CN105731628A - In-situ chemical oxidation repair system and method for underground water polluted by hydrochloric ether - Google Patents
In-situ chemical oxidation repair system and method for underground water polluted by hydrochloric ether Download PDFInfo
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- CN105731628A CN105731628A CN201610082033.4A CN201610082033A CN105731628A CN 105731628 A CN105731628 A CN 105731628A CN 201610082033 A CN201610082033 A CN 201610082033A CN 105731628 A CN105731628 A CN 105731628A
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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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
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/782—Ozone generators
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/784—Diffusers or nozzles for ozonation
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- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides an in-situ chemical oxidation repair method for underground water polluted by hydrochloric ether through micro-nano ozone bubbles, and an in-situ chemical oxidation repair system for underground water polluted by hydrochloric ether.The system comprises an ozone preparation system, a micro-nano ozone bubble water preparation system, an enhancer injection system, a waste gas collection processing system and underground injection, monitoring and air extracting systems.The ozone preparation system and the micro-nano ozone bubble water preparation system are connected through a pipeline, the water gas collection processing system and the underground air extracting system through a pipeline, micro-nano ozone bubble water preparation system and the enhancer injection system are connected into the underground injection system through a pipeline, and the underground water polluted by hydrochloric ether is processed in situ.A using method of the processing system is provided.The in-situ chemical oxidation repair system and method for underground water polluted by hydrochloric ether are used for repairing underground water polluted by hydrochloric ether, and repair efficiency is greatly improved; the system can be used in a mobile mode, controllers are placed in a container, and automation can be achieved.
Description
Technical field
The present invention relates to a kind of equipment for underground water pollution reparation and using method thereof.More particularly, the present invention relates to a kind of in situ chemical oxidation repair system for the pollution of subsoil water chlorohydrocarbon and method.
Background technology
Chlorinated hydrocarbon is high-efficiency cleaning chemicals, it is widely used in the fields such as aircraft engine, metal parts, electronic component and laundry industry, groundwater environment pollution is caused owing to unordered discharge and/or storage facility leak, it is pollutant common in subsoil water, it is not degradable, and there is " three cause " effect, in subsoil water, chlorohydrocarbon pollution control causes wide sending out to pay close attention to.Chlorohydrocarbon belongs to heavy non-aqueous phase liquids (DNAPL), density is big, viscosity is low, strong in underground migration ability, aeration zone and zone of saturation is entered under gravity after entering underground environment, easily assembling in subsoil water water barrier, become a persistency and the very strong polluter of hazardness, thoroughly repairing that chlorohydrocarbon pollutes has suitable difficulty.
The restorative procedure being presently used for chlorohydrocarbon underground water pollution has chemical redemption, biological restoration and peripheral doses method etc., and biological renovation method is mainly by the pollutant in microbial degradation subsoil water.Physical method includes gas phase extracting, underground water aeration and thermal desorption technology etc., utilizes the boiling characteristics of chlorinated hydrocarbon contaminants, extracts volatile organic matter from subsoil water and soil, and extracting is collected behind ground and processes.Chemical repair method includes the technology such as chemical oxidation and electronation, chemical oxidation or reduction technique refer to and inject in subsoil water by oxidant or reducing agent, by aoxidizing or reduction reaction makes the pollutant in subsoil water be destroyed within a short period of time, be degraded into nontoxic or that harm is less material.Chemical repair method is quick because of it, react thorough and less costly, becomes the restorative procedure that in subsoil water chlorohydrocarbon reparation field, development potentiality is huge.
Organic carbon in chlorohydrocarbon can be oxidized to carbon dioxide and water by subsoil water in situ chemical oxidation technology, organochlorine is discharged with the form of chloride or chlorine, because its process thoroughly, the response time is short, less costly and obtains broad development, is one of major technique of repairing of subsoil water chlorohydrocarbon.The oxidant of the in situ chemical oxidation technology being currently employed for chlorohydrocarbon mainly has 4 kinds: hydrogen peroxide, permanganate, activation persulfuric acid are received and ozone.Wherein ozone is because having very strong Oxidation, its electrode potential is 2.07V, substantial amounts of Superoxide radicalanion and hydroxyl radical free radical can be produced, can be used for the dissolving phase in exhaustive oxidation subsoil water, Adsorption Phase and nonaqueous phase chlorinated hydrocarbon contaminants, environmental disturbances is less, and generate without secondary by-product, receive extensive concern.But ozone generally moves with the separated foam form of grade particle diameter in injecting subsoil water process at present, and the bubble persistent period is short, it is insufficient to react, mass-transfer efficiency is low, and coverage is less, and remediation efficiency is in urgent need to be improved.
Owing to lacking corresponding equipment, cause that the enforcement of this kind of reparation there is also great difficulty.Polluted underground water is strengthened the method and system of in-situ immobilization by Chinese patent CN102583712B disclosed in prior art with micro-nano bubble, it is directly use air as bubble source, its mechanism of action is to promote the degraded of pollutant aerobic bioreactor, and the time of required reparation is longer；And the present invention utilizes ozone to originate as bubble, mainly by its oxidative degradation to pollutant, it is considered that, oxidation recovery technique is higher than the remediation efficiency of bioremediation technology, and repairing effect is more thorough.It addition, this patent be not provided with waste gas collecting system, it is possible to there is the risk of secondary pollution.
Summary of the invention
For the reparation of chlorohydrocarbon underground water pollution, the present invention adopts ozone as micro-nano bubble source, and adds prooxidant, can further improve remediation efficiency, adds gas sampling simultaneously and processes absorption system, it is to avoid causes secondary pollution.
Current ozone generally moves with the separated foam form of millimeter-Centimeter Level particle diameter in injecting subsoil water process, and the bubble persistent period is short, it is insufficient to react, mass-transfer efficiency is low, and coverage is less, and remediation efficiency is in urgent need to be improved.
