CN102276095B - Method for degrading organic pollutants in water by gradient ozone catalytic oxidation - Google Patents
Method for degrading organic pollutants in water by gradient ozone catalytic oxidation Download PDFInfo
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Abstract
The invention relates to a method for degrading organic pollutants in water by gradient ozone catalytic oxidation, and relates to a gradient ozone catalytic oxidation combination method for degrading organic pollutants in water. By the method, the problem that the conventional advanced oxidation technology has defects during individual use, the problem that the organic pollutants in the water cannot be removed efficiently, the problem that the influence of the pH value and temperature of the water on the method is large, and the problem that high-toxicity byproducts are formed are solved. In the method, water treatment is realized by combining two or three of a process for treating O3 individually, an enhanced catalytic oxidation process for O3 and an O3/ultraviolet (UV) process sequentially. By the reasonable optimizing and gradient combination of the three treatment modes, the method is suitable for wide pH values and a wide temperature range, the pollutants with intermediate toxicity are controlled to be formed, the toxicity of the pollutants is reduced, the pollutants in the water is degraded efficiently and completely, and the content of oxidative species in effluent is controlled. An efficient oxidation treatment effect is kept at low temperature, and the generation of bromate, nitroso dimethylamine, chlorate, perchlorate, iodate and periodate can be controlled greatly.
Description
Technical field
The present invention relates to a kind of gradient catalytic ozonation combined method of the organic pollutants of degrading.
Background technology
In recent years, water body is subject to polluting increasingly widely, comprise micro quantity organic pollutant and the heavy metal contaminations such as endocrine disrupter (EDCs), medicine (PPCPs), agricultural chemicals, microbiotic, persistence organic pollutant (POPs), conventional water treatment process is obviously not enough to its removal ability, chlorination also can produce the disinfection byproduct (DBP) larger to human health damage (DBPs), has " three cause " (carcinogenic, teratogenesis, mutagenesis) effect, serious harm drinking person healthy.Therefore, in the removal water of maximum possible micro quantity organic pollutant, disinfection byproduct (DBP) etc. as the drinking water deep purification engineering of purpose, significant.
High-level oxidation technology (Advaced Oxidation Technologies, abbreviation AOT) claims again the deep oxidation technology, be to utilize the Novel oxygen of the organic pollutant of high stability, difficult degradation in extremely strong free radical (such as OH) the oxygenolysis water of activity to eliminate the pollution technology, mainly comprise Fenton reagent method and Fenton-like reagent method, ozone and combination process method, Photocatalytic Oxidation With Semiconductors method, ferric acid salt oxidation style.
Fenton reagent method is to utilize ferrous ion (Fe
2+) and H
2O
2A kind of mode of the OH oxidize contaminants that produces.But the pH narrow range that it is applicable requires strongly-acid; Ferric iron iron mud easily accumulates; H
2O
2The throwing amount is large, energy consumption is high.
The Photocatalytic Oxidation With Semiconductors technology is to utilize semiconductor catalyst to produce organism in the free-radical oxidn water of strong oxidation capacity under the UV radiation.Its main drawback is: TiO
2The trickle inconvenience of powder particle is reclaimed; Processing costs is higher; Equipment is complicated.
Ferrate (permanganate) oxidation style is to utilize ferrate (permanganate) to have strong oxidizing property in whole pH scope, and organic pollutants is carried out oxidation removal.Its main drawback is: toxicant in the middle of can producing; More limited and the thorough mineralising of the material that can remove; Reaction process requires stricter to temperature, pH scope and part situation.
Ozone is widely used in tap water and the sewage disposal as a kind of Green Oxidant commonly used, and the multiple advanced oxidation mode that it is derived comprises ozone oxidation, O
3/ H
2O
2, O
3/ ultrasonic, O
3/ UV, O
3/ potassium permanganate, O
3Transition ion homogeneous catalysis, O
3/ hydrous iron oxide (zinc oxyhydroxide) heterocatalysis, O
3/ ceramic honey comb/ultrasonic coupling etc.But various ozone oxidation mode, each have their own advantage is with not enough.
The ozone oxidation reaction system is the OH degradation of organic substances that utilizes ozone and ozone oxidation to produce.Ozone is the selective oxidation agent, and oxidizing potential is 2.07V, oxidation capacity slightly a little less than, can only oxidation some be easy to oxidized organism; The oxidizing potential of the OH of ozone generation is 2.8V, is strong oxidizer, and non-selectivity can be reacted with most organic in the water.Simple ozone is easy to use, is a kind of Green Oxidant, and majority of organic pollutants in the energy oxidizing water is a kind of very effective oxygenant.But it is very large that ozone oxidation is affected by temperature, pH value, and cryogenic effect is poor, and low pH value is substantially without the advanced oxidation ability; The ozone utilising efficiency is low in the treating processes, and bromate produces the concentration height; Residual ozone concentration is high in the water, needs the extra reductive agent that adds to process; Pollutant oxidation speed for difficult degradation is slow.
O
3/ H
2O
2Method mainly utilizes ozone and hydrogen peroxide synergy can produce the hydroxyl radical free radical with extremely strong oxidation capacity, H
2O
2Introducing, can improve the oxidation rate of ozone, make it be subjected to the impact of temperature and pH slightly little, but its shortcoming is: it is slightly large affected by temperature, pH; Also can produce certain density bromate; Need to add O
3And H
2O
2, energy consumption is high; The actual effective rate of utilization of middle active specy is low; Remain O in the water
3And H
2O
2Concentration is high, need to add extra reductive agent except O
3And H
2O
2, and easily the application of follow-up BAC process is had a negative impact.
O
3/ ultrasonic method is introduced ultrasonicly, can strengthen the oxidation rate of ozone, and the Accelerative mass transfer process improves the utilising efficiency of gaseous ozone; Its main drawback is: introduce ultrasonic device, operational management complexity and energy consumption are high; Affected greatly by temperature, pH; It is high that bromate produces concentration; The utilization ratio of ozone is low, and residual ozone concentration is high in the water, may produce some such as H
2O
2Etc. intermediate by-products, need the extra reductive agent that adds to process.
O
3Catalysis method, the introducing of catalyzer can obviously improve the oxide treatment speed of ozone, and to a certain extent, certain special catalyst can suppress the generation of bromate.But catalyzer itself is contaminated easily, loses easily catalytic activity; And catalyzer easily runs off, and discharges easily heavy metal ion and enters water body, causes secondary pollution; The utilising efficiency of ozone does not obviously improve, and can generate some such as H
2O
2Etc. intermediate by-products, need the extra reductive agent that adds to process; Also can produce certain density bromate; Temperature, pH value also have obvious impact to it.
O
3/ UV method, ultraviolet have the advantages such as green, safety, environmental protection, convenience as emerging high-level oxidation technology, are combined with ozone, can increase substantially the decomposition rate of ozone, improve its rate of oxidation and utilising efficiency; By reducing the CT value of ozone, can reduce the growing amount of bromate, oxymuriate and iodate; Not affected by temperature and pH value; Residual ozone concentration is low in the water; The middle toxicity species that generate are few, suppress nitrite ion (NO
2 -) generation, the generation of establishment disinfection byproduct (DBP), bio-toxicity obviously reduces; Can take full advantage of the metal ion synergistic catalysis in the water.But the oxidation capacity of this technology ozone is not fully used, and the hydroxyl radical free radical in the organism competition system of the easy oxidation of part causes the decline of efficient; The penetrativity of ultraviolet is subjected to the impact of water body itself to a certain extent, causes the ultraviolet utilising efficiency on the low side; Processing cost is relatively high; Process if be used alone as advanced oxidation, the huge and complex structure of reactor is unfavorable for operation, operation and management.
