CN109607745A - Catalytic ozonation processing system and catalysed oxidation processes and application - Google Patents
Catalytic ozonation processing system and catalysed oxidation processes and application Download PDFInfo
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- CN109607745A CN109607745A CN201910015839.5A CN201910015839A CN109607745A CN 109607745 A CN109607745 A CN 109607745A CN 201910015839 A CN201910015839 A CN 201910015839A CN 109607745 A CN109607745 A CN 109607745A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/782—Ozone generators
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Abstract
The present invention provides a kind of catalytic ozonation system and catalysed oxidation processes and application, the catalytic ozonation system include O3 catalytic oxidation reactor tank (6), bubble-free high-concentration ozone water preparing device (5) and low energy consumption refrigerating plant (2)；High-concentration ozone water (15) enters O3 catalytic oxidation reactor tank (6) by jet stream release (16), form fine gas bubbles, it is sufficiently mixed and occurs ozone oxidation reaction with by pretreated waste water (18), some organic pollutants in removal waste water (18)；Mineral bed course (4) and catalyst (17) are filled in O3 catalytic oxidation reactor tank (6), respectively with the supersaturated dissolved oxygen and remaining dissolubility ozonization generation hydroxyl radical free radical in high-concentration ozone water, organic matter difficult to degrade in waste water (18) is decomposed into removal.Compared with conventional catalytic ozonation technique, catalytic ozonation system of the invention can more efficiently go the persistent organic pollutants in water removal.
Description
Technical field
The present invention relates to the advanced treatment system of persistent organic pollutants in waste water and its applications, in particular to a kind of smelly
Oxygen catalytic oxidation treatment system and its application.
Background technique
The waste water of many industrial enterprises discharge after secondary biochemical treatment also the difficult for biological degradation containing large amount of complex, hold
Long, toxic, carcinogenic or mutagenic organic pollutant, such as drug, personal-care supplies (PPCPs), endocrine disruption
Object (EDCs) and other biodegradable organic compounds, these substances are discharged into the beauty that water body has not only broken up water body, and upset
The food chain of water ecosystem.These organic pollutants of human contact then can Central nervous system, hematological system and liver
The major organs such as dirty, lung, kidney damage, and therefore, industrial wastewater is before being discharged into environment water, it is necessary to pass through strictly
Pollutant is reduced to acceptable limit by advanced treating.Since water standard is more and more tighter, these persistent organic pollutants
Presence will lead to waste water and be difficult to qualified discharge or recycling, it is therefore desirable to carry out advanced treating using advanced oxidation processes.
In these techniques, Ozonation is due to having many apparent advantages, as ozone has good oxidation, disappears
Poison, decoloring ability, are widely used in the advanced treating of industrial wastewater.However, traditional Ozonation is also deposited in the application
In some shortcomings: selective oxidation, intermediate product it is more and there may be more toxic intermediate product, mineralising efficiency is insufficient, smelly
Oxygen transfer efficiency is low, can also generate bromate by-product etc..Catalytic ozonation is the one kind to grow up in recent years
The method of the novel organic pollutant that those are difficult to individually be aoxidized by ozone of capable of degrading, due to generating during the reaction
OH substantially increases oxidation efficiency and effect.
United States Patent (USP) US6315887B1 discloses a kind of device for purifying contaminated water, especially from contaminated water
The middle device for removing organic pollutant, which is utilized a reactor, in the reactor, generates by electrolysis scene
Oxidation reaction catalyst in the presence of with the contaminated water of the gas treatment containing ozone.
CN105771630A discloses the VOCs Processing tecchnics and equipment of a kind of heterogeneous catalytic oxidation, is integrated with O3、H2O2、
UV and Hydrodynamic cavitation effect, make oxidant and mode of oxidizing generate synergistic effect, so that it is next real to generate a large amount of hydroxyl radical free radical
Existing oxidation effectiveness, can synchronized desulfuring, removing heavy metals, except exhaust gas constituents such as dioxin.Contamination gas can be effectively treated in this method
Body, but contaminated fluid can not be handled and be especially contaminated water.
