阅读说明：本技术 一种石墨烯双亲纳米材料以及修复污染土壤的方法 (Graphene amphiphilic nano material and method for repairing polluted soil ) 是由 徐骏 安登波 戴春森 于 2019-04-19 设计创作，主要内容包括：本发明提供了一种用于净化石油污染土壤的石墨烯双亲纳米材料以及修复处理石油污染土壤的方法,取石油污染土壤,加入一定质量比的石墨烯双亲纳米材料配制成石墨烯双亲纳米修复液,然后搅拌,形成修复分散液-污染土壤混合体系,然后对上述混合体系进行离心,即得到石油脱附液和净化后的土壤,即实现土壤修复。将所述石油脱附液进行离心,形成油相和水相,然后进行分液,即可将油水分离,进而回收水相和油相。该方法简便易行,且石墨烯双亲纳米材料和水均可多次循环使用,兼顾了节能和环保的效果,特别利于工业化批量处理被石油污染的土壤。(The invention provides a graphene amphiphilic nano material for purifying petroleum-polluted soil and a method for repairing and treating the petroleum-polluted soil. And centrifuging the petroleum desorption solution to form an oil phase and a water phase, separating the liquid to separate the oil phase from the water phase, and recovering the water phase and the oil phase. The method is simple and easy to implement, the graphene amphiphilic nano material and water can be recycled for multiple times, the effects of energy conservation and environmental protection are considered, and the method is particularly beneficial to industrial batch treatment of the soil polluted by petroleum.)

1. The graphene amphiphilic nano material for purifying the petroleum-polluted soil is characterized by being graphene oxide grafted with lipophilic carbon chains.

2. The graphene amphiphilic nanomaterial according to claim 1, wherein the lipophilic carbon chain is long-chain alkane or long-chain alkane substituted by one or more of aryl, ester, ether, amine and amide.

3. The graphene amphiphilic nanomaterial according to claim 1, wherein the long-chain alkane is one or more of straight-chain alkanes containing at least ten carbons; preferably, the lipophilic carbon chain is one or more of n-dodecyl chain, n-tetradecyl chain, n-hexadecyl chain and n-octadecyl chain.

4. The repairing dispersion liquid for purifying the petroleum-polluted soil is characterized by comprising the following components: the graphene amphiphilic nanomaterial powder of any one of claims 1 to 3, and sodium dodecyl sulfate, polyoxyethylene sorbitan monooleate, sodium dodecyl benzene sulfonate and water.

5. The repairing dispersion liquid for purifying petroleum-contaminated soil according to claim 4, wherein the concentration of the graphene amphiphilic nano material is 0.002-0.1%.

6. The repairing dispersion liquid for purifying petroleum-contaminated soil according to claim 4, wherein the mass concentration of the sodium lauryl sulfate is 100 to 500 mg/L.

7. The repairing dispersion liquid for purifying petroleum-contaminated soil according to claim 4, wherein the mass concentration of the polyoxyethylene sorbitan monooleate is 5 to 50 mg/L.

8. The repairing dispersion liquid for purifying petroleum-contaminated soil according to claim 4, wherein the mass concentration of the sodium dodecylbenzenesulfonate is 20 to 100 mg/L.

9. The repairing dispersion liquid for purifying petroleum-contaminated soil according to claim 4, wherein the particle size of the graphene amphiphilic nano-material powder is 50 to 1000 nm.

10. The remedial dispersion for decontaminating soil contaminated with petroleum according to claim 4, wherein the degree of mineralization of the water is <1000 ppm.

11. A method for purifying petroleum-contaminated soil by using a remediation dispersion is characterized by comprising the following steps:

s1, preparation of a repairing dispersion liquid: mixing the graphene amphiphilic nano-material powder as defined in any one of claims 1 to 3 with sodium dodecyl sulfate, polyoxyethylene sorbitan monooleate, sodium dodecyl benzene sulfonate and water according to a certain mass ratio, and stirring to prepare a repair dispersion liquid;

s2, repairing: adding the repairing dispersion liquid in S1 into the petroleum-polluted soil, stirring to form a repairing dispersion liquid-polluted soil mixed system, and performing centrifugal separation treatment on the mixed system to obtain a petroleum desorption liquid;

s3, oil-water separation: and S2, centrifuging the petroleum desorption solution, separating oil and water in the petroleum desorption solution to form an oil phase and a water phase, separating the liquid to separate the oil and the water, and recovering the water phase and the oil phase to realize soil remediation.