In sum, advanced oxidation is eliminated the pollution technology as a kind of Novel oxygen, aspect processing micro-polluted source water and degrading difficult removal organic pollutant, is with a wide range of applications; But each technology all has defective to a certain degree when using, wherein, and O
3/ UV method generates, generates the advantages such as middle toxicity species are few owing to have the control bromate, has more in actual applications practicality; But the ultraviolet penetrativity is subjected to that water body itself affects greatly, the ultraviolet utilization ratio is on the low side, and application response device bulky complex causes the shortcoming such as high expensive also to can not be ignored separately.Therefore can consider to adopt the kinds of processes coupling technique, with O
3/ UV technique is other high-level oxidation technologies of core coupling, compensates its defect, and realizes efficient, safe, the economic removal of organic pollutant.
Summary of the invention
The objective of the invention is in order to solve existing high-level oxidation technology and to use separately, equal Shortcomings, can not efficiently remove organic pollutants, be subjected to pH value and the temperature effect of water body large during use, and can produce the problem of the stronger by product of toxicity, the invention provides the method for degrading organic pollutants in water by gradient ozone catalytic oxidation, degraded organic pollutants that can highly effective and safe.
The method of degrading organic pollutants in water by gradient ozone catalytic oxidation of the present invention is by two kinds or three kinds in following three kinds of processing modes are made up in turn, the graded of utilizing ozone concn carries out to water body that oxide treatment realizes, the first processing mode is O
3Individual curing, the second processing mode are O
3The fortifying catalytic oxidizing process; The third processing mode is O
3/ UV technique.
Wherein, the first processing mode O
3The treatment process of individual curing is: add O in water body
3Process the O that adds in the control water body
3Concentration be 0.5～30mg/L, the water conservancy residence time is 0.5～30min; O
3Dosing method for adding with ozone gas or with the form of ozone water, add or the segmentation multi-point adding ozone is disposable.
The second processing mode O
3The treatment process of fortifying catalytic oxidizing process is: add O in water body
3, and adding O
3The time or add O
3Afterwards water body is applied the reinforcement means, the O that adds in the control water body
3Concentration range be 0.5～25mg/L, hydraulic detention time is 1～20min, wherein, the reinforcement means are that power is that process the ultrasonic energy field of 1～10000W, add H in water body
2O
2Perhaps in water body, add catalyzer, the H that adds in the control water body
2O
2Concentration be 0.2～20mg/L, the concentration of the catalyzer that adds is 0.1～20mg/L.Described catalyzer is homogeneous phase metal ion catalyst or heterogeneous catalyst, and homogeneous catalyst is iron, manganese, nano-TiO
2Perhaps nano Ce O
2, heterogeneous catalyst is TiO
2, CeO
2, hydrous iron oxide, zinc oxyhydroxide, gac or ceramic honey comb fill or load on the carrier, carrier be ceramic, silica gel or gac.
The third processing mode O
3The treatment process of/UV technique is: add O in water body
3, and simultaneously water body is carried out ultraviolet light irradiation, the O that adds in the control water body
3Concentration range be 0.1～10mg/L, UV-light metering is 1.5～10000 joules/liter, hydraulic detention time is 0.1～5min.Wherein UV-light excites one or several ultraviolet lamps in ultraviolet lamp, xenon lamp and the halogen lamp to provide by low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, amalgam ultraviolet lamp, quasi-molecule; The decoration form of ultraviolet lamp is immersion or unsettled irradiation formula.
In the method for degrading organic pollutants in water by gradient ozone catalytic oxidation of the present invention in three kinds of processing modes the concentration of ozone reduce successively, form gradient concentration, realize the graded oxidation of ozone in the treating processes, and then water body processed.
Water body described in the method for degrading organic pollutants in water by gradient ozone catalytic oxidation of the present invention is tap water, the water outlet of sewage second pond, underground water, seawater, middle water reuse, process water or domestic water, to pH value, temperature, turbidity, colourity, TOC, the COD of water body
Mn, ionic strength, pollutant type, the equal no requirement (NR) of pollution concentration scope.
In the method for degrading organic pollutants in water by gradient ozone catalytic oxidation of the present invention, preferably, the pH value of control water body (water inlet) is 3～11, and the temperature of water body (water inlet) is 0～40 ℃.
The present invention is applicable to wide region pH value and wide temperature range by reasonably optimizing, the gradient combination of three kinds of processing modes, and toxic pollutants generates and reduction toxicity in the middle of controlling, efficient degradation water pollutant, the content of oxidisability species in the control water outlet.
The first processing mode of the present invention mainly is to utilize the strong oxidizing property of ozone molecule to realize easy degradation of contaminant in the direct oxidation water, in order to improve the actual utilising efficiency of ozone; In addition, in the first processing mode, because ozone also can produce certain hydroxyl radical free radical, therefore, hardly degraded organic substance also can be realized the hydroxylation of small portion, is beneficial to next step further degraded.But the first processing mode can produce a certain amount of bromate, therefore, need to reasonably regulate duration of contact, and the throwing amount of ozone, and the bromate of generation is remained in the certain standard.Can control the growing amount of bromate by the CT value of regulating ozone.
The second processing mode of the present invention has been introduced H on the basis of ozonize
2O
2, catalyzer (homogeneous phase metal ion catalysis or heterogeneous catalyst) or ultrasonic energy field, greatly strengthen ozone and be converted into hydroxyl radical free radical, the water conservancy residence time can greatly reduce.The second processing mode of the present invention mainly is to utilize the great amount of hydroxy group free radical that produces to realize the fast degradation of difficult degradation pollutent, even realizes organic mineralising.Owing in the second treatment process, have simultaneously ozone and a large amount of hydroxyl radical free radicals, can produce the toxic by-products such as a large amount of NDMA, bromate, periodate, perchlorate, therefore, need rationally control ozone concn, H
2O
2, the dosage of catalyzer or the power of ultrasonic energy field, and adjust hydraulic detention time, realize the abundant degraded of difficult degradation pollutent, and the growing amount of the toxic by-products such as control NDMA, bromate, periodate, perchlorate.The difficult degradation pollutent can be degraded quickly and efficiently in the second treatment process.
The third treatment process of the present invention is introduced UV on the basis of simple ozone process and is strengthened, utilize strong absorbent and the excitability of ozone in the uv-absorbing scope to produce a large amount of OH, the effect of synergy ozone molecular oxidation realizes the removal to organic pollutant.The third treatment process reduces the CT value of ozone by introducing a large amount of hydroxyl radical free radical of ozone generation in the ultraviolet fast decoupled water, can greatly reduce and control the growing amount of bromate, oxymuriate and iodate; Can obviously control the methylamine severe toxicity intermediate product that generates in the ozone oxidation process, and greatly reduce the generation of middle toxic substance; Can suppress nitrous acid (NO
2 -) generation; Generation that can the follow-up chlorine disinfection by-product of establishment; Can obviously reduce bio-toxicity; Residual ozone in the water outlet, concentration of hydrogen peroxide are low, do not need follow-up interpolation reductive agent to carry out extra process.Because the processing of the simple processing of leading portion ozone or ozone catalytic reinforcing process, extinction material and photomask agent in the water obviously reduce, greatly increased the transmittance of water body, therefore, can take full advantage of the excitation of ultraviolet in the third treatment process, realize that the high-level efficiency of ozone/ultraviolet is processed pollutent.The flow pattern of water body in treatment unit adopts circulation batch type, complete hybrid or continuously streamed in the third processing mode of the present invention, requires to stir, and reaching the state of turbulent flow, and water layer thickness is less than 0.5m.
