CN112588807B - Method for eluting aged aromatic hydrocarbon component adhered to clay mineral in petroleum-polluted soil - Google Patents
Method for eluting aged aromatic hydrocarbon component adhered to clay mineral in petroleum-polluted soil Download PDFInfo
- Publication number
- CN112588807B CN112588807B CN202011587635.8A CN202011587635A CN112588807B CN 112588807 B CN112588807 B CN 112588807B CN 202011587635 A CN202011587635 A CN 202011587635A CN 112588807 B CN112588807 B CN 112588807B
- Authority
- CN
- China
- Prior art keywords
- cleaning
- soil
- agent
- aromatic hydrocarbon
- petroleum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to an elution method of an aging aromatic hydrocarbon component adhered to a clay mineral in petroleum-polluted soil. The method mainly adopts two-stage cleaning process, and adopts cleaning agents with different compatibility conditions. The first-stage cleaning pretreatment mainly comprises desorption and separation of saturated alkanes adhered to minerals, wherein under specific cleaning parameters, the first-stage cleaning treatment uses a nonionic surfactant, namely nonylphenol polyoxyethylene ether, as a main agent, is compounded with petroleum sulfonate, and uses sodium silicate as an auxiliary agent for cleaning; the second stage of cleaning treatment is mainly to separate aging aromatic hydrocarbon adsorbed by clay by desorption, and the cleaning is carried out by taking anionic sodium octadecyl xylene sulfonate as a main agent, compounding sodium dodecyl benzene sulfonate and taking diethylamine as an auxiliary agent. In the invention, the primary cleaning pretreatment is mainly used for separating saturated alkanes; the secondary cleaning focuses on desorbing aged aromatic hydrocarbon components containing benzene rings. The method has the advantages of simple process, strong target property and low medicament cost, and can improve the total elution efficiency of petroleum in soil.
Description
Technical Field
The invention relates to the field of soil pollution remediation, in particular to petroleum-polluted soil accumulated in an oil field exploitation area, which is characterized in that light organic pollution components are volatilized, oxidized and biodegraded, the content is obviously reduced, the petroleum pollutants are obviously aged, and the heavy components in the group composition are high. In particular to an aging aromatic hydrocarbon component elution method for clay mineral adhesion in petroleum polluted soil.
Background
The petroleum polluted soil in the oil field area is produced in multiple production links such as exploitation, transportation and storage. The oil stain soil has complex composition, high pollution aging degree and great difficulty in soil remediation. The water-based agent cleaning is a preferred method for solving the problem of oil pollution of oil field soil, and is mainly characterized in that dirty oil components adhered to the surface of minerals in the soil are desorbed and separated step by heating a water-soil dispersion system and adding a surfactant and a cleaning auxiliary agent for cleaning. The technology has high degree of freedom and strong universality.
The factors influencing the cleaning effect of the petroleum-polluted soil have two aspects: firstly, the composition of soil minerals and the volatilization and aging degree of petroleum pollutants; the second is the formula of the cleaning agent and the cleaning process conditions. In the aspect of mineral composition, the oil-soil interaction of the polluted soil is obvious, and in the soil minerals, the primary minerals account for 30-60 percent in general and are SiO2Mainly, the petroleum pollutants adsorbed on the surface layer of the primary mineral are easy to desorb, and under the chemical actions of wetting, emulsifying, solubilizing and the like and the physical action of frictional shearing of the surface of the mineral, dirty oil on the surface of the primary mineral can generally obtain higher pollution desorption efficiency by adding a surfactant under the common mechanical stirring; correspondingly, petroleum pollutants adhered to the clay minerals are relatively difficult to desorb, mainly the illite smectite mixed layer minerals in the clay have large specific surface area and surface charge, and form stronger adsorption binding force with the petroleum pollutants, and the desorption rate of the pollutants adsorbed by the clay minerals determines the overall soil remediation efficiency to a great extent. In the aspect of pollutant properties, the fresh oil stain soil which is not weathered has not tight combination of petroleum hydrocarbon and soil, and the aromatic hydrocarbon or thickening degree is not increased due to the long-term natural oxidation and other actions of pollutant compositions; however, after the soil is accumulated for a certain period of time, the proportion of high molecular weight and heavy component petroleum contents is increased by volatilization, oxidation, biodegradation and other actions of low molecular weight and light hydrocarbons in the soil, and the pollution desorption of the part is difficult. In conclusion, for the aging type polluted soil accumulated in the oil field, the cleaning and repairing technology focuses on petroleum desorption adsorbed by clay minerals and aromatic hydrocarbon component desorption in pollutants. Therefore, to improve the desorption efficiency of the total petroleum in the soil, it is important to improve the desorption rate of the aged aromatic hydrocarbon pollutants adhered to the clay minerals.