We have discovered that in recent years, by reducing the bubble diameter of ozone, improve ozone bubbles anelasticity in subsoil water, strengthen it and dissolve mass transfer ability and gas dissolution rate, increase the generation amount of free radical, it is the effective ways improving ozone oxidation subsoil water chlorinated hydrocarbon contaminants, is the method applying more reduction ozone bubbles particle diameter in recent years by ozone bubbles micro-nanoization.After ozone micro-nanoization, the diameter of bubble becomes between 60nm to 50 μm, owing to particle diameter is small, under the effect of viscous force and buoyancy, can stopping the longer time at water body, maximum duration is up to more than the several months, and under the effect of groundwater flow, expand and groundwater pollutant contact range.When ozone micro-nano bubbles burst moment, due to the acute variation that gas-liquid interface disappears, the chemical energy of savings is sharply discharged by the high concentration ion gathered on interface, the substantial amounts of hydroxyl radical free radical of generation can be excited, hydroxyl radical free radical has the oxidation-reduction potential (2.8V) of superelevation, the chlorinated hydrocarbon contaminants in the superpower Oxidation degradable water of its generation.Owing to the micro-nano bubble diameter of ozone is minimum, self pressurized effect is notable, can so that more gas be dissolved in water through bubble interface, when even if this characteristic makes ozone microbubble, in water body, gas content reaches supersaturated condition, may continue to carry out the mass transport process of gas and keep efficient mass-transfer efficiency, high mass-transfer efficiency provides dissolved oxygen high in subsoil water, it is possible to promote the biodegradation of chlorinated hydrocarbon contaminants further.
Therefore, in order to improve remediation efficiency, can pass through to reduce ozone bubbles particle diameter, use the ozone bubbles of micro/nano level, increase dissolved ozone concentration, excite more hydroxyl radical free radical, extend ozone and reactant time of contact, improve mass-transfer efficiency, add ozone oxidation hardening agent simultaneously, improve oxidation remediation efficiency.
Present invention solves the technical problem that and be to provide a kind of process system, it can use the subsoil water that chlorohydrocarbon is polluted by micro-nano ozone bubbles to process, can overcome that the persistent period that in prior art, ozone exists as oxidant is short, it is insufficient to react, mass-transfer efficiency is low, coverage is less, the technical problem that remediation efficiency is in urgent need to be improved.
On the other hand, the technology of the present invention solves problem: reduce ozone particle diameter by manufacturing micro-nano ozone bubbles, increase substantially dissolved ozone concentration, excite more hydroxyl radical free radical, extend ozone time of staying in water, expand ozone and the contact range of chlorinated hydrocarbon contaminants in subsoil water, improve mass-transfer efficiency；By adding ozone-enhanced dose, improve the ozone oxidation removal efficiency to chlorinated hydrocarbon contaminants；Systemic absorption system is processed, it is prevented that the secondary pollution caused of ozone and volatile organic contaminant by being equipped with gas sampling.
In order to solve described technical problem, the present invention provides a kind of and processes the in situ chemical oxidation restorative procedure that subsoil water chlorohydrocarbon pollutes, it is characterised in that described method is by micro-nano ozone bubbles, subsoil water to be repaired；Preferably, described micro-nano ozone bubbles is of a size of 60nm to 50 μm.
Wherein, described method comprises the steps:
(1) Ozone generation step: prepare ozone gas；
(2) the soaked forming step of micro-nano ozone gas: ozone gas prepared by step (1) is formed micro-nano air-bubble, and carry out with step (1) circulation, until micro-nano bubble Measuring Ozone Concentration in Water reaches appointment scope, use it for the reparation of chlorohydrocarbon in subsoil water；
(3) hardening agent implantation step: when the soaked injection subsoil water of the micro-nano ozone gas that step (2) prepares, simultaneously hardening agent is injected in subsoil water；And
(4) gas sampling process step: when in soil and groundwater organic pollutant more than 1000mg/m3, carry out gas sampling process.
Wherein, the appointment of the micro-nano bubble Measuring Ozone Concentration in Water of described method step (2) ranges for 1mg/L-1.5mg/L, and the micro-nano ozone bubbles of generation is of a size of 60nm to 50 μm.
A kind of in situ chemical oxidation repair system polluted for subsoil water chlorohydrocarbon, described system includes: Ozone generation system, the soaked preparation system of micro-nano ozone gas, hardening agent injected system, gas sampling process system and down-hole is injected, monitored and extract system；Being connected by pipeline between wherein said Ozone generation system with the soaked preparation system of micro-nano ozone gas, gas sampling is processed system and is connected by pipeline with down-hole extract system；The soaked preparation system of micro-nano ozone gas and hardening agent injected system are connected in downhole injection system by pipeline, the subsoil water that in-situ treatment is polluted by chlorohydrocarbon.
Wherein, described system farther includes central control system, and each system is coupled in order to control each system.
Wherein, described Ozone generation system includes ozone water preparation device, water feed apparatus and ozone generating-device.
Wherein, the described soaked preparation system of micro-nano ozone gas includes micro-nano ozone bubbles water preparation apparatus, micro-nano ozone bubbles water generating device and ozone-detecting element.
Wherein, described hardening agent injected system includes hardening agent injection device and agitating device；Down-hole inject, monitoring and extract system include inject well, monitoring well, water quality parameter instrument, extraction well, organic pollutant detector, ozone detector.
Wherein, described gas sampling process system includes gas-liquid separation device, exhaust gas absorption device and waste collecting device.
Wherein, between described Ozone generation system with the soaked preparation system of micro-nano ozone gas, extraction line by being provided with effusion meter, vacuum pump and water pump is connected and is circulated；Preferably, the ozone gas that Ozone generation system produces is drawn into the soaked preparation system of micro-nano ozone gas by being connected with the extraction line being provided with flow monitoring device and vacuum pump, and the ozone gas that Ozone generation system produces is soaked by pumping in the soaked preparation system of micro-nano ozone gas equipped with the extraction tube of water pump；The soaked preparation system of micro-nano ozone gas produce micro-nano ozone gas is soaked, ozone gas and ozonated water mixture are pumped back in Ozone generation system by being provided with the extraction tube of water pump, thus being circulated between two systems.
