CN112724981A - Petroleum-polluted soil eluting agent composition and preparation method thereof - Google Patents
Petroleum-polluted soil eluting agent composition and preparation method thereof Download PDFInfo
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- CN112724981A CN112724981A CN201911032418.XA CN201911032418A CN112724981A CN 112724981 A CN112724981 A CN 112724981A CN 201911032418 A CN201911032418 A CN 201911032418A CN 112724981 A CN112724981 A CN 112724981A
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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
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
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- 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
Abstract
The invention relates to the field of petroleum hydrocarbon polluted soil remediation, in particular to a petroleum polluted soil eluting agent composition and a preparation method thereof. The eluent composition contains the following components which are respectively stored independently or in a mixed manner: a nonionic surfactant, an amphoteric surfactant, an alkaline substance and water; wherein the nonionic surfactant is selected from at least one of a compound with a structure shown in a formula (I) and a compound with a structure shown in a formula (II). The petroleum-polluted soil eluting agent composition provided by the invention is used for treating petroleum-polluted soil, so that the content of petroleum hydrocarbon in the polluted soil can be greatly reduced, and the aim of soil remediation and utilization is finally fulfilled.
Description
Technical Field
The invention relates to the field of petroleum hydrocarbon polluted soil remediation, in particular to a petroleum polluted soil eluting agent composition and a preparation method thereof.
Background
Soil contamination is a worldwide problem and petroleum hydrocarbon contamination of soil is an important type of soil contamination.
In the process of petroleum drilling, oil extraction, transportation and processing, crude oil leakage and great harm to soil pollution caused by falling crude oil due to corrosion of oil pipelines and the like are caused, and great influence is caused to the environment due to slow degradation speed of petroleum hydrocarbons and certain toxicity of aromatic hydrocarbons contained in the petroleum hydrocarbons.
The technology for repairing the polluted soil is more and more concerned by people. The existing repair technologies comprise physical repair, biological repair, chemical repair and the like. Some oil contaminated soil remediation work has entered an industrial implementation stage.
Chemical cleaning and restoring petroleum polluted soil is an important method. However, the current situation of petroleum-polluted soil is complex, the types of the polluted soil are many, and the components of petroleum hydrocarbon have great difference due to different sources. One type of eluent is difficult to adapt to the cleaning of different types of petroleum-contaminated soil.
In addition, the soil polluted by petroleum is often subjected to a long-term exposure process in the air, light components in the petroleum volatilize, the relative content of heavy components in the soil is increased, and in addition, the soil is contacted with the air for a long time to oxidize partial hydrocarbon substances and increase polar compounds. These all contribute to the difficulty of removing oil from long-term contaminated soils.
Meanwhile, the types of the soil polluted by petroleum are various, the petroleum hydrocarbon removal difficulty is different due to different soil properties, and the crude oil removal difficulty in the clay soil is higher than that in the sandy soil.
The crude oil produced by various countries has large property difference from light crude oil to super heavy oil. The greater the viscosity of the crude oil, the higher the content of heavy components, and the more difficult it is to remove the soil contaminated with heavy oil. The prior art develops the eluting agent for some types of petroleum-polluted soil, but the chemical eluting agent needs to be developed specifically for various types of petroleum-polluted soil to meet the removal requirements of different types of petroleum pollutants.
Disclosure of Invention
The invention aims to provide a chemical eluting agent for a soil remediation process polluted by thick oil so as to achieve the purpose of removing the thick oil attached to the soil for a long time.
In order to achieve the above object, a first aspect of the present invention provides a petroleum-contaminated soil eluting detergent composition, which contains the following components, each of which is stored independently or in admixture:
a nonionic surfactant, an amphoteric surfactant, an alkaline substance and water;
wherein the nonionic surfactant is at least one selected from the group consisting of a compound having a structure represented by formula (I) and a compound having a structure represented by formula (II),
in the compound with the structure shown in the formula (I) and the compound with the structure shown in the formula (II), m is any integer selected from 1 to 50, n is any integer selected from 2 to 8, and R1Is C4-C20Alkyl of R2Is polyether, the monomer forming the polyether is ethylene oxide and/or propylene oxide, and the polymerization degree of the polyether is 5-100.
In a second aspect, the present invention provides a method for preparing an eluent for petroleum-contaminated soil, which is performed by using the components of the eluent composition according to the first aspect of the present invention, and which comprises: a nonionic surfactant, an amphoteric surfactant and an alkaline substance are contacted with water.
