CN115304194A - Method and device for treating underground water polluted by petroleum hydrocarbon - Google Patents
Method and device for treating underground water polluted by petroleum hydrocarbon Download PDFInfo
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- 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
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention provides a method and a device for treating underground water polluted by petroleum hydrocarbon. The method for treating the petroleum hydrocarbon polluted underground water comprises the following steps: step S1, carrying out electrocatalytic oxidation treatment on petroleum hydrocarbon polluted underground water to obtain electrocatalytic oxidized wastewater; and S2, carrying out deep oxidation treatment on the wastewater after the electrocatalytic oxidation. Under the condition of using the treatment method and the treatment device for the petroleum hydrocarbon polluted groundwater, the problems of low efficiency and necessity of adding an oxidant in the prior treatment technology are solved, and the effect of quickly and efficiently treating the petroleum hydrocarbon pollutants in the groundwater is realized.
Description
Technical Field
The invention relates to a technology for treating underground water polluted by petroleum hydrocarbon, in particular to a method and a device for treating underground water polluted by petroleum hydrocarbon.
Background
In the processes of oil extraction, storage, transportation, processing, petrochemical product production, gathering and transportation and the like, oil leakage, sudden leakage accidents, unreasonable discharge of oily wastewater and the like cause a large amount of petroleum hydrocarbons to enter a ground water system, the petroleum hydrocarbons contain various toxic substances such as alkane, cycloalkane and aromatic hydrocarbon and become the most common pollutants in organic pollution of ground water, and benzene, naphthalene, anthracene and derivatives thereof and the like are chemical substances with carcinogenic, teratogenic and mutational potentials and directly harm human health.
Taking a certain petroleum pollution site as an example, the organic pollution of soil and underground water at different depths is investigated and sample analysis is carried out by adopting geophysical prospecting, pit prospecting, drilling comprehensive investigation technology, fixed-depth sampling and other sampling methods. The results show that: the soil and the underground water of the whole field are polluted to different degrees, the aeration zone and the saturated zone at the depth of 30 meters are polluted, and the organic pollutants can be detected in the underground water at the depth of 50 meters. The pollution characteristics of petroleum fields are mainly characterized in that soil and underground water thereof contain high-concentration monocyclic aromatic hydrocarbon and halogenated hydrocarbon, and the concentration of the monocyclic aromatic hydrocarbon in the soil and the underground water is higher than that of other organic pollutants.
The methods used in the prior art for treating groundwater pollution include filtering groundwater to remove petroleum hydrocarbon contaminants therefrom, however, the methods are inefficient and still leave a significant amount of contaminants in the filtered water.
Disclosure of Invention
The invention mainly aims to provide a method and a device for treating underground water polluted by petroleum hydrocarbon, which aim to solve the problems that the method for treating underground water pollution in the prior art is low in efficiency and a large amount of pollutants still exist in filtered water.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for treating petroleum hydrocarbon-contaminated groundwater, comprising: step S1, carrying out electrocatalytic oxidation treatment on petroleum hydrocarbon polluted underground water to obtain electrocatalytic oxidized wastewater; and S2, carrying out deep oxidation treatment on the wastewater after the electrocatalytic oxidation.
Further, in the above treatment method, in step S1, the petroleum hydrocarbon-contaminated groundwater is lifted to electrocatalytic oxidation treatment by a vacuum extraction device, and the electrocatalytic oxidation treatment is performed on the petroleum hydrocarbon-contaminated groundwater by electrocatalytic oxidation and using an oxidizing agent; and/or in step S2, carrying out advanced oxidation treatment on the wastewater after the electrocatalytic oxidation by using an oxidant.
Further, in the above-mentioned treatment method, the anode of the electrocatalytic oxidation is a lead oxide electrode plate, the cathode is a titanium substrate, the electric field intensity applied to the electrocatalytic oxidation is preferably 100v/m to 300v/m, and the treatment time of the electrocatalytic oxidation is preferably 1 minute to 30 minutes.
Further, in the above-described processing method, step S2 further includes a process of recovering the suspended oil phase.
Further, in the above treatment method, the petroleum hydrocarbon contaminated groundwater contains gas phase waste, and before step S1, the treatment method further comprises: the petroleum hydrocarbon polluted groundwater containing the gas phase waste is subjected to gas-liquid separation to separate the gas phase waste, and preferably the gas-liquid separation is performed by using a gravity type gas-liquid separator, a baffling type gas-liquid separator or a packing type gas-liquid separator.
Further, in the above treatment method, the treatment method further comprises a process of removing volatile organic compounds in the gas phase waste by an adsorbent comprising one or more of bentonite, activated carbon, walnut shells, wood chips, zeolite, and fiber balls; preferably, bentonite and/or activated carbon is used as an adsorbent to remove volatile organic compounds from the gas phase waste.
