyoxyethylene polyoxypropylene siloxane. The above three components are similar in structure to petroleum hydrocarbons of different compositions. According to the principle of like dissolves like, they have good solubility in petroleum hydrocarbons, pollutants are easily biodegraded, and the solubilizer is non-toxic, which facilitates the subsequent microbial treatment of petroleum hydrocarbon-contaminated soil.

[0031] 2. Petroleum hydrocarbons have a complex composition, especially a wide distribution of carbon numbers, including hydrocarbon compounds with molecular weights ranging from C1 to C50 or even higher. The composite solubilizer of the present invention can achieve a better solubilizing effect on petroleum hydrocarbons in soil by changing the alkyl carbon number, the degree of polymerization of polyoxyethylene, and the carbon number of fatty alcohol in the dibasic acid ester molecule in the alkylphenol polyoxyethylene dibasic acid ester, and changing the alkyl carbon number and the degree of polymerization of polyoxyethylene and polyoxypropylene in the alkyl polyoxyethylene polyoxypropylene ether. DETAILED DESCRIPTION

[0032] The technical solution of the present invention will be clearly and completely described below in conjunction with specific embodiments.

[0033] Example 1

[0034] A composite solubilizer for remediating petroleum hydrocarbon-contaminated soil is composed of the following raw materials in percentage by weight: 50% of alkylphenol polyoxyethylene dibasic acid ester, 45% of alkyl polyoxyethylene polyoxypropylene ether, and 5% of polyoxyethylene polyoxypropylene siloxane.

[0035] Among them, the molecular formula of alkylphenol polyoxyethylene dicarboxylic acid ester is: R1-C6H5O-(-C2H4O-) m OOC-C n H 2n -COO-(-C2H4O-) m -C6H5O-R1, wherein R1 is a C4 alkyl group, m=10, n=10.

[0036] Among them, the molecular formula of alkyl polyoxyethylene polyoxypropylene ether is: R2-(-C2H4O-) p -(-CH2CH(CH3)O-) q -H, where R2 is C 10 Alkyl, p=12, q=24.

[0037] Wherein, the molecular formula of polyoxyethylene polyoxypropylene siloxane is: (C n H 2n+1 )3-Si-O-(-(C n H 2n+1 )2Si-O-) r -(-CH2CH2O-) s -(-CH2CH(CH3)O-) t -Si-(-C n H 2n+1 )3, where n=1, s=10, and t=12.

[0038] The composite solubilizer was prepared into a 10.0% aqueous solution and then sprayed onto the petroleum hydrocarbon-contaminated soil using a water sprayer at a water-to-soil ratio of 1:10. After stirring evenly, the biological agent was sprayed and a solubilization biopile was built. The solubilization and microbial treatment soil was sampled and analyzed at different times. After 10 days, the total petroleum hydrocarbon (TPH) concentration in the soil was 6950 mg / m 3 , while the TPH concentration in untreated soil was 14470 mg / m 3 The removal rate was 52.0%, and the effect was obvious.

[0039] Example 2

[0040] A composite solubilizer for remediating petroleum hydrocarbon-contaminated soil is composed of the following raw materials in percentage by weight: 50% of alkylphenol polyoxyethylene dibasic acid ester, 45% of alkyl polyoxyethylene polyoxypropylene ether, and 5% of polyoxyethylene polyoxypropylene siloxane.

[0041] Among them, the molecular formula of alkylphenol polyoxyethylene dicarboxylic acid ester is: R1-C6H5O-(-C2H4O-) m OOC-C n H 2n-COO-(-C2H4O-) m -C6H5O-R1, where R1 is C 24 Alkyl, m=30, n=24.

[0042] Among them, the molecular formula of alkyl polyoxyethylene polyoxypropylene ether is: R2-(-C2H4O-) p -(-CH2CH(CH3)O-) q -H, where R2 is C 24 Alkyl, p=4, q=2.

[0043] Wherein, the molecular formula of polyoxyethylene polyoxypropylene siloxane is: (C n H 2n+1 )3-Si-O-(-(C n H 2n+1 )2Si-O-) r -(-CH2CH2O-) s -(-CH2CH(CH3)O-) t -Si-(-C n H 2n+1 )3, where n=12, s=24, and t=2.

[0044] The above-mentioned composite solubilizer was prepared into a 1% aqueous solution and then sprayed onto the petroleum hydrocarbon-contaminated soil using a water sprayer at a water-to-soil ratio of 1:1. After stirring evenly, the biological agent was sprayed and a solubilization biopile was built. The solubilization and microbial treatment soil was sampled and analyzed at different times. After 20 days, the total petroleum hydrocarbon (TPH) concentration in the soil was 4015 mg / m 3 , while the TPH concentration in untreated soil was 14203 mg / m 3 The removal rate was 71.7%, with significant results.

[0045] Example 3

[0046] A composite solubilizer for remediating petroleum hydrocarbon-contaminated soil is composed of the following raw materials in percentage by weight: 60% of alkylphenol polyoxyethylene dibasic acid ester, 30% of alkyl polyoxyethylene polyoxypropylene ether, and 10% of polyoxyethylene polyoxypropylene siloxane.

[0047] Among them, the molecular formula of alkylphenol polyoxyethylene dicarboxylic acid ester is: R1-C6H5O-(-C2H4O-) m OOC-C n H 2n -COO-(-C2H4O-) m -C6H5O-R1, where R1 is C 12 Alkyl, m=20, n=12.

[0048] Among them, the molecular formula of alkyl polyoxyethylene polyoxypropylene ether is: R2-(-C2H4O-) p -(-CH2CH(CH3)O-) q -H, where R2 is C 12 Alkyl, p=16, q=18.

[0049] Wherein, the molecular formula of polyoxyethylene polyoxypropylene siloxane is: (C n H 2n+1 )3-Si-O-(-(C n H 2n+1 )2Si-O-) r -(-CH2CH2O-) s -(-CH2CH(CH3)O-) t -Si-(-C n H 2n+1 )3, where n=6, s=12, and t=16.

[0050] The composite solubilizer was prepared into a 20.0% aqueous solution and then sprayed onto the petroleum hydrocarbon-contaminated soil using a water sprayer at a water-to-soil ratio of 1:30. After stirring evenly, the biological agent was sprayed and a solubilization biopile was built. The solubilization and microbial treatment soil was sampled and analyzed at different times. After 15 days, the total petroleum hydrocarbon (TPH) concentration in the soil was 4172 mg / m 3 , while the TPH content in untreated soil was 14203 mg / m 3 The removal rate was 70.625%, and the effect was obvious.

[0051] Comparative Example

[0052] In this comparative example, no solubilizing agent solution was added, only the microbial preparation was added, and the water-soil ratio conditions were the same as those in Example 2. The mixture was then stirred evenly, and soil samples were taken for analysis at different times. After 20 days, the total petroleum hydrocarbon (TPH) concentration in the soil was 12905 mg / m 3 , while the TPH concentration in untreated soil was 14203 mg / m 3 The removal rate is only 10.1%, which is effective but not obvious.

[0053] The above describes the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art may make various variations or modifications within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A composite solubilizing agent for remediation of petroleum hydrocarbon contaminated soil, characterized in that: It is composed of the following raw materials in percentage by weight: 10-98% alkylphenol polyoxyethylene dibasic acid ester; 1-75% alkyl polyoxyethylene polyoxypropylene ether; and 0.05-15% polyoxyethylene polyoxypropylene siloxane.

2. The composite solubilizing agent for remediation of petroleum hydrocarbon contaminated soil according to claim 1, characterized in that: It is composed of the following raw materials in percentage by weight: 40-80% alkylphenol polyoxyethylene dibasic acid ester; 15-50% alkyl polyoxyethylene polyoxypropylene ether; and 1-10% polyoxyethylene polyoxypropylene siloxane.

3. The composite solubilizing agent for remediation of petroleum hydrocarbon contaminated soil according to claim 1 or 2, characterized in that: The molecular formula of the alkylphenol polyoxyethylene dicarboxylic acid ester is: R1-C6H5O-(-C2H4O-) m OOC-C n H 2n -COO-(-C2H4O-) m -C6H5O-R1, where R1 is C1-C 36 Alkyl, m is any integer from 1 to 40, and n is any integer from 1 to 30.

4. The composite solubilizing agent for remediation of petroleum hydrocarbon contaminated soil according to claim 3, characterized in that: The R1 is C2-C 24 Alkyl, m is any integer from 2 to 30, and n is any integer from 2 to 24.

5. The composite solubilizing agent for remediation of petroleum hydrocarbon contaminated soil according to claim 1 or 2, characterized in that: The molecular formula of the alkyl polyoxyethylene polyoxypropylene ether is: R2-(-C2H4O-) p -(-CH2CH(CH3)O-) q -H, where R2 is C1-C 36 Alkyl, p is any integer from 1 to 36, and q is any integer from 1 to 36.

6. The composite solubilizing agent for remediation of petroleum hydrocarbon contaminated soil according to claim 5, characterized in that: The R2 is C2-C 24 Alkyl, p is any integer from 4 to 24, and q is any integer from 2 to 24.

7. A petroleum hydrocarbon contaminated soil remediation formulation, characterized by: The invention is composed of water and the composite solubilizer according to any one of claims 1 to 6, wherein the concentration of the composite solubilizer is 0.1-20%.

8. A method for remediating soil contaminated by petroleum hydrocarbons, characterized by: The remediation preparation according to claim 7 is sprayed into the soil contaminated by petroleum hydrocarbons. During the spraying process, the soil is continuously stirred to mix it evenly with the remediation preparation. After the spraying of the remediation preparation is completed, the biological preparation is sprayed. At the same time, the soil is stirred evenly and a solubilization-biopile is formed. The formed soil solubilization-biopile is regularly maintained.

9. The method for remediating petroleum hydrocarbon-contaminated soil according to claim 8, wherein: The weight ratio of the remediation preparation to the petroleum hydrocarbon contaminated soil is 1 / 1-1 / 50.