Summary of the invention
The purpose of the invention is to overcome the deficiencies in the prior art, improve Ozone Gas Mass Transfer Efficiency and make full use of high concentration
Oxygen reduces energy consumption, improves purification efficiency, the organic pollutant of bio-refractory in effective degrading waste water, and rationally utilizes
The energy recycled in system.Such as although United States Patent (USP) US6315887B1 discloses O3 catalytic oxidation and purifies contaminated water
Device and the device application method.But there are still some disadvantages for this catalytic ozonation.Firstly, reacting
Ozone needs carry out mass transfer in gas-liquid-solid three-phase in journey, and resistance to mass tranfer is big；Secondly, solubility is smaller at normal temperature for ozone, gas
Mass transfer force is relatively low during liquid is solid；Finally, ozone content value accounts for 10% in the mixed gas that ozone generator generates, ozone is dense
It spends relatively low.These will lead to that Ozone Gas Mass Transfer Efficiency is not high, and the ozone concentration contacted with catalyst is low, and a large amount of oxygen cannot get
It makes full use of, and eventually leads to organic matter removal low efficiency.
The present invention provides a kind of catalytic ozonation system comprising O3 catalytic oxidation reactor tank 6, the catalysis ozone oxygen
Change 6 bottom of reactor tank and be provided with jet stream release 16, high-concentration ozone water 15 enters catalysis ozone oxygen by jet stream release 16
Change reactor tank 6, fine gas bubbles (particularly preferably formation subtle cell of the diameter less than 50 microns)；By pretreated waste water 18
Into O3 catalytic oxidation reactor tank 6, it is sufficiently mixed with the high-concentration ozone water 15 of fine gas bubbles form, O3 catalytic oxidation is anti-
It answers in tank 6 filled with mineral bed course 4 and catalyst 17；O3 catalytic oxidation reactor tank (6) upper layer is equipped with vortex generator (22).
Wherein, enter O3 catalytic oxidation reactor tank 6 by pretreated waste water 18, the high concentration with fine gas bubbles form
Ozone Water 15 is sufficiently mixed, so that some organic pollutants are by ozone oxidation；It is arranged on O3 catalytic oxidation reactor tank (6) upper layer
Vortex generator (22) to be chopped under vortex generator (22) effect by the underwater bubble of catalyst layer, and then utilizes
Residual ozone is by the organic matter removal in waste water.
Wherein it is preferred to contain hydroxyl ferrous oxide in the mineral bed course (4).The hydroxyl ferrous oxide with height
Great amount of hydroxy group free radical, catalyst (17) catalytic decomposition are generated after supersaturated dissolved oxygen contact in concentration of ozone water (15) in situ
Ozone also generates great amount of hydroxy group free radical, thus organic pollutant after catalysis oxidation in waste water (18) and hydroxyl radical free radical into
Single step reaction is largely removed；Therefore, the organic pollutant after catalysis oxidation in waste water (18) and hydroxyl radical free radical are further
Reaction is largely removed；The vortex generator (22) of O3 catalytic oxidation reactor tank (6) upper layer setting, by the water of catalyst layer
Middle bubble is since collision increases, and underwater bubble is chopped under vortex generator (22) effect, and water is gentle to be mixed again, into one
Step is utilized residual ozone and is aoxidized.
Wherein it is preferred to which the ratio of above-mentioned catalytic ozonation system, high-concentration ozone water 15 and waste water 18 is with smelly
The O of oxygen molecule and Δ COD meter3: Δ COD=0.4-1.5.
Wherein it is preferred to above-mentioned catalytic ozonation system, the tail gas through being discharged at the top of O3 catalytic oxidation reactor tank 6
It is handled into vent ozone destructor 7.
Wherein it is preferred to above-mentioned catalytic ozonation system, further includes bubble-free high-concentration ozone water preparing device 5,
It is provided with aeration head 21 in bubble-free high-concentration ozone water preparing device 5, passes through aeration head 21 into no gas containing ozone gas 10
High-concentration ozone water preparing device 5 is steeped, forms high-concentrated ozone with the water 11 for entering bubble-free high-concentration ozone water preparing device 5
Water 15 supplies O3 catalytic oxidation reactor tank 6.
Wherein, containing high-concentrated ozone and supersaturated dissolved oxygen in the high-concentration ozone water (15), dissolubility ozone is dense
Degree is 50~500mg/L, and supersaturated dissolved oxygen concentration is 200~1000mg/L.