Further, in the above processing method, the processing method further includes: pumping the petroleum hydrocarbon polluted underground water out of the ground to obtain the petroleum hydrocarbon polluted underground water containing gas phase wastes.
Further, in the above treatment method, after step S2, the treatment method further comprises performing solid-liquid separation on the wastewater treated in step S2 to remove suspended solids, preferably performing solid-liquid separation by means of filtration, and further preferably filtering the wastewater by using a filter material comprising any one or more of walnut shells, quartz sand or activated carbon.
According to another aspect of the present invention, there is provided an apparatus for treating petroleum hydrocarbon contaminated groundwater comprising: the electrocatalytic oxidation unit is used for carrying out electrocatalytic oxidation treatment on the petroleum hydrocarbon polluted underground water to generate electrocatalytic treated wastewater; and the deep oxidation unit is connected with the electrocatalytic oxidation unit and is used for deeply oxidizing the wastewater after the electrocatalytic treatment.
Further, in the above treatment equipment, an oil phase collecting device is further disposed at the top of the deep oxidation unit, and preferably, the oil phase collecting device is a chain type slag scraper.
Further, in the above treatment apparatus, the treatment apparatus further comprises a gas-liquid separation unit for gas-liquid separation of the petroleum hydrocarbon contaminated groundwater, the gas-liquid separation unit has a liquid phase outlet and a gas phase outlet, the liquid phase outlet is connected with the electrocatalytic oxidation unit, and preferably the gas-liquid separation unit is a gravity type gas-liquid separator, a deflection type gas-liquid separator or a packing type gas-liquid separator.
Further, in the above treatment apparatus, the treatment apparatus further comprises a volatile organic compound removal unit, the volatile organic compound removal unit is connected to the gas phase outlet, preferably, the volatile organic compound removal unit is an adsorption unit, and further preferably, the adsorbent of the adsorption unit is bentonite and/or activated carbon.
Further, in the above treatment apparatus, the treatment apparatus further comprises a suction unit for sucking the petroleum hydrocarbon-contaminated groundwater from the underground, the suction unit being connected to the gas-liquid separation unit.
Further, in the above processing apparatus, the processing apparatus further includes: and the solid-liquid separation unit is connected with the deep oxidation unit and is used for carrying out solid-liquid separation on the wastewater after deep oxidation, the solid-liquid separation unit is preferably a filtering device, and a filtering material of the filtering device preferably comprises any one or combination of more of walnut shells, quartz sand or activated carbon.
In the case of using the method and apparatus for treating petroleum hydrocarbon-contaminated groundwater of the present invention, the above-mentioned problems in the prior art are overcome, and the effect of rapidly and efficiently treating petroleum hydrocarbon-contaminated groundwater is achieved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiment(s) of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a flow diagram of a method for treating petroleum hydrocarbon contaminated groundwater according to the present invention;
FIG. 2 shows a flow chart of a method for treating petroleum hydrocarbon contaminated groundwater according to example 5 of the present invention.
Detailed Description
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As can be understood from the foregoing background, the prior art methods are not effective for removing petroleum hydrocarbon contaminants from groundwater, and therefore, in order to solve the problem, the present application provides a method and apparatus for treating groundwater contaminated with petroleum hydrocarbon.
In an exemplary embodiment of the present application, there is provided a method for treating petroleum hydrocarbon-contaminated groundwater, the method comprising: step S1, carrying out electrocatalytic oxidation treatment on petroleum hydrocarbon polluted underground water to obtain waste water after electrocatalytic oxidation; and S2, carrying out deep oxidation treatment on the wastewater after the electrocatalytic oxidation.
Unlike the prior art method, as shown in fig. 1, the method for treating petroleum hydrocarbon-contaminated groundwater according to the present application comprises: in the step S1, carrying out electrocatalysis reaction treatment on the petroleum hydrocarbon polluted underground water so as to ensure that most of the petroleum hydrocarbon pollutants in the underground water can be demulsified and decomposed; and in step S2, the electrocatalyzed wastewater is advanced to an advanced oxidation unit for advanced treatment, thereby completely decomposing most of the petroleum hydrocarbon substances present in the groundwater.