The eluent composition provided by the invention is particularly suitable for the remediation process of petroleum-polluted soil, and has important significance for the subsequent remediation and utilization of the soil.
The petroleum-polluted soil eluting agent composition provided by the invention is bio-friendly, has an obvious oil removing effect, can effectively remove petroleum hydrocarbon attached to soil, is suitable for repairing the petroleum-polluted soil, can greatly reduce the content of the petroleum hydrocarbon in the polluted soil, and finally achieves the aim of repairing and utilizing the soil.
The novel petroleum-polluted soil eluting agent composition can be used for cleaning the soil polluted by common crude oil and the soil polluted by common thick oil, and has good adaptability to the petroleum-polluted soil.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a petroleum-contaminated soil eluting agent composition, which contains the following components stored separately or in a mixture:
a nonionic surfactant, an amphoteric surfactant, an alkaline substance and water;
wherein the nonionic surfactant is at least one selected from the group consisting of a compound having a structure represented by formula (I) and a compound having a structure represented by formula (II),
in the compound with the structure shown in the formula (I) and the compound with the structure shown in the formula (II), m is any integer selected from 1 to 50, n is any integer selected from 2 to 8, and R1Is C4-C20Alkyl of R2Is polyetherAnd the monomer forming the polyether is ethylene oxide and/or propylene oxide, and the polymerization degree of the polyether is 5-100. The method for obtaining the degree of polymerization of the present invention can be obtained by various methods conventionally used in the art, for example, see CN105505365A example, specifically, the molecular weight of the molecule can also be measured by vapor pressure permeation method, and then a back calculation is performed according to the structure and molecular weight of the intermediate product in the preparation process.
Some of the terms involved in the present invention are explained below:
“C4-C20the "alkyl group" of (a) represents an alkyl group having 4 to 20 carbon atoms in total, and includes a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group, and may be, for example, a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group having 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 carbon atoms in total.
“C8-C12The alkyl group of (1) represents an alkyl group having 8 to 12 carbon atoms in total, and includes a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group, and may be, for example, a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group having 8, 9, 10, 11 or 12 carbon atoms in total.
According to the invention, preferably, the nonionic surfactant plays a role in stripping petroleum from the soil surface, and researches show that the nonionic surfactant provided by the invention has very low critical micelle concentration and good biocompatibility, and can promote the petroleum to be stripped from the soil surface at a lower concentration; the amphoteric surfactant is used for dispersing the stripped petroleum into a water phase; the alkaline substance can enhance the stripping and dispersing effects of petroleum from the soil surface, and the eluent composition provided by the invention has a good synergistic effect and is particularly suitable for the remediation process of petroleum-polluted soil.
According to a preferred embodiment of the present invention, in the compound of the structure represented by the formula (I) and the compound of the structure represented by the formula (II), m is any integer selected from 2 to 10, n is any integer selected from 2 to 5, R is1Is C8-C12Alkyl of R2Is a polyether and the monomer forming said polyether is an epoxyEthane and/or propylene oxide, the degree of polymerization of the polyether is 7-20. In the preferred embodiment, the nonionic surfactant is more beneficial in promoting the stripping of oil from the soil surface, thereby more effectively removing the petroleum hydrocarbons that are attached to the soil.
In the present invention, the compound having the structure represented by the formula (I) and the nonionic surfactant having the structure represented by the formula (II) may be commercially available or may be prepared by themselves. For example, the compound having the structure shown in formula (I) and the nonionic surfactant having the structure shown in formula (II) of the present invention can be prepared by the preparation method provided in CN105505365A, which is herein incorporated by reference in its entirety.
In the invention, the intermediate product and the structural formula of the nonionic surfactant in the process of preparing the nonionic surfactant can be determined by detection means such as a hydrogen spectrum, a carbon spectrum, a mass spectrum and the like.
In a preferred aspect, the amphoteric surfactant is betaine. The eluent composition in this preferred case provides better oil removal of petroleum-based contaminants in the contaminated soil.
Preferably, the amphoteric surfactant is selected from at least one or more of alkyl dimethyl carboxyl betaine, alkyl hydroxy sulfobetaine and cocamide betaine, and the chain length of the alkyl in the amphoteric surfactant is 8-20 carbon atoms. The chain length of the alkyl group is 8-20 carbon atoms, which means that the total number of carbon atoms on the alkyl group is 8-20, and the alkyl group comprises a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group, for example, the straight-chain alkyl group, the branched-chain alkyl group or the cyclic alkyl group can be 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 carbon atoms in total.