Wherein it is preferred to above-mentioned catalytic ozonation system comprising bubble-free high-concentration ozone water preparing device 5
Yet another form is provided with the fixed device 20 of aeration head in bubble-free high-concentration ozone water preparing device 5, contains ozone gas
10 enter bubble-free high-concentration ozone water preparing device 5 through end aeration head 24 by capillary 23, and bubble-free is highly concentrated with entering
The water 11 for spending ozone water preparation device 5 forms high-concentration ozone water 15 and supplies O3 catalytic oxidation reactor tank 6；Capillary end exposes
Gas head 24 is fixed on the fixed device 20 of aeration head, is entering bubble-free high-concentration ozone water preparing device containing ozone gas 10
Internal water is set to form circulation stirring when 5.Wherein, high-concentrated ozone and supersaturation dissolution are contained in the high-concentration ozone water (15)
Oxygen, dissolubility ozone concentration are 50~500mg/L, and supersaturated dissolved oxygen concentration is 200~1000mg/L.
Wherein it is preferred to which above-mentioned catalytic ozonation system, further includes low energy consumption refrigerating plant 2, by low energy consumption system
The cooling temperature containing ozone gas 10 of device for cooling 2 is 0-10 DEG C.
Wherein it is preferred to which above-mentioned catalytic ozonation system, contains ozone gas by the cooling of low energy consumption refrigerating plant 2
10 enter bubble-free high-concentration ozone water preparing device 5 after the pressurization of gas booster pump 9.
Wherein it is preferred to above-mentioned catalytic ozonation system, water 11 is from 6 top of O3 catalytic oxidation reactor tank
Recirculation water, temperature are 5-40 DEG C.
Wherein it is preferred to above-mentioned catalytic ozonation system, the recirculation water from 6 top of O3 catalytic oxidation reactor tank
It is 0-5 DEG C by its temperature after the cooling of low energy consumption refrigerating plant 2.
Wherein it is preferred to above-mentioned catalytic ozonation system, by the water after cooling of low energy consumption refrigerating plant 2 11 through liquid
Body booster pump 8 enters bubble-free high-concentration ozone water preparing device 5 after being pressurized.
Wherein it is preferred to which above-mentioned catalytic ozonation system, further includes ozone generator 3, contain ozone gas to generate
Body 10.
Wherein it is preferred to above-mentioned catalytic ozonation system, the temperature containing ozone gas 10 that ozone generator 3 generates
It is 25-40 DEG C.
Wherein it is preferred to above-mentioned catalytic ozonation system, what ozone generator 3 generated contains ozone gas 10 by low energy
It is cooling to consume refrigerating plant 2.
Wherein it is preferred to which above-mentioned catalytic ozonation system, further includes ozone generator 3, liquid oxygen storage tank 1 and low energy
Consume refrigerating plant 2, wherein liquid oxygen storage tank 1, low energy consumption refrigerating plant 2 and ozone generator 3 are sequentially connected；Liquid in liquid oxygen storage tank 1
Oxygen 12 is gas source of the purity oxygen 13 as ozone generator 3 by the gasification of low energy consumption refrigerating plant 2.
Wherein it is preferred to above-mentioned catalytic ozonation system, wherein the structure of low energy consumption refrigerating plant 2 is double heat exchanger tubes
Outside installs star fin structure additional, and inner tube is containing 11 channel of ozone gas 10 or recirculation water, and outer tube is 15 channel of liquid oxygen, star wing
Piece is the heat exchange area in order to increase air side；Low energy consumption refrigerating plant 2 utilizes the cold energy of gasification liquid oxygen (12), while will be smelly
11 cooling down of recirculation water containing 6 top of ozone gas 10 and O3 catalytic oxidation reactor tank that Oxygen Generator 3 generates.
Wherein it is preferred to above-mentioned catalytic ozonation system, wherein flow velocity of the control containing ozone gas 10, so that it is passed through
The residence time for crossing low energy consumption refrigerating plant 2 and pipeline is 1-10min.
Wherein it is preferred to above-mentioned catalytic ozonation system, wherein contain ozone gas 10 and recirculation water 11 after cooling
Enter bubble-free high-concentration ozone water preparing device 5 after being pressurized by gas booster pump 9 and liquid booster pump 8 respectively to mix, shape
At high-concentration ozone water 15, the ozone concentration in high-concentration ozone water 15 is 50~500mg/L, the concentration of dissolved oxygen is 200~
1000mg/L。
Wherein it is preferred to above-mentioned catalytic ozonation system, wherein the outlet of gas booster pump 9 and liquid booster pump 8
Pressure is 0.3-0.8MPa.
Wherein it is preferred to above-mentioned catalytic ozonation system, wherein the structure of O3 catalytic oxidation reactor tank 6 is the bottom of from
Upwards be followed successively by water distribution gas distribution area, mineral bed course and catalyst fill area, vortex reaction zone, buffer area, catchment Efflux District and
Exhaust collection area.