12. The method for purifying petroleum-contaminated soil using the remedial dispersion according to claim 11, further comprising the steps of:

s4: the soil remediation process may be repeated by adding the remediation dispersion to the aqueous phase recovered at S3 and repeating steps S2 and S3.

13. The method for purifying petroleum-contaminated soil using the remedial dispersion according to claim 11, wherein the stirring speed of S1 is 50 to 1000 r/min; the stirring time is 10-60 min.

14. The method for purifying petroleum-contaminated soil using the remedial dispersion according to claim 11, wherein the stirring speed of S2 is 50 to 1000 r/min; the stirring time is 10-120 min.

15. The method for purifying petroleum-contaminated soil using the remedial dispersion according to claim 11, wherein the mass ratio of the petroleum-contaminated soil to the remedial dispersion at S2 is 1:1 to 25.

16. The method for purifying petroleum-contaminated soil using the remedial dispersion according to claim 11, wherein the centrifugal rotation speed of S2 is 500 to 5000 r/min; the centrifugation time is 5-60 min.

17. The method for purifying petroleum-contaminated soil using the remedial dispersion as set forth in claim 11, wherein the centrifugal rotation speed of S3 is 500 to 7500 r/min; the centrifugation time is 1-15 min.

Technical Field

The invention belongs to the field of polluted soil remediation, and particularly relates to a graphene amphiphilic nano material and a method for remediating polluted soil.

Background

Currently about 2/3 in total world oil production is produced from land fields. And in the modern oil exploration, exploitation and processing process, the soil is often seriously polluted. Hydrocarbon contamination is present in soils around the world. Such petroleum pollution often poses health hazards to humans or local ecosystems, and it is therefore necessary to remove such pollution. At present, the surfactant synergistic remediation mode is adopted internationally to treat petroleum-polluted soil, and although the method has the advantages of low energy consumption, simple process, wide application range, high speed and the like, in the desorption solution, a large amount of petroleum and the surfactant are mixed together and are not easy to separate. If not treated, not only causes the waste of resources, but also is easy to cause secondary pollution to soil, water body and the like.

At present, extraction method, resin adsorption method, evaporation concentration method and the like are adopted internationally for treating petroleum desorption liquid, and although the effect of separating petroleum and surfactant can be achieved, the methods still have respective defects. For example, the extraction method mainly utilizes an organic solvent for treatment, so that the operation is complex, and the harm to a human body is easy to cause; the resin adsorption method has higher cost; the evaporation concentration method has high treatment cost and unsatisfactory effect. Therefore, a new method is needed for treating contaminated soil, which can avoid mixing a large amount of petroleum with a surfactant, has low cost, and can be widely applied to the treatment of contaminated soil.

The graphene amphiphilic nano material is a material which has hydrophilicity, lipophilicity and huge specific surface area, and has strong adsorption capacity. However, at present, researches on the repairing effect of the graphene amphiphilic nano material on petroleum-polluted soil are few, and the application of the graphene amphiphilic nano material in the field is limited.

Technical scheme

The invention mainly aims to overcome the defects in the prior art and provide the method which has low cost, high benefit and simple operation and can effectively treat the petroleum-polluted soil.

In order to solve the technical problems, the invention provides a graphene amphiphilic nanomaterial for purifying petroleum-polluted soil, which is characterized in that the amphiphilic nanomaterial is graphene oxide grafted with lipophilic carbon chains;

furthermore, the oleophylic carbon chain is long-chain alkane or long-chain alkane substituted by one or more of aryl, ester, ether, amine and amide;

furthermore, the long-chain alkane is one or more of straight-chain alkanes containing at least more than ten carbons; preferably, the lipophilic carbon chain is one or more of n-dodecyl chain, n-tetradecyl chain, n-hexadecyl chain and n-octadecyl chain;

on the other hand, the invention also provides a restoration dispersion liquid for purifying petroleum-polluted soil, which is characterized by comprising the following components: any one of the graphene amphiphilic nano material powder, Sodium Dodecyl Sulfate (SDS), polyoxyethylene sorbitan monooleate (Tween 80), sodium dodecyl benzene sulfonate (LAS) and water;