In some embodiments of the present application, the electrocatalytic reaction in step S1 is performed under an applied electric field. After the petroleum hydrocarbon polluted underground water enters the electrocatalytic oxidation unit, oxidation reaction is carried out at the anode under the action of an external electric field, so that petroleum hydrocarbon substances are oxidized into carbon dioxide, water and simple organic matters. In addition, at the anode, the electrode surface can generate a large amount of hydroxyl radicals (OH.) and ozone due to redox, which can directly react with petroleum hydrocarbon substances in the groundwater to be treated and generate carbon dioxide, water and simple organic substances, as shown in the following specific reaction formula, wherein the metal oxide catalyzes the electrode substances from MO x The petroleum hydrocarbon is represented by R:
after electrification, the active substance on the surface of the electrode reacts with water molecules to generate an oxidative hydroxyl radical OH:
MO x +H 2 O→MO x (OH·)+H + +e
a small portion of the oxidizing hydroxyl radicals OH "combine with lattice oxygen in the metal oxide electrode and are converted to a more oxidizing, highly oxidizing state:
MO x (OH·)→MO x O·+H + +e
the oxidizing hydroxyl radical OH & contacts with the pollutants to completely react, so that the pollutants are oxidized, and the metal oxide anode is reduced to restore the activity:
MO x (OH·)+R→MO x +MCO 2 +nH 2 O+H + +e
after undergoing the electrocatalysis reaction treatment, part of petroleum hydrocarbon pollutants in the petroleum hydrocarbon polluted underground water are decomposed, thereby obtaining the wastewater after the electrocatalysis treatment. In a subsequent step S2, the electrocatalytic treated wastewater is conveyed to an advanced oxidation unit. Because a large number of hydroxyl radicals are generated in step S1, the petroleum hydrocarbon pollutants remaining in the electrocatalytic treated wastewater can further react with the hydroxyl radicals in the electrocatalytic treated wastewater in step S2, so that almost all of the petroleum hydrocarbon pollutants are oxidized into carbon dioxide, water and non-toxic organic substances.
In conclusion, by using the method for treating petroleum hydrocarbon-contaminated groundwater of the present application, the above-mentioned problems in the prior art are overcome, and the effect of rapidly and efficiently treating petroleum hydrocarbon-contaminated groundwater is achieved. The waste water treated by the method can effectively remove more than 90 percent of petroleum hydrocarbon pollutants and suspended wastes contained in the waste water.
In some embodiments of the present application, the above processing method further comprises: in step S1, lifting the petroleum hydrocarbon polluted underground water to a treatment device through a vacuum extraction device for electrocatalytic oxidation treatment, and carrying out electrocatalytic oxidation treatment on the petroleum hydrocarbon polluted underground water through electrocatalytic oxidation and using an oxidant; and/or carrying out deep oxidation treatment on the wastewater after the electrocatalytic oxidation by using an oxidant in the step S2. In the process of using the method, the oxidant can be added into the electrocatalytic oxidation treatment process and/or the deep oxidation treatment process, so that the petroleum hydrocarbon pollutants can be rapidly subjected to oxidation reaction under the action of the oxidant to be decomposed into pollution-free dischargeable substances such as water, carbon dioxide and the like. Preferably, the oxidizing agent used in the present application is ozone, hydrogen peroxide, dichromate or hypochlorous acid. The oxidant used in the application has higher oxidation-reduction potential, and can quickly react with petroleum hydrocarbon substances in the process of electrocatalytic oxidation treatment or deep oxidation treatment, so that the decomposition of pollutants is accelerated.
In some embodiments of the present application, the anode of the electrocatalytic oxidation is a lead oxide electrode plate, the cathode is a titanium substrate, the intensity of the applied electric field of the electrocatalytic oxidation is 100v/m to 300v/m, and the treatment time of the electrocatalytic oxidation is preferably 1 minute to 30 minutes. In some embodiments, the anode of the electrocatalytic oxidation is a 1 to 15 fast lead oxide catalytic electrode plate. In the case where the anode is a plurality of sets of lead oxide electrode plates, the oxidation reaction at the anode can be simultaneously performed by the contact of the wastewater with the plurality of sets of electrode plates, and preferably, the number of anode electrode plates is 5 to 12. In the case of using the electric field strength in the above range, the petroleum hydrocarbon substances in the sewage can be rapidly decomposed. When the electric field strength is less than 100v/m, the voltage is too small so that the oxidation reaction at the anode does not proceed efficiently, and when the electric field strength is more than 300v/m, the excessive voltage makes the decomposition rate of water molecules too fast, thereby generating excessive hydrogen, thereby causing unnecessary safety hazards.
In some embodiments of the present application, the treatment time for electrocatalytic oxidation is from 1 minute to 30 minutes. After the petroleum hydrocarbon polluted underground water enters the electrocatalytic oxidation unit, the electrocatalytic oxidation treatment is started, and the treatment time is in the range of 1 minute to 30 minutes, preferably in the range of 15 minutes to 25 minutes. In the time range, the petroleum hydrocarbon polluted underground water can effectively contact with the anode and the generated hydroxyl free radicals, so that the petroleum hydrocarbon pollutants are effectively oxidized and decomposed.