Wherein it is preferred to above-mentioned catalytic ozonation system, wherein the vortex reaction in O3 catalytic oxidation reactor tank 6
Multiple groups swirling device is provided in area, every group is connected on axis by multiple circular vortex generators 22.Swirl generator 22 is advantageous
It is cut in the mixing of waste water and residual ozone gas after catalysis reaction, and by the bubble that catalyst layer collision generates will be passed through
It is cut into micro-bubble.
Wherein it is preferred to above-mentioned catalytic ozonation system, wherein high-concentration ozone water 15 and waste water 18 to be processed
Reaction time is 45-120min.
Wherein it is preferred to above-mentioned catalytic ozonation system, wherein the mineral are the mineral of hydroxyl ferrous oxide,
It is further preferred that the mineral are one of nontronite, montmorillonite, illite, goethite, lepidocrocite, rock bridgeite or several
Kind.
In addition, the present invention also provides a kind of method for carrying out catalytic ozonation using above-mentioned catalytic ozonation system,
It is characterized in that, the liquid oxygen 12 from liquid oxygen storage tank 1 is vaporized by low energy consumption refrigerating plant 2, oxygen is formed, and ozone supply is sent out
Raw device 3 generates ozone, and the ozone of generation and the recirculation water from 6 top of O3 catalytic oxidation reactor tank all enter low energy consumption refrigeration
Device 2, ozone are cooled to odor at low temperature 10, and recirculation water is cooled into low temperature reflux water 11, and odor at low temperature 10 is increased by gas
Press pump 9 enters bubble-free high-concentration ozone water preparing device 5 after being pressurized, after low temperature reflux water 11 is pressurized by liquid booster pump 8
Into bubble-free high-concentration ozone water preparing device 5, the two is pressurizeed in bubble-free high-concentration ozone water preparing device 5 mixes shape
At high-concentration ozone water 15, high-concentration ozone water 15 is generated carefully by jet stream release 16 into O3 catalytic oxidation reactor tank 6
Microbubble enters O3 catalytic oxidation reactor tank (6) by pretreated waste water (18) and (is preferably promoted by pump (14) bottom of from
Portion), the high-concentration ozone water (15) of the fine gas bubbles form with diameter less than 50 microns is sufficiently mixed, and it is fast to be first dissolved property ozone
Fast a part of organic matter of oxygenolysis, then in the case where mineral bed course 4 and catalyst 17 act on there is remaining major part in removal waste water
Machine object.
Specifically, high-concentrated ozone will the be easy to ozone reaction quick oxygenolysis of substance in waste water, high-concentrated ozone
Supersaturated dissolved oxygen in water and remaining dissolubility ozone respectively with layer mineral and catalyst layer containing hydroxyl ferrous oxide
Effect generates hydroxyl radical free radical, and organic matter difficult to degrade in waste water is decomposed removal.
Wherein it is preferred to which in the above-mentioned methods, the temperature of the recirculation water from 6 top of O3 catalytic oxidation reactor tank is
5-40℃。
Wherein it is preferred to which in the above-mentioned methods, the temperature of low temperature reflux water 11 is 0-5 DEG C.It is pressurized through liquid booster pump 8
Into bubble-free high-concentration ozone water preparing device 5.
Wherein it is preferred to which in the above-mentioned methods, the temperature of odor at low temperature 10 is 0-10 DEG C.Through gas booster pump 9 be pressurized into
Enter bubble-free high-concentration ozone water preparing device 5.
Wherein it is preferred in the above-mentioned methods, dissolubility ozone concentration is 50~500mg/L in high-concentration ozone water 15,
The concentration of dissolved oxygen is 200~1000mg/L.
Wherein it is preferred to which in the above-mentioned methods, the outlet pressure of gas booster pump 9 is 0.3-0.8MPa.
Wherein it is preferred to which in the above-mentioned methods, the outlet pressure of liquid booster pump 8 is 0.3-0.8MPa.
Wherein it is preferred to which in the above-mentioned methods, the reaction time of high-concentration ozone water 15 and waste water 18 to be processed is 45-
120min。
Wherein it is preferred to above-mentioned catalytic ozonation system, wherein the mineral are the mineral of hydroxyl ferrous oxide,
It is further preferred that the mineral are one of nontronite, montmorillonite, illite, goethite, lepidocrocite, rock bridgeite or several
Kind.