The petroleum polluted soil cleaning agent material can be divided into the following categories: firstly, hot water is added with a strong alkaline solution type cleaning agent (the pH value of the system is about more than 12), and the petroleum on the surface of the soil mineral is emulsified into a water phase by reducing the tension of an oil-water interface; secondly, conventional surfactants (such as sodium dodecyl sulfate, Tween80 and the like) are added into hot water, and the short molecular chain surfactant system can directly desorb petroleum pollutants with low molecular weight and low boiling point; thirdly, hot water, cationic surfactant, oil phase (n-heptanes), auxiliary agent (alcohols), salt (sodium chloride) and the like are prepared into microemulsion to realize three-phase separation of oil, water and soil.
The three types of cleaning agents have common defects, namely, daily washing surfactants are used as main cleaning agents, the materials have insufficient deoiling capacity on crude oil components, and secondary adsorption of minerals is easily caused; secondly, the design of a target desorption cleaning agent for specific petroleum group components is lacked, and particularly, a desorption technical method for a specific target is not considered for the aged petroleum-polluted soil with aromatic rings and high heavy component content; thirdly, the cleaning materials have different chemical properties, and the cleaning temperature range, the medicament ratio, the optimal shearing condition and the like need to be correspondingly designed. Generally, the cleaning effect of the petroleum-polluted soil is improved, and the total petroleum desorption efficiency of the polluted soil can be improved only by innovating the target of the cleaning object and the structural design of the cleaning agent.
Disclosure of Invention
The invention aims to solve the technical problem of providing an elution method of an aging aromatic hydrocarbon component adhered to clay minerals in petroleum-polluted soil.
In order to achieve the purpose, the invention adopts the technical scheme that:
an agent for eluting aged aromatic hydrocarbon components adhered to clay minerals in oil-contaminated soil: the reagent is divided into a pretreatment reagent and an aromatic elution reagent; the pretreatment agent consists of a cleaning main agent and an auxiliary agent, wherein the cleaning main agent is nonylphenol polyoxyethylene ether and petroleum sulfonate in a mass ratio of 1:0.4-0.7, the adding amount is 8-10% of the oil content of the soil, the auxiliary agent is sodium silicate, and the adding amount is 15-20 g/kg of soil; the aromatic hydrocarbon elution reagent is also divided into a main cleaning agent and an auxiliary agent, wherein the main cleaning agent is a mixture of one substance of C16-C24 alkyl substituted sodium xylene sulfonate and sodium dodecyl benzene sulfonate and is mixed according to the mass ratio of 1:1.6-2.0, the adding amount is 5% of the oil content of soil to be cleaned, the auxiliary agent is diethylamine, and the adding amount is 5-10 mL/kg of soil.
One of the C16-C24 alkyl substituted sodium xylene sulfonate is prepared by synthesizing alpha-olefin (alpha-C)16 =，C18 =，C20 =Etc.) and benzene or substituted benzene are mixed (1: 5-1: 6) as raw materials, liquid aluminum trichloride is used as a catalyst (the molar ratio of the catalyst to olefin is 0.03:1-0.05: 1) to carry out alkylation reaction, and the alkylation reaction is carried out for 2-2.5 hours at the constant temperature of 60-70 ℃; after alkylation reaction, keeping the temperature at 50-60 ℃ under the condition of water bath, and adding SO3Carrying out a sulfonation reaction to make SO3The mol ratio of the alpha-olefin is 1.1:1, and the sulfonation reaction is carried out for 1 hour; and after the reaction is finished, neutralizing the reaction product by using a 50% sodium hydroxide aqueous solution until the pH value is more than 10.
An elution method of an aging aromatic hydrocarbon component adhered to clay minerals in oil soil comprises the following steps: the two-stage cleaning realizes the elution of the aging aromatic hydrocarbon component adhered to the clay mineral in the oil soil; wherein, the first-stage cleaning adopts a pretreatment agent, and the second-stage cleaning adopts an aromatic hydrocarbon elution agent; the main dosage of the cleaning agent in the two-stage elution process is correspondingly increased according to the concentration proportion of the pollutants, and the total adding amount is controlled in the range of 0.8-1.4% (wt) of the amount of the polluted soil.
In the cleaning process, the primary cleaning is mainly to separate large-particle primary minerals and fine-particle clay minerals through low-temperature and low-shear desorption and separation, specific cleaning parameters are that the temperature of a cleaning system is 50-60 ℃, the solid-liquid ratio of soil to a cleaning solution system is 1:10-1:20, the rotation number of a mechanical stirrer for cleaning is 200-300 r/m, and a centrifugal mode is adopted after cleaning to separate a bottom soil solid phase; the second-stage cleaning is to adopt pollution desorption of the medicament to the clay adsorption, aromatic hydrocarbon elution medicament is added into the soil solid separated after the first-stage cleaning, the cleaning system is cleaned at the temperature of 60-80 ℃, the solid-liquid ratio of the soil to the cleaning fluid system is 1:5-1:10, and the rotation number of a mechanical stirrer is 300-.