In some embodiments of the present application, the deep oxidation treatment is a standing electrocatalytic oxidation of the wastewater for 1 to 40 minutes. After the electrocatalytic oxidation treatment, the wastewater after the electrocatalytic treatment is introduced into a deep oxidation unit and is left to stand for 1 to 40 minutes, so that the petroleum hydrocarbon pollutants remained in the wastewater are sufficiently reflected by hydroxyl radicals and are further oxidatively decomposed, and preferably, the rest time is in the range of 20 to 30 minutes. Within the above range, the hydroxyl radical can be sufficiently contacted with the contaminants without losing its oxidizing property. When the standing time is less than 1 minute, the contaminants cannot be completely decomposed; when the standing time is more than 40 minutes, hydroxyl radicals in the wastewater are completely consumed, so that the efficiency of wastewater treatment is reduced by an excessively long time.
In some embodiments of the present application, step S2 further comprises recovering the suspended oil phase using an oil recovery device. After the wastewater is transported to the deep oxidation unit after the electrocatalytic treatment, gas such as carbon dioxide is generated due to the reaction of the petroleum hydrocarbon substances with the anode substances and the hydroxyl radicals, and thus a large amount of water-soluble bubbles are generated. Under the lifting action of the bubbles, the undecomposed oily substances in the water are lifted to the surface of the liquid phase. The oil collecting device, such as a slag scraper, arranged on the deep oxidation unit can collect and separate the oil phase from the wastewater, so that organic pollutants in the water phase are further removed.
In some embodiments of the present application, the petroleum hydrocarbon contaminated groundwater contains gas phase waste, and prior to step S1, the treatment method further comprises: the petroleum hydrocarbon contaminated groundwater containing the gas phase waste is subjected to gas-liquid separation to separate the gas phase waste. During the pumping of groundwater from the subsurface soil, groundwater, soil gas and water vapor are typically pumped together into a filtration device. In the overlying soil of contaminated groundwater, contaminants are also typically present therein. In some embodiments of the present application, a gas-liquid mixture comprising groundwater, soil gas and water vapor is pumped up from the groundwater and soil by a water-circulating cooled vacuum pump prior to electrocatalytic reaction of petroleum hydrocarbon contaminated groundwater. The pumped gas-liquid mixture is then passed to a gas-liquid separation device, wherein the degree of vacuum of pumping is 0.01MPa to 0.05MPa, preferably 0.02MPa. In the gas-liquid separation device, a separator separates a gas-liquid mixture by using the difference of the weight of gas-liquid components. Because gas and liquid density are different, when liquid and gas flow together, liquid can receive the effect of gravity, produces a decurrent speed, and gas still flows towards original direction, and decurrent liquid adheres to and gathers together on the wall and discharges through the delivery pipe of bottom, gets into air supporting edulcoration device and carries out the edulcoration. The gas is exhausted through the upper exhaust pipe, so that the gas phase is separated from the liquid phase. Then the liquid phase (petroleum hydrocarbon polluted underground water) is led into an electrocatalytic oxidation unit for electrocatalytic reaction. In a preferred embodiment, the liquid phase of the treatment is condensed, thereby condensing the liquid in the vapour state to a liquid state, and the condensed liquid phase is then passed to an electrocatalytic oxidation unit. After undergoing gas-liquid separation, the method can effectively remove pollutants from underground water and soil gas at the same time. In some preferred embodiments of the present application, the gas-liquid separation is performed using a gravity type gas-liquid separator, a baffled gas-liquid separator, or a packed gas-liquid separator.
In some embodiments of the present application, the treatment method further comprises a process of removing volatile organic compounds from the gas phase waste by an adsorbent comprising one or more of bentonite, activated carbon, walnut shells, wood chips, zeolites, fiber balls. Preferably, bentonite and/or activated carbon is used as an adsorbent to remove volatile organic compounds from the gas phase waste. After undergoing gas-liquid separation, the process of the present application further includes introducing the gas phase waste into the adsorptive waste removal unit via a fan. In the waste removing apparatus, the gas-phase waste removes volatile organic compounds contained therein by means of adsorption, so that the gas-phase waste meets the emission standard. By the process of the present application, greater than 99% of the volatile organic compounds are removed. In a preferred embodiment, the material for adsorbing volatile organic compounds includes, but is not limited to, bentonite, activated carbon, or a combination thereof.
