CN115491204A - Composite solubilizer, restoration preparation and restoration method for petroleum hydrocarbon contaminated soil restoration - Google Patents

Composite solubilizer, restoration preparation and restoration method for petroleum hydrocarbon contaminated soil restoration Download PDF

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Publication number
CN115491204A
CN115491204A CN202210928405.6A CN202210928405A CN115491204A CN 115491204 A CN115491204 A CN 115491204A CN 202210928405 A CN202210928405 A CN 202210928405A CN 115491204 A CN115491204 A CN 115491204A
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soil
solubilizer
petroleum hydrocarbon
composite
integer
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Inventor
左世伟
时东兴
张瑞波
李克文
丁宁
师新阁
朱宗博
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China Petroleum and Chemical Corp
Sinopec Engineering Group Co Ltd
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China Petroleum and Chemical Corp
Sinopec Engineering Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
    • C09K17/18—Prepolymers; Macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Soil Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • Molecular Biology (AREA)
  • Mycology (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Biomedical Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a composite solubilizer, a remediation preparation and a remediation method for petroleum hydrocarbon polluted soil. And (3) spraying the remediation preparation into the soil polluted by petroleum hydrocarbon, continuously stirring the soil to uniformly mix the remediation preparation with the soil in the spraying process, spraying the biological preparation after the remediation preparation is sprayed, uniformly stirring the soil to build a soil solubilization-biological pile, and periodically maintaining the built soil solubilization-biological pile. The three components of the composite solubilizer are similar to the structures of different types of petroleum hydrocarbons, and according to the principle of similarity and intermiscibility, the composite solubilizer has good solubility to the petroleum hydrocarbons, so that pollutants are easily dissolved into the solubilizer from soil, the soil is easier to biodegrade, and the solubilizer is nontoxic and easy to degrade, so that the subsequent microbial treatment of the soil polluted by the petroleum hydrocarbons is facilitated.

Description

Composite solubilizer, restoration preparation and restoration method for petroleum hydrocarbon contaminated soil restoration
Technical Field
The invention relates to the technical field of petroleum hydrocarbon polluted soil remediation, and particularly relates to a composite solubilizer, a remediation preparation and a remediation method for petroleum hydrocarbon polluted soil remediation.
Background
The demand of petroleum is rapidly increased due to the continuous and high-speed development of domestic economy, but during the process of petroleum exploitation, storage, processing, storage, transportation and use of petroleum products, a large amount of unused petroleum hydrocarbon substances are generated due to leakage, leakage and the like, and the petroleum hydrocarbon substances flow into the soil surface without being utilized and treated, then permeate into the soil and further permeate into underground water, thereby causing petroleum hydrocarbon pollution of the soil and the underground water. Therefore, how to remove petroleum hydrocarbon pollutants in soil quickly and efficiently while maintaining the original biological activity of soil has become one of the key contents in the soil remediation technology development required by enterprises such as oil fields, refineries, petrochemical processing and application. In a plurality of petroleum hydrocarbon polluted soil remediation technologies, pollutants adsorbed in soil are quickly dissolved out to the soil surface under the action of a solubilizer through the solubilizer technology, and then the concentration of the petroleum hydrocarbon in the soil meets the standard requirement through the degradation of microorganisms, and the activity and the original application of the soil are recovered to the greatest extent.
The solubilizer mainly comprises a surfactant, and the molecules of the surfactant simultaneously contain hydrophilic groups and lipophilic groups. According to the type and molecular composition of petroleum hydrocarbon in the polluted soil, the surfactant with a suitable molecular structure is determined and synthesized, so that the surfactant has good dissolving and solubilizing effects on different types of petroleum hydrocarbon, has no toxic or harmful effect on microorganisms for further treatment, can be preferably used as a nutrient substance of the microorganisms, and does not reduce the content of organic matters in the soil.