In the elution process, the proportion between the polluted soil and the cleaning agent is actually adjusted according to different mass ratios of clay minerals adhered to the minerals in the soil to be treated:
when the clay mineral adhesion aging aromatic hydrocarbon in the soil to be treated is less than 30%, the ratio of the primary cleaning agent to the secondary cleaning agent is 3:1-1: 1;
when the clay mineral adhesion aging aromatic hydrocarbon in the soil to be treated is higher than 30 percent but less than 50 percent, the ratio of the main agent dosage of the first-stage cleaning and the second-stage cleaning ranges from 1.5:1 to 1: 1;
when the clay mineral adhesion aging aromatic hydrocarbon in the soil to be treated is higher than 50%, the ratio of the main agent dosage of the first-stage cleaning and the second-stage cleaning ranges from 1:1 to 1: 2.
Compared with the prior art, the invention has the advantages that:
the invention aims at the elution of aging aromatic hydrocarbon pollutants adhered to clay minerals in oil soil, and comprises a specific medicament formula and corresponding cleaning process parameters; the method has the advantages of high elution rate of petroleum pollutants accumulated in polluted soil for a long time, simple process, low medicament cost, simple medicament synthesis process, simple cleaning equipment and higher practical application value.
The agent is divided into two-stage cleaning liquid systems, wherein the first-stage cleaning liquid mainly uses mixed cleaning liquid of nonylphenol polyoxyethylene ether and petroleum sulfonate in a specific ratio as pretreatment, and the interference of saturated aromatic hydrocarbon on the action of a special desorption agent for aged aromatic hydrocarbon components is reduced by separating saturated hydrocarbon; the secondary cleaning is to compound one substance in C16-C24 alkyl substituted sodium xylene sulfonate and sodium dodecyl benzene sulfonate in a specific proportion, further desorb aromatic hydrocarbon pollutants under the combined action of an auxiliary agent diethylamine, and finally improve the total petroleum desorption efficiency of the polluted soil.
According to the invention, specific medicaments and targeted condition setting are utilized, so that the medicaments can be used for mainly separating saturated alkanes through the compound medicament of nonylphenol polyoxyethylene ether and petroleum sulfonate, the interference of part of saturated alkane pollutants on the medicament for subsequent cleaning is reduced, and then the medicament with a long chain alkylbenzene structure is used for targeted desorption of aromatic hydrocarbon pollutants, so that the target of improving the elution efficiency of the polluted soil with high aromatic hydrocarbon pollutant content is realized.
Drawings
Fig. 1 is a GC-MS analysis diagram of the composition of saturated alkanes and aromatic hydrocarbons in soil before and after elution of contaminated soil according to an embodiment of the present invention. Wherein A is before elution and B is after elution.
The specific implementation mode is as follows:
the following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
The oil contaminated soil of the samples of the following examples is a contaminated soil sample with a clay mineral proportion of more than 40% and an aromatic hydrocarbon content of more than 30%.
Example 1: the main cleaning agent is prepared from sodium octadecyl xylene sulfonate.
With alpha-olefins (alpha-C)18 =) Mixing the raw materials with dimethylbenzene according to the proportion of 1:5, carrying out alkylation reaction by using liquid aluminum trichloride as a catalyst (the molar ratio of the catalyst to olefin is 0.05: 1), and carrying out alkylation reaction for 2 hours at the constant temperature of 60 ℃; after alkylation reaction, under the condition of water bath, keeping the temperature at 50-60 ℃, and adding SO3Carrying out sulfonation reaction to design SO3The mol ratio of alpha-olefin is 1.1:1, and the sulfonation reaction is carried out for 1 hour; after the sulfonation reaction was completed, the reaction mixture was neutralized with 50% aqueous sodium hydroxide solution to a pH of 10.7. Through the preparation method, sodium octadecyl xylene sulfonate is prepared, and the yield of active substances contained in the sodium octadecyl xylene sulfonate is 61.5 percent through testing.
Example 2: and (3) eluting the aging type greasy dirt soil accumulated in the oil field.
An aged oil contaminated soil sample accumulated in a Jilin oil field for a long time is taken, the oil content is measured to be 10.6 percent (wt), dirty oil components in the contaminated soil are extracted, and family composition analysis is carried out, wherein saturated hydrocarbon is 23.2 percent, aromatic hydrocarbon is 49.7 percent, and colloid asphaltene is 27.1 percent.