In some embodiments of the present application, the treatment method further comprises pumping the petroleum hydrocarbon contaminated groundwater from the ground resulting in the petroleum hydrocarbon contaminated groundwater containing gas phase waste. A gas-liquid mixture containing groundwater, soil gas and water vapor can be pumped from groundwater and soil by using a water circulating cooling type vacuum pump, wherein the vacuum degree of pumping is in the range of 0.01MPa to 0.05MPa.
In some embodiments, after step S2, the treatment method further comprises performing solid-liquid separation on the wastewater treated in step S2 to remove suspended solids, preferably performing solid-liquid separation by means of filtration, and further preferably, the filter material used for filtration comprises any one or more of walnut shells, quartz sand or activated carbon. After the wastewater is treated by the deep oxidation unit, the wastewater is introduced into a filtration unit. The wastewater is subjected to solid-liquid separation in a filtration unit, thereby removing solid insoluble substances or undecomposed organic substances contained therein.
In another exemplary embodiment of the present application, there is provided a treatment facility for petroleum hydrocarbon contaminated groundwater, the treatment facility comprising an electrocatalytic oxidation unit for electrocatalytic oxidation treatment of petroleum hydrocarbon contaminated groundwater to produce electrocatalytic treated wastewater; the deep oxidation unit is connected with the electrocatalytic oxidation unit and is used for deep oxidation of the wastewater after electrocatalytic treatment. By using the apparatus for treating petroleum hydrocarbon-contaminated groundwater of the present application, the problems of the prior art are overcome, and the effect of rapidly and efficiently treating petroleum hydrocarbon contaminants in groundwater is achieved. The wastewater treated by the apparatus of the present application can effectively remove 90% of the wastewater contained therein by hydrocarbon contaminants and suspended waste.
In some embodiments of the present application, the anode of the electrocatalytic oxidation unit is a lead oxide catalytic electrode plate, and the cathode is a titanium substrate. In some embodiments, the anode for electrocatalytic oxidation is 1 to 15 lead oxide catalytic electrode plates. Under the condition that the anode is provided with a plurality of lead oxide catalytic electrode plates, the oxidation reaction at the anode can be simultaneously carried out through the contact of the wastewater and a plurality of groups of electrode plates, thereby realizing the rapid catalytic oxidation of the petroleum hydrocarbon pollutants in the wastewater. And because a plurality of groups of anode electrode plates are used, a large amount of hydroxyl radicals can be rapidly generated. Preferably, the anode electrode plates are 5 to 12 pieces.
In some embodiments of the present application, the top of the deep oxidation unit is further provided with an oil phase collecting device, and the oil phase collecting device is a chain type slag scraper. After the wastewater is transported to the deep oxidation unit after the electrocatalytic treatment, gas such as carbon dioxide is generated due to the reaction of the petroleum hydrocarbon substances with the anode substances and the hydroxyl radicals, and thus a large amount of water-soluble bubbles are generated. Under the lifting action of the bubbles, the undecomposed oily substances in the water are lifted to the surface of the liquid phase. The oil collecting device, such as a slag scraper, arranged on the deep oxidation unit can collect and separate the oil phase from the wastewater, so that organic pollutants in the water phase are further removed.
According to a further embodiment, the treatment apparatus further comprises a gas-liquid separation unit for gas-liquid separation of the petroleum hydrocarbon contaminated groundwater, the gas-liquid separation unit having a liquid phase outlet and a gas phase outlet, the liquid phase outlet being connected to the electrocatalytic oxidation unit, preferably the gas-liquid separation unit is a gravity type gas-liquid separator, a baffled type gas-liquid separator or a packed type gas-liquid separator. Before carrying out electrocatalytic reaction on the petroleum hydrocarbon polluted underground water, pumping a gas-liquid mixture containing underground water, soil gas and water vapor from the underground water and the soil by a water circulation cooling type vacuum pump. The pumped gas-liquid mixture is then passed to a gas-liquid separation device, wherein the degree of vacuum of pumping is 0.01MPa to 0.05MPa, preferably 0.02MPa. In the gas-liquid separation device, a separator separates a gas-liquid mixture by using the difference of the weight of gas-liquid components. Because gas and liquid density are different, when liquid and gas flow together, liquid can receive the effect of gravity, produces a decurrent speed, and gas still flows towards original direction, and decurrent liquid adheres to and gathers together on the wall and discharges through the delivery pipe of bottom, gets into air supporting edulcoration device and carries out the edulcoration. The gas is exhausted through the upper exhaust pipe, so that the gas phase is separated from the liquid phase. Then the liquid phase (petroleum hydrocarbon polluted underground water) is introduced into an electrocatalytic oxidation unit for electrocatalytic reaction. In a preferred embodiment, the separated liquid phase is condensed, thereby condensing the liquid in the vapor state to a liquid state, and then the condensed liquid phase is passed to an electrocatalytic oxidation unit. After undergoing gas-liquid separation, the device of the application can effectively remove pollutants from underground water and soil gas simultaneously. In the embodiment using the apparatus of the present application including the gas-liquid separation unit, more than 95% of petroleum hydrocarbon contaminants and suspended waste contained therein can be effectively removed, and 99% of gaseous organic waste contained therein can be removed.