optionally, the concentration of the graphene amphiphilic nano material is 0.002-0.1%; preferably, the concentration is 0.004-0.2%; most preferably, 0.005%;

optionally, the mass concentration of the SDS is 100-500 mg/L; preferably, the mass concentration is 200 mg/L;

optionally, the mass concentration of the Tween80 is 5-50 mg/L; preferably, the mass concentration is 10 mg/L;

optionally, the mass concentration of the LAS is 20-100 mg/L; preferably, the mass concentration is 50 mg/L;

optionally, the particle size of the graphene amphiphilic nano material powder is 50-1000 nm; preferably, the particle size of the graphene amphiphilic nano material powder is 100-500 nm; most preferably, the particle size of the graphene amphiphilic nano material powder is 200 nm;

optionally, said water has a degree of mineralization <1000 ppm;

in another aspect, the present invention also provides a method for purifying petroleum-contaminated soil using the above-mentioned remediation dispersion, which is characterized by comprising the steps of:

s1, preparation of a repairing dispersion liquid: mixing the graphene amphiphilic nano material powder with SDS, Tween80, LAS and water according to a certain mass ratio, stirring and preparing a repair dispersion liquid;

s2, repairing: adding the repairing dispersion liquid in S1 into the petroleum-polluted soil, stirring to form a repairing dispersion liquid-polluted soil mixed system, and performing centrifugal separation treatment on the mixed system to obtain a petroleum desorption liquid;

s3, oil-water separation: and S2, centrifuging the petroleum desorption solution, separating oil and water in the petroleum desorption solution to form an oil phase and a water phase, separating the liquid to separate the oil and the water, and recovering the water phase and the oil phase to realize soil remediation.

Optionally, the method for purifying the petroleum-contaminated soil by using the repairing dispersion liquid is characterized by further comprising the following steps:

s4: the soil remediation process may be repeated by adding the remediation dispersion to the aqueous phase recovered at S3 and repeating steps S2 and S3.

Optionally, the stirring speed of S1 is 50-1000 r/min, preferably 100-750 r/min, and most preferably 500 r/min; the stirring time of S1 is 10-60 min, preferably 15-45 min, and most preferably 30 min;

optionally, the rotation speed of S2 is 50-1000 r/min at normal temperature, preferably 100-750 r/min, and most preferably 500 r/min; the stirring time of S2 is 10-120 min, preferably 30-90 min, and most preferably 60 min;

optionally, the mass ratio of the petroleum-polluted soil to the repairing dispersion liquid of S2 is 1:1 to 25, preferably 1:1 to 15, most preferably 1: 10;

optionally, the centrifugal rotation speed of S2 is 500-5000 r/min, preferably 1000-3000 r/min, and most preferably 2500 r/min; the centrifugation time of S2 is 5-60 min, preferably 10-45 min, and most preferably 30 min.

Optionally, the centrifugal rotation speed of S3 is 500-7500 r/min, preferably 1500-6000 r/min, and most preferably 5000 r/min; the centrifugation time of S3 is 1-15 min, preferably 3-10 min, and most preferably 5 min.

Advantageous effects

1. The graphene amphiphilic nano material adopted by the invention has excellent biocompatibility, is easy to carry out chemical modification and has good dispersion stability in water and physiological solution, and the amphiphilic nano material grafted with the long-chain oleophylic carbon chain can obviously reduce the interfacial tension of a contact surface, improve the migration capacity of petroleum, enable water to wet the surfaces of soil and oil, and have obvious effect of separating water and oil.

2. The operation method for purifying the petroleum-polluted soil is simple and easy to implement, and is particularly beneficial to large-scale industrial treatment of the petroleum-polluted soil.

3. The graphene amphiphilic nano material, the surfactant and the water can be recycled for multiple times, and the petroleum can be recycled, so that the effects of energy conservation and environmental protection are considered.

4. The oil removing composition disclosed by the invention is added with the graphene oxide material, so that the dosage of the surfactant is greatly reduced, and the secondary pollution to the environment is reduced as much as possible.

5. The technical scheme of the invention only adopts physical mixing, stirring and centrifugation, does not relate to chemical reaction, and has less secondary pollution to the environment.

Drawings

FIG. 1 is a schematic structural diagram of a graphene amphiphilic nanomaterial used in the present invention

Detailed Description

Repair dispersion