Carrying out petroleum elution on the polluted soil, weighing 20 g of a soil sample to be tested, putting the soil sample into a 300 mL triangular flask, carrying out primary cleaning, adding a pretreatment cleaning agent into the sample, wherein the solid-liquid mass ratio is 1:10, putting the triangular flask into a six-unit electric stirrer, stirring and cleaning the sample at the temperature of 55 +/-2 ℃ at the intensity of 300 revolutions per minute, transferring the sample into a centrifuge tube for centrifugation after the primary cleaning is finished, discarding the liquid phase, naturally drying the rest solid in a ventilated kitchen, and weighing 4 g of the sample which is subjected to primary cleaning and natural drying for soil oil content determination. Weighing 10 g of sample subjected to primary cleaning and natural air drying treatment, adding a secondary cleaning agent into the sample at a solid-liquid mass ratio of 1:5, placing a triangular flask into a six-unit electric stirrer, stirring and cleaning the sample at the temperature of 68 +/-2 ℃ at the strength of 400 rpm, desorbing aged petroleum components in soil, and measuring the oil content of the soil in the treated sample.
In the two-stage cleaning, the total concentration of the first-stage cleaning agent is 0.5 wt%, the mass ratio of the nonylphenol polyoxyethylene ether to the petroleum sulfonate is 1: 0.5, and the addition amount of the sodium silicate is 5.0 g/L; adding nonylphenol polyoxyethylene ether into a sample, stirring and cleaning for 5 minutes, adding petroleum sulfonate, stirring for 8 minutes, and finally adding sodium silicate, wherein the total cleaning time is 30 minutes;
the total concentration of the secondary cleaning agent is 0.5 wt%, the mass ratio of sodium octadecyl xylene sulfonate to sodium dodecyl benzene sulfonate is 1:2, and the final concentration of the added diethylamine is 2.5 g/L; the method comprises the following steps of adding sodium octadecyl xylene sulfonate and sodium dodecyl benzene sulfonate simultaneously, stirring and cleaning for 5 minutes, and adding a diethylamine solution, wherein the total cleaning time is 30 minutes.
The cleaning results show that: after the first-stage cleaning treatment, the content of the residual petroleum pollutants in the polluted soil is 2.85%, after the second-stage cleaning treatment, the content of the petroleum pollutants in the soil is 0.79% and is far lower than the local standard (2%), meanwhile, after the cleaning treatment, the apparent color of the soil is changed into yellow brown, no obvious oil gas taste exists, the petroleum pollutants in the soil are removed, and the substance quantity and the total content of the aromatic hydrocarbons are remarkably reduced through GC-MS analysis of the alkane and the aromatic hydrocarbons in the cleaned soil (see figure 1).
Example 3: and (3) eluting the oil contaminated soil with high-proportion aromatic hydrocarbon content in the oil field.
Taking a Liaohe oil field oil stain soil sample, measuring the oil content to be 12.1 percent (wt), extracting the oil stain components in the polluted soil, and analyzing the group composition, wherein the saturated hydrocarbon is 26 percent, the aromatic hydrocarbon is 55 percent, and the colloid asphaltene is 19 percent. Liaohe oil field is an important thickened oil production area in China, and the content of aromatic hydrocarbon components in the polluted soil is more than half of the proportion as seen from component analysis results. Therefore, the increase of the cleaning efficiency of the aromatic hydrocarbon pollutants is the key for improving the desorption efficiency of the petroleum in the polluted soil. In addition, the analysis of mineral composition shows that the content of clay minerals is high, and the proportion of secondary clay minerals accounts for more than 47%.
The amount of soil to be cleaned, the cleaning steps and instruments are the same as those in example 1, and the proportions of the two-stage cleaning and adding agents are different. The method specifically comprises the following steps: the total concentration of the first-stage cleaning agent is 0.5 wt%, nonylphenol polyoxyethylene ether and petroleum sulfonate are mixed according to the mass ratio of 1:0.7, and then 5.0 g/L sodium silicate is added and mixed uniformly. The total concentration of the secondary cleaning agent is 0.8 wt%, the mass ratio of the sodium octadecyl xylene sulfonate to the sodium dodecyl benzene sulfonate is 1:1.6, and after mixing, 3.0 g/L diethylamine is added.
The cleaning result shows that: after the first-stage cleaning treatment, the residual petroleum content in the polluted soil is 4.85%, and after the second-stage cleaning treatment, the petroleum pollutant content in the soil is 1.79% which is lower than the local standard (2%).
In this embodiment, because the source of the greasy dirt soil is different from that in embodiment 1, the content of the aromatic hydrocarbon component in the sample in this embodiment is higher, and therefore, in the cleaning process, the aromatic hydrocarbon desorption capacity of the cleaning is general under the condition that the dosage of the first-stage cleaning agent is not changed. Therefore, the oil content in the discharged soil of the first-stage cleaning is relatively high, the adding amount of the medicament is increased during the second-stage cleaning, the relative proportion of the sodium octadecyl xylene sulfonate is improved, the aromatic hydrocarbon pollutants are desorbed, and the desorption efficiency of the pollutants is improved through the second-stage cleaning.