The method of degrading organic pollutants in water by gradient ozone catalytic oxidation of the present invention is O
3Individual curing, O
3Fortifying catalytic oxidizing process and O
3Three kinds of high-level oxidation technologies of/UV technique, the deficiency when remedying its each self-application reaches organic high-efficiency detoxicating, removal and thorough mineralising.Advantage of the present invention is: (1) can improve active specy and (comprise O
3, OH,
1O
2, HO
2, O
2 -, H
2O
2, SO
4 -) utilising efficiency; (2) can widen the pH scope of application for the treatment of process, be subjected to the impact of pH little; (3) can expand the Applicable temperature scope of technique, keep at low temperatures efficient oxide treatment effect; (4) can utilize simultaneously the metal ion in the former water to work in coordination with homogeneous catalysis; (5) can carry out efficient mineralising to organic pollutant; (6) can greatly reduce even not toxigenous intermediate product (methylamines that comprises nitrosodimethylamine); (7) compare with other advanced oxidation processes, can obviously reduce the bio-toxicity that is caused by by product that produces in the treating processes; (8) can greatly control the generation of bromate, nitrosodimethylamine (NDMA), oxymuriate, perchlorate, iodate, periodate; (9) can increase the transmittance of processing water body, improve the utilising efficiency of UV-light; (10) can overcome the shortcoming of ultraviolet, prevent nitrite ion (NO
2 -) generation; (11) need not carry out extra ozone tail gas processes; (12) remain O in the water after the processing
3And H
2O
2Concentration is low, does not need further to add reductive agent and processes.
Description of drawings
Fig. 1 is the clearance-time plot of oil of mirbane in the embodiment 25, among the figure "-●-" curve is gradient catalytic ozonation degradation method, "-■-" curve only carries out O for contrast experiment's 7
3Independent oxide treatment; Fig. 2 is the clearance-time plot of ozone in the embodiment 26, among the figure "-●-" curve is gradient catalytic ozonation degradation method, "-■-" curve only carries out O for contrast experiment's 8
3Independent oxide treatment.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment is the method for degrading organic pollutants in water by gradient ozone catalytic oxidation, it is by two kinds or three kinds in following three kinds of processing modes are made up in turn, the graded of utilizing ozone concn carries out to water body that oxide treatment realizes, the first processing mode is O
3Individual curing, the second processing mode are O
3The fortifying catalytic oxidizing process; The third processing mode is O
3/ UV technique;
Wherein, the first processing mode O
3The treatment process of individual curing is: add O in water body
3Process the O that adds in the control water body
3Concentration be 0.5～30mg/L, the water conservancy residence time is 0.5～30min;
The second processing mode O
3The treatment process of fortifying catalytic oxidizing process is: add O in water body
3, and adding O
3The time or add O
3Afterwards water body is applied the reinforcement means, the O that adds in the control water body
3Concentration range be 0.5～25mg/L, hydraulic detention time is 1～20min, wherein, the reinforcement means are that power is that process the ultrasonic energy field of 1～10000W, add H in water body
2O
2Perhaps in water body, add catalyzer, the H that adds in the control water body
2O
2Concentration be 0.2～20mg/L, the concentration of the catalyzer that adds is 0.1～20mg/L; Described catalyzer is homogeneous phase metal ion catalyst or heterogeneous catalyst;
The third processing mode O
3The treatment process of/UV technique is: add O in water body
3, and simultaneously water body is carried out ultraviolet light irradiation, the O that adds in the control water body
3Concentration range be 0.1～10mg/L, UV-light metering is 1.5～10000 joules/liter, hydraulic detention time is 0.1～5min.
The first processing mode (O in the present embodiment
3Individual curing) organic degraded is mainly contained two approach, the one, utilize the strong oxidizing property oxidation of organic compounds of ozone; The 2nd, the hydroxyl radical free radical that utilizes ozone decomposed to produce carries out oxidation to organism.The ozone oxidation current potential is 2.07V, and oxidation capacity is stronger, and some are easy to oxidized organism the energy oxidation, and a small amount of hydroxyl radical free radical of its generation, can the fast degradation pollutent.In the first processing mode of present embodiment, the oxygenizement of ozone molecule has selectivity, can optionally remove the organism (comprising phenolic compound, endocrine disrupter, part agricultural chemicals, some drugs and some other organic pollutant that contains unsaturated functional group) of easy oxidation, make pollutent realize hydroxylation, be beneficial to bio-oxidation, oxidation efficiency is high, and energy consumption is low, and can produce middle toxicant still less; The oxygenizement of hydroxyl radical free radical does not have selectivity, therefore can process the pollutent of the overwhelming majority, especially the organic pollutant of difficult degradation (comprising persistent pollutant), with respect to simple ozone molecule oxidation, oxidation capacity is stronger, but efficient is lower, can produce multiple poisonous intermediate product.Therefore, the first processing mode oxidisability that can take full advantage of ozone molecule realizes fast and the easy degradation of contaminant in the degradation water efficiently.
The second processing mode is at simple O in the present embodiment
3By the reinforcement means, comprise adding H on the basis of technique
2O
2, catalyzer (homogeneous phase metal ion catalysis or heterogeneous catalyst) or ultrasonic energy field, improve speed and the efficient of the ozone generation OH of system, improve the usefulness of its degraded difficult degradation pollutent.The advantage of the second processing mode is that ozone can become OH by fast decoupled, and a large amount of OH that produce fast can the most pollutents of high efficiency degraded; Can remove efficiently hardly degraded organic substance; It is little that treating processes is subjected to the pH value to affect more simple ozone oxidation, can realize degraded and the mineralising of pollutent under solutions of weak acidity; By the catalyzer of special processing, can realize the control of bromate in to a certain degree; Can carry out to a certain degree removal to the natural organic matter in the water, improve the transmittance of water body; Can realize the control of ozone concn, use Measuring Ozone Concentration in Water and greatly reduce; The concentration of using water pollutant reduces greatly; Make can greatly reduce by biological assimilation organic carbon (AOC) in the water; Lower than senior oxidizing process costs such as ultraviolets.