In a further embodiment, the treatment apparatus further comprises a voc removal unit, the voc removal unit being connected to the gas phase outlet, preferably the voc removal unit is an adsorption unit, further preferably the adsorbent of the adsorption unit is bentonite and/or activated carbon. In the waste removing apparatus, the gas-phase waste removes volatile organic compounds contained therein by means of adsorption, so that the gas-phase waste meets the emission standard. In a preferred embodiment, the material for adsorbing volatile organic compounds includes, but is not limited to, bentonite, activated carbon, or a combination thereof.
In some embodiments, the treatment facility further comprises a suction unit for sucking the petroleum hydrocarbon contaminated groundwater from the underground, the suction unit being connected to the gas-liquid separation unit. A gas-liquid mixture containing groundwater, soil gas and water vapor can be pumped from groundwater and soil by using a water circulating cooling type vacuum pump, wherein the vacuum degree of pumping is in the range of 0.01MPa to 0.05MPa.
According to a further embodiment of the application, the treatment equipment further comprises a solid-liquid separation unit connected with the deep oxidation unit for carrying out solid-liquid separation on the wastewater after deep oxidation, preferably, the solid-liquid separation unit is a filtering device, and preferably, a filter material of the filtering device comprises any one or more of walnut shells, quartz sand or activated carbon. After the wastewater is treated by the deep oxidation unit, the wastewater is introduced into a filtration unit. The wastewater is subjected to a filtration unit to remove undecomposed organic matter or insoluble solids therefrom.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
Pumping underground water polluted by petroleum hydrocarbon out of the ground, then introducing the underground water polluted by the petroleum hydrocarbon into an electrocatalytic oxidation unit, and detecting that the oil content in the wastewater is 1000mg/L at an inlet of the electrocatalytic oxidation unit. In the electrocatalytic oxidation unit, the anode used was 1 lead oxide catalytic electrode plate, and the cathode was a titanium substrate. The wastewater was subjected to electrocatalytic oxidation at a voltage of 5 v for 30 minutes. The resulting electrocatalytic treated wastewater is then introduced into a deep oxidation unit.
In the deep oxidation unit, the wastewater was treated by standing for 1 minute. After a large amount of petroleum hydrocarbon substances and lighter suspended substances contained in the wastewater are lifted to the surface layer of the liquid surface by the bubbles, the petroleum hydrocarbon and the suspended substances are recovered by the slag scraping and oil collecting device. And detecting the oil content in the treated wastewater, wherein the oil content is less than 0.5mg/L.
Example 2
And pumping a gas-liquid mixture containing underground water, soil gas and water vapor from the underground water and the soil by using a water circulating cooling type vacuum pump, wherein the pumping vacuum degree is 0.05MPa. The gas-liquid mixture is introduced into a gas-liquid separation device. The gas-liquid mixture is separated into a gas phase and a liquid phase by a gas-liquid separation device, and the gas phase is introduced into an adsorption type waste removal device. The content of volatile organic compounds in the gas phase was measured to be 600mg/L at the inlet of the adsorption type waste removing apparatus. In the adsorption type waste removing device, volatile organic compounds in the gas phase are removed by the adsorption effect of the bentonite-activated carbon composite adsorbent. The content of volatile organic compounds in the gas phase was measured at the outlet to be 0.55mg/L.
And introducing the liquid phase obtained by the gas-liquid separation device into an electrocatalytic oxidation unit, and detecting that the oil content in the liquid phase is 1000mg/L at an inlet of the electrocatalytic oxidation unit. In the electrocatalytic oxidation unit, 5 lead oxide catalytic electrode plates were used as the anode, and a titanium substrate was used as the cathode. The wastewater was subjected to electrocatalytic oxidation at a voltage of 5 v for 1 minute. The resulting electrocatalytic treated wastewater is then introduced into a deep oxidation unit.
In the deep oxidation unit, the wastewater is treated for 40 minutes by standing. After a large amount of petroleum hydrocarbon substances and lighter suspended substances contained in the wastewater are lifted to the surface layer of the liquid level by bubbles, the petroleum hydrocarbon and the suspended substances are recovered by a slag scraping and oil collecting device. The wastewater is then introduced into a filtration unit. And detecting the oil content of the treated wastewater, wherein the oil content is 0.73mg/L.