Preferably, the amphoteric surfactant is selected from at least one of dodecyl dimethyl carboxy betaine, cocamide betaine, tetradecyl dimethyl carboxy betaine, octadecyl hydroxysultaine.
The invention has wide selection range of the alkaline substances, and the invention only needs to realize the purpose of strengthening the stripping and dispersion of the petroleum from the soil surface. Preferably, the alkaline substance is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate, and sodium hydroxide is particularly preferred.
According to the eluent composition provided by the invention, in a preferable case, the nonionic surfactant is at least one of the following compounds:
compound 1: a compound of the structure shown in formula (I), wherein m is 5, n is 2, R1Is C9H19，R2Is polyethylene oxide with a degree of polymerization of 10;
compound 2: a compound of the structure shown in formula (I), wherein m is 2, n is 4, R1Is C8H17，R2Is polyethylene oxide with a polymerization degree of 7;
compound 3: a compound of the structure shown in formula (II), wherein m is 7, n is 3, R1Is C9H19，R2Is polyethylene oxide with a polymerization degree of 9;
the amphoteric surfactant is at least one selected from dodecyl dimethyl carboxyl betaine, cocoamide betaine, tetradecyl dimethyl carboxyl betaine and octadecyl hydroxysulfobetaine, and is especially preferably tetradecyl dimethyl carboxyl betaine. Under the preferable condition, the synergistic effect of the nonionic surfactant, the amphoteric surfactant and the alkaline substance is better, and the oil removal rate of the oil-containing soil is more favorably improved.
Preferably, the content of the nonionic surfactant is 0.03-3 wt%, the content of the amphoteric surfactant is 0.05-3 wt%, and the content of the alkaline substance is 0.05-2 wt%, based on the total weight of the eluent composition.
In a preferred aspect, the nonionic surfactant is present in an amount of 0.05 to 1 wt%, the amphoteric surfactant is present in an amount of 0.1 to 1 wt%, and the basic substance is present in an amount of 0.1 to 1 wt%, based on the total weight of the eluent composition.
The inventors of the present invention have found that balancing the relationship between the production cost and the rinsing effect of the eluent composition, it is the most preferred option to employ an eluent composition as follows: in a more preferred aspect, the nonionic surfactant is present in an amount of 0.05 to 0.5 wt%, the amphoteric surfactant is present in an amount of 0.1 to 0.5 wt%, and the basic substance is present in an amount of 0.1 to 1 wt%, based on the total weight of the eluent composition.
As previously mentioned, a second aspect of the present invention provides a method for preparing an eluent for petroleum-contaminated soil, which is prepared by using the components of the eluent composition as described above, and which comprises: a nonionic surfactant, an amphoteric surfactant and an alkaline substance are contacted with water.
Preferably, the contacting is carried out under stirring conditions at a rate of 100-300 rpm.
The stirring is not particularly limited in the present invention, and may be selected conventionally in the art. Preferably, a magnetic stirrer is used.
According to the invention, the water can be water with various hardness, and commonly used tap water, well water, distilled water, purified water and deionized water can be used, and can also be mineralized water with total ion concentration not greater than 50000mg/L and calcium and magnesium ion concentration not greater than 2000 mg/L. The amount of the water is not particularly limited, and may be added according to the actual situation as long as the components in the petroleum-contaminated soil eluting composition satisfy the above contents.
Preferably, the conditions of the contacting include: the temperature is 10-50 deg.C, and the time is 1-60 min.
The eluent composition provided by the invention is particularly suitable for the remediation process of petroleum-polluted soil, and therefore, the invention provides the petroleum-polluted soil eluent prepared by the method.
The present invention will be described in detail below by way of examples.
Unless otherwise specified, the room temperature below indicates 25. + -. 1 ℃.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal way unless otherwise specified. The experimental methods, detection methods, and the like, which are mentioned in the following examples, are conventional experimental methods, detection methods, and the like, which are known in the prior art, unless otherwise specified.
In the invention, the preparation method of the oil-containing soil sample comprises the following steps: crushing unpolluted soil, drying in a thermostat at 150 ℃ for 6h, and screening to obtain 100-mesh dried soil. And (3) placing the sieved soil and the crude oil in a constant temperature box at 80 ℃ for constant temperature for 8 h. 80g of dried soil is taken, 20g of crude oil (with the density of 0.95g/mL) of the Shengli oilfield is added, and the mixture is uniformly mixed at the temperature of 80 ℃. The soil mixed with the crude oil is placed in a constant temperature box at 50 ℃ for aging for one week to prepare an oil-containing soil sample with 20% of oil content.
