CN112453034A - Method for reducing concentration of petroleum hydrocarbon in underground water and application thereof - Google Patents
Method for reducing concentration of petroleum hydrocarbon in underground water and application thereof Download PDFInfo
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- CN112453034A CN112453034A CN201910843435.5A CN201910843435A CN112453034A CN 112453034 A CN112453034 A CN 112453034A CN 201910843435 A CN201910843435 A CN 201910843435A CN 112453034 A CN112453034 A CN 112453034A
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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
- B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5209—Regulation methods for flocculation or precipitation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Soil Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of groundwater remediation, in particular to a method for reducing the concentration of petroleum hydrocarbon in groundwater and application thereof, wherein the method comprises the following steps: (1) adding cyclodextrin or a derivative thereof into underground water, and carrying out first mixing treatment; (2) adding a coagulant into the underground water subjected to the first mixing treatment, and performing second mixing treatment; (3) and enabling the groundwater after the second mixing treatment to reach a stable state. The method has the advantages of simple and easy operation and simple equipment, does not need large-scale equipment, and is easy to implement on site; the used repairing agent has simple components, basically has no pollution to underground water, and has no secondary pollution in the treatment process; the influence of the environmental temperature and the pH value of the water body is small, and the application range is wide; the mixing treatment time is short, the treatment speed is high, the effect is obvious, the petroleum hydrocarbon content in the petroleum-polluted underground water can be reduced by more than 99 percent to the maximum extent, and the concentration of other pollutants can be reduced.
Description
Technical Field
The invention relates to the field of groundwater remediation, in particular to a method for reducing the concentration of petroleum hydrocarbon in groundwater and application thereof.
Background
With the rapid development of the petroleum industry, nearly 60 million tons of petroleum hydrocarbon in China per year causes soil-underground water system pollution through various ways. Petroleum hydrocarbons enter the soil-groundwater system mainly through several routes: crude oil leakage and oil spill accidents, stacking of oily slag, sludge and garbage, irrigation of oily sewage, atmospheric pollution and settlement of automobile exhaust and pollution caused by application of oily pesticides. At present, petroleum hydrocarbon becomes a common pollutant in groundwater pollution, and the harmfulness and influence range of the petroleum hydrocarbon is wider due to the fluidity of the groundwater.
The remediation of petroleum hydrocarbon polluted groundwater can be divided into ex-situ remediation and in-situ remediation according to a remediation mode. Ex-situ remediation, wherein the existing mature and widely applied technology is extraction treatment technology, when the density of pollutants is lower than that of water, the pollutants are all positioned on the upper layer of underground water, and the extraction treatment technology can achieve a good effect; however, for oil contaminants having a density greater than that of water, the extraction treatment technique is less effective. Meanwhile, the pumping treatment technology easily causes the invasion of the ground lower layer and the surrounding water body, and has certain influence on the environmental structure. The in-situ remediation of the groundwater is carried out on the polluted original site on the premise of not damaging the environmental structure. Compared with ex-situ remediation, in-situ remediation has small influence on the environment and low cost, and is widely concerned and applied to the remediation of oil-polluted underground water in recent years.
The main oil pollution underground water in-situ remediation technologies comprise the following types: permeable reactive barrier repair technology (PRB), aeration repair technology (AS), microorganism repair technology and the like. The PRB technology has the defects of high difficulty, high investment cost and long repair time; the AS technology has limited removal effect on pollutants; the microorganism restoring technology has the advantages of simple operation, economy, high efficiency, little secondary pollution and the like; the limitation is limited by the concentration of electron acceptors and nutrients, and in addition, the time to reach the degradation target is limited due to slow degradation of the microorganism.
In patent application CN105668689A, a multifunctional slow-release repairing agent applied to in-situ repair of underground water is provided, which mainly applies the underground water repairing technology of a permeable reactive barrier and removes pollutants in water by adding repairing agents of calcium peroxide, clay, iron salt, cyclodextrin and an adhesive. The process mainly removes organic matters in the underground water by means of calcium peroxide oxidation, a permeable reactive barrier needs to be placed in the underground water, the engineering is large, and the preparation of the repairing agent is complex.