Patent document 1: chinese patent document with publication number CN111346909A
Patent document 1 proposes an in situ remediation method of petroleum hydrocarbon contamination based on foam enhancement, which claims to add a foamed solubilizer, oxidant, activator, etc. through an injection well. The chemical component of the solubilizer is polyoxyethylene sorbitan ester, namely Tween-80; the oxidant is sodium percarbonate. Obviously, the solubilizing agent Tween-80 is only suitable for polluted soil with low petroleum hydrocarbon content (not more than 1%) due to weak lipophilicity, and the leaching solubilization effect is very limited. The oxidant sodium percarbonate has super strong oxidizability, has super strong bactericidal action on microorganisms in a subsequent biological treatment process, and makes solubilized soil incapable of being biologically treated.
Patent document 2: chinese patent document with publication number CN112742855A
Patent document 2 proposes a modified eluting agent containing sophorolipid sulfonate surfactant as an eluting component, which has properties similar to those of tween-80 described above, has low lipophilicity, is a biosurfactant and has good biodegradability, but has a poor eluting solubilization effect on petroleum hydrocarbon pollution and is high in cost.
Patent document 3: chinese patent document with publication number CN112724981A
Patent document 3 proposes a petroleum-contaminated soil eluting agent composition, the main components of which are nonionic surfactants, namely alkylphenol ethoxylates and amphoteric surfactants, the composition has a good eluting effect on petroleum hydrocarbons in contaminated soil, can be used as a soil remediation eluting agent, but has poor solubilizing performance and dispersion performance, and is not suitable for being applied to soil remediated by a solubilization and microbial degradation coupling method.
Disclosure of Invention
The invention aims to solve the technical problems that the existing solubilizer has poor eluting solubilization effect on petroleum hydrocarbon pollution and is not suitable for being applied to soil repaired by a solubilization and microbial degradation coupling method, and provides a composite solubilizer, a repairing preparation and a repairing method for repairing the petroleum hydrocarbon polluted soil.
In order to solve the technical problems, the invention adopts the technical scheme that: a composite solubilizer for petroleum hydrocarbon contaminated soil remediation is composed of the following raw materials in percentage by weight:
10-98% of alkylphenol polyoxyethylene dibasic acid ester;
1-75% of alkyl polyoxyethylene polyoxypropylene ether; and
0.05-15% of polyoxyethylene polyoxypropylene siloxane.
The alkylphenol polyoxyethylene dibasic acid ester and the alkyl polyoxyethylene polyoxypropylene ether have the effects of solubilizing, cleaning, dispersing, emulsifying and the like, and the polyoxyethylene polyoxypropylene siloxane has the effects of dispersing, defoaming, solubilizing and reducing surface tension; different types of surfactants may be suitable for use in different compositions of petroleum hydrocarbon contaminated soil.
The composite solubilizer for petroleum hydrocarbon contaminated soil remediation is further optimized by the following steps: the composite solubilizer comprises the following raw materials in percentage by weight:
40-80% of alkylphenol polyoxyethylene dibasic acid ester;
15-50% of alkyl polyoxyethylene polyoxypropylene ether; and
1-10% polyoxyethylene polyoxypropylene siloxane.
The composite solubilizer for restoring the petroleum hydrocarbon polluted soil is further optimized as follows: the molecular formula of the alkylphenol polyoxyethylene dibasic acid ester is as follows: r 1 -C 6 H 5 O-(-C 2 H 4 O-) m OOC-C n H 2。n -COO-(- C 2 H 4 O-) m -C 6 H 5 O-R 1 Wherein R is 1 Is C 1 -C 36 And m is any integer from 1 to 40, and n is any integer from 1 to 30.
The composite solubilizer for petroleum hydrocarbon contaminated soil remediation is further optimized by the following steps: said R is 1 Is C 2 -C 24 And m is any integer from 2 to 30, and n is any integer from 2 to 24.
The composite solubilizer for petroleum hydrocarbon contaminated soil remediation is further optimized by the following steps: the molecular formula of the alkyl polyoxyethylene polyoxypropylene ether is as follows: r 2 -(-C 2 H 4 O-) p -(-CH 2 CH(CH 3 )O-) q -H, wherein R 2 Is C 1 -C 36 And p is any integer from 1 to 36, and q is any integer from 1 to 36.