Correspondingly, according to the records, the corresponding polluted soil is treated, and only the treatment comparison of the single-agent addition elution effect is carried out: if only primary cleaning is carried out, the total concentration of the primary cleaning agent is 1.3 wt%, and the residual petroleum content in the polluted soil after cleaning is 3.24%; if only secondary cleaning is carried out, the total concentration of the added secondary cleaning agent is 1.3 wt%, and the residual petroleum content in the cleaned polluted soil is 2.86%. As a result, the petroleum elution effect is not as good as the grading washing effect even if the first-stage or second-stage washing agent is added independently under the same washing condition and agent concentration.
Example 4: and (3) self-making clay-based polluted soil elution simulating high-concentration saturated alkane.
Preparation of a simulation sample:
three clay minerals of kaolinite, montmorillonite and illite are selected to prepare the simulated polluted soil, and the mass proportions of the three minerals are respectively 60%, 30% and 10%. Dissolving fresh crude oil in a trichloromethane solution, uniformly mixing with simulated soil, controlling the concentration content of petroleum in the soil to be 8%, stirring for 2-3 times every day until the trichloromethane in the soil is completely volatilized after one week, and storing for later use. Weighing 20 g of sample, extracting petroleum components in the sample, and performing group composition analysis, wherein the results show that the proportions of the petroleum components in the simulated soil are 55.3% of saturated alkane, 32.4% of aromatic hydrocarbon and 12.3% of colloid asphaltene.
And (3) cleaning: the amount of the soil to be cleaned, the cleaning steps and instruments are the same as those in example 2, and the dosage of the two-stage cleaning and adding agents is the same as that in example 2.
And (3) cleaning results: after the first-stage cleaning treatment, the residual petroleum content in the simulated contaminated soil is 3.73%, after the second-stage cleaning treatment, the petroleum pollutant content in the simulated contaminated soil is 1.94%, although the residual petroleum pollutant content is lower than the local standard (2%), compared with the actual contaminated soil (example 2), even under the condition that the pollution concentration is lower (example 4 is 8%, and is lower than 10.6% of example 2), the cleaning effect is slightly poor under the same medicament level, because the cleaning difficulty of the soil configured by clay minerals in the embodiment is higher than that of the actual natural soil, and the pollutant composition and the mineral composition in the contaminated soil are further proved to be important factors influencing the cleaning effect.
Example 5: and (3) self-preparing clay-based polluted soil elution simulating high-concentration aromatic hydrocarbons.
Preparation of a simulation sample:
three clay minerals of kaolinite, montmorillonite and illite are selected to prepare the simulated polluted soil, and the mass proportions of the three minerals are respectively 60%, 30% and 10%. Aging of pollutants and preparation of a polluted sample: dissolving the artificially aged (aged for 24 hours at 120 ℃ in an oven) crude oil in a trichloromethane solution, uniformly mixing with simulated soil, controlling the petroleum concentration content of the soil to be 8%, stirring for 2-3 times every day until the trichloromethane in the soil is completely volatilized after one week, and storing for later use. Weighing 20 g of sample, extracting petroleum in soil, and performing family composition analysis, wherein the result shows that the aged pollutant composition comprises 33% of saturated alkane, 42% of aromatic hydrocarbon and 25% of colloid asphaltene.
And (3) a cleaning process: the amount of soil to be cleaned and the cleaning steps and instruments are the same as in example 2, and the dosage of the two-stage cleaning and adding medicament is compared with that in example 2. Two condition experiments are carried out, firstly, the agent is added according to the embodiment 2, the total concentration of the primary cleaning agent is 0.5 wt%, and the total concentration of the secondary cleaning agent is 0.5 wt%; secondly, the dosage of a secondary cleaning agent is increased, the total concentration of the primary cleaning agent is 0.5 wt%, and the total concentration of the secondary cleaning agent is 0.8 wt%.
And (3) cleaning results: after the first-stage cleaning treatment, the residual oil content in the simulated polluted soil is 4.25%, the second-stage cleaning is carried out, when the adding amount of the agent is 0.5 wt%, the oil content in the simulated polluted soil is 2.75%, and when the adding amount of the agent is 0.8 wt%, the oil content in the simulated polluted soil is 0.88%. Therefore, the adding amount of the secondary medicament is increased, and the total petroleum desorption efficiency is improved. Compare with embodiment 4, the content of aromatic hydrocarbon is higher in the contaminated soil of this embodiment, adjusts the input of second grade cleaning agent, has obvious promotion to improving overall cleaning efficiency.
Example 6: and (5) performing an experiment on the adding sequence of the cleaning agent.