Example 3
And pumping a gas-liquid mixture containing underground water, soil gas and water vapor from the underground water and the soil by using a water circulating cooling type vacuum pump, wherein the pumping vacuum degree is 0.01MPa. The gas-liquid mixture is introduced into a gas-liquid separation device. The gas-liquid mixture is separated into a gas phase and a liquid phase by a gas-liquid separation device, and the gas phase is introduced into an adsorption type waste removal device. The content of volatile organic compounds in the gas phase was measured at the inlet of the adsorption type waste removing apparatus to be 800mg/L. In the adsorption type waste removing device, volatile organic compounds in the gas phase are removed by the adsorption effect of the bentonite-activated carbon composite adsorbent. The content of volatile organic compounds in the gas phase was measured at the outlet to be 0.5mg/L.
And introducing the liquid phase obtained by the gas-liquid separation device into an electrocatalytic oxidation unit, and detecting that the oil content in the liquid phase is 1000mg/L at an inlet of the electrocatalytic oxidation unit. In the electrocatalytic oxidation unit, 8 lead oxide catalytic electrode plates were used as the anode, and a titanium substrate was used as the cathode. The wastewater was subjected to electrocatalytic oxidation at a voltage of 5 v for 20 minutes. The resulting electrocatalytic treated wastewater is then introduced into a deep oxidation unit.
In the deep oxidation unit, the wastewater is treated for 20 minutes by standing. The wastewater is then introduced into a filtration unit.
In the filtering unit, the combination of walnut shells and quartz sand is used as a filtering material to filter the wastewater. And detecting the oil content in the filtered wastewater, wherein the oil content is 0.65mg/L.
Example 4
And pumping a gas-liquid mixture containing underground water, soil gas and water vapor from the underground water and the soil by using a water circulation cooling type vacuum pump, wherein the pumping vacuum degree is 0.04MPa.
The gas-liquid mixture obtained by suction was passed to an electrocatalytic oxidation unit, and the oil content in the liquid phase was measured at the inlet of the electrocatalytic oxidation unit to be 1000mg/L. In the electrocatalytic oxidation unit, 5 lead oxide catalytic electrode plates were used as the anode, and a titanium substrate was used as the cathode. The wastewater was subjected to electrocatalytic oxidation at a voltage of 780mg/L V for 10 minutes. The resulting electrocatalytic treated wastewater is then introduced into a deep oxidation unit.
In the deep oxidation unit, the wastewater is treated for 10 minutes by standing. After a large amount of petroleum hydrocarbon substances and lighter suspended substances contained in the wastewater are lifted to the surface layer of the liquid surface by the bubbles, the petroleum hydrocarbon and the suspended substances are recovered by the slag scraping and oil collecting device. The wastewater is then introduced into a filtration unit.
In the filtering unit, the combination of walnut shells and quartz sand is used as a filtering material to filter the wastewater. And detecting the oil content in the filtered wastewater, wherein the oil content is 0.8mg/L.
Example 5
As shown in fig. 2, in step 201, a gas-liquid mixture containing groundwater, soil gas and water vapor is pumped up from groundwater and soil by a water circulation cooling type vacuum pump, wherein the degree of vacuum for pumping is 0.02MPa. In step 202, the gas-liquid mixture is passed into a gas-liquid separation device. The gas-liquid mixture is separated into a gas phase and a liquid phase by a gas-liquid separation device, and the gas phase is introduced into an adsorption type waste removal device. In step 203, the content of volatile organic compounds in the gas phase was measured to be 700mg/L at the inlet of the adsorption type waste removing device. In the adsorption type waste removing apparatus, volatile organic compounds in the gas phase are removed by adsorption of the bentonite-activated carbon composite adsorbent. The content of volatile organic compounds in the gas phase was detected at the outlet to be less than 0.5mg/L.
In step 204, the liquid phase obtained from the gas-liquid separation device is passed to an electrocatalytic oxidation unit, and the oil content in the liquid phase is detected at the inlet of the electrocatalytic oxidation unit to be 1000mg/L. In the electrocatalytic oxidation unit, 10 lead oxide catalytic electrode plates were used as the anode, and a titanium substrate was used as the cathode. The wastewater was subjected to electrocatalytic oxidation at a voltage of 5 v for 15 minutes. The resulting electrocatalytic treated wastewater is then introduced into a deep oxidation unit.
In step 205, the wastewater is treated by standing for 30 minutes in the deep oxidation unit. In step 206, after a large amount of petroleum hydrocarbons and lighter suspended substances contained in the wastewater are lifted to the surface layer of the liquid surface by the bubbles, the petroleum hydrocarbons and suspended substances are recovered by the slag scraping and oil collecting device. The wastewater is then introduced into a filtration unit.