The third processing mode is to utilize oxidisability and strong absorbent and the excitability of ozone in ultraviolet spectral range of ozone in the present embodiment, the OH of collaborative quick generation strong oxidizing property produces than simple ozone oxidation that the speed of OH is faster, efficient is higher, be subjected to system to affect less (comprising temperature and pH value).The advantage of the third processing mode is green, safety, environmental protection, convenience; UV is combined with ozone, can increase substantially the decomposition rate of ozone, improves its rate of oxidation and utilising efficiency; By reducing the CT value of ozone, can reduce the growing amount of bromate, oxymuriate and iodate; Not affected by temperature and pH value; Residual ozone in the water, concentration of hydrogen peroxide are low; Can obviously control the methylamine severe toxicity intermediate product that generates in the ozone oxidation process, and greatly reduce the generation of middle toxic substance; Can suppress nitrous acid (NO
2 -) generation; Generation that can the follow-up chlorine disinfection by-product of establishment; Can obviously reduce bio-toxicity; Can take full advantage of the metal ion synergistic catalysis in the water, but O
3When/UV technique is carried out separately, character to processed water body itself has following requirement: pH to be applicable between 3～11,0～40 ℃ of temperature, turbidity requires less than 1 degree, content of oxygen dissolved in water 0.1～8.2mg/L, TOC concentration 0.1～20mg/L, carbonate alkalinity 0.1～300mg/L (in calcium carbonate) does not require the colourity in the water, ammonia nitrogen, ionic strength.By the processing of the first and/or the second processing mode, can reduce pollutent and natural organic matter concentration in the water body, improve the penetration coefficient of ultraviolet, and then improve the utilization ratio of ultraviolet; Can obviously reduce the concentration of organic pollutants, reduce the residence time of the third processing mode process, reduce cost; O has been satisfied in water outlet after the first and/or the processing of the second processing mode
3The requirement of/UV art breading water body.Than O
3/ UV technique individual curing can obviously reduce complexity and the size of reactor, easy handling, operation and management.
Adopting catalyzer in the second processing mode can be homogeneous catalyst, for example iron, manganese, nano-TiO particularly
2Perhaps nano Ce O
2Also can be heterogeneous catalyst, for example be TiO
2, CeO
2, hydrous iron oxide, zinc oxyhydroxide, gac or ceramic honey comb fill or load on the carrier, carrier be ceramic, silica gel or gac.
The method of the degrading organic pollutants in water by gradient ozone catalytic oxidation of present embodiment is by with O
3Individual curing, O
3Fortifying catalytic oxidation, O
3/ UV technique reasonably optimizing, organically combination, fully played the oxidation capacity of different activities species, the generation of middle toxicant suppresses the generation of bromate in the control water outlet, reduce the overall toxicity of intermediate material that produces in the degradation process, ozone, H in the control water outlet
2O
2Content, reduce and even not carry out subsequent disposal with the interpolation reductive agent.
Embodiment two: what present embodiment and embodiment one were different is that described water body is tap water, the water outlet of sewage second pond, underground water, seawater, middle water reuse, process water or domestic water.Other step and parameter are identical with embodiment one.
Embodiment three: that present embodiment is different from embodiment one or two is O in the first processing mode, the second processing mode and the third processing mode
3Dosing method for adding with ozone gas or with the form of ozone water.Other step and parameter are identical with embodiment one or two.
Add or the segmentation multi-point adding ozone is disposable in the present embodiment.The concentration range of the ozone gas that adds is 1%～100%.
Embodiment four: present embodiment is different from embodiment one or two is that the pH value of control water body (for the first time water inlet) is 3～11, and temperature is 0～40 ℃.Other step and parameter are identical with embodiment one or two.
Embodiment five: that present embodiment is different from one of embodiment one to four is the first processing mode O
3The treatment process of individual curing is: add O in water body
3Process the O that adds in the control water body
3Concentration be 0.5～3mg/L, the water conservancy residence time is 0.5～10min, described water body is tap water, underground water, seawater or middle water reuse.Other step and parameter are identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is that the second processing mode is O
3/ ultrasonic energy field treatment process, treatment process is: add O in water body
3, and adding O
3The time or add O
3Afterwards water body is applied the ultrasonic energy field that power is 1～10000W, the O that adds in the control water body
3Concentration be 0.5～25mg/L, the control hydraulic detention time is 1～20min.Other step and parameter are identical with one of embodiment one to five.
In the second processing mode of present embodiment, the water body of processing can be the water outlet after processing through the first processing mode.
When water body is water outlet after tap water, underground water, seawater or middle water reuse are processed through the first processing mode, water body is applied the ultrasonic energy field that power is 1～1000W in the present embodiment.According to Organic Pollutants In Water content height, appropriateness is adjusted the power of ultrasonic energy field.
In the second processing mode of present embodiment, the difficult degradation pollutent can be degraded quickly and efficiently.
Embodiment seven: what present embodiment was different from one of embodiment one to five is that the second processing mode is O
3/ H
2O
2Treatment process, treatment process is: add O in water body
3, and adding O
3The time or add O
3Add H in the backward water body
2O
2, the O that adds in the control water body
3Concentration be 0.5～25mg/L, the H that adds in the water body
2O
2Concentration be 0.2～20mg/L, hydraulic detention time is 1～20min.Other step and parameter are identical with one of embodiment one to five.
In the second processing mode of present embodiment, the water body of processing can be the water outlet after processing through the first processing mode.
Embodiment eight: what present embodiment was different from one of embodiment one to five is that the second processing mode is O
3/ H
2O
2Treatment process, treatment process is: add O in water body
3, and adding O
3The time or add O
3Add H in the backward water body
2O
2, the O that adds in the control water body
3Concentration be 0.5～3mg/L, the H that adds in the water body
2O
2Concentration be 0.2～5mg/L, the control hydraulic detention time is 1～10min, described water body is tap water, underground water, seawater or middle water reuse.Other step and parameter are identical with one of embodiment one to five.
In the second processing mode of present embodiment, the water body of processing can also be the water outlet after tap water, underground water, seawater or middle water reuse are processed through the first processing mode.
Embodiment nine: what present embodiment was different from one of embodiment one to five is that the second processing mode is O
3/ catalyst treatment technique, treatment process is: add O in water body
3, and adding O
3The time or add O
3Add catalyzer in the backward water body, the O that adds in the control water body
3Concentration be 0.5～25mg/L, the concentration of the catalyzer that adds in the water body is 0.1～20mg/L, hydraulic detention time is 1～20min, described homogeneous phase metal ion catalyst or heterogeneous catalyst.Other step and parameter are identical with one of embodiment one to five.
Adopting catalyzer in the present embodiment can be homogeneous catalyst, for example iron, manganese, nano-TiO particularly
2Perhaps nano Ce O
2Also can be heterogeneous catalyst, for example be TiO
2, CeO
2, hydrous iron oxide, zinc oxyhydroxide, gac or ceramic honey comb fill or load on the carrier, carrier be ceramic, silica gel or gac.
In the second processing mode of present embodiment, the water body of processing can be the water outlet after processing through the first processing mode.
Embodiment ten: what present embodiment was different from one of embodiment one to five is that the second processing mode is O
3/ catalyst treatment technique, treatment process is: add O in water body
3, and adding O
3The time or add O
3Add catalyzer in the backward water body, the O that adds in the control water body
3Concentration be 0.5～3mg/L, the concentration of the catalyzer that adds in the water body is 0.1～2mg/L, hydraulic detention time is 1～10min, and described catalyzer is homogeneous phase metal ion catalyst or heterogeneous catalyst, and described water body is tap water, underground water, seawater or middle water reuse.Other step and parameter are identical with one of embodiment one to five.
Adopting catalyzer in the present embodiment can be homogeneous catalyst, for example iron, manganese, nano-TiO particularly
2Perhaps nano Ce O
2Also can be heterogeneous catalyst, for example be TiO
2, CeO
2, hydrous iron oxide, zinc oxyhydroxide, gac or ceramic honey comb fill or load on the carrier, carrier be ceramic, silica gel or gac.
In the second processing mode of present embodiment, the water body of processing can be the water outlet after processing through the first processing mode.
Embodiment 11: that present embodiment is different from one of embodiment one to ten is the third processing mode O
3The treatment process of/UV technique is: add O in water body
3, and simultaneously the tap water water body is carried out ultraviolet light irradiation, the O that adds in the control water body
3Concentration be 0.1～3mg/L, UV-light metering is 1.5～1000 joules/liter, hydraulic detention time is 0.1～5min.Other step and parameter are identical with one of embodiment one to ten.
The water body that present embodiment is processed is through the tap water after the first processing mode and/or the processing of the second processing mode or the water outlet of domestic water.
Embodiment 12: that present embodiment is different from one of embodiment one to ten is the third processing mode O
3The treatment process of/UV technique is: add O in water body
3, and simultaneously the underground water water body is carried out ultraviolet light irradiation, the O that adds in the control water body
3Concentration be 0.1～2.5mg/L, UV-light metering is 1～600 joule/liter, hydraulic detention time is 0.1～5min.Other step and parameter are identical with one of embodiment one to ten.
The water body that present embodiment is processed is the water outlet through the underground water after the first processing mode and/or the processing of the second processing mode.
Embodiment 13: that present embodiment is different from one of embodiment one to ten is the third processing mode O
3The treatment process of/UV technique is: add O in water body
3, and simultaneously the underground water water body is carried out ultraviolet light irradiation, the O that adds in the control water body
3Concentration be 0.3～10mg/L, UV-light metering is 10～10000 joules/liter, hydraulic detention time is 0.1～5min.Other step and parameter are identical with one of embodiment one to ten.
The water body that present embodiment is processed is the water outlet through the sewage second pond water outlet after the first processing mode and/or the processing of the second processing mode.
Embodiment 14: that present embodiment is different from one of embodiment one to ten is the third processing mode O
3The treatment process of/UV technique is: add O in water body
3, and simultaneously the underground water water body is carried out ultraviolet light irradiation, the O that adds in the control water body
3Concentration be 0.1～5mg/L, UV-light metering is 5～6000 joules/liter, hydraulic detention time is 0.1～5min.Other step and parameter are identical with one of embodiment one to ten.
The water body that present embodiment is processed is the water outlet through the process water after the first processing mode and/or the processing of the second processing mode.
Embodiment 15: what present embodiment was different from one of embodiment one to 14 is that the third processing mode medium ultraviolet light excites one or several ultraviolet lamps in ultraviolet lamp, xenon lamp and the halogen lamp to provide by low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, amalgam ultraviolet lamp, quasi-molecule.Other step and parameter are identical with one of embodiment one to 14.
The decoration form of present embodiment medium ultraviolet lamp is immersion or unsettled irradiation formula.
Embodiment 16: what present embodiment was different from one of embodiment one to 14 is that the flow pattern of water body in treatment unit adopts circulation batch type, complete hybrid or continuously streamed in the third processing mode, requirement stirs, to reach the state of turbulent flow, and water layer thickness is less than 0.5m.Other step and parameter are identical with one of embodiment one to 14.
Embodiment 17: present embodiment is different from one of embodiment one to 16 is that the method for degrading organic pollutants in water by gradient ozone catalytic oxidation is by the first processing mode and the second processing mode are made up in turn, and the graded of utilizing ozone concn carries out to water body that oxide treatment realizes.Other step and parameter are identical with one of embodiment one to 16.
In the present embodiment since the first processing mode in ozonization have selectivity, the organic pollutant of the difficult degradation of substantially can not degrading; The ozone oxidation temperature influence is very large, and cryogenic effect is poor; Affected greatly by the pH value, low pH value is substantially without the advanced oxidation ability; The ozone utilising efficiency is low in the treating processes, and bromate produces the concentration height; Residual ozone concentration is high in the water, needs the extra reductive agent that adds to process; O
3Simple processing is slow for the pollutant oxidation speed of difficult degradation.Therefore, it is combined with the second processing mode, is taking full advantage of on the advantage basis of the first processing mode, and remedy the deficiency of the first processing mode, realize efficient, quick, safe degraded water pollutant.
The organism that present embodiment utilizes the first processing mode promptly to degrade and easily be degraded in the water body then in conjunction with the second processing mode, makes oxidation capacity more by force and does not have the organic pollutant that OH optionally processes difficult degradation in the water.Because the first processing mode is with the organic matter removal of easily degrading in the water body, Pollutant levels reduce greatly, avoid the OH of its competition strong oxidizing property, therefore, have improved it and have processed the utilization ratio of hardly degraded organic substance, realize that the difficult degradation pollutent is in the efficient removal of this section.
After the first processing mode finished in the present embodiment, ozone concn generally can be very high, can satisfy the concentration of ozone in the water body of needs in the second processing mode, can no longer additionally add ozone; If ozone concn does not satisfy the requirement of the second processing mode, can add again ozone, reach requirement to keep Measuring Ozone Concentration in Water.
Embodiment 18: present embodiment is different from one of embodiment one to 16 is that the method for degrading organic pollutants in water by gradient ozone catalytic oxidation is by the first processing mode and the third processing mode are made up in turn, and the graded of utilizing ozone concn carries out to water body that oxide treatment realizes.Other step and parameter are identical with one of embodiment one to 16.
Because ozonization has selectivity, the organic pollutant of the difficult degradation of substantially can not degrading in the first processing mode; The ozone oxidation temperature influence is very large, and cryogenic effect is poor; Affected greatly by the pH value, low pH value is substantially without the advanced oxidation ability; The ozone utilising efficiency is low in the treating processes, and bromate produces the concentration height; Residual ozone concentration is high in the water, needs the extra reductive agent that adds to process; O
3Simple processing is slow for the pollutant oxidation speed of difficult degradation.Therefore, it is combined with the third processing mode, is taking full advantage of on the advantage basis of the first processing mode, and remedy the deficiency of the first processing mode, realize efficient, quick, safe degraded water pollutant.
The organism that present embodiment utilizes the first processing mode promptly to degrade and easily be degraded in the water body, then in conjunction with the third processing mode, utilize strong absorbent and the excitability of ozone in the uv-absorbing scope to produce a large amount of OH, the effect of synergy ozone molecular oxidation, realization is to the removal of organic pollutant, the transmittance of water outlet water body improves after the first processing mode is processed simultaneously, has improved the penetration coefficient of UV in water, thereby has improved the utilising efficiency of UV; The existence of the third processing mode can significantly reduce O simultaneously
3The residence time of individual curing technique and O
3The throwing amount has significantly been controlled the generation of the middle toxicants such as bromate; Water outlet residue O
3And H
2O
2Concentration is low, do not need further to add reductive agent processes; O
3The minimizing of throwing amount and the raising of utilization ratio can significantly reduce O
3Exhaust emissions has been saved O
3Tail gas treatment process.
After the first processing mode finished in the present embodiment, ozone concn generally can be very high, can satisfy the concentration of ozone in the water body of needs in the third processing mode, can no longer additionally add ozone; If ozone concn does not satisfy the requirement of the third processing mode, can add again ozone, reach requirement to keep Measuring Ozone Concentration in Water.
Embodiment 19: present embodiment is different from one of embodiment one to 16 is that the method for degrading organic pollutants in water by gradient ozone catalytic oxidation is by the second processing mode and the third processing mode are made up in turn, and the graded of utilizing ozone concn carries out to water body that oxide treatment realizes.Other step and parameter are identical with one of embodiment one to 16.
Present embodiment has remedied the second processing mode and the third processing mode combination when adopting catalyzer in the second processing mode, and catalyzer itself is contaminated easily, loses easily catalytic activity; And catalyzer easily runs off, and discharges easily heavy metal ion and enters water body, causes secondary pollution; The utilising efficiency of ozone does not obviously improve, and can generate some such as H
2O
2Etc. intermediate by-products, water outlet needs the extra reductive agent that adds to process; Also can produce a large amount of bromates; Temperature influence is obvious; The pH value also has the deficiency of certain impact to it, and so that the easily fouling of the ultraviolet lamp silica tube that exists in the UV radiation treatment in the third processing mode surface need to regularly clean; The ultraviolet lamp life-span, limited the need regularly changed, and the photoreactor structure is complicated, and cost is higher, and when adopting separately the third processing mode, hydraulic detention time is oversize, and the deficiency that causes cost of water treatment to raise is resolved.Both in conjunction with after, improved ozone utilising efficiency, can be applicable to widely pH value scope and temperature range, and control does not even produce the by force toxicity intermediate product such as bromate, NDMA.
After the second processing mode finished in the present embodiment, ozone concn generally can be very high, can satisfy the concentration of ozone in the water body of needs in the third processing mode, can no longer additionally add ozone; If ozone concn does not satisfy the requirement of the third processing mode, can add again ozone, reach requirement to keep Measuring Ozone Concentration in Water.
Embodiment 20: present embodiment is different from one of embodiment one to 16 is that the method for degrading organic pollutants in water by gradient ozone catalytic oxidation is by the first processing mode, the second processing mode and the third processing mode are made up in turn, and the graded of utilizing ozone concn carries out to water body that oxide treatment realizes.Other step and parameter are identical with one of embodiment one to 16.
Water inlet (water body) is at first by having optionally O in the present embodiment
3Process, the organism that easily is degraded in the degradation water rapidly, and bring into play fully O
3Oxidation capacity, improved O
3Practical efficiency.Then O is passed through in this section water outlet
3The fortifying catalytic oxidizing process is processed, and utilizes oxidation capacity more by force and does not have the organic pollutant that OH optionally processes difficult degradation in the water.Because the O of leading portion
3Individual curing technique is removed the easily biodegradable organics in the water, and Pollutant levels reduce greatly, avoids the OH of its competition strong oxidizing property, therefore, has improved it and has processed the utilization ratio of hardly degraded organic substance, realizes that the difficult degradation pollutent is in the efficient removal of this section.Adopt at last O
3/ UV processes, because front two-stage process effect most organic pollutants of degrading, and the natural organic matter in the water, impurity also there is certain removal, can greatly improves the transmittance of water body, improve the penetration coefficient of UV in water, thereby improved the utilising efficiency of UV; And because the existence of this segment process can significantly reduce O
3Individual curing technique and O
3The residence time of fortifying catalytic oxidizing process and O
3The throwing amount has significantly been controlled the generation of the middle toxicants such as bromate; Water outlet residue O
3And H
2O
2Concentration is low, do not need further to add reductive agent processes; O
3The minimizing of throwing amount and the raising of utilization ratio can significantly reduce O
3Exhaust emissions has been saved O
3Tail gas treatment process.
Embodiment 21: present embodiment is the method for degrading organic pollutants in water by gradient ozone catalytic oxidation, it is that following three kinds of processing modes are made up in turn, the graded of utilizing ozone concn carries out to water body that oxide treatment realizes, the first processing mode is O
3Individual curing, the second processing mode are O
3/ H
2O
2Fortifying catalytic oxidizing process, the third processing mode are O
3/ UV technique; Concrete processing mode is as follows: one, add O in the tap water water body
3Process the O that adds in the control water body
3Concentration be 3mg/L, the water conservancy residence time is 3min; Two, the ozone concn in the water outlet after step 1 is processed is adjusted into 2.5mg/L, in the water outlet after step 1 is processed, adds H again
2O
2, the H that adds in the control water body
2O
2Concentration be 1.5mg/L, the control hydraulic detention time is 5min; Three, the ozone concn in the water outlet after step 2 is processed is adjusted into 1.2mg/L, and simultaneously water body is carried out ultraviolet light irradiation, the UV-light metering is 2000 joules/liter, and hydraulic detention time is 2min.
18 ℃ of the tap water water temperatures of present embodiment, pH value 7.0, wherein bromide anion Br
-Be 0.2mg/L, nitrobenzene 2 μ M.After the method for present embodiment was processed, the oil of mirbane clearance can reach 94%, and the actual generation 2.2 μ g/L of bromate are far below 10 μ g/L of drinking water safety standard.
The contrast experiment 1: the tap water water body to present embodiment only carries out O
3Oxide treatment is controlled the O that adds in the water body separately
3Concentration be 3mg/L, the water conservancy residence time is 20min.Oil of mirbane removes 57% in the water outlet after the processing, and bromate generates 120 μ g/L.
The contrast experiment 2: the tap water water body to present embodiment only carries out O
3/ H
2O
2The fortifying catalytic oxide treatment, the O that adds in the control water body
3Concentration be 2.5mg/L, the H that adds
2O
2Concentration be 1.5mg/L, the water conservancy residence time is 15min.Oil of mirbane clearance 97% in the water outlet after the processing, bromate generate 74 μ g/L.
As seen, gradient catalysis can be controlled the growing amount of bromate effectively on the basis that guarantees pollutant removal.
Embodiment 22: present embodiment is the method for degrading organic pollutants in water by gradient ozone catalytic oxidation, it is that processing mode among the first processing mode and the 3rd is made up in turn, the graded of utilizing ozone concn carries out to water body that oxide treatment realizes, the first processing mode is O
3Individual curing, the third processing mode are O
3/ UV technique; Concrete processing mode is as follows: one, add O in water body
3Process the O that adds in the control water body
3Concentration be 2.5mg/L, the water conservancy residence time is 7min; Two, the ozone concn in the water outlet after step 1 is processed is adjusted into 1.0mg/L, and simultaneously water body is carried out ultraviolet light irradiation, the UV-light metering is 3000 joules/liter, and hydraulic detention time is 5min.
18 ℃ of the water body of present embodiment (natural water body) temperature, pH value 7.0, nitrobenzene 2 μ M.After the method for present embodiment was processed, the NDMA growing amount was not for detecting.
The contrast experiment 3: the water body to present embodiment only carries out O
3Oxide treatment is controlled the O that adds in the water body separately
3Concentration be 2.5mg/L, the water conservancy residence time is 20min.The NDMA growing amount is 28ng/L in the water outlet after the processing.
As seen, gradient catalysis can be controlled the NDMA growing amount effectively on the basis that guarantees pollutant removal.
Embodiment 23: present embodiment is the method for degrading organic pollutants in water by gradient ozone catalytic oxidation, it is that processing mode in second and the third processing mode are made up in turn, the graded of utilizing ozone concn carries out to water body that oxide treatment realizes, the second processing mode is O
3/ hydrous iron oxide fortifying catalytic oxidizing process, the third processing mode are O
3/ UV technique; Concrete processing mode is as follows: one, add O in the tap water water body
3, make the O that adds in the water body
3Concentration be 2.5mg/L, and then in water body, add the hydroxyl oxidize iron catalyst, the concentration of the hydrous iron oxide that control adds is 1.5mg/L, the control hydraulic detention time is 5min; Two, the ozone concn in the water outlet after step 1 is processed is adjusted into 2.0mg/L, and simultaneously water body is carried out ultraviolet light irradiation, the UV-light metering is 3000 joules/liter, and hydraulic detention time is 5min.
The tap water water temperature of present embodiment is 18 ℃, and the pH value is 7.0, nitrobenzene 2 μ M.Oil of mirbane clearance 97% in the water outlet after present embodiment is processed, perchlorate growing amount 10 μ g/L.
The contrast experiment 4: the water body to present embodiment only carries out O
3/ hydrous iron oxide fortifying catalytic oxide treatment adds O in water body
3, the O that adds in the control water body
3Concentration be 2.5mg/L, and then in water body, add the hydroxyl oxidize iron catalyst, the concentration of the hydrous iron oxide that control adds is 1.5mg/L, the control hydraulic detention time is 15min.Oil of mirbane clearance 95% in the water outlet after the processing, perchlorate growing amount 37 μ g/L.
As seen, gradient catalysis can be controlled the perchlorate growing amount effectively on the basis that guarantees pollutant removal.
Embodiment 24: present embodiment is the method for degrading organic pollutants in water by gradient ozone catalytic oxidation, it is that processing mode in second and the third processing mode are made up in turn, the graded of utilizing ozone concn carries out to water body that oxide treatment realizes, the second processing mode is O
3/ H
2O
2Fortifying catalytic oxidizing process, the third processing mode are O
3/ UV technique; Concrete processing mode is as follows: one, add O in the tap water water body
3, make the O that adds in the water body
3Concentration be 2.5mg/L, and then in water body, add H
2O
2, the H that control adds
2O
2Concentration be 1.2mg/L, the control hydraulic detention time is 7min; Two, the ozone concn in the water outlet after step 1 is processed is adjusted into 1.5mg/L, and simultaneously water body is carried out ultraviolet light irradiation, the UV-light metering is 2500 joules/liter, and hydraulic detention time is 5min.
The tap water water temperature of present embodiment is 18 ℃, and the pH value is 7.0, nitrobenzene 2 μ M, iodide ion I
-50 μ g/L.Oil of mirbane clearance 99% in the water outlet after present embodiment is processed, periodate growing amount 1 μ g/L.
The contrast experiment 5: the water body to present embodiment only carries out O
3Oxide treatment is controlled the O that adds in the water body separately
3Concentration be 2.5mg/L, the water conservancy residence time is 20min.Oil of mirbane clearance 59% in the water outlet after the processing, periodate growing amount 1 μ g/L.
The contrast experiment 6: the water body to present embodiment only carries out O
3/ H
2O
2Oxidation is processed, and adds O in water body
3, the O that adds in the control water body
3Concentration be 2.5mg/L, and then in water body, add H
2O
2, the H that control adds
2O
2Concentration be 1.5mg/L, the control hydraulic detention time is 15min.Oil of mirbane clearance 97% in the water outlet after the processing, periodate growing amount 18 μ g/L.
As seen, gradient catalysis can be controlled the periodate growing amount effectively on the basis that guarantees pollutant removal.
Embodiment 25: present embodiment is the method for degrading organic pollutants in water by gradient ozone catalytic oxidation, it is that following three kinds of processing modes are made up in turn, the graded of utilizing ozone concn carries out to water body that oxide treatment realizes, the first processing mode is O
3Individual curing, the second processing mode are O
3/ H
2O
2Fortifying catalytic oxidizing process, the third processing mode are O
3/ UV technique; Concrete processing mode is as follows: one, add O in the tap water water body
3Process the O that adds in the control water body
3Concentration be 2mg/L, the water conservancy residence time is 3min; Two, the ozone concn in the water body after step 1 is processed is adjusted into 1.5mg/L, in the water outlet after step 1 is processed, adds H again
2O
2, the H that adds in the control water body
2O
2Concentration be 2.0mg/L, the control hydraulic detention time is 5min; Three, the ozone concn in the water body after step 2 is processed is adjusted into 1.0mg/L, and simultaneously water body is carried out ultraviolet light irradiation, the UV-light metering is 1600 joules/liter, and hydraulic detention time is 5min.
Ozone in the present embodiment step 3/UV oxidizing process adopts cylindrical reactor, and UV-light is provided by low pressure mercury lamp, and power is 10W, place the reactor axis, the nested silica tube of outer wall is immersed in the reaction solution, reactive mode is for fully hybrid, and the volume of processing water body is 800mL.
The water temperature of the tap water water body of present embodiment is 5.8 ℃, pH=7.20, and wherein containing the oil of mirbane starting point concentration is 2 μ M, tap water total organic carbon in waterbody TOC 3.95mg/L.The clearance of oil of mirbane reaches 82% in the tap water water body after the method for present embodiment is processed.
In the gradient catalytic ozonation degradation method of present embodiment in the clearance-time curve such as Fig. 1 of oil of mirbane "-●-" shown in the curve.
The contrast experiment 7: the tap water water body to present embodiment only carries out O
3Oxide treatment is controlled the O that adds in the water body separately
3Concentration be 2mg/L, the water conservancy residence time is 13min.Clearance-the time curve of oil of mirbane is shown in "-■-" curve among Fig. 1 among the contrast experiment 7.
As seen, contain the oil of mirbane starting point concentration and be the tap water water body of 2 μ M after the gradient catalytic ozonation combination degradation method of present embodiment is processed 10min, the clearance of oil of mirbane reaches 82%, after ozone individual curing art breading, and the clearance of oil of mirbane only 19.7%.Can find out that gradient catalytic ozonation combination process treatment effect of the present invention is better than ozone individual curing technique far away.
Embodiment 26: present embodiment is the method for degrading organic pollutants in water by gradient ozone catalytic oxidation, it is that following three kinds of processing modes are made up in turn, the graded of utilizing ozone concn carries out to water body that oxide treatment realizes, the first processing mode is O
3Individual curing, the second processing mode are O
3/ hydrous iron oxide fortifying catalytic oxidizing process, the third processing mode are O
3/ UV technique; Concrete processing mode is as follows: one, add O in the tap water water body
3Process the O that adds in the control water body
3Concentration be 2.5mg/L, the water conservancy residence time is 3min; Two, with the O in the water body after step 1 is processed
3Concentration be adjusted into 2.0mg/L, and then in water body, add hydrogen peroxide, the concentration of the hydrogen peroxide that control adds is 1.0mg/L, the control hydraulic detention time is 5min; Three, the ozone concn in the water body after step 2 is processed is adjusted into 1.5mg/L, and simultaneously water body is carried out ultraviolet light irradiation, the UV-light metering is 1500 joules/liter, and hydraulic detention time is 5min.
Ozone in the present embodiment step 3/UV oxidizing process adopts cylindrical reactor, and UV-light is provided by low pressure mercury lamp, and power is 10W, place the reactor axis, the nested silica tube of outer wall is immersed in the reaction solution, reactive mode is for fully hybrid, and the volume of processing water body is 800mL.