The soil samples for experiments were the same as in example 2, and the first-stage cleaning and the second-stage cleaning were carried out in the same order (the first-stage addition of mixed solution of sodium octadecyl xylene sulfonate and sodium dodecyl benzene sulfonate, diethylamine, and the second-stage addition of nonylphenol polyoxyethylene ether, petroleum sulfonate, and sodium silicate), except for the application order of the agents, the other experimental parameters were the same as in example 2. The cleaning results show that: after the first-stage cleaning treatment, the residual petroleum content in the polluted soil is 3.43%, and after the second-stage cleaning treatment, the petroleum pollutant content in the soil is 2.66%. Results comparative example 2, the efficiency of the petroleum cleaning was poor and the results show that the order of application of the agents is very important to the petroleum cleaning results.
Example 7: and (5) verifying the effect of different secondary cleaning agent adding amounts.
The soil sample for experiments is the same as the soil sample for the example 2, the adding proportion of the first-stage cleaning agent and the second-stage cleaning agent is changed, the total concentration of the first-stage cleaning agent is 0.5 wt%, the mass ratio of the nonylphenol polyoxyethylene ether to the petroleum sulfonate is 1: 0.5, and the adding amount of the sodium silicate is 5.0 g/L; the total concentration of the secondary cleaning agent is 0.3 wt%, the mass ratio of the sodium octadecyl xylene sulfonate to the sodium dodecyl benzene sulfonate is 1:2, and the final concentration of the added diethylamine is 2.5 g/L. The total adding concentration of the two-stage medicament is 0.8 wt%. Other cleaning experimental parameters were the same as in example 2. The cleaning results show that: after the first-stage cleaning treatment, the residual petroleum content in the contaminated soil is 2.85%, and after the second-stage cleaning treatment, the petroleum pollutant content in the soil is 1.47%. As a result, compared with the example 2, the petroleum cleaning efficiency is reduced because the adding concentration of the agent for the secondary cleaning is reduced, and when the aging aromatic hydrocarbon in the soil is not more than 50%, the dosage ratio of the main agent for the primary cleaning to the secondary cleaning is 1:1-1: 2.
The results from examples 1-7 show that: the octadecyl xylene sodium sulfonate synthesized by the method has the active matter yield of 61.5 percent and meets the use requirement of medicaments; in order to verify the two-stage cleaning method, the medicament adding proportion and the cleaning parameter conditions of the invention, three types of contaminated soil are selected: cleaning and verifying a plurality of experimental conditions of accumulated aged oil contaminated soil, oil contaminated soil with high aromatic hydrocarbon content and self-made simulated clay-based contaminated soil, wherein the results show that the desorption material and the desorption process aiming at aged aromatic hydrocarbon pollutant components adhered to clay minerals in the soil are designed according to the adding sequence and adding concentration ratio of the two medicaments designed by the invention, so that the total desorption efficiency of petroleum in the soil can be obviously improved.
Claims (2)
1. An elution reagent for an aging aromatic hydrocarbon component adhered to a clay mineral in petroleum-contaminated soil, which is characterized in that: the agent is divided into a pretreatment agent and an aromatic hydrocarbon elution agent; the pretreatment agent consists of a cleaning main agent and an auxiliary agent, wherein the cleaning main agent is a mixture of nonylphenol polyoxyethylene ether and petroleum sulfonate in a mass ratio of 1:0.4-0.7, the adding amount is 8-10% of the oil content of soil to be cleaned, the auxiliary agent is sodium silicate, and the adding amount is 15-20 g/kg of soil; the aromatic elution reagent is also divided into a main cleaning agent and an auxiliary agent, wherein the main cleaning agent is a mixture of one substance in C16-C24 alkyl substituted sodium xylene sulfonate and sodium dodecyl benzene sulfonate, the main cleaning agent and the auxiliary agent are mixed according to the mass ratio of 1:1.6-2.0, the adding amount is 5% of the oil content of soil to be cleaned, the auxiliary agent is diethylamine, and the adding amount is 5-10 mL/kg of soil;
the synthesis preparation of one substance in the C16-C24 alkyl substituted sodium xylene sulfonate is characterized in that alpha-olefin and benzene or substituted benzene are mixed at a ratio of 1:5-1:6 as raw materials, liquid aluminum trichloride is used as a catalyst for alkylation reaction, the molar ratio of the catalyst to the alpha-olefin is 0.03:1-0.05:1, and the alkylation reaction is carried out for 2-2.5 hours at a constant temperature of 60-70 ℃; after alkylation reaction, under the condition of water bath, the temperature of a medicament system is kept at 50-60 ℃, and SO is added3By sulphonation with SO3The mol ratio of the alpha-olefin to the alpha-olefin is 1.1:1, and the sulfonation reaction is carried out for 1 hour; after the reaction is finished, neutralizing with 50% sodium hydroxide solution to ensure that the pH value of the medicine system is more than 10.