The method for determining the oil removal rate and the residual oil content of the soil sample comprises the following steps: and (3) adding the prepared eluent solution into the oil-containing soil with the mass M, heating to the temperature of 80 ℃, stirring by using a mechanical stirrer until the eluent solution is fully contacted and uniformly mixed with the oil-containing soil, and continuing stirring for 10 min. Standing, settling and separating, taking out the upper solution, transferring the upper solution into a scale centrifugal test tube, performing centrifugal separation, and reading the volume V of the separated oil; the lower solid was dried and weighed as m. The oil removal rate and residual oil content of the oil-containing soil treated by the eluent composition were calculated by the following formulas, respectively:
oil removal rate of oil-containing soil is rho V/(M omega) × 100%
The content of residual oil in the soil after cleaning is (M omega-rho V)/M is 100%
In the formula:
rho is the density of the crude oil, g/mL
V is the volume of oil separated by eluent, mL
Omega is the oil content in the initial oil-containing soil sample by mass percent%
M is the mass of the initial oil-containing soil sample, g
m is the mass of the oil-containing soil after the drenching agent treatment, g
Example 1
Nonionic surfactant (I) was prepared in the same manner as in preparation example 1 of CN 105505365A.
The preparation method of the petroleum-polluted soil eluting agent comprises the following steps: 98g of water was stirred with 0.5g of nonionic surfactant (Compound 1), 0.5g of amphoteric surfactant (tetradecyldimethylbetaine) and 1g of alkali (sodium hydroxide) and was stirred for 10min to be completely dissolved. The eluent S1 was obtained. The specific composition conditions of the eluent are shown in Table 1.
Other embodiments
Following the procedure for the preparation of the petroleum-contaminated soil eluent in example 1, except for the structure and the amounts of the nonionic surfactant, the amphoteric surfactant, the alkaline substance and water, the specific composition conditions of the obtained eluent are shown in Table 1.
Comparative example 1
The procedure for preparation of the petroleum-contaminated soil eluent in example 1 was followed, except that the amphoteric surfactant and the alkaline substance were not added, and the specific composition conditions of the obtained eluent were as shown in Table 1.
Comparative example 2
The procedure for preparation of the petroleum-contaminated soil eluent in example 1 was followed, except that the nonionic surfactant and the alkaline substance were not added, and the specific composition conditions of the obtained eluent were as shown in Table 1.
Comparative example 3
The procedure for preparation of the petroleum-contaminated soil eluent in example 1 was followed, except that the nonionic surfactant and the amphoteric surfactant were not added, and the specific composition conditions of the obtained eluent were as shown in Table 1.
Test example 1
The oil removal effect of the prepared eluent on the petroleum-polluted soil is evaluated respectively: and (3) taking a soil sample containing oil with the mass M of 40g, adding 200g of prepared eluent, heating to the temperature of 80 ℃, stirring by using a mechanical stirrer until the eluent solution is fully contacted and uniformly mixed with the soil containing oil, and continuing stirring for 10 min. Standing, settling and separating, taking out the upper solution, transferring the upper solution into a scale centrifugal test tube, performing centrifugal separation, and reading the volume V of the separated oil; the lower solid was dried and weighed as m. The oil removal rate of the eluent on oil-containing soil and the residual oil content in the soil were calculated, and the results are shown in Table 2.
TABLE 1
TABLE 2
From the above results, it can be seen that after the eluent provided by the present invention is used for treating the petroleum-contaminated soil, the oil removal effect is better (the oil removal rate is more than 91.4%), the content of petroleum hydrocarbon in the contaminated soil is lower (the content of residual oil is less than 2.1%), the oil removal rate of the oil-containing soil is up to 95%, and the content of residual oil in the soil is as low as 1.2%. The petroleum-polluted soil eluting agent composition provided by the invention has a remarkable oil removing effect and is suitable for repairing petroleum-polluted soil.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The petroleum-contaminated soil eluting agent composition is characterized by comprising the following components which are stored independently or in a mixed manner:
a nonionic surfactant, an amphoteric surfactant, an alkaline substance and water;
wherein the nonionic surfactant is at least one selected from the group consisting of a compound having a structure represented by formula (I) and a compound having a structure represented by formula (II),
in the compound with the structure shown in the formula (I) and the compound with the structure shown in the formula (II), m is any integer selected from 1 to 50, n is any integer selected from 2 to 8, and R1Is C4-C20Alkyl of R2Is polyether, the monomer forming the polyether is ethylene oxide and/or propylene oxide, and the polymerization degree of the polyether is 5-100.
2. The eluent composition according to claim 1, wherein in the compound of the structure shown in formula (I) and the compound of the structure shown in formula (II), m is any integer selected from 2-10, n is any integer selected from 2-5, R is any integer selected from 2-51Is C8-C12Alkyl of R2Is polyether, the monomer forming the polyether is ethylene oxide and/or propylene oxide, and the polymerization degree of the polyether is 7-20.
3. The lotion composition of claim 1 or 2, wherein the amphoteric surfactant is a betaine.
4. The lotion composition of claim 3, wherein the amphoteric surfactant is selected from at least one or more of alkyl dimethyl carboxy betaine, alkyl hydroxy sultaine, and cocamide betaine, and the alkyl group in the amphoteric surfactant has a chain length of 8-20 carbon atoms;
preferably, the chain length of the alkyl group in the amphoteric surfactant is 12 to 18 carbon atoms.
5. The eluent composition according to any of claims 1-4, wherein said alkaline substance is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate; sodium hydroxide is preferred.
6. The lotion composition of any one of claims 1-5, wherein the non-ionic surfactant is at least one of the following compounds:
compound 1: a compound of the structure shown in formula (I), wherein m is 5, n is 2, R1Is C9H19，R2Is polyethylene oxide with a degree of polymerization of 10;
compound 2: a compound of the structure shown in formula (I), wherein m is 2, n is 4, R1Is C8H17，R2Is polyethylene oxide with a polymerization degree of 7;
compound 3: a compound of the structure shown in formula (II), wherein m is 7, n is 3, R1Is C9H19，R2Is polyethylene oxide with a polymerization degree of 9;
the amphoteric surfactant is at least one of dodecyl dimethyl carboxyl betaine, cocoamide betaine, tetradecyl dimethyl carboxyl betaine and octadecyl hydroxysulfobetaine.
7. The eluent composition according to any of claims 1-6, wherein said nonionic surfactant is present in an amount of 0.03-3 wt.%, said amphoteric surfactant is present in an amount of 0.05-3 wt.%, and said basic material is present in an amount of 0.05-2 wt.%, based on the total weight of the eluent composition.
8. The eluent composition of claim 7, wherein said nonionic surfactant is present in an amount of 0.05-1 wt%, said amphoteric surfactant is present in an amount of 0.1-1 wt%, and said basic material is present in an amount of 0.1-1 wt%, based on the total weight of said eluent composition;
preferably, the nonionic surfactant is present in an amount of 0.05 to 0.5 wt%, the amphoteric surfactant is present in an amount of 0.1 to 0.5 wt%, and the basic substance is present in an amount of 0.1 to 1 wt%, based on the total weight of the eluent composition.
9. A method for preparing an eluent for petroleum-contaminated soil, which is prepared by using the components of the eluent composition according to any one of claims 1 to 8, and which comprises: contacting a nonionic surfactant, an amphoteric surfactant, and an alkaline substance with water;
preferably, the contacting is carried out under stirring conditions at a rate of 100-300 rpm.
10. The method of claim 9, wherein the conditions of the contacting comprise: the temperature is 10-50 deg.C, and the time is 1-60 min.
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| CN112745855A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Synergist in microbial remediation process of petroleum-polluted soil and preparation method thereof |
| CN114713619A (en) * | 2022-04-07 | 2022-07-08 | 中石化石油工程技术服务有限公司 | Treatment method of soil polluted by aged crude oil |
| CN114956491A (en) * | 2022-05-13 | 2022-08-30 | 大连理工大学盘锦产业技术研究院 | Chemical cleaning agent and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112745855A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Synergist in microbial remediation process of petroleum-polluted soil and preparation method thereof |
| CN114713619A (en) * | 2022-04-07 | 2022-07-08 | 中石化石油工程技术服务有限公司 | Treatment method of soil polluted by aged crude oil |
| CN114956491A (en) * | 2022-05-13 | 2022-08-30 | 大连理工大学盘锦产业技术研究院 | Chemical cleaning agent and preparation method and application thereof |
| CN114956491B (en) * | 2022-05-13 | 2024-01-30 | 大连理工大学盘锦产业技术研究院 | Chemical cleaning agent and preparation method and application thereof |
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