Disclosure of Invention
The invention aims to overcome the problems of complex process equipment and complex preparation of a repairing agent in the prior art, and provides a method for reducing the concentration of petroleum hydrocarbon in underground water, which has the advantages of simple and easy operation and simple repairing agent and equipment.
In order to achieve the above objects, one aspect of the present invention provides a method for reducing the concentration of petroleum hydrocarbons in groundwater, the method comprising the steps of:
(1) adding cyclodextrin or a derivative thereof into underground water, and carrying out first mixing treatment;
(2) adding a coagulant into the underground water subjected to the first mixing treatment, and performing second mixing treatment;
(3) and enabling the groundwater after the second mixing treatment to reach a stable state.
Preferably, the method further comprises: and adding coagulant aid into the groundwater after the second mixing treatment, performing third mixing treatment, and uniformly mixing to enable the groundwater after the third mixing treatment to reach a stable state.
In another aspect of the invention, there is provided the use of a method as described above for the in situ or ex situ remediation of petroleum hydrocarbon contaminated groundwater.
Through the technical scheme, the method for reducing the concentration of the petroleum hydrocarbon in the underground water has the advantages of simplicity and easiness in operation, simplicity in equipment, no need of large-scale equipment and easiness in field implementation.
The repairing agent used in the method has simple components, basically has no pollution to the underground water body, and has no secondary pollution in the treatment process.
Under the optimal conditions, the cyclodextrin or the derivative thereof, the coagulant and the coagulant aid are added according to the specific sequence, so that the effects of short mixing treatment time and high treatment speed can be achieved, and the petroleum hydrocarbon content in the petroleum-polluted underground water can be reduced by more than 99 percent at most.
The method of the invention is less influenced by the environmental temperature and the pH value of the water body, is suitable for various water qualities, and can be used for the in-situ or ex-situ remediation treatment of the petroleum hydrocarbon polluted underground water with different water qualities.
In addition, the method of the invention can reduce the concentration of other pollutants, such as chlorine-containing organic matters or sulfur-containing organic matters, aiming at different groundwater.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
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.
In one aspect, the present invention provides a method for reducing the concentration of petroleum hydrocarbons in groundwater, the method comprising the steps of:
(1) adding cyclodextrin or a derivative thereof into underground water, and carrying out first mixing treatment;
(2) adding a coagulant into the underground water subjected to the first mixing treatment, and performing second mixing treatment;
(3) and enabling the groundwater after the second mixing treatment to reach a stable state.
In the present invention, the groundwater includes, but is not limited to, groundwater contaminated with only petroleum hydrocarbons, that is, may contain other contaminants such as chlorinated organics or sulfur-containing organics in addition to contamination with petroleum hydrocarbons.
In addition, the present invention has no particular limitation on the pH, the degree of mineralization and the concentration of petroleum hydrocarbons in the groundwater.
In the present invention, the cyclodextrin in the cyclodextrin or the derivative thereof refers to α -cyclodextrin, β -cyclodextrin and γ -cyclodextrin; the derivative, namely the cyclodextrin derivative, is a product obtained by introducing a modification group and modifying a cyclodextrin parent (alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin) under the condition of keeping the basic skeleton of a large ring of the cyclodextrin parent unchanged. The modifying group may be a sulfonic acid group or an optionally substituted alkyl group of C1-C4 (e.g., optionally substituted methyl, optionally substituted ethyl, optionally substituted propyl and isomers thereof, optionally substituted butyl and isomers thereof), and the optionally substituted substituent may be a hydroxyl group or a carboxyl group.