In step 207, the wastewater is filtered in a filter unit using a combination of walnut shells and quartz sand as filter materials. And detecting the oil content in the filtered wastewater, wherein the oil content is 0.31mg/L.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. A method for treating petroleum hydrocarbon-contaminated groundwater, comprising:
step S1, carrying out electrocatalytic oxidation treatment on the petroleum hydrocarbon polluted underground water to obtain electrocatalytic oxidized wastewater;
and S2, carrying out deep oxidation treatment on the wastewater after the electrocatalytic oxidation.
2. The processing method according to claim 1,
in the step S1, the petroleum hydrocarbon polluted underground water is lifted to the electrocatalytic oxidation treatment by a vacuum extraction device, and the electrocatalytic oxidation treatment is carried out on the petroleum hydrocarbon polluted underground water by electrocatalytic oxidation and using an oxidant; and/or
In the step S2, the wastewater after the electrocatalytic oxidation is subjected to deep oxidation treatment by using an oxidant.
3. The treatment method according to claim 1, wherein the anode of the electrocatalytic oxidation is a lead oxide electrode plate, the cathode is a titanium substrate, the electric field intensity applied to the electrocatalytic oxidation is preferably 100v/m to 300v/m, and the treatment time of the electrocatalytic oxidation is preferably 1 minute to 30 minutes.
4. The treatment method according to claim 1, wherein the step S2 further comprises a process of recovering the suspended oil phase.
5. The treatment method according to claim 1 or 4, wherein the petroleum hydrocarbon contaminated groundwater contains gas phase waste, and before the step S1, the treatment method further comprises: the petroleum hydrocarbon-contaminated groundwater containing the gas-phase waste is subjected to gas-liquid separation to separate the gas-phase waste, preferably, the gas-liquid separation is performed using a gravity type gas-liquid separator, a deflection type gas-liquid separator, or a packing type gas-liquid separator.
6. The treatment method of claim 5, further comprising a process of removing volatile organic compounds from the gas phase waste by an adsorbent comprising one or more of bentonite, activated carbon, walnut shells, wood chips, zeolites, fiber balls; preferably, bentonite and/or activated carbon is used as an adsorbent to remove volatile organic compounds from the gas phase waste.
7. The processing method according to claim 5, characterized in that it further comprises: pumping the petroleum hydrocarbon contaminated groundwater from the ground to obtain the petroleum hydrocarbon contaminated groundwater containing the gas phase waste.
8. The treatment method according to claim 1, wherein after the step S2, the treatment method further comprises performing solid-liquid separation on the wastewater treated in the step S2 to remove suspended solids, preferably performing the solid-liquid separation by means of filtration, and further preferably performing the filtration by using a filter material comprising any one or more of walnut shells, quartz sand or activated carbon.
9. An apparatus for treating petroleum hydrocarbon contaminated groundwater comprising:
the electrocatalytic oxidation unit is used for carrying out electrocatalytic oxidation treatment on the petroleum hydrocarbon polluted underground water to generate electrocatalytic treated wastewater; and
and the deep oxidation unit is connected with the electrocatalytic oxidation unit and is used for deeply oxidizing the wastewater subjected to electrocatalytic treatment.
10. The treatment plant according to claim 9, wherein the top of the deep oxidation unit is further provided with an oil phase collection device, preferably the oil phase collection device is a chain scraper.
11. The treatment apparatus according to claim 9, further comprising a gas-liquid separation unit for gas-liquid separation of the petroleum hydrocarbon contaminated groundwater, the gas-liquid separation unit having a liquid phase outlet and a gas phase outlet, the liquid phase outlet being connected to the electrocatalytic oxidation unit, preferably the gas-liquid separation unit is a gravity type gas-liquid separator, a baffled gas-liquid separator, or a packed gas-liquid separator.
12. The treatment apparatus according to claim 11, further comprising a voc removal unit connected to the gas phase outlet, preferably the voc removal unit is an adsorption unit, further preferably the adsorbent of the adsorption unit is bentonite and/or activated carbon.
13. The treatment facility of claim 11, further comprising a suction unit for sucking the petroleum hydrocarbon contaminated groundwater from the ground, the suction unit being connected to the gas-liquid separation unit.
14. The processing apparatus according to claim 9, characterized in that the processing apparatus further comprises:
and the solid-liquid separation unit is connected with the deep oxidation unit and is used for carrying out solid-liquid separation on the wastewater after deep oxidation, preferably, the solid-liquid separation unit is a filtering device, and preferably, a filtering material of the filtering device comprises any one or combination of more of walnut shells, quartz sand or activated carbon.
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