In addition, the present invention also provides a kind of above-mentioned catalytic ozonation system answering in terms of the advanced treating of organic wastewater
With.
In above-mentioned application, organic wastewater is coal chemical industry, fine chemistry industry, petrochemical industry, pharmacy, organic agricultural chemicals, printing and dyeing etc.
The organic wastewater that industry generates.
Catalytic ozonation system through the invention can generate subtle in waste water of the processing containing organic pollutant
Bubble, especially fine gas bubbles of the output diameter less than 50 microns can be improved gaseous solubility, along with it rises in water
Slow-paced feature, this can greatly improve gas-liquid mixed ratio, can increase the solubility of ozone in water, thus greatly
Its efficiency for handling Organic Pollutants in Wastewater is improved greatly.
Detailed description of the invention
Fig. 1 shows a kind of process flow charts of catalytic ozonation system of the invention.
Fig. 2 indicates the process flow chart of another catalytic ozonation system of the invention.
Fig. 3 indicates the bubble-free high-concentration ozone water preparing device 5 in present invention catalytic ozonation system shown in Fig. 2
Internal aeration head is fixed on the structural schematic diagram on the fixed device of aeration head.
Wherein, 1- liquid oxygen storage tank, 2- low energy consumption refrigerating plant, 3- ozone generator, 4- mineral bed course, 5- bubble-free are highly concentrated
Degree ozone water preparation device, 6- O3 catalytic oxidation reactor tank, 7- vent ozone destructor, 8- liquid booster pump, 9- gas booster pump,
10- is pumped containing ozone gas, 11- recirculation water, 12- liquid oxygen, 13- oxygen, 14-, 15- high-concentration ozone water, 16- jet stream release,
17- catalyst, 18- waste water, 19- line temperature sensor, the fixed device of 20- aeration head, 21- aeration head, 22-, which is vortexed, to be generated
Device, 23- capillary, 24- capillary end aeration head (fixation), 25- water outlet.
Specific embodiment
Catalytic ozonation is that those are difficult to by ozone list for a kind of novel capable of degrading for growing up in recent years
The method of the organic pollutant solely aoxidized substantially increases oxidation efficiency and effect due to generating OH during the reaction.But
It is that current catalytic ozonation has that ozone utilization efficiency is not high, to influence to handle the efficiency of organic pollutant
The problem of.
The present inventor passes through the discovery that studies for a long period of time: in waste water of the processing containing organic pollutant, if it is possible to effectively improve
Dissolubility ozone concentration is simultaneously with the shape of fine gas bubbles of the fine gas bubbles especially diameter less than 50 microns containing ozone gas
Formula exists, then, can significantly because of its large specific surface area, the features such as rate of climb is slow in water, the residence time is long, dissolved efficiency is high
The mass-transfer efficiency of ozone is improved, in addition, the ozone water surface as existing in the form of fine gas bubbles charges, it is especially subtle to straight
Diameter can generate the characteristics such as the free radical of a large amount of strong oxidizing properties less than 50 microns, additionally it is possible to improve gaseous solubility, add it
The slow feature of the rate of climb in water, this can greatly improve gas-liquid mixed ratio, can increase ozone to a certain extent
Solubility in water, to greatly improve its efficiency for handling Organic Pollutants in Wastewater.
The present inventor can improve ozone oxidation effect by studying for a long period of time when it is also found that: high-concentration ozone water is with waste water
Rate；High-concentration ozone water can generate a large amount of hydroxyl radical free radical when reacting in the presence of a catalyst with waste water；It is highly concentrated
Dissolved oxygen is spent to be easy to generate great amount of hydroxy group free radical in situ when the mineral with hydroxyl ferrous oxide contact.
Based on this discovery, the present invention provides a kind of catalytic ozonation system comprising O3 catalytic oxidation reactor tank 6,
6 bottom of O3 catalytic oxidation reactor tank is provided with jet stream release 16, high-concentration ozone water 15 by jet stream release 16 into
Enter O3 catalytic oxidation reactor tank 6, forms the fine gas bubbles of fine gas bubbles, especially diameter less than 50 microns；By pretreatment
Waste water 18 O3 catalytic oxidation reactor tank 6 is entered by pump 14, it is sufficiently mixed with the high-concentration ozone water 15 of fine gas bubbles form
It closes, partially has pollutant by ozone oxidation；Mineral bed course 4 and catalyst 17, catalysis are filled in O3 catalytic oxidation reactor tank 6
Ozone oxidation reaction tank (6) upper layer is equipped with vortex generator 22, by the underwater bubble of catalyst layer due to collision increase, in whirlpool
It is chopped under flow generator (22) effect, water is gentle to be mixed again, and then will be remaining organic in waste water using residual ozone
Object removal.