Preferably, the cyclodextrin or its derivative is selected from at least one of α -cyclodextrin, β -cyclodextrin, γ -cyclodextrin, methyl- β -cyclodextrin, hydroxypropyl- β -cyclodextrin, carboxymethyl- β -cyclodextrin, hydroxyethyl- β -cyclodextrin and sulfonated- β -cyclodextrin, more preferably at least one of β -cyclodextrin, methyl- β -cyclodextrin, hydroxypropyl- β -cyclodextrin, carboxymethyl- β -cyclodextrin, hydroxyethyl- β -cyclodextrin and sulfonated- β -cyclodextrin, and further preferably β -cyclodextrin.
In the present invention, the amount of cyclodextrin added is not particularly limited as long as the cyclodextrin is added to the groundwater and the subsequent process according to the present invention can reduce the content of petroleum hydrocarbons in the groundwater, but the amount of cyclodextrin or its derivative added is 2 to 5g/L of groundwater under preferable conditions, that is, when the concentration of petroleum hydrocarbons in the groundwater is 100mg/L or more and 200mg/L or less; when the concentration of petroleum hydrocarbon in the underground water is more than or equal to 50mg/L and less than 100mg/L, the adding amount of cyclodextrin or the derivative thereof is 1-2g/L of underground water; when the concentration of the petroleum hydrocarbon in the underground water is less than 50mg/L, the addition amount of the cyclodextrin or the derivative thereof is 0.2-1g/L of the underground water, so that the removal rate of the petroleum hydrocarbon in the underground water can be obviously improved.
The method for measuring the concentration of the petroleum hydrocarbon comprises the steps of extracting underground water by using carbon tetrachloride, adsorbing an obtained organic solvent layer by using magnesium silicate, removing polar substances such as animal and vegetable oil and the like, and then measuring by using an infrared oil tester. Reference may be made to the measurement method described in infrared photometry for measuring soil petroleum (manuscript for comments).
In the present invention, the mixing of groundwater and cyclodextrin or a derivative thereof can be promoted by the first mixing treatment, and the removal rate of petroleum hydrocarbons can be improved. The method of the first mixing treatment is not particularly limited as long as the purpose of mixing can be achieved, and preferably, when groundwater is remediated in situ, the method of the first mixing treatment is an aeration treatment, and the aeration flow rate of the aeration treatment is not particularly limited and may be an aeration flow rate that can be achieved by an aerator conventionally used in the art. When groundwater is ex-situ remediated, the method of the first mixing treatment may be aeration and/or agitation.
In the present invention, the time of the first mixing process can be selected in a wide range, and preferably, the time of the first mixing process is 20-60min, such as 20, 25, 30, 35, 40, 45, 50, 55, 60min, and any range between any two values. Under the preferred conditions, a higher petroleum hydrocarbon removal rate can be achieved while controlling the process of reducing the concentration of petroleum hydrocarbons in the groundwater within a shorter time.
In the present invention, the removal rate of petroleum hydrocarbons can be significantly improved by adding a coagulant, the kind of which is not particularly limited, preferably, the coagulant is at least one selected from the group consisting of chitosan, aluminum sulfate, ferric chloride, ferrous sulfate, polyaluminum chloride (PAC), polyaluminum sulfate (PAS), polyferric chloride (PFC) and polyferric sulfate (PFS), more preferably at least one selected from the group consisting of PAC, PAS, PFC and PFS, and still more preferably PAC. In the preferred range, the removal rate of petroleum hydrocarbons from groundwater can be further improved.
In the present invention, the amount of the coagulant to be added is not particularly limited, but the amount of the coagulant to be added is preferably 2 to 10mg/L, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10mg/L and any range of the two values, and more preferably 3 to 8mg/L, as the amount of the groundwater, the removal rate of the petroleum hydrocarbon can be remarkably increased.
In the present invention, the second mixing treatment can promote the mixing of groundwater, cyclodextrin or a derivative thereof, and a coagulant, thereby increasing the removal rate of petroleum hydrocarbons. The method of the second mixing treatment is not particularly limited as long as the mixing can be achieved, and preferably, when groundwater is remediated in situ, the method of the second mixing treatment is an aeration treatment, and the aeration flow rate of the aeration treatment is not particularly limited and may be an aeration flow rate that can be achieved by an aerator conventionally used in the art. When groundwater is repaired ex situ, the second mixing treatment method can be aeration and stirring.
In the present invention, the time of the second mixing process is preferably 20-40min, and may be, for example, 20, 25, 30, 35, 40min and any range between any two values. Under the preferred conditions, a higher petroleum hydrocarbon removal rate can be achieved while controlling the process of reducing the concentration of petroleum hydrocarbons in the groundwater within a shorter time.
In the invention, the stable state refers to that the motion state of the treated groundwater is stable, for example, when in-situ remediation is carried out, the stable state refers to that the treated groundwater naturally flows according to the original direction, and in the process, natural phenomena such as substance sedimentation and floating can occur; when ectopic remediation is carried out, the stable state means that the treated underground water is in a relatively static state, and natural phenomena such as substance sedimentation and floating can occur in the relatively static state. It will be appreciated that when ex situ remediation is carried out, the steady state groundwater supernatant may be subjected to a recharge process to re-enter the groundwater system.
In the invention, the method for stabilizing the groundwater after the second mixing treatment can be standing or no external force is applied, and only the precipitate obtained by flocculating the groundwater after the second mixing treatment with the coagulant is settled downwards. During in-situ remediation, preferably, no external force is applied to the groundwater subjected to the second mixing treatment in a stable state; in the case of ex-situ remediation, the method for stabilizing the groundwater after the second mixing treatment is preferably a standing method.
In the invention, the standing time or the time without applying external force is not particularly limited, and the groundwater system can reach a stable state; it should be understood that the petroleum hydrocarbon content in the groundwater can be gradually reduced and then stabilized as the time of standing or no external force is prolonged. Preferably, when the standing time or the time without applying external force is more than 5min, the removal rate of petroleum hydrocarbon in the groundwater can be obviously improved.
Preferably, the time for standing is 5-30min in ectopic repair. The settled groundwater may then be recharged into a groundwater system. It should be understood that the groundwater that is backwashed into the groundwater system after standing does not include sediment that settles to the bottom.
Preferably, the time for not applying external force is 5-30min during in-situ repair.
When the standing time or the time without applying external force is 5-30min, the petroleum hydrocarbon removing rate can be higher in a shorter time.
In the invention, the method can also comprise adding coagulant aids into the underground water, wherein the coagulant aids can be added together with the coagulant or into the underground water after the second mixing treatment, and the removal rate of petroleum hydrocarbon can be improved by adding the coagulant aids.
In a preferred embodiment of the present invention, the method further comprises: and adding coagulant aid into the groundwater after the second mixing treatment, performing third mixing treatment, and uniformly mixing to enable the groundwater after the third mixing treatment to reach a stable state. Although the addition of the coagulant aid at the same time as the addition of the coagulant aid can achieve a higher petroleum hydrocarbon removal rate, in the preferred case, the petroleum hydrocarbon removal rate can be further improved.
In the present invention, the coagulant aid may be selected from inorganic coagulant aids and/or organic coagulant aids, preferably, the inorganic coagulant aids are calcium oxide and/or sodium silicate, and the organic coagulant aids are polyacrylamide and/or sodium polyacrylate; further preferred is polyacrylamide. In the above preferable case, the removal rate of petroleum hydrocarbons in the groundwater can be further improved, and the removal of other impurities in the groundwater can be promoted.
In the present invention, the amount of the coagulant aid to be added may be selected from a wide range, and is preferably 0.01 to 0.2mg/L of groundwater, for example, may be 0.01, 0.02, 0.04, 0.06, 0.08, 0.10, 0.12, 0.14, 0.16, 0.18, 0.20mg/L or any range of any two values, and is more preferably 0.05 to 0.12 mg/L. In the above preferable case, the removal rate of petroleum hydrocarbons in the groundwater can be further improved, and the removal of other impurities in the groundwater can be promoted.