2. An elution method of an aging aromatic hydrocarbon component adhered to a clay mineral in petroleum-contaminated soil is characterized by comprising the following steps: the elution method is two-stage washing, wherein a pretreatment agent is adopted in the first-stage washing, and an aromatic hydrocarbon elution agent is adopted in the second-stage washing; the main dosage of the cleaning agent in the two-stage elution process is correspondingly increased according to the concentration proportion of the pollutants, and the total dosage is controlled to be 0.8-1.4% (wt) of the amount of the polluted soil;
the first-stage cleaning parameters comprise 50-60 ℃ of the cleaning system, 1:10-1:20 of the solid-liquid ratio of soil to the cleaning liquid system, 200 revolutions of a mechanical stirrer for cleaning and 300 revolutions per minute, and the solid of the soil at the bottom layer is separated by adopting a centrifugal mode after cleaning; second-stage cleaning, namely adding an aromatic hydrocarbon elution agent into the soil solid separated after the first-stage cleaning, and cleaning at the temperature of 60-80 ℃, the solid-liquid ratio of soil to a cleaning liquid system of 1:5-1:10 and the rotation number of a mechanical stirrer of 300-500 revolutions per minute to realize elution of the aged aromatic hydrocarbon component;
the pretreatment agent consists of a cleaning main agent and an auxiliary agent, wherein the cleaning main agent is a mixture of nonylphenol polyoxyethylene ether and petroleum sulfonate in a mass ratio of 1:0.4-0.7, the adding amount is 8-10% of the oil content of the soil to be cleaned, the auxiliary agent is sodium silicate, and the adding amount is 15-20 g/kg of soil; the aromatic elution reagent is also divided into a main cleaning agent and an auxiliary agent, wherein the main cleaning agent is a mixture of one substance in C16-C24 alkyl substituted sodium xylene sulfonate and sodium dodecyl benzene sulfonate, the main cleaning agent and the auxiliary agent are mixed according to the mass ratio of 1:1.6-2.0, the adding amount is 5% of the oil content of soil to be cleaned, the auxiliary agent is diethylamine, and the adding amount is 5-10 mL/kg of soil;
the first-stage cleaning reduces the interference of the saturated aromatic hydrocarbon on the action of a special desorption agent for the aged aromatic hydrocarbon component by separating the saturated hydrocarbon; and the secondary cleaning further desorbs the aromatic hydrocarbon pollutants under the combined action of the auxiliary agent diethylamine, so that the total petroleum desorption efficiency of the polluted soil is finally improved.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011587635.8A CN112588807B (en) | 2020-12-29 | 2020-12-29 | Method for eluting aged aromatic hydrocarbon component adhered to clay mineral in petroleum-polluted soil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011587635.8A CN112588807B (en) | 2020-12-29 | 2020-12-29 | Method for eluting aged aromatic hydrocarbon component adhered to clay mineral in petroleum-polluted soil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112588807A CN112588807A (en) | 2021-04-02 |
| CN112588807B true CN112588807B (en) | 2022-06-24 |
Family
ID=75204012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011587635.8A Active CN112588807B (en) | 2020-12-29 | 2020-12-29 | Method for eluting aged aromatic hydrocarbon component adhered to clay mineral in petroleum-polluted soil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112588807B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001137792A (en) * | 1999-11-16 | 2001-05-22 | Japan Energy Corp | Cleaning method |
| JP2002372803A (en) * | 2001-06-14 | 2002-12-26 | Canon Inc | Method for manufacturing polymerized toner |
| JP2011020066A (en) * | 2009-07-16 | 2011-02-03 | Jx Nippon Oil & Energy Corp | Cleaning method |
| CN110986575A (en) * | 2019-10-16 | 2020-04-10 | 中国科学院生态环境研究中心 | Thermal desorption energy-saving system and method for repairing polycyclic aromatic hydrocarbon contaminated soil |
| CN111099956A (en) * | 2019-11-20 | 2020-05-05 | 复榆(张家港)新材料科技有限公司 | Method for separating C6 mixed hydrocarbon by two-stage PSA |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7332460B2 (en) * | 2004-07-15 | 2008-02-19 | Chevron Oronite Company Llc | Alkylxylene sulfonates for enhanced oil recovery processes |
| CN101683600A (en) * | 2008-09-26 | 2010-03-31 | 南开大学 | Novel desorbing agent for removing petroleum hydrocarbon class pollutant of soil |
| CN102303042B (en) * | 2011-05-31 | 2013-06-05 | 北京师范大学 | Circulation washing system device and method for polluted soil washing and repair |