The composite solubilizer for restoring the petroleum hydrocarbon polluted soil is further optimized as follows: the R is 2 Is C 2 -C 24 And p is any integer from 4 to 24, and q is any integer from 2 to 24.
The composite solubilizer for petroleum hydrocarbon contaminated soil remediation is further optimized by the following steps: the molecular formula of the polyoxyethylene polyoxypropylene siloxane is as follows: (C) n H 2n+1 ) 3 -Si-O-(-(C n H 2n+1 ) 2 Si-O-) r -(-CH 2 CH 2 O-) s -(-CH 2 CH(CH 3 )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.
The composite solubilizer for restoring the petroleum hydrocarbon polluted soil is further optimized as follows: 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.
A preparation for restoring petroleum hydrocarbon polluted soil comprises water and the composite solubilizer, wherein the concentration of the composite solubilizer is 0.1-20%.
A method for restoring petroleum hydrocarbon contaminated soil comprises the following steps: and (3) spraying the remediation preparation into the soil polluted by petroleum hydrocarbon, continuously stirring the soil to uniformly mix the remediation preparation with the soil in the spraying process, spraying the biological preparation after the remediation preparation is sprayed, uniformly stirring the soil to build a solubilization-biological pile, and periodically maintaining the built soil solubilization-biological pile.
The method for repairing the petroleum hydrocarbon polluted soil is further optimized as follows: the weight ratio of the remediation preparation to the petroleum hydrocarbon contaminated soil is 1/1-1/50.
The invention has the following beneficial effects:
1. the components of the composite solubilizer are alkylphenol polyoxyethylene dibasic acid ester, alkyl polyoxyethylene polyoxypropylene ether and polyoxyethylene polyoxypropylene siloxane, the three components have similar structures with petroleum hydrocarbons with different compositions, the solubility of the three components to the petroleum hydrocarbons is good according to the principle of similarity and intermiscibility, pollutants are easy to biodegrade, and the solubilizer has no toxicity and is convenient for the subsequent microbial treatment of the soil polluted by the petroleum hydrocarbons.
2. The composite solubilizer of the invention can lead the composite solubilizer to have better solubilization effect on petroleum hydrocarbon in soil by changing the alkyl carbon number, the polyoxyethylene polymerization degree and the fatty alcohol carbon number in dibasic acid ester molecules and changing the alkyl carbon number and the polyoxyethylene and polyoxypropylene polymerization degrees in alkyl polyoxyethylene polyoxypropylene ether by changing the alkyl carbon number, the polyoxyethylene polymerization degree and the fatty alcohol carbon number in alkylphenol polyoxyethylene dibasic acid ester molecules.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the specific embodiments.
Example 1
A composite solubilizer for restoring 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.
Wherein, the molecular formula of the alkylphenol polyoxyethylene dibasic acid ester is as follows: r is 1 -C 6 H 5 O-(-C 2 H 4 O-) m OOC -C n H 2n -COO-(-C 2 H 4 O-) m -C 6 H 5 O-R 1 Wherein R is 1 Is C 4 Alkyl, m =10,n =10.
Wherein the molecular formula of the alkyl polyoxyethylene polyoxypropylene ether is as follows: r 2 -(-C 2 H 4 O-) p -(-CH 2 CH(C H 3 )O-) q -H, wherein R 2 Is C 10 Alkyl, p =12,q =24.
Wherein the molecular formula of the polyoxyethylene polyoxypropylene siloxane is as follows: (C) n H 2n+1 ) 3 -Si-O-(-(C n H 2n+1 ) 2 Si-O-) r -(-CH 2 CH 2 O-) s -(-CH 2 CH(CH 3 )O-) t -Si-(-C n H 2n+1 ) 3 Wherein n =1,s =10,t =12.
Preparing the composite solubilizer into 10.0% aqueous solution, spraying the aqueous solution to the soil polluted by petroleum hydrocarbon by using a water spraying device, wherein the water-soil ratio is 1/10, uniformly stirring, spraying the biological agent to form a solubilization biological pile, periodically maintaining, and sampling and analyzing the soil after solubilization and microbial treatment at different time. The Total Petroleum Hydrocarbon (TPH) concentration in the soil after 10 days was 6950mg/m 3 And the TPH concentration in untreated soil was 14470mg/m 3 The removal rate is 52.0 percent, and the effect is obvious.
Example 2
A composite solubilizer for restoring 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.
Wherein, the molecular formula of the alkylphenol polyoxyethylene dibasic acid ester is as follows: r 1 -C 6 H 5 O-(-C 2 H 4 O-) m OOC -C n H 2n -COO-(-C 2 H 4 O-) m -C 6 H 5 O-R 1 Wherein R is 1 Is C 24 Alkyl, m =30,n =24.
Wherein the molecular formula of the alkyl polyoxyethylene polyoxypropylene ether is as follows: r is 2 -(-C 2 H 4 O-) p -(-CH 2 CH(C H 3 )O-) q -H, wherein R 2 Is C 24 Alkyl, p =4,q =2.
Wherein the molecular formula of the polyoxyethylene polyoxypropylene siloxane is as follows: (C) n H 2n+1 ) 3 -Si-O-(-(C n H 2n+1 ) 2 Si-O-) r -(-CH 2 CH 2 O-) s -(-CH 2 CH(CH 3 )O-) t -Si-(-C n H 2n+1 ) 3 Wherein n =12,s =24,t =2.
Preparing the composite solubilizer into 1% aqueous solution, spraying the aqueous solution into the soil polluted by petroleum hydrocarbon by using a water spraying device, wherein the water-soil ratio is 1/1, uniformly stirring, spraying the biological agent, constructing a solubilization biological pile, periodically maintaining, and sampling and analyzing the soil after solubilization and microbial treatment at different time. The Total Petroleum Hydrocarbon (TPH) concentration in the soil after 20 days was 4015mg/m 3 And the concentration of TPH in untreated soil is 14203mg/m 3 The removal rate is 71.7%, and the effect is remarkable.
Example 3
A composite solubilizer for restoring 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.
Wherein, the molecular formula of the alkylphenol polyoxyethylene dibasic acid ester is as follows: r is 1 -C 6 H 5 O-(-C 2 H 4 O-) m OOC -C n H 2n -COO-(-C 2 H 4 O-) m -C 6 H 5 O-R 1 Wherein R is 1 Is C 12 Alkyl, m =20,n =12.
Wherein the molecular formula of the alkyl polyoxyethylene polyoxypropylene ether is as follows: r 2 -(-C 2 H 4 O-) p -(-CH 2 CH(C H 3 )O-) q -H, wherein R 2 Is C 12 Alkyl, p =16,q =18.
Wherein, the molecular formula of the polyoxyethylene polyoxypropylene siloxane is as follows: (C) n H 2n+1 ) 3 -Si-O-(-(C n H 2n+1 ) 2 Si-O-) r -(-CH 2 CH 2 O-) s -(-CH 2 CH(CH 3 )O-) t -Si-(-C n H 2n+1 ) 3 Wherein n =6,s =12,t =16.
Preparing the composite solubilizer into a 20.0% aqueous solution, spraying the aqueous solution to the soil polluted by petroleum hydrocarbon by using a water spraying device, wherein the water-soil ratio is 1/30, uniformly stirring, spraying the biological agent to form a solubilization biological pile, periodically maintaining, and sampling and analyzing the soil after solubilization and microbial treatment at different time. The Total Petroleum Hydrocarbon (TPH) concentration in the soil after 15 days was 4172mg/m 3 And the untreated soil had a TPH content of 14203mg/m 3 The removal rate is 70.6.5%, and the effect is obvious. Comparative example (influence of concentration
In this comparative example, no solubilizer solution was added, only the microbial preparation and the water-soil ratio conditions equivalent to those of example 2 were added, and then the mixture was stirred uniformly, and soil was sampled and analyzed at different times. The Total Petroleum Hydrocarbon (TPH) concentration analysis result in the soil after 20 days was 12905mg/m 3 And the concentration of TP H in untreated soil is 14203mg/m 3 The removal rate is only 10.1%, and the effect is not obvious.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (11)

1. The composite solubilizer for restoring the petroleum hydrocarbon polluted soil is characterized by comprising the following raw materials in percentage by weight:
10-98% of alkylphenol polyoxyethylene dibasic acid ester;
1-75% of alkyl polyoxyethylene polyoxypropylene ether; and
0.05-15% polyoxyethylene polyoxypropylene siloxane.