In the present invention, the purpose of stabilizing the groundwater after the third mixed treatment is the same as the purpose of stabilizing the groundwater after the second mixed treatment, so the method for stabilizing the groundwater after the third mixed treatment can be selected from the methods for stabilizing the groundwater after the second mixed treatment, and the detailed description thereof is omitted.
In the present invention, the time of the third mixing process is preferably 20-40min, and may be, for example, 20, 25, 30, 35, 40min and any range between any two values. Under the preferred conditions, a higher petroleum hydrocarbon removal rate can be achieved while controlling the process of reducing the concentration of petroleum hydrocarbons in the groundwater within a shorter time.
In another aspect of the invention, there is provided the use of a method as described above for the in situ or ex situ remediation of petroleum hydrocarbon contaminated groundwater.
It should be understood that the method for in-situ remediation of petroleum hydrocarbon contaminated groundwater according to the present invention refers to
The present invention will be described in detail below by way of examples.
In the following examples, reagents and materials are commercially available unless otherwise specified.
And (3) preparing a PAM solution with the weight percent of 0.1-0.3 before using the PAM, and calculating the using amount of the PAM solution according to the target adding amount when adding the PAM.
Unless otherwise specified, the following examples and comparative examples are in situ remediation methods, and the contaminated groundwater is treated directly.
Examples 1 to 3
Examples 1-3 illustrate the method of reducing the concentration of petroleum hydrocarbons in groundwater according to the invention
Adding beta-cyclodextrin into underground water polluted by petroleum hydrocarbon, adding PAC after first aeration stirring, adding PAM after second aeration stirring, applying no external force after third aeration stirring, sampling supernatant after maintaining for a certain time, and measuring and analyzing the concentration of the petroleum hydrocarbon in the supernatant.
Wherein the petroleum hydrocarbon concentration, the amount of beta-cyclodextrin, the amount of PAC and the amount of PAM added in the groundwater are shown in Table 1.
Wherein, the time of the first aeration, the second aeration, the third aeration and the non-application of external force are shown in table 2.
The results of the concentration of petroleum hydrocarbon in the ground water, the concentration of petroleum hydrocarbon in the supernatant after the treatment, and the removal rate of petroleum hydrocarbon are shown in Table 3.
TABLE 1
TABLE 2
Example 4 and example 5
Examples 4 and 5 are provided to illustrate the effect of the type of cyclodextrin or its derivatives on the method of reducing the concentration of petroleum hydrocarbons in groundwater according to the invention
Example 4: the procedure was followed as described in example 2, except that an equal amount of hydroxypropyl-beta-cyclodextrin was used instead of beta-cyclodextrin.
Example 5: the procedure was followed as described in example 2, except that an equal amount of alpha-cyclodextrin was used instead of beta-cyclodextrin.
The results of the concentration of petroleum hydrocarbon in the ground water, the concentration of petroleum hydrocarbon in the supernatant after the treatment, and the removal rate of petroleum hydrocarbon are shown in Table 3.
Example 6-example 8
Examples 6 and 7 are provided to illustrate the effect of the coagulant in the method of reducing the concentration of petroleum hydrocarbons in groundwater according to the invention
Example 6: the procedure was followed as described in example 2, except that an equal amount of PAS was used instead of PAC.
Example 7: the procedure was followed as described in example 2, except that an equal amount of aluminum sulfate was used instead of PAC.
Example 8: the procedure was followed as described in example 2, except that an equal amount of PAM was used instead of PAC.
The results of the concentration of petroleum hydrocarbon in the ground water, the concentration of petroleum hydrocarbon in the supernatant after the treatment, and the removal rate of petroleum hydrocarbon are shown in Table 3.
Examples 9 to 11
Examples 9-11 are provided to illustrate the effect of the coagulant aid in the method of reducing the concentration of petroleum hydrocarbons in subterranean water according to the present invention
Example 9: the procedure was followed as described in example 2, except that equal amounts of sodium polyacrylate were used instead of PAM.
Example 10: the procedure was followed as described in example 2, except that equal amounts of sodium silicate were used instead of PAM.
Example 11: the procedure was followed as described in example 2, except that an equal amount of PAC was used instead of PAM.
The results of the concentration of petroleum hydrocarbon in the ground water, the concentration of petroleum hydrocarbon in the supernatant after the treatment, and the removal rate of petroleum hydrocarbon are shown in Table 3.
Example 12
This example illustrates the method of reducing the concentration of petroleum hydrocarbons in groundwater according to the invention
The operation was carried out as described in example 2, except that PAC and PAM were simultaneously added to the first aerated and stirred groundwater, and then aerated and stirred for 60min, and then maintained for 30min without applying external force.
The results of the concentration of petroleum hydrocarbon in the ground water, the concentration of petroleum hydrocarbon in the supernatant after the treatment, and the removal rate of petroleum hydrocarbon are shown in Table 3.
Example 13
This example illustrates the method of reducing the concentration of petroleum hydrocarbons in groundwater according to the invention
In this embodiment, ectopic repair is performed by the following specific steps:
pumping underground water polluted by petroleum hydrocarbon, placing the underground water in a container, adding beta-cyclodextrin according to the proportion of 1.5g/L of underground water, stirring for 40min, then adding PAC according to the proportion of 5mg/L of underground water, aerating for 30min, then adding PAM according to the proportion of 0.08mg/L of underground water, aerating for 30min, standing for 30min, and sampling to determine the content of petroleum hydrocarbon in the underground water.
The results of the concentration of petroleum hydrocarbon in the ground water, the concentration of petroleum hydrocarbon in the supernatant after the treatment, and the removal rate of petroleum hydrocarbon are shown in Table 3.
Comparative example 1
This comparative example is illustrative of a reference method for reducing the concentration of petroleum hydrocarbons in groundwater
The operation was performed according to the method described in example 2, except that no PAC and PAM were added, i.e., beta-cyclodextrin was added, and after 100min of aeration stirring, no external force was applied and the mixture was maintained for 30 min.
The results of the concentration of petroleum hydrocarbon in the ground water, the concentration of petroleum hydrocarbon in the supernatant after the treatment, and the removal rate of petroleum hydrocarbon are shown in Table 3.
Comparative example 2
This comparative example is illustrative of a reference method for reducing the concentration of petroleum hydrocarbons in groundwater
The operation was performed according to the method described in example 2, except that no β -cyclodextrin was added, i.e. the amount of β -cyclodextrin added was 0, PAC was directly added to the groundwater, PAM was added after 30min of aeration stirring, and no external force was applied and maintained for 30min after 30min of aeration stirring.
The results of the concentration of petroleum hydrocarbon in the ground water, the concentration of petroleum hydrocarbon in the supernatant after the treatment, and the removal rate of petroleum hydrocarbon are shown in Table 3.
Comparative example 3
This comparative example is illustrative of a reference method for reducing the concentration of petroleum hydrocarbons in groundwater
The procedure was followed as described in example 2, except that beta-cyclodextrin, PAC and PAM were added simultaneously, and then stirred under aeration for 100min, and then maintained for 30min without applying external force.
The results of the concentration of petroleum hydrocarbon in the ground water, the concentration of petroleum hydrocarbon in the supernatant after the treatment, and the removal rate of petroleum hydrocarbon are shown in Table 3.
TABLE 3
| Numbering | The petroleum hydrocarbon content in raw water is mg/L | The petroleum hydrocarbon content in the treated water is mg/L | Removal rate% |
| Example 1 | 173.14 | 1.51 | 99.1 |
| Example 2 | 83.81 | 0.65 | 99.2 |
| Example 3 | 35.64 | 0.37 | 99.0 |
| Example 4 | 83.81 | 3.81 | 95.5 |
| Example 5 | 83.81 | 4.22 | 95.0 |
| Example 6 | 83.81 | 1.90 | 97.7 |
| Example 7 | 83.81 | 2.06 | 97.5 |
| Example 8 | 83.81 | 2.85 | 97.3 |
| Example 9 | 83.81 | 1.27 | 98.5 |
| Example 10 | 83.81 | 1.58 | 98.1 |
| Example 11 | 83.81 | 2.53 | 97.0 |
| Example 12 | 83.81 | 3.64 | 95.7 |
| Example 13 | 83.81 | 0.59 | 99.3 |
| Comparative example 1 | 83.81 | 17.57 | 79 |
| Comparative example 2 | 83.81 | 68.50 | 18.3 |
| Comparative example 3 | 83.81 | 15.80 | 81.1 |
As can be seen from Table 3, the method of the present invention can rapidly remove petroleum hydrocarbon contaminants from groundwater and can achieve a higher removal rate of petroleum hydrocarbons than the comparative example.