Wherein, described ozone generating-device is electrolysis type ozone generator；The ozone bubbles Measuring Ozone Concentration in Water that described micro-nano ozone bubbles water generating device produces is 1mg/L-1.5mg/L, and the micro-nano ozone bubbles of generation is of a size of 60nm to 50 μm.
The present invention also provides for another kind of technical scheme, and a kind of in situ chemical oxidation repair system polluted for subsoil water chlorohydrocarbon, described Ozone generation system includes Ozone Water preparation tank, water inlet and ozonator, and ozonator is placed in Ozone Water preparation tank；The described soaked preparation system of micro-nano ozone gas includes the soaked preparation tank of micro-nano ozone gas, micro-nano ozone bubbles water generator and ozone detector, micro-nano ozone bubbles water generator is placed in the soaked preparation tank of micro-nano ozone gas, and ozone detector is placed in the soaked preparation tank of micro-nano ozone gas for monitoring ozone concentration in tank；Described Ozone generation system is connected by extraction line with the described soaked preparation system of micro-nano ozone gas, is provided with effusion meter, water pump and/or vacuum pump on extraction line, makes to circulate between the two；Described hardening agent injected system includes hardening agent and injects tank and agitator disposed within, and this system is connected by pipeline with injecting well；Described down-hole is injected, monitoring and extract system include injecting well, monitoring well and being placed in the water quality parameter instrument in monitoring well, extraction well and be placed in the ozone detector in extraction well and organic pollutant detector；Described gas sampling processes system and includes gas and liquid collecting device, liquid waste collector and charcoal trap；Described extraction well is connected with gas-liquid separator by being provided with the extraction line of piezometer, effusion meter and vacuum pump, and gas-liquid separator is connected with liquid waste collector in order to drain, and gas-liquid separator is connected to locate process gases with charcoal trap；Above-mentioned all devices carries out parameter setting each through the automatic control cabinet of central control system, runs control and data storage.
Wherein, inject well, monitoring well and extraction well and all open sieve, wherein inject under well and monitoring well screen pipe water water level located underground, on the screen casing water water level located underground of extraction well；The width of preferred sieve aperture is 0.5-1.5mm；It is highly preferred that the material of screen casing is PVC or steel pipe.
The present invention also provides for a kind of method using above-mentioned process system, and described method comprises the steps:
Ozone gas and air-bubble ozoniferous is prepared by Ozone generation system, it is introduced into that the soaked preparation system of micro-nano ozone gas prepares micro-nano ozone gas soaked, afterwards soaked for micro-nano ozone gas, ozone gas and ozonated water mixture are imported to Ozone generation system to be circulated, until micro-nano ozone bubbles Measuring Ozone Concentration in Water reaches requirement；It is then poured in the subsoil water that pending chlorinated hydrocabon pollutes；By hardening agent injected system, hardening agent is injected in the subsoil water that pending chlorinated hydrocabon pollutes, by water quality parameter in underground monitoring and extract system monitoring subsoil water and ozone and organic pollutant concentration；By quality of groundwater Parameters variation, adjust the soaked injection rate with hardening agent of ozone gas.When ozone and organic pollutant concentration exceed particular value, start gas sampling process system and the waste gas produced is collected and processes.
Wherein, when in the soaked preparation system of micro-nano ozone gas, ozone concentration is be more than or equal to 1-1.5mg/L, when micro-nano bubble size is 60nm to 50 μm, it is injected into soaked for micro-nano ozone gas in injection well；Preferably, the monitoring numerical value shown when organic pollutant detector is more than 1000mg/m3, the concentration of Ozone Monitor is more than 0.10mg/m3Time, start gas sampling and process system.
Beneficial effects of the present invention is as follows:
(1) the invention provides system and the application process that a kind of in situ chemical oxidation polluted for subsoil water chlorohydrocarbon is repaired, it is possible to process the chlorinated hydrocarbon contaminants in subsoil water, including the chlorinated hydrocarbon contaminants dissolving phase, Adsorption Phase and nonaqueous phase.
(2) the micro-nano ozone bubbles that the present invention uses particle diameter to be 60nm to 50 μm is as the material of oxidation chlorohydrocarbon, dramatically increase ozone dissolubility in water body, excite more hydroxyl radical free radical, extend the ozone time of staying in water, expand ozone and the sphere of action of chlorinated hydrocarbon contaminants in subsoil water, add mass-transfer efficiency, remediation efficiency can be increased substantially.
(3) present invention uses the micro-nano bubble hardening agent of ozone, system comprises the injection device of the strengthening micro-nano bubble oxidation effectiveness of ozone, in the micro-nano bubble injection process of ozone, inject liquid reinforced dose, the oxidability of micro-nano ozone bubbles can be increased further, increase considerably the hydroxyl radical free radical in subsoil water, strengthen repairing effect.
(4) present invention is equipped with gas sampling and processes system, so that collect and process can releasable ozone and volatile organic thing, it is to avoid environment is caused secondary pollution.
(5) present invention removableization uses.Controller is all placed in container, it is possible to mobile use between different places.
(6) automatization can be realized.The processes such as the generation of micro-nano ozone bubbles, prooxidant injection, gas phase adsorption are controlled by digital control implement.
(7) present invention is reduced in described scope indeed through by ozone particle diameter, is used for aoxidizing chlorinated hydrocarbon contaminants in subsoil water, improves remediation efficiency.
Accompanying drawing explanation
Fig. 1: a kind of detailed description of the invention of the in situ chemical oxidation repair system that the present invention pollutes for subsoil water chlorohydrocarbon；
Wherein: 1-Ozone Water preparation tank, 2-water inlet, 3-ozonator, the first-class gauge of 41-, 42-second gauge, 51-the first vacuum pump, 52-the second vacuum pump, 6-extraction line, 71-the first water pump, 72-the second water pump, 73-the 3rd water pump, the soaked preparation tank of the micro-nano ozone gas of 8-, the micro-nano ozone bubbles water generator of 9-, 101-the first ozone detector, 102-the second ozone detector, 11-hardening agent injects tank, 12-agitator, 13-piezometer, 14-gas-liquid separator, 15-liquid waste collector, 16-charcoal trap, 17-injects well, 18-monitors well, 19-water quality parameter instrument, 20-organic pollutant detector, 21-extraction well, 22-automatic control cabinet, 23-container body.
Detailed description of the invention
Below in conjunction with accompanying drawing, the specific embodiment of the present invention being illustrated, description below is exemplary illustration, and not as limitations on the claims, any embodiment that can realize claim technical scheme is all in protection scope of the present invention.
The present invention provides a kind of and processes the in situ chemical oxidation restorative procedure that subsoil water chlorohydrocarbon pollutes, and described method is by micro-nano ozone bubbles, subsoil water to be repaired；Preferably, described micro-nano ozone bubbles is of a size of 60nm to 50 μm.
In a kind of detailed description of the invention, described method comprises the steps:
(1) Ozone generation step: prepare ozone gas；
(2) the soaked forming step of micro-nano ozone gas: ozone gas prepared by step (1) is formed micro-nano air-bubble, and carry out with step (1) circulation, until micro-nano bubble Measuring Ozone Concentration in Water reaches appointment scope, use it for the reparation of chlorohydrocarbon in subsoil water；
(3) hardening agent implantation step: when the soaked injection subsoil water of the micro-nano ozone gas that step (2) prepares, simultaneously hardening agent is injected in subsoil water；And
(4) gas sampling process step: when in soil and groundwater organic pollutant more than 1000mg/m3, carry out gas sampling process.
In a preferred embodiment, the appointment of the micro-nano bubble Measuring Ozone Concentration in Water of described method step (2) ranges for 1mg/L-1.5mg/L, and the micro-nano ozone bubbles of generation is of a size of 60nm to 50 μm.
Said method is by reducing ozone bubbles particle diameter, use the ozone bubbles of micro/nano level, increase dissolved ozone concentration, excite more hydroxyl radical free radical, extend ozone and reactant time of contact, improve mass-transfer efficiency, add ozone oxidation hardening agent simultaneously, improve oxidation remediation efficiency, be finally reached the purpose of reparation.
The present invention provides the system that a kind of in situ chemical oxidation polluted for subsoil water chlorohydrocarbon is repaired, described system includes: Ozone generation system, the soaked preparation system of micro-nano ozone gas, hardening agent injected system, gas sampling process system and down-hole is injected, monitored and extract system, being connected by pipeline between Ozone generation system with the soaked preparation system of micro-nano ozone gas, gas sampling is processed system and is connected by pipeline with down-hole extract system；The soaked preparation system of micro-nano ozone gas and hardening agent injected system are connected in downhole injection system by pipeline, the subsoil water that in-situ treatment is polluted by chlorohydrocarbon；
With the use of being finally reached increase ozone dissolubility in water body between above-mentioned each system, excite more hydroxyl radical free radical, extend ozone time of staying in water, expand ozone and the contact range of chlorinated hydrocarbon contaminants in subsoil water, improve mass-transfer efficiency；Overcome and prior art adopts persistent period of existing directly as oxidant of ozone is short, react insufficient, mass-transfer efficiency is low, the problems such as coverage is less and remediation efficiency is low.
In a kind of detailed description of the invention, described system farther includes central control system, and each system is coupled in order to control each system；By central control system, the control making whole system is easier, is advantageously implemented Automated condtrol.
In a kind of detailed description of the invention, described Ozone generation system includes ozone water preparation device, water feed apparatus and ozone generating-device；The described soaked preparation system of micro-nano ozone gas includes micro-nano ozone bubbles water preparation apparatus, micro-nano ozone bubbles water generating device and ozone-detecting element；
Preferably, the ozone gas that Ozone generation system produces is drawn into the soaked preparation system of micro-nano ozone gas by being connected with the extraction line being provided with flow monitoring device and vacuum pump, and the ozone gas that Ozone generation system produces is soaked by pumping in the soaked preparation system of micro-nano ozone gas equipped with the extraction tube of water pump；The soaked preparation system of micro-nano ozone gas produce micro-nano ozone gas is soaked, ozone gas and ozonated water mixture are pumped back in Ozone generation system by being provided with the extraction tube of water pump, thus being circulated between two systems.
Especially, between described Ozone generation system with the soaked preparation system of micro-nano ozone gas, extraction line by being provided with flow monitoring device, vacuum pump and water pump is connected and is circulated；The micro-nano ozone bubbles concentration making particle diameter be 60nm to 50 μm due to the application of the technological means of circulation improves, pass in the subsoil water of pollution afterwards again, not only increase the concentration of micro-nano ozone bubbles, and make the intake of micro-nano ozone bubbles and speed controlled, be conducive to the control of whole device, provide sufficient condition for automated production.
In a kind of other detailed description of the invention, described hardening agent injected system includes hardening agent injection device and agitating device；System comprises the strengthening micro-nano bubble injection device of ozone, in the micro-nano bubble injection process of ozone, inject liquid reinforced dose, it is possible to increase the oxidability of micro-nano ozone bubbles further, increase considerably the hydroxyl radical free radical in subsoil water, strengthen repairing effect；Hardening agent wherein commonly used in the art such as hydrogen peroxide, ferrate etc. may be incorporated in the present invention.
In a kind of other detailed description of the invention, down-hole injection, monitoring and extract system include injecting well, monitoring well, water quality parameter determinator, ozone detector, organic pollutant detector and extraction well；
Described gas sampling processes system and includes gas-liquid separation device, exhaust gas absorption device and waste collecting device.
Described ozone generating-device is electrolysis type ozone generator；The ozone bubbles Measuring Ozone Concentration in Water that described micro-nano ozone bubbles water generating device produces is 1mg/L-1.5mg/L, and the micro-nano ozone bubbles of generation is of a size of 60nm to 50 μm.
In another detailed description of the invention, described Ozone generation system includes Ozone Water preparation tank, water inlet and ozonator, and ozonator is placed in Ozone Water preparation tank；The described soaked preparation system of micro-nano ozone gas includes the soaked preparation tank of micro-nano ozone gas, micro-nano ozone bubbles water generator and ozone detector, micro-nano ozone bubbles water generator is placed in the soaked preparation tank of micro-nano ozone gas, and ozone detector is placed in the soaked preparation tank of micro-nano ozone gas for monitoring ozone concentration in tank；Described Ozone generation system is connected by extraction line with the described soaked preparation system of micro-nano ozone gas, is provided with effusion meter, water pump and/or vacuum pump on extraction line, makes to circulate between the two；Described hardening agent injected system includes hardening agent and injects tank and agitator disposed within, and this system is connected by pipeline with injecting well；Described down-hole is injected, monitoring and extract system include injecting well, monitoring well and being placed in the water quality parameter instrument in monitoring well, extraction well and be placed in extraction well organic pollutant detector；Described gas sampling processes system and includes gas-liquid separation, liquid waste collector and charcoal trap；Described extraction well is connected with gas-liquid separator by being provided with the extraction line of piezometer, effusion meter and vacuum pump, and gas-liquid separator is connected with liquid waste collector in order to drain, and gas-liquid separator is connected to locate process gases with charcoal trap；Above-mentioned all devices carries out parameter setting each through the automatic control cabinet of central control system, runs control and data storage.
Described ozone circulates between Ozone generation system and the soaked preparation system of micro-nano ozone gas, until reaching described concentration, the ozone gas of Ozone generation tank by being connected in the micro-nano ozone bubbles water generator being drawn in the soaked preparation tank of micro-nano ozone gas with the extraction line being provided with effusion meter and vacuum pump, and the ozone gas that Ozone generation tank produces is soaked by pumping in the soaked preparation tank of micro-nano ozone gas equipped with the extraction tube of water pump；Micro-nano ozone bubbles water generator produce micro-nano ozone gas is soaked, ozone gas and ozonated water mixture are pumped back in ozone conservation tank are circulated by being provided with the extraction tube of water pump.
It addition, in one embodiment of the invention, additionally providing a kind of method that described use repair system processes the subsoil water that chlorohydrocarbon pollutes, described method comprises the steps:
Ozone gas and air-bubble ozoniferous is prepared by Ozone generation system, it is introduced into that the soaked preparation system of micro-nano ozone gas prepares micro-nano ozone gas soaked, afterwards soaked for micro-nano ozone gas, ozone gas and ozonated water mixture are imported to Ozone generation system to be circulated, until the soaked concentration of micro-nano ozone gas reaches requirement；It is then poured in the subsoil water that pending chlorinated hydrocabon pollutes；By hardening agent injected system, hardening agent is injected in the subsoil water that pending chlorinated hydrocabon pollutes, by water quality parameter in underground monitoring and extract system monitoring subsoil water and the ozone in aeration zone and organic pollutant；By quality of groundwater Parameters variation, adjust the soaked injection rate with hardening agent of ozone gas.When ozone and organic pollutant concentration exceed particular value, start gas sampling process system and the waste gas produced is collected and processes.
When wherein in the soaked preparation system of micro-nano ozone gas, ozone concentration reaches 1.5mg/L, when micro-nano bubble size is 60nm to 50 μm, inject the ozone in injection well.The 0.10mg/m when ozone concentration exceedes3, the monitoring numerical value that organic pollutant detector shows is more than 1000mg/m3, start gas sampling and process system.
In a kind of particularly preferred embodiment, the present invention provides the integrated equipment and application process that a kind of in situ chemical oxidation for chlorohydrocarbon underground water pollution repairs, can process the subsoil water by chlorohydrocarbon pollution.nullThe integrated equipment that the described in situ chemical oxidation for chlorohydrocarbon underground water pollution is repaired，It is characterized in that including: Ozone Water preparation tank (1)、Water inlet (2)、Ozonator (3)、First-class gauge (41)、Second gauge (42)、First vacuum pump (51)、Second vacuum pump (52)、Extraction line (6)、First water pump (71)、Second water pump (72)、3rd water pump (73)、The soaked preparation tank of micro-nano ozone gas (8)、Micro-nano ozone bubbles water generator (9)、First ozone detector (101)、Second ozone detector (102)、Hardening agent injects tank (11)、Agitator (12)、Piezometer (13)、Gas-liquid separator (14)、Liquid waste collector (15)、Charcoal trap (16)、Inject well (17)、Monitoring well (18)、Water quality parameter instrument (19)、Organic pollutant detector (20)、Extraction well (21)、Automatic control cabinet (22)、Container body (23).
Ozonator (3) and micro-nano ozone bubbles water generator (9) are respectively placed in Ozone Water preparation tank (1) and the soaked preparation tank of micro-nano ozone gas (8).nullFrom water inlet (2), pass into tap water enter in Ozone generation tank (1)，Utilize ozonator (3) the electrolysis water being placed in，Produce ozone gas and air-bubble ozoniferous，First-class gauge (41) and the first vacuum pump (51) are connected by extraction line (6)，The ozone gas that Ozone generation tank produces is drawn in the micro-nano ozone bubbles water generator (9) in the soaked preparation tank of micro-nano ozone gas (8)，Ozone generation tank (1) and the soaked preparation tank of micro-nano ozone gas (8) are connected by extraction tube (6) and the first water pump (71)，The ozone bubbles water produced in Ozone generation tank (1) is pumped in micro-nano ozone bubbles water preparation tank (8)，It is soaked that ozone gas and Ozone Water are made micro-nano ozone gas by micro-nano ozone bubbles water generator (9)，Under the effect of the second water pump (72)，It is pumped back in ozone conservation tank by soaked for micro-nano ozone gas/ozone gas/ozonated water mixture by extraction tube to circulate，Improve micro-nano ozone gas soaked in ozone content，The content of micro-nano ozone bubbles is monitored with ozone detector (10)，Soaked being injected into of micro-nano ozone gas that the 3rd water pump (73) is up to certain concentration is utilized to inject in well (17).Hardening agent injects in tank (11) and has disposed agitator (12), it is possible to the strengthening medicament of configuration desired concn, is injected in injection well (17) by extraction line (6).Monitoring well (18) is used for monitoring water quality parameter in subsoil water (dissolved oxygen, oxidation-reduction potential and pH value), according to analyzing result, regulates the amount injecting micro-nano air-bubble.Second ozone detector (102) and organic pollutant detector (20) are placed in extraction well (21), it is used for monitoring ozone and organic pollutant concentration in aeration zone, when exceeding particular value, start process of bleeding, the second vacuum pump (52) is utilized to drive gas flowing for extraction line is formed negative pressure, piezometer (13) and second gauge (42) are used for monitoring the flow of the gas in extraction line, gas-liquid separator (14) is used for the gas containing moisture extracted is carried out gas-liquid separation, isolated liquid is drained in liquid waste collector (15), isolated gas utilizes charcoal trap (16) to remove.Piezometer (13), gas-liquid separator (14), the second vacuum pump (52), liquid waste collector (15), charcoal trap (16) are coupled together by extraction line.The integrated equipment that the in situ chemical oxidation of a whole set of chlorohydrocarbon underground water pollution is repaired is controlled by the touch screen on automatic control cabinet (22), on the one hand for instrument power supplies such as ozonator (3), micro-nano ozone bubbles water generator (9), the first water pump (71), the first vacuum pump (51), agitators (12), ensure the properly functioning of package unit, on the other hand package unit is carried out parameter setting, runs control and data storage.Touch screen on automatic control cabinet (22) can arrange the different flows injecting the soaked amount of micro-nano ozone gas and extracting SOIL GAS, it is achieved first water pump (71) soaked to the micro-nano ozone gas of injection and startup and the stopping of second vacuum pump (52) of extracting SOIL GAS control；The Monitoring Data of effusion meter (4), ozone detector (101 and 102), piezometer (13), organic pollutant detector (20) and water quality parameter instrument (19) reflects on the touchscreen and realizes real-time storage in real time and the later stage downloads；Ozone Water preparation tank (1), ozonator (3), first-class gauge (41), second gauge (42), first vacuum pump (51), second vacuum pump (52), extraction line (6), first water pump (71), , second water pump (72), 3rd water pump (73), the soaked preparation tank of micro-nano ozone gas (8), micro-nano ozone bubbles water generator (9), ozone detector (10), hardening agent injects tank (11), agitator (12), gas-liquid separator (14), liquid waste collector (15), charcoal trap (16), automatic control cabinet (22) all reasonable placement are in container body (23).
Wherein, described ozonator (3) is electrolysis type ozone generator, and ozone gas soluble end is 20%-30%, and producing ozone gas concentration is 0.06mg/L.The ozone bubbles Measuring Ozone Concentration in Water that micro-nano ozone bubbles water generator (9) produces is up to 1-1.5mg/L, it is seen then that after micro-nano ozone equipment, the concentration of ozone can bring up to 1-1.5mg/L.The micro-nano ozone bubbles produced is of a size of 60nm to 50 μm.
Wherein, inject well (16) and monitoring well (17) and extraction well (21) is both needed to out sieve, wherein inject under well (16) and monitoring well (17) screen casing water water level located underground, the screen casing of extraction well is positioned on water level, the width of sieve aperture is 0.5-1.5mm, material can select to select PVC or steel pipe according to the concentration of chlorohydrocarbon, when the concentration of chlorohydrocarbon selects pvc pipe lower than 1mg/L, when the concentration of chlorohydrocarbon is select steel pipe higher than 1mg/L.
The present invention also provides for the system and method for the in situ chemical oxidation reparation that described a kind of subsoil water chlorohydrocarbon pollutes, it is characterised in that realize step as follows:
nullFrom water inlet (2), pass into tap water enter in Ozone generation tank (1)，Utilize ozonator (3) the electrolysis water being placed in，Produce ozone gas and air-bubble ozoniferous，Vacuum pump (5) is utilized to be drawn in the micro-nano air-bubble generator (9) in the soaked preparation tank of micro-nano ozone gas (8) ozone gas that Ozone generation tank produces，The ozone bubbles water produced in Ozone generation tank (1) is pumped in micro-nano ozone bubbles water preparation tank (8)，It is soaked that ozone gas and Ozone Water are made micro-nano ozone gas by micro-nano ozone bubbles water generator (9)，Under the effect of the first water pump (71)，Soaked for micro-nano ozone gas/ozone gas/ozonated water mixture is pumped back in ozone conservation tank by extraction tube and is circulated，Improve micro-nano ozone gas soaked in ozone content，The content that micro-nano ozone gas is soaked is monitored with ozonesonde (101)，Automatic control cabinet (22) is utilized to set the soaked water yield of ozone gas of injection，Soaked being injected into of micro-nano ozone gas that the 3rd water pump (73) is up to certain concentration is utilized to inject in well (17).Utilize hardening agent to inject tank (11), the strengthening medicament of configuration desired concn, be injected in injection well (17) by extraction line (6).Utilize water quality parameter (dissolved oxygen, oxidation-reduction potential and pH value) in monitoring well monitoring subsoil water, according to analyzing result, regulate the amount injecting micro-nano air-bubble.When ozonesonde (102) and organic pollutant detector (20) exceed particular value, automatic control cabinet (22) starts process of bleeding, vacuum pump (5) is utilized to drive gas flowing for extraction line is formed negative pressure, gas-liquid separator (14) is used for the gas containing moisture extracted is carried out gas-liquid separation, isolated liquid is drained in liquid waste collector (15), and isolated gas utilizes charcoal trap (16) to remove.
Embodiment
Embodiment 1
The subsoil water that the method for the in-situ oxidation reparation of chlorohydrocarbon underground water pollution is polluted by high concentration chlorohydrocarbon for certain pesticide factory site, south is utilized to repair.Place can be divided into artificial earth fill's layer, Quaternary system deposition layer from top to bottom.Artificial earth fill's layer comprises miscellaneous fill and plain fill, miscellaneous fill thickness 0.3～2m, and average thickness is 1m, plain fill thickness 0.5～3.6m, and average thickness is 1.9m；Quaternary system deposition layer can be divided into silty clay and silt two-layer, upper strata uniform soil quality, and lower floor is more containing gravel particle, and slide rock is formed, silty clay thickness 0.3～7.4m, silt thickness 0.5～1.8m；Place basement rock comprises mud stone, shale and conglomerate three types, and basement rock discloses the degree of depth from 1.2～8.1m not etc..The average buried depth 1.28m of subsoil water of groundwater monitoring well.Major pollutants are chloralkane and chloroalkene.The in-situ oxidation repair system of chlorohydrocarbon underground water pollution, 50m is built in reparation place2Having laid 1 mouthful of injection well, 2 mouthfuls of monitoring wells and 2 mouthfuls of extraction wells in underground water pollution region, injected well and monitoring well average well depth is 4.3 meters, open sieve under groundwater level, length is 3 meters.The well depth of extraction well is 1 meter, opens the sieve degree of depth 0.3 meter, underground, and length is 0.5 meter.Individually starting ozonator, when ozone concentration reaches 1.5mg/L, carry out Ozone Water injection, every day is soaked to injecting the ozone gas injecting about 1000L in well, when the dissolved oxygen monitored in well significantly raises, utilizes hardening agent to inject the H of tank configuration 5%2O2, it is injected in injection well.In this on-the-ground test process, the monitoring numerical value shown when organic pollutant detector is higher than 1000mg/m3, ozone concentration is more than 0.10mg/m3, start gas sampling process system and waste gas absorbed.After processing 14 days, polluter main in this subsoil water, the remediation efficiency of 1,2-dichloropropane, 1,2-dichloroethanes, trichloro ethylene, 1,3-dichloropropane and glyceryl trichloride is 36.92%, 36.22%, 22.46%, 18.18%, 18.95%.
Embodiment 2
In the Same Site of embodiment 1, in the region that subsoil water hydrogeologic condition is similar with pollution concentration, utilize that micro-nano ozone gas is soaked carries out underground water pollution reparation.At 50m2Having laid 1 mouthful of injection well, 2 mouthfuls of monitoring wells and 2 mouthfuls of extraction wells in underground water pollution region, injected well and monitoring well average well depth is 4.3 meters, open sieve under groundwater level, length is 3 meters.The well depth of extraction well is 1 meter, opens the sieve degree of depth 0.3 meter, underground, and length is 0.5 meter.
Start ozonator and micro-nano ozone bubbles water generator, when ozone concentration reaches 1.5mg/L, when micro-nano bubble size is 60nm to 50 μm, carry out the soaked injection of micro-nano ozone gas, every day is soaked to injecting the micro-nano ozone gas injecting about 1000L in well, when the dissolved oxygen monitored in well significantly raises, hardening agent is utilized to inject the H of tank configuration 5%2O2, it is injected in injection well.In this on-the-ground test process, the monitoring numerical value shown when organic pollutant detector is higher than 1000mg/m3, ozone concentration is more than 0.10mg/m3, start gas sampling process system and waste gas absorbed.
After processing 14d, polluter main in this subsoil water, 1,2-dichloropropane, 1,2-dichloroethanes, trichloro ethylene, 1,3-dichloropropane and 1, the removal efficiency of 2,3-trichloropropanes respectively 70.19%, 77.30%, 45.96%, 100.00%, 64.79%.
Being shown by the data of embodiment 1 and embodiment 2, ozone gas after micro-nanoization is soaked is relatively used alone Ozone Water, and remediation efficiency obtains and increases substantially, and has reached the purpose of efficient pollution administration subsoil water.
Claims (15)
1. one kind processes the in situ chemical oxidation restorative procedure that subsoil water chlorohydrocarbon pollutes, it is characterised in that described method is by micro-nano ozone bubbles, subsoil water to be repaired；Preferably, described micro-nano ozone bubbles is of a size of 60nm to 50 μm.
2. method as claimed in claim 1, wherein said method comprises the steps:
(1) Ozone generation step: prepare ozone gas；
(2) the soaked forming step of micro-nano ozone gas: ozone gas prepared by step (1) is formed micro-nano air-bubble, and carry out with step (1) circulation, until micro-nano bubble Measuring Ozone Concentration in Water reaches appointment scope, use it for the reparation of chlorohydrocarbon in subsoil water；
(3) hardening agent implantation step: when the soaked injection subsoil water of the micro-nano ozone gas that step (2) prepares, simultaneously hardening agent is injected in subsoil water；And
(4) gas sampling process step: when in soil and groundwater organic pollutant more than 1000mg/m3, carry out gas sampling process.
3. method as claimed in claim 2, the appointment of the micro-nano bubble Measuring Ozone Concentration in Water of wherein said method step (2) ranges for 1mg/L-1.5mg/L, and the micro-nano ozone bubbles of generation is of a size of 60nm to 50 μm.
4. the in situ chemical oxidation repair system polluted for subsoil water chlorohydrocarbon based on method described in any one of claim 1-3, it is characterized in that, described system includes: Ozone generation system, the soaked preparation system of micro-nano ozone gas, hardening agent injected system, gas sampling process system and down-hole is injected, monitored and extract system；Being connected by pipeline between wherein said Ozone generation system with the soaked preparation system of micro-nano ozone gas, gas sampling is processed system and is connected by pipeline with down-hole extract system；The soaked preparation system of micro-nano ozone gas and hardening agent injected system are connected in downhole injection system by pipeline, the subsoil water that in-situ immobilization is polluted by chlorohydrocarbon.