2. The composite solubilizer for remediating petroleum hydrocarbon-contaminated soil as set forth in claim 1, wherein: the composite material consists of the following raw materials in percentage by weight:
40-80% of alkylphenol polyoxyethylene dibasic acid ester;
15-50% of alkyl polyoxyethylene polyoxypropylene ether; and
1-10% of polyoxyethylene polyoxypropylene siloxane.
3. The composite solubilizer for remediating petroleum hydrocarbon-contaminated soil as set forth in claim 1 or 2, wherein: the molecular formula of the alkylphenol polyoxyethylene dibasic acid ester is as follows: r 1 -C 6 H 5 O-(-C 2 H 4 O-) m OOC-C n H 2n -COO-(-C 2 H 4 O-) m -C 6 H 5 O-R 1 Wherein R is 1 Is C 1 -C 36 And m is any integer from 1 to 40, and n is any integer from 1 to 30.
4. The composite solubilizer for remediating petroleum hydrocarbon-contaminated soil as set forth in claim 3, wherein: the R is 1 Is C 2 -C 24 And m is any integer from 2 to 30, and n is any integer from 2 to 24.
5. The composite solubilizer for remediating petroleum hydrocarbon-contaminated soil as set forth in claim 1 or 2, wherein: the molecular formula of the alkyl polyoxyethylene polyoxypropylene ether is as follows: r 2 -(-C 2 H 4 O-) p -(-CH 2 CH(CH 3 )O-) q -H, wherein R 2 Is C 1 -C 36 And p is any integer from 1 to 36, and q is any integer from 1 to 36.
6. The composite solubilizer for remediating petroleum hydrocarbon-contaminated soil as set forth in claim 4, wherein: said R is 2 Is C 2 -C 24 And p is any integer from 4 to 24, and q is any integer from 2 to 24.
7. The composite solubilizer for remediating petroleum hydrocarbon-contaminated soil as set forth in claim 1 or 2, wherein: the molecular formula of the polyoxyethylene polyoxypropylene siloxane is as follows: (C) n H 2n+1 ) 3 -Si-O-(-(C n H 2n+1 ) 2 Si-O-) r -(-CH 2 CH 2 O-) s -(-CH 2 CH(CH 3 )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.
8. The composite solubilizer for remediating petroleum hydrocarbon-contaminated soil as set forth in claim 6, wherein: 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.
9. A preparation for restoring petroleum hydrocarbon polluted soil is characterized in that: the composite solubilizer as claimed in any one of claims 1 to 8, wherein the concentration of the composite solubilizer is 0.1 to 20 percent.
10. A method for restoring petroleum hydrocarbon contaminated soil is characterized by comprising the following steps: the remediation preparation of claim 9, wherein the remediation preparation is sprayed onto petroleum hydrocarbon contaminated soil, the soil is continuously stirred during the spraying process to be uniformly mixed with the remediation preparation, the biological preparation is sprayed after the remediation preparation is sprayed, the soil is uniformly stirred and a solubilization-biological pile is formed, and the formed solubilization-biological pile is periodically maintained.
11. The method of remediating petroleum hydrocarbon contaminated soil as recited in claim 10, further comprising: the weight ratio of the remediation preparation to the petroleum hydrocarbon contaminated soil is 1/1-1/50.
CN202210928405.6A 2022-08-03 2022-08-03 Composite solubilizer, restoration preparation and restoration method for petroleum hydrocarbon contaminated soil restoration Pending CN115491204A (en)

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