| CN102757810B (en) * | 2012-06-28 | 2014-09-24 | 神华集团有限责任公司 | Method for separating component from direct-coal-liquefaction full distillate oil by utilizing solid-phase extraction method |
| CN103193688B (en) * | 2013-04-17 | 2014-12-31 | 中国石油天然气股份有限公司 | Hexadecyl xylene sulfonate industrial product and production method thereof, surfactant and application thereof |
| JP6534282B2 (en) * | 2015-04-06 | 2019-06-26 | 住友化学株式会社 | High purity aluminum granular material and method for producing the same |
| CN106077060A (en) * | 2016-02-28 | 2016-11-09 | 湖南先科环保有限公司 | A kind of heavy-metal contaminated soil processing means and process technique thereof |
| CN107321779A (en) * | 2017-08-18 | 2017-11-07 | 上海憬图环境工程有限公司 | A kind of organic material contaminated soil wet method prosthetic device and technique |
| CN110404952A (en) * | 2019-08-02 | 2019-11-05 | 知合环境（北京）有限责任公司 | A kind of eluent of repairing polluted soil and its preparation method and application |
-
2020
- 2020-12-29 CN CN202011587635.8A patent/CN112588807B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001137792A (en) * | 1999-11-16 | 2001-05-22 | Japan Energy Corp | Cleaning method |
| JP2002372803A (en) * | 2001-06-14 | 2002-12-26 | Canon Inc | Method for manufacturing polymerized toner |
| JP2011020066A (en) * | 2009-07-16 | 2011-02-03 | Jx Nippon Oil & Energy Corp | Cleaning method |
| CN110986575A (en) * | 2019-10-16 | 2020-04-10 | 中国科学院生态环境研究中心 | Thermal desorption energy-saving system and method for repairing polycyclic aromatic hydrocarbon contaminated soil |
| CN111099956A (en) * | 2019-11-20 | 2020-05-05 | 复榆(张家港)新材料科技有限公司 | Method for separating C6 mixed hydrocarbon by two-stage PSA |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112588807A (en) | 2021-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | The influence of clay minerals and surfactants on hydrocarbon removal during the washing of petroleum-contaminated soil | |
| Riding et al. | A review of the laboratory preparation of palynomorphs with a description of an effective non-acid technique | |
| WO2019011044A1 (en) | Emulsion-type water-based detergent for oily sludge, preparation method and use method therefor | |
| CN107055990A (en) | A kind of oily sludge cleaning agent and its preparation method and application | |
| US20190299180A9 (en) | Methods for Changing Stability of Water and Oil Emulsions | |
| CN100469862C (en) | Multicomponent compound drip washing liquid, repair method and its apparatus | |
| CA2889424A1 (en) | Continuous destabilization of emulsions | |
| Li et al. | Modification technology for separation of oily sludge | |
| Chirwa et al. | Biosurfactants as demulsifying agents for oil recovery from oily sludge–performance evaluation | |
| Loh et al. | Suspended particles enhance biodegradation of oil in sea | |
| CN112588807B (en) | Method for eluting aged aromatic hydrocarbon component adhered to clay mineral in petroleum-polluted soil | |
| CN106669978A (en) | Charcoal floating agent, application thereof, and flyash floating charcoal extracting method | |
| MX2012000253A (en) | Composition of biodegradable surfactants for separating hydrocarbon impurities. | |
| CN102295397A (en) | Method for enhancing recovery rate of oil from oily sludge | |
| CN104556081A (en) | Modified kaolin as well as preparation method and application thereof | |
| Dantas et al. | Study of new alternatives for removal of sulfur from diesel | |
| Nejad | Remediation of Waste Drilling Mud Using Surfactantenhanced Washing: Influencing Factors and Petroleum Hydrocarbon Removal | |
| Li et al. | Multiphase redistribution differences of polycyclic aromatic hydrocarbons (PAHs) between two successive sediment suspensions | |
| Zawrah et al. | Organo modified Nanoclay/sawdust mixtures for hydrocarbon removal from water | |
| Ren et al. | De-oiling characteristics and mechanism of oil-bearing sludge cleaned by CGAs | |
| Hou et al. | Safe disposal technology of waste oil-based drilling fluids | |
| Altunina et al. | Detergent compositions for oil sludge reclamation | |
| Sapronova et al. | Obtaining Sorption Material from the Leaves of Aésculus Hippocastanum L. | |
| CN111978977B (en) | Efficient water-soluble compound aging oil demulsifier and preparation method thereof | |
| RU2228432C1 (en) | Compound for removal of asphalt-resin-paraffin sedimentations |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Gang Inventor after: Guo Shuhai Inventor after: Wu Bo Inventor after: Wang Sa Inventor after: Li Bailin Inventor before: Guo Shuhai Inventor before: Li Gang Inventor before: Wu Bo Inventor before: Wang Sa Inventor before: Li Bailin |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |