CN103951028A - Water treatment method for catalytic ozonation of refractory organics in water by ceramic membrane - Google Patents
Water treatment method for catalytic ozonation of refractory organics in water by ceramic membrane Download PDFInfo
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- CN103951028A CN103951028A CN201410141090.6A CN201410141090A CN103951028A CN 103951028 A CN103951028 A CN 103951028A CN 201410141090 A CN201410141090 A CN 201410141090A CN 103951028 A CN103951028 A CN 103951028A
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Abstract
The invention relates to water deep treatment technology of heterogeneous catalytic ozonation depollution. With the combination of catalytic ozonation depollution technology with membrane filtration technology, a novel, high-efficient, and economical catalytic ozonation water deep treatment technology is provided, which combines the advantages of the two technologies, overcomes their disadvantages, effectively improves the ozone utilization rate and the ozone oxidation capability, reduces some toxic and harmful substances generated due to incomplete oxidation, alleviates the problem of ceramic membrane contamination, and prolongs the system operation period. An experiment device mainly comprises three parts: an ozone generation device, a ceramic membrane device, and a computer data acquisition and analysis system; an ozone outlet of the ozone generation device is connected with a water inlet valve of the ceramic membrane assembly through a silicone flexible pipe to realize the coupling of the two system. The method of the invention can improve the purifying effect of routine water treatment technology, and provides novel, high-efficient and cheap water deep treatment technology for enhanced removal of low-concentration high-toxicity refractory organic pollutants in water.
Description
Technical field
The present invention relates to a kind of heterogeneous catalytic ozonation depollution or membrane filtration water depth treatment technology.
Background technology
In recent years, along with the extensive application of chemical industry synthetics in people's daily life and industrial and agricultural production, in water surrounding, the kind of Persistent organic pollutants and emerging pollutant, content obviously increase.Increasingly sophisticated water pollution situation, has proposed new challenge to China's water quality safety safeguards technique.Due to routine to water treatment and sewage treatment process be remove in water suspend, colloid pollution thing and nutrition pollutent be main, to the organic pollutant existing in water, particularly very limited to the removal ability of Persistent organic pollutants, even helpless.Therefore, must further ensure water quality safety by advanced treatment technology.Wherein, heterogeneous catalytic ozonation technology is not introduced other energy and poisonous and hazardous chemical agent in technique, and catalyzer can disposablely be loaded in reactor, simple to operate, be convenient to apply in actual water technology.But traditional heterogeneous catalytic ozonation technology has some limitations:
(1) solid catalyst activeconstituents is single, and lower for the coexist activity of system of multiple pollutant in Complex water body, mineralization ability is poor.
(2) solid catalyst poisoning and deactivation, because multiple pollutant in natural water body coexists, the adsorption of part material and intermediate oxidation product thereof and make catalytic activity decline or lose.
(3) there is the problem of active ingredient stripping in solid catalyst in reaction process, so not only reduces the work-ing life of catalyzer, and increased toxic metal ionic concn in water outlet, improved its health risk or Ecology risk.
In recent years, take the application in Practical Project of water technology that ceramic microfiltration membrane, ultra-filtration membrane be representative has made great progress.Ceramic membrane (ceramic membrane) is a kind of in mineral membrane, mainly by Al
2o
3, ZrO
2, TiO
2and SiO
2the porous-film of preparing etc. inorganic materials, its aperture is 1～50nm.In wastewater treatment, the general filtering membrane using in ceramic membrane, adopts the various ultra-filtration membranes of so-gel legal system, and correlative study shows that the development prospect of the filtering membrane of making by inorganic materials is likely better than organic filtering membrane when processing suspended matter and colloidal solid.It is good that it has chemical stability, acidproof, alkaline-resisting, the organic solvent-resistant of energy; Physical strength is large, can counterflush; Anti-microbe ability is strong; High temperature resistant; Pore size distribution is narrow, and separation efficiency high is widely used in engineering of water treatment field.But, in the process of the application of ceramic membrane in processing engineering of water treatment, still come with some shortcomings:
(1) film pollution is the major issue facing in the application of ceramic membrane engineering, and it will have influence on the steady running of film, and determines the replacement frequency of film, is considered to affect the major reason of ceramic membrane application art economy.Film pollution source is in two aspects, and the one, irreversible membrane fouling, is due to irreversible adsorption, stops up the pollution causing; Being reversible membrane fouling on the other hand, is mainly due to reversible concentration polarization, to cause the formation of gel coat, and both cause the decay of membrane flux in operational process jointly.
(2) energy consumption and cost are relatively high.Membrane sepn process is due to the existence of the problems such as concentration polarization and film pollution, and permeation flux declines with the prolongation of working time.For controlling concentration polarization and film, pollute, in operation engineering, need to consume a large amount of energy consumptions and maintain higher crossflow velocity.Film support physical strength is low in addition, in use, easily damages, and the replacing of film is also a no small expense.In addition, matting also makes process cost too high frequently.
The present invention combines heterogeneous catalytic ozonation technology with ceramic membrane filter technology, utilize the active ingredient in ceramic membrane structure to realize the strengthening removal of ozone to Persistent organic pollutants; By means of heterogeneous catalytic ozonation effect, reduce membrane pollution problem, improve the life cycle of ceramic membrane, extend its work-ing life.The present invention, by the effective combination of the filtration of heterogeneous catalytic ozonation technology and ceramic membrane, can provide a kind of novel, efficient and economic O3 catalytic oxidation water depth treatment technology.
Summary of the invention
The object of the invention is deficiency and defect for ozonation technology and the existence of ceramic membrane filter technology, to after above-mentioned two technological improvements, effectively combine, this technique and device can be realized in single processing unit effectively removing in suspended particle, colloid and hardly degraded organic substance etc., system can obtain good effluent quality, and apparatus structure is relatively simple, in the situation that providing compared with low-ozone, the development that controlling diaphragm pollutes effectively, can obtain higher membrane flux simultaneously.
1. technical scheme of the present invention is as follows:
Machinery mainly comprises three large integral parts: ozone generating-device (comprising oxygen cylinder, moisture eliminator, gas meter, ozonizer and ozone concn analyser), ceramic membrane equipment (comprising water tank, intake pump, ceramic film component, pressure warning unit, thermometer, under meter, back-purge system and effluent collection system), computer data acquiring and analytical system.Wherein ceramic membrane is the core component of system, is carrying out the removal reaction of main catalytic ozonation organism, suspended substance and colloidal solid on ceramic membrane.The main operational process of this association system is summarized as follows:
(1) debugging ozonizer: use oxygen cylinder to provide oxygen to ozonizer, enter the oxygen input aperture of ozonizer after by moisture eliminator, gas meter by silica gel hose.Changeover valve before the operation of ceramic membrane system, makes ozone generating-device and ceramic membrane equipment in off-state.Now, open oxygen cylinder, ozonizer switch, observe the reading of gas meter, ozone concn analyser, when ozone output is stabilized in 1～6mg/L, ozonizer is in steady-working state.The ozone that this produces in stage is absorbed by KI solution by silica gel hose or is directly disposed to atmosphere.
(2) O3 catalytic oxidation step of reaction: after ozonizer is stable, changeover valve, makes ozone generating-device and ceramic membrane equipment in on-state.Now, open ceramic membrane system switching, pending former water, through the supercharging of the intake pump ceramic membrane of flowing through, at film surface and ozone generation catalysed oxidn, is processed water outlet and is stored by effluent collection device.The pressure of this stage ceramic membrane, water temperature, discharge and ozone concn all complete analysis by on-line analysis pressure warning unit, thermometer, under meter and ozone concn detector equipment, then machine system realizes collection and the analytic record of data as calculated.
(3) water outlet detection up to standard and discharge: open effluent collection device switch, to processing water, sample, analyzing and processing water COD, BOD, hardly degraded organic substance equal size, monitoring can will be processed water discharge after reaching emission standard.
(4) back flushing: after pending water is emptied completely, close ozonizer, ceramic membrane facility switching, ceramic membrane filter flow process is closed.Then open back flushing switch, back-purge system starts water inlet (clear water), can carry out as required clear water back flushing or in clear water, add suitable citric acid or sodium hydroxide carries out chemical back flushing, synchronously discharges backwashing wastewater.General backwashing time is 5.0min, and the cycle is 24.0h, and backwashing water flow velocity is 1.2m/s.
(5) idle: after backwash process end of run, close back flushing switch and all valves, neither air inlet of membrane module, water inlet, do not process water yet, and system is in closing condition.
2. outstanding effect of the present invention is as follows:
(1) utilization ratio and the oxidation capacity thereof of ozone in single processing unit, have effectively been improved, ceramic membrane surface active ingredient can be decomposed by catalysis ozone, produce the hydroxyl radical free radical of strong oxidation capacity, lower concentration, the high stability organic pollutant existing in water removed in strengthening, greatly increase degradation efficiency and the mineralization degree of hardly degraded organic substance, reduced the generation of some hazardous and noxious substances that not exclusively generate due to oxidation.This system has good effluent quality, processes water and can be widely used in Drinking Water, be back to that life is used mixedly or the field such as industrial production.
(2) effectively control film pollution, extended the cycle of operation of system.For membrane module, prolongation along with filtration time, fenestra is likely stopped up in the accumulation of small-molecule substance on face, film surface also can form gel coat and the cake layer being comprised of colloid and particulate matter respectively gradually, especially the formation of cake layer, to the filtration resistance of film be increased rapidly, membrane flux will be decreased significantly.When having ozone to pass into membrane module, the pressurized gas under pressure and flow status, by seeing through the hole of film, can effectively be removed the cake layer on film surface, Pore Blocking and face gel coat is also had to certain removal effect simultaneously, has significantly improved membrane flux.The more important thing is, the active ingredient in ceramic membrane structure can be decomposed by catalysis ozone, and the hydroxyl radical free radical that produces high oxidative capacity is realized the efficient degradation to film pollution layer or cake layer, has realized effective control that film is polluted.。
(3) whole device simple structure, is easy to automatically control and running maintenance.Because heterogeneous catalytic ozonation process is to realize by means of fully contacting of ceramic membrane surface and ozone gas, therefore degrade hardly degraded organic substance and membrane sepn is to complete in same reactor, the system cycle of operation further shortens, floor space is more saved, and system control and operational management are also more convenient.
Accompanying drawing explanation
Accompanying drawing is according to the basic flow sheet of hardly degraded organic substance in the ceramic membrane O3 catalytic oxidation water of ultimate principle of the present invention and actual design.This experimental installation mainly comprises three large integral parts: ozone generating-device, ceramic membrane equipment (comprising ceramic film component and back washing device), computer data acquiring and analytical system.
(1) water tank (2) ceramic film component (3) KI solution (4) intake pump (5) pressure warning unit (6) thermometer (7) under meter (8) backwashing water (9) backwashing wastewater (10) effluent collection device (11) moisture eliminator (12) gas meter (13) valve (14) ozone concn analyser (15) ozonizer (16) computer data acquiring and analytical system (17) oxygen cylinder in diagram
Embodiment
Below in conjunction with drawings and Examples, explain detailedly, further to understand the present invention.
In accompanying drawing, machinery mainly comprises three large integral parts: ozone generating-device (comprising oxygen cylinder, moisture eliminator, gas meter, ozonizer and ozone concn analyser), ceramic membrane equipment (comprising water tank, intake pump, ceramic film component, pressure warning unit, thermometer, under meter, back-purge system and effluent collection system), computer data acquiring and analytical system.Wherein ceramic membrane is the core component of system, is carrying out the removal reaction of main catalytic ozonation organism, suspended substance and colloidal solid on ceramic membrane.The main operational process of this association system is summarized as is summarized as follows:
(1) debugging ozonizer: use oxygen cylinder to provide oxygen to ozonizer, enter the oxygen input aperture of ozonizer after by moisture eliminator, gas meter by silica gel hose.Changeover valve before the operation of ceramic membrane system, makes ozone generating-device and ceramic membrane equipment in off-state.Now, open oxygen cylinder, ozonizer switch, observe the reading of gas meter, ozone concn analyser, when ozone output is stabilized in 1～6mg/L, ozonizer is in steady-working state.The ozone that this produces in stage is absorbed by KI solution by silica gel hose or is directly disposed to atmosphere.
(2) O3 catalytic oxidation step of reaction: after ozonizer is stable, changeover valve, makes ozone generating-device and ceramic membrane equipment in on-state.Now, open ceramic membrane system switching, pending former water, through the supercharging of the intake pump ceramic membrane of flowing through, at film surface and ozone generation catalysed oxidn, is processed water outlet and is stored by effluent collection device.The pressure of this stage ceramic membrane, water temperature, discharge and ozone concn all complete analysis by on-line analysis pressure warning unit, thermometer, under meter and ozone concn detector equipment, then machine system realizes collection and the analytic record of data as calculated.
(3) water outlet detection up to standard and discharge: open effluent collection device switch, to processing water, sample, analyzing and processing water COD, BOD, hardly degraded organic substance equal size, monitoring can will be processed water discharge after reaching emission standard.
(4) back flushing: after pending water is emptied completely, close ozonizer, ceramic membrane facility switching, ceramic membrane filter flow process is closed.Then open back flushing switch, back-purge system starts water inlet (clear water), can carry out as required clear water back flushing or in clear water, add suitable citric acid or sodium hydroxide carries out chemical back flushing, synchronously discharges backwashing wastewater.General backwashing time is 5.0min, and the cycle is 24.0h, and backwashing water flow velocity is 1.2m/s.
(5) idle: after backwash process end of run, close back flushing switch and all valves, neither air inlet of membrane module, water inlet, do not process water yet, and system is in closing condition.
Core component of the present invention is ceramic film component, and the ceramic membrane equipment of selecting is by α-Al
2o
3for inner packing material, ZrO
2for the tubular ceramic film of propping material, its concrete specification is length 25.0cm, port number 4～19, external diameter 30mm, membrane area 0.12～0.20m
2, fenestra size is 20.0～50.0nm.This equipment can additional back-purge system, and when combining catalyzed oxidation hardly degraded organic substance with ozone, removing suspended substance and colloid, controlling diaphragm pollutes effectively.
Embodiment mono-
Joint test device with reference to the accompanying drawings, using ozonizer to control ozone air flow is 1～6mg/L; The concrete specification of tubular ceramic film is length 25.0cm, port number 4～19, external diameter 30mm, membrane area 0.12～0.20m
2, fenestra size is 20.0～50.0nm; The compressive strength of membrane module is that 1.0Mpa, applicable pH are 0～14, Applicable temperature is-10 ℃～150 ℃.Use oxygen cylinder (17) to provide oxygen to ozonizer, the oxygen input aperture by silica gel hose and ozonizer after by moisture eliminator (11), under meter (12) is connected, and the delivery port of ozonizer is used
the silicone tube of resistance to ozone is connected with ceramic membrane element lower end by valve, and in ozonizer use procedure, air-out need not connect, and pneumatic pump switch needn't be opened.After ozonizer is stable, open the switch of ceramic membrane system, former water is through the effect of the topping-up pump ceramic membrane of flowing through, at film surface and ozone generation catalysed oxidn, organic pollutants is by efficient oxidation, after question response is complete, open effluent collection device thief hole switch, process the sampling analysis of water.
Embodiment bis-
What present embodiment was different from embodiment mono-is to adopt FeOOH nanoparticle particle to carry out modification to ceramic membrane, and other step and parameter are identical with specific examples one.
Embodiment tri-
What present embodiment was different from embodiment mono-is to adopt nano Co
3o
4particle carries out modification to ceramic membrane, and other step and parameter are identical with specific examples one.
Embodiment tetra-
What present embodiment was different from embodiment mono-is to adopt nano-MgO particle to carry out modification to ceramic membrane, and other step and parameter are identical with specific examples one.
Embodiment five
What present embodiment was different from embodiment mono-is to adopt nano Ce O
2particle carries out modification to ceramic membrane, and other step and parameter are identical with specific examples one.
Embodiment six
Utilize hardly degraded organic substance in ceramic membrane O3 catalytic oxidation water to have wide practical use in water treatment.Combine with traditional secondary biochemical water technology, general waste water is successively behind the unit such as grid, preliminary sedimentation tank, active sludge aeration tank, second pond, again in conjunction with the water technology that the present invention relates to, can obtain high-quality more, stable water outlet, be widely used in wastewater treatment.
Technical solution of the present invention is not limited to above exemplified embodiment, also comprises the arbitrary combination that each embodiment is shown in.
Claims (5)
1. a water treatment method that utilizes hardly degraded organic substance in ceramic membrane O3 catalytic oxidation water, it is characterized in that heterogeneous ozone oxidation to combine with ceramic membrane filter technology, utilize ceramic membrane structure and lip-deep active ingredient realize strengthening ozone oxidation hardly degraded organic substance and prevent the formation that film pollutes, mainly comprise three integral parts: ozone generating-device (comprises oxygen cylinder, moisture eliminator, gas meter, ozonizer and ozone concn analyser), ceramic membrane equipment (comprises water tank, intake pump, ceramic film component, pressure warning unit, thermometer, under meter, back-purge system and effluent collection system), computer data acquiring and analytical system.
2. the ozone generating-device in the water treatment method that utilizes hardly degraded organic substance in ceramic membrane O3 catalytic oxidation water claimed in claim 1, it is characterized in that using oxygen cylinder to provide oxygen to ozonizer, control ozone dosage is 1.0～6.0mg/L, by ozone proof silica gel hose
oxygen cylinder is connected with ceramic film component with ozonizer input terminus, ozonizer output terminal.
3. according to the ceramic membrane equipment in the water treatment method that utilizes hardly degraded organic substance in ceramic membrane O3 catalytic oxidation water claimed in claim 1, it is characterized in that described membrane module adopts by α-A1
2o
3for inner packing material, ZrO
2tubular ceramic film for propping material; Its concrete specification is length 25.0cm, port number 4～19, external diameter 30mm, membrane area 0.12～0.20m
2, fenestra size is 20.0～50.0nm; The steady operation conditions of its system, membrane module compressive strength is that 1.0Mpa, applicable pH are 0～14, Applicable temperature is-10 ℃～150 ℃.
4. according to the water treatment method that utilizes hardly degraded organic substance in ceramic membrane O3 catalytic oxidation water claimed in claim 1, it is characterized in that this association system operation comprises following process:
(1) debugging ozonizer: use oxygen cylinder to provide oxygen to ozonizer, enter the oxygen input aperture of ozonizer after by moisture eliminator, gas meter through silica gel hose.Changeover valve before the operation of ceramic membrane system, makes ozone generating-device and ceramic membrane equipment in off-state.Now, open oxygen cylinder, ozonizer switch, observe the reading of gas meter, ozone concn analyser, when ozone output is stabilized in 1.0～6.0mg/L, ozonizer is in steady-working state.The ozone that this produces in stage is absorbed by KI solution by silica gel hose or is directly disposed to atmosphere.
(2) O3 catalytic oxidation step of reaction: after ozonizer is stable, changeover valve, makes ozone generating-device and ceramic membrane equipment in on-state.Now, open ceramic membrane system switching, pending former water, through the supercharging of the intake pump ceramic membrane of flowing through, at film surface and ozone generation catalysed oxidn, is processed water outlet and is stored by effluent collection device.The pressure of this stage ceramic membrane, water temperature, discharge and ozone concn all complete analysis by on-line analysis pressure warning unit, thermometer, under meter and ozone concn detector equipment, then machine system realizes collection and the analytic record of data as calculated.
(3) water outlet detection up to standard and discharge: open effluent collection device switch, to processing water, sample, analyzing and processing water COD, BOD, hardly degraded organic substance equal size, monitoring can will be processed water discharge after reaching emission standard.
(4) back flushing: after pending water is emptied completely, close ozonizer, ceramic membrane facility switching, ceramic membrane filter flow process is closed.Then open back flushing switch, back-purge system starts water inlet (clear water), can carry out as required clear water back flushing or in clear water, add suitable citric acid or sodium hydroxide carries out chemical back flushing, synchronously discharges backwashing wastewater.General backwashing time is 5.0min, and the cycle is 24.0h, and backwashing water flow velocity is 1.2m/s.
(5) idle: after backwash process end of run, close back flushing switch and all valves, neither air inlet of membrane module, water inlet, do not process water yet, and system is in closing condition.
5. according to heterogeneous ozone oxidation claimed in claim 1 and ceramic membrane filter combined technology, it is characterized in that: combine with traditional secondary biochemical water technology, general waste water is successively behind the unit such as grid, preliminary sedimentation tank, active sludge aeration tank, second pond, again in conjunction with the water technology the present invention relates to, can obtain high-quality more, stable water outlet, be widely used in wastewater treatment.
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| CN201410141090.6A CN103951028A (en) | 2014-04-10 | 2014-04-10 | Water treatment method for catalytic ozonation of refractory organics in water by ceramic membrane |
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| CN201410141090.6A CN103951028A (en) | 2014-04-10 | 2014-04-10 | Water treatment method for catalytic ozonation of refractory organics in water by ceramic membrane |
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| CN104803512A (en) * | 2015-04-21 | 2015-07-29 | 大连理工大学 | Ozone catalytic oxidation and self-cleaning ceramic membrane combined water treatment method and device |
| CN104841292A (en) * | 2015-05-25 | 2015-08-19 | 哈尔滨工业大学 | Ozone-catalytic functional ceramic membrane, preparation method thereof and circulating coating device |
| CN105060458A (en) * | 2015-07-21 | 2015-11-18 | 黑龙江大学 | Water-purification device by utilizing catalytic oxidation of ozone-PVDF hybrid membrane |
| CN105800735A (en) * | 2015-10-14 | 2016-07-27 | 北京林业大学 | Novel manganese-cobalt complex oxide nanoparticle modified ceramic membrane, and assembly and application method thereof in water treatment |
| CN106045005A (en) * | 2016-08-08 | 2016-10-26 | 苏州希克曼物联技术有限公司 | Device and method for multiphase catalytic ozonation of organic matter and oxygen charging |
| CN106745970A (en) * | 2016-12-07 | 2017-05-31 | 清华大学深圳研究生院 | A kind of processing system and method for removing organic extracts from water and ammonia nitrogen |
| CN107337326A (en) * | 2017-09-06 | 2017-11-10 | 江西博鑫精陶环保科技有限公司 | A kind of ceramic membrane aeration and pressure-fired ozone film reused water processing method and processing unit |
| CN107410836A (en) * | 2017-04-07 | 2017-12-01 | 淮阴师范学院 | A kind of fruit juice clavacin ozone detoxification device and method |
| CN107628702A (en) * | 2017-09-25 | 2018-01-26 | 广东粤港供水有限公司 | A kind of ozone ceramics dual-membrane process water treatment facilities and method for treating water |
| CN108101266A (en) * | 2018-01-31 | 2018-06-01 | 济南大学 | A kind of integrated apparatus and its application method of granular activated carbon coupling ceramic membrane advanced treatment of industrial wastewater |
| CN109179888A (en) * | 2018-09-30 | 2019-01-11 | 浙江工商大学 | The wastewater treatment equipment and technique of integrated ozone coupling membrane bioreactor |
| CN109775892A (en) * | 2019-03-11 | 2019-05-21 | 山东建筑大学 | A kind of low energy consumption gravity stream catalytic membrane integral water purifying device and its operation method |
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| CN111977747A (en) * | 2019-05-22 | 2020-11-24 | 南京悠泉环保科技有限公司 | Water treatment system and method |
| CN112010475A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Photocatalysis and membrane catalysis combined water treatment method and device |
| CN112047455A (en) * | 2020-09-25 | 2020-12-08 | 北京首创股份有限公司 | Advanced treatment system and method for sewage through catalytic ozonation |
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| CN105060458A (en) * | 2015-07-21 | 2015-11-18 | 黑龙江大学 | Water-purification device by utilizing catalytic oxidation of ozone-PVDF hybrid membrane |
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| CN106045005B (en) * | 2016-08-08 | 2023-10-20 | 苏州希克曼物联技术有限公司 | Device and method for synergistic oxygenation of organic matters by heterogeneous catalytic ozonation |
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| CN110436607B (en) * | 2019-09-02 | 2022-09-16 | 北京林业大学 | Assembly of catalytic separation membrane capable of regulating and controlling interface catalytic performance and application method of catalytic separation membrane in water treatment |
| CN110436607A (en) * | 2019-09-02 | 2019-11-12 | 北京林业大学 | A kind of assembling of controllable interfacial catalysis performance catalytic separation film and its application method in water process |
| CN112678985A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Method and device for pretreating negative hardness water containing scale inhibitor |
| CN112047455A (en) * | 2020-09-25 | 2020-12-08 | 北京首创股份有限公司 | Advanced treatment system and method for sewage through catalytic ozonation |
| CN115477420A (en) * | 2021-05-31 | 2022-12-16 | 中国石油化工股份有限公司 | Polymer-containing oil field wastewater treatment method and treatment device |
| CN115477420B (en) * | 2021-05-31 | 2024-02-13 | 中国石油化工股份有限公司 | Polymer-containing oilfield wastewater treatment method and treatment device |
| CN113443697A (en) * | 2021-07-09 | 2021-09-28 | 哈尔滨工业大学 | Continuous flow device for catalyzing ozone oxidation by multistage membrane module |
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| CN114835306A (en) * | 2022-06-10 | 2022-08-02 | 苏州新能环境技术股份有限公司 | High-difficulty wastewater treatment method based on ozone and ceramic membrane |
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