In a preferred embodiment of the invention, the removal of petroleum hydrocarbons from the groundwater can be further enhanced, for example by using the preferred cyclodextrin or its derivative, coagulant and/or coagulant aid, or by operating in a particular order of addition.
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. A method for reducing the concentration of petroleum hydrocarbons in groundwater, the method comprising the steps of:
(1) adding cyclodextrin or a derivative thereof into underground water, and carrying out first mixing treatment;
(2) adding a coagulant into the underground water subjected to the first mixing treatment, and performing second mixing treatment;
(3) and enabling the groundwater after the second mixing treatment to reach a stable state.
2. The method according to claim 1, wherein the cyclodextrin or derivative thereof is selected from at least one of a-cyclodextrin, β -cyclodextrin, γ -cyclodextrin, methyl- β -cyclodextrin, hydroxypropyl- β -cyclodextrin, carboxymethyl- β -cyclodextrin, hydroxyethyl- β -cyclodextrin and sulfonated- β -cyclodextrin, preferably β -cyclodextrin.
3. The method of claim 1 or 2, wherein the cyclodextrin or its derivative is added in an amount of 2-5g/L of groundwater when the petroleum hydrocarbon concentration in the groundwater is greater than or equal to 100mg/L and less than or equal to 200 mg/L;
when the concentration of petroleum hydrocarbon in the underground water is more than or equal to 50mg/L and less than 100mg/L, the adding amount of cyclodextrin or the derivative thereof is 1-2g/L of underground water;
when the concentration of petroleum hydrocarbon in the underground water is less than 50mg/L, the adding amount of the cyclodextrin or the derivative thereof is 0.2-1g/L of the underground water.
4. The method according to any one of claims 1 to 3, wherein the time of the first mixing treatment is 20 to 60 min; and/or
The time of the second mixing treatment is 20-40 min.
5. The method according to claim 1, wherein the coagulant is selected from at least one of chitosan, aluminum sulfate, ferric chloride, ferrous sulfate, polyaluminum chloride, polyaluminum sulfate, polyferric chloride and polyferric sulfate, preferably polyaluminum chloride;
preferably, the addition amount of the coagulant is 2-10mg/L of underground water, and more preferably 3-8 mg/L.
6. The method of claim 1, wherein the method further comprises: adding coagulant aid into the groundwater after the second mixing treatment, performing third mixing treatment, and uniformly mixing to enable the groundwater after the third mixing treatment to reach a stable state;
preferably, the addition amount of the coagulant aid is 0.01-0.2mg/L of underground water, more preferably 0.05-0.12 mg/L;
preferably, the time of the third mixing treatment is 20-40 min.
7. The method of claim 6, wherein the coagulant aid is selected from inorganic coagulant aids and/or organic coagulant aids;
preferably, the inorganic coagulant aid is calcium oxide and/or sodium silicate, and the organic coagulant aid is polyacrylamide and/or sodium polyacrylate;
more preferably, the coagulant aid is polyacrylamide.
8. The method according to claim 1 or 6, wherein the second mixed treated groundwater of claim 1 or the third mixed treated groundwater of claim 6 is allowed to stand still or no external force is applied.
9. The method of claim 8, wherein the time of standing or no external force application is 5min or more.
10. Use of the method of claims 1-9 for in situ or ex situ remediation of petroleum hydrocarbon contaminated groundwater.
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