The water temperature of the water body of present embodiment is 5.8 ℃, and pH=7.20, the starting point concentration that wherein contains ozone are 2.5mg/L (i.e. the oil of mirbane of 2 μ M), total organic carbon in waterbody TOC 3.95mg/L.The clearance of ozone reaches more than 99% in the tap water water body after the method for present embodiment is processed.
In the gradient catalytic ozonation degradation method of present embodiment in the clearance-time curve such as Fig. 2 of ozone "-●-" shown in the curve.Wherein among the ordinate zou Ct/C0, the ozone concn when Ct is treatment time t, C0 are the starting point concentration of ozone in the tap water water body.
The contrast experiment 8: the water body to present embodiment only carries out O
3Oxide treatment is controlled the O that adds in the water body separately
3Concentration be 2.5mg/L, the water conservancy residence time is 10min.Clearance-the time curve of ozone is shown in "-■-" curve among Fig. 2 among the contrast experiment 8.
As seen, when water body was processed 9min through the gradient catalytic ozonation combination process of present embodiment, the degradation rate of ozone had reached 100%, and simple ozone process is processed 10min, and the ozone degradation rate is approximately 77%.Can find significantly that the gradient catalytic ozonation combination process of present embodiment can very well be controlled the residual ozone content of processing water body, not carry out the deozonization processing and do not need again to add reductive agent.
Claims (7)
1. the method for degrading organic pollutants in water by gradient ozone catalytic oxidation, it is characterized in that the method is by passing through successively the first processing mode, the second processing mode, the third processing mode, perhaps pass through successively the second processing mode, the third processing mode, the graded of utilizing ozone concn carries out to water body that oxide treatment realizes; Wherein the first processing mode is O
3Individual curing, the second processing mode are O
3The fortifying catalytic oxidizing process; The third processing mode is O
3/ UV technique; Described graded is that ozone concn reduces successively, forms gradient concentration;
Wherein, the first processing mode O
3The treatment process of individual curing is: add O in water body
3Process the O that adds in the control water body
3Concentration be 0.5～30mg/L, the water conservancy residence time is 0.5～30min;
The second processing mode O
3The treatment process of fortifying catalytic oxidizing process is: add O in water body
3, and adding O
3The time or add O
3Afterwards water body is applied the reinforcement means, the O that adds in the control water body
3Concentration range be 0.5～25mg/L, hydraulic detention time is 1～20min, wherein, the reinforcement means are that power is that process the ultrasonic energy field of 1～10000W, add H in water body
2O
2Perhaps in water body, add catalyzer, the H that adds in the control water body
2O
2Concentration be 0.2～20mg/L, the concentration of the catalyzer that adds is 0.1～20mg/L; Described catalyzer is homogeneous phase metal ion catalyst or heterogeneous catalyst;
The third processing mode O
3The treatment process of/UV technique is: add O in water body
3, and simultaneously water body is carried out ultraviolet light irradiation, the O that adds in the control water body
3Concentration range be 0.1～10mg/L, UV-light metering is 1.5～10000 joules/liter, hydraulic detention time is 0.1～5min; The flow pattern of water body in treatment unit adopts circulation batch type, complete hybrid or continuously streamed, stir to reach the state of turbulent flow, and water layer thickness is less than 0.5m.
2. the method for degrading organic pollutants in water by gradient ozone catalytic oxidation according to claim 1, the pH value that it is characterized in that controlling water body is 3～11, temperature is 0～40 ℃.
3. the method for degrading organic pollutants in water by gradient ozone catalytic oxidation according to claim 1 is characterized in that the second processing mode O
3The treatment process of fortifying catalytic oxidizing process is: add O in water body
3, and adding O
3The time or add O
3Afterwards water body is applied the reinforcement means, the O that adds in the control water body
3Concentration range be 0.5～25mg/L, hydraulic detention time is 1～20min, wherein, the reinforcement means are that power is that process the ultrasonic energy field of 1～10000W, and are adding O
3The time or add O
3Add H in the backward water body
2O
2, the O that adds in the control water body
3Concentration be 0.5～3mg/L, the H that adds in the water body
2O
2Concentration be 0.2～5mg/L, hydraulic detention time is 1～10min, described water body is tap water, underground water, seawater or middle water reuse.
4. the method for degrading organic pollutants in water by gradient ozone catalytic oxidation according to claim 1 is characterized in that the second processing mode O
3The treatment process of fortifying catalytic oxidizing process is: add O in water body
3, and adding O
3The time or add O
3Afterwards water body is applied the reinforcement means, the O that adds in the control water body
3Concentration range be 0.5～25mg/L, hydraulic detention time is 1～20min, wherein, the reinforcement means are that power is that process the ultrasonic energy field of 1～10000W, and are adding O
3The time or add O
3Add catalyzer in the backward water body, the O that adds in the control water body
3Concentration be 0.5～3mg/L, the concentration of the catalyzer that adds in the water body is 0.1～2mg/L, hydraulic detention time is 1～10min, wherein, described water body is tap water, underground water, seawater or middle water reuse, described catalyzer is homogeneous phase metal ion catalyst or heterogeneous catalyst, and the homogeneous phase metal ion catalyst is iron, manganese, nano-TiO
2Perhaps nano Ce O
2, heterogeneous catalyst is TiO
2, CeO
2, hydrous iron oxide, zinc oxyhydroxide, gac or ceramic honey comb fill or load on the carrier, carrier be ceramic, silica gel or gac.
5. the method for degrading organic pollutants in water by gradient ozone catalytic oxidation according to claim 1 is characterized in that the third processing mode O
3The treatment process of/UV technique is: add O in the tap water water body
3, and simultaneously the tap water water body is carried out ultraviolet light irradiation, the O that adds in the control water body
3Concentration range be 0.1～3mg/L, UV-light metering is 1.5～1000 joules/liter, hydraulic detention time is 0.1～5min.
6. the method for degrading organic pollutants in water by gradient ozone catalytic oxidation according to claim 1 is characterized in that the third processing mode O
3The treatment process of/UV technique is: add O in the water outlet of sewage second pond
3, and simultaneously to the sewage second pond water outlet carry out ultraviolet light irradiation, the O that control adds in the water body
3Concentration be 0.3～10mg/L, UV-light metering is 10～10000 joules/liter, hydraulic detention time is 0.1～5min.
7. the method for degrading organic pollutants in water by gradient ozone catalytic oxidation according to claim 1 is characterized in that the third processing mode O
3The treatment process of/UV technique is: add O in the process water water body
3, and simultaneously the process water water body is carried out ultraviolet light irradiation, the O that adds in the control water body
3Concentration be 0.1～5mg/L, UV-light metering is 5～6000 joules/liter, hydraulic detention time is 0.1～5min.
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| CN102701424B (en) * | 2012-05-16 | 2013-12-25 | 四川大学 | Method for promoting hydroxyl radical generation by ozone at low pH and prepared agent thereby |
| CN103589661B (en) * | 2013-07-24 | 2015-02-18 | 冯明良 | Gemmobacter aquaticus as well as application thereof |
| CN103570099B (en) * | 2013-09-13 | 2015-05-06 | 上海大学 | Method for inhibiting production of bromated in ozonization process |
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| CN101654313B (en) * | 2009-09-15 | 2012-07-04 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Method for utilizing advanced oxidation for carrying out pretreatment on sewage and culturing engineering microalgae for carrying out sewage deep treatment and carbon dioxide emission reduction |
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