5. processing system as claimed in claim 4, it is characterised in that described system farther includes central control system, each system is coupled in order to control each system.
6. the process system as described in claim 4 or 5, it is characterised in that described Ozone generation system includes ozone water preparation device, water feed apparatus and ozone generating-device.
7. the process system as described in any one of claim 4-6, it is characterised in that the described soaked preparation system of micro-nano ozone gas includes micro-nano ozone bubbles water preparation apparatus, micro-nano ozone bubbles water generating device and ozone-detecting element.
8. the process system as described in any one of claim 4-7, it is characterised in that described hardening agent injected system includes hardening agent injection device and agitating device；Down-hole injection, monitoring and extract system include injecting well, monitoring well, water quality parameter instrument, extraction well, organic pollutant detector, ozone detector.
9. the process system as described in any one of claim 4-8, it is characterised in that described gas sampling processes system and includes gas-liquid separation device, exhaust gas absorption device and waste collecting device.
10. the process system as described in any one of claim 4-9, it is characterised in that between described Ozone generation system with the soaked preparation system of micro-nano ozone gas, extraction line by being provided with effusion meter, vacuum pump and water pump is connected and is circulated；Preferably, the ozone gas that Ozone generation system produces is drawn into the soaked preparation system of micro-nano ozone gas by being connected with the extraction line being provided with flow monitoring device and vacuum pump, and the ozone gas that Ozone generation system produces is soaked by pumping in the soaked preparation system of micro-nano ozone gas equipped with the extraction tube of water pump；The soaked preparation system of micro-nano ozone gas produce micro-nano ozone gas is soaked, ozone gas and ozonated water mixture are pumped back in Ozone generation system by being provided with the extraction tube of water pump, thus being circulated between two systems.
11. the process system as described in any one of claim 4-10, it is characterised in that described ozone generating-device is electrolysis type ozone generator；The ozone bubbles Measuring Ozone Concentration in Water that described micro-nano ozone bubbles water generating device produces is 1mg/L-1.5mg/L, and the micro-nano ozone bubbles of generation is of a size of 60nm to 50 μm.
12. the process system as described in any one of claim 4-11, it is characterised in that described Ozone generation system includes Ozone Water preparation tank, water inlet and ozonator, and ozonator is placed in Ozone Water preparation tank；The described soaked preparation system of micro-nano ozone gas includes the soaked preparation tank of micro-nano ozone gas, micro-nano ozone bubbles water generator and ozone detector, micro-nano ozone bubbles water generator is placed in the soaked preparation tank of micro-nano ozone gas, and ozone detector is placed in the soaked preparation tank of micro-nano ozone gas for monitoring ozone concentration in tank；Described Ozone generation system is connected by extraction line with the described soaked preparation system of micro-nano ozone gas, is provided with effusion meter, water pump and/or vacuum pump on extraction line, makes to circulate between the two；Described hardening agent injected system includes hardening agent and injects tank and agitator disposed within, and this system is connected by pipeline with injecting well；Described down-hole is injected, monitoring and extract system include injecting well, monitoring well and being placed in the water quality parameter instrument in monitoring well, extraction well and be placed in the ozone detector in extraction well and organic pollutant detector；Described gas sampling processes system and includes gas and liquid collecting device, liquid waste collector and charcoal trap；Described extraction well is connected with gas-liquid separator by being provided with the extraction line of piezometer, effusion meter and vacuum pump, and gas-liquid separator device is connected with liquid waste collector in order to drain, and gas-liquid separator is connected to locate process gases with charcoal trap；Above-mentioned all devices carries out parameter setting each through the automatic control cabinet of central control system, runs control and data storage.
13. process system as claimed in claim 12, wherein inject well, monitoring well and extraction well and all open sieve, wherein inject under well and monitoring well screen pipe water water level located underground, on the screen casing water water level located underground of extraction well；The width of preferred sieve aperture is 0.5-1.5mm；It is highly preferred that the material of screen casing is PVC or steel pipe.
14. one kind uses the method processing system described in any one of claim 4-13, it is characterised in that described method comprises the steps:
Ozone gas and air-bubble ozoniferous is prepared by Ozone generation system, it is introduced into that the soaked preparation system of micro-nano ozone gas prepares micro-nano ozone gas soaked, afterwards soaked for micro-nano ozone gas, ozone gas and ozonated water mixture are imported to Ozone generation system to be circulated, until micro-nano ozone bubbles Measuring Ozone Concentration in Water reaches requirement；It is then poured in the subsoil water that pending chlorinated hydrocabon pollutes；By hardening agent injected system, hardening agent is injected in the subsoil water that pending chlorinated hydrocabon pollutes, by water quality parameter in underground monitoring and extract system monitoring subsoil water and ozone and organic pollutant concentration；By quality of groundwater Parameters variation, adjust the soaked injection rate with hardening agent of ozone gas；When ozone and organic pollutant concentration exceed particular value, start gas sampling process system and the waste gas produced is collected and processes.
15. using method as claimed in claim 14, when wherein in the soaked preparation system of micro-nano ozone gas, ozone concentration is be more than or equal to 1-1.5mg/L, when micro-nano bubble size is 60nm to 50 μm, it is injected into soaked for micro-nano ozone gas in injection well；Preferably, the monitoring numerical value shown when organic pollutant detector is more than 1000mg/m3, the concentration of Ozone Monitor is more than 0.10mg/m3Time, start gas sampling and process system.
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| CN112551799A (en) * | 2020-10-10 | 2021-03-26 | 西华师范大学 | Underground water pollution treatment strengthening treatment device and treatment method |
| CN112642847A (en) * | 2020-12-25 | 2021-04-13 | 上海勘察设计研究院(集团)有限公司 | Remediation method based on structural evolution of chlorinated hydrocarbon polluted soil |
| CN113683180A (en) * | 2021-08-27 | 2021-11-23 | 宝航环境修复有限公司 | Ozone advanced oxidation system for underground water in-situ pumping treatment |
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