Organic pollutant after catalysis oxidation in waste water 18 is removed.
Wherein, it is further preferred that, in the mineral bed course 4 contain hydroxyl ferrous oxide, with high-concentration ozone water
Great amount of hydroxy group free radical is generated in situ after supersaturated dissolved oxygen contact in 15, and catalyst 17 is catalytically decomposed ozone and also generates largely
Hydroxyl radical free radical, therefore the organic pollutant after catalysis oxidation in waste water 18 is further reacted with hydroxyl radical free radical and is largely gone
It removes；The vortex generator (22) of O3 catalytic oxidation reactor tank (6) the upper layer setting, by gas in the water of catalyst layer
Bubble is since collision increases, and underwater bubble is chopped under vortex generator (22) effect, and water is gentle to be mixed again, further benefit
It is aoxidized with residual ozone.
" high-concentration ozone water " of the present invention refers to that concentration is the dissolubility Ozone Water of 50~500mg/L, contains simultaneously
There is the supersaturated dissolved oxygen of 200~1000mg/L.
In above-mentioned catalytic ozonation system, the ratio of high-concentration ozone water 15 and waste water 18 is with ozone molecule and Δ
COD usage ratio meter, O3: Δ COD=0.4-1.5.The COD for herein referring to every removal 1mg/L, consumes the O of 0.4~1.5mg/L3。
In above-mentioned catalytic ozonation system, the tail gas through being discharged at the top of O3 catalytic oxidation reactor tank 6 enters tail gas
Destructor 7 is handled.
In above-mentioned catalytic ozonation system, the structure of O3 catalytic oxidation reactor tank 6 is Down-Up to be followed successively by cloth
Water cloth gas area, mineral bed course and catalyst fill area, vortex reaction zone, buffer area, catchment Efflux District and exhaust collection area.
In above-mentioned catalytic ozonation system, it is provided in the vortex reaction zone in O3 catalytic oxidation reactor tank 6 more
Group swirling device, every group is connected on an axis by multiple circular vortex generators 22.Swirl generator 22 is conducive to through being catalyzed
The mixing of waste water after reaction and residual ozone gas, and will will pass through the bubble that catalyst layer collision generates be cut into it is small
Bubble.
In above-mentioned catalytic ozonation system, the reaction time of high-concentration ozone water 15 and waste water 18 to be processed is with water quality
Difference and change, generally 45-120min.
In above-mentioned catalytic ozonation system, it is provided in the water distribution gas distribution area of 6 bottom of O3 catalytic oxidation reactor tank
Air purge and washer wrinkle fabric water cloth tracheae, backwash frequency are 7-30 days primary, and backwash intensity is 5-15L/m2·s。
In above-mentioned catalytic ozonation system, the high activated catalyst filled in catalyst fill area is heterogeneous catalysis
Agent, catalyst used in all catalytic ozonation technologies can be used in the present invention.
Through research, the inventor has found that the solubility of ozone in water reduces as the temperature rises, at low temperature
It is easy to produce the Ozone Water of high concentration.Therefore the present invention is cooled down using the cold energy of the generation of liquid oxygen system to Ozone Water, energy consumption
It is very low, while enhancing the solubility and mass transfer rate of ozone, ozone utilization rate is improved, the effect of catalysis oxidation is further increased
Fruit.
For this purpose, the present inventor is also provided with bubble-free high-concentration ozone water preparation in above-mentioned catalytic ozonation system
Device 5, as shown in Figure 1, aeration head 21 is provided in bubble-free high-concentration ozone water preparing device 5,21 concrete example of aeration head
It such as can be lateral stud aeration head, centrally disposed aeration head is fixed on device, and the fixed device of the aeration head in the center is set
It is set to rotary shaft (the pillar A of center upright is the rotary shaft in Fig. 1), aeration head 21 can be driven to rotate, contains ozone gas
Body 10 enters bubble-free high-concentration ozone water preparing device 5 by aeration head 21, prepares with bubble-free high-concentration ozone water is entered
The water 11 of device 5 forms high-concentration ozone water 15 and supplies O3 catalytic oxidation reactor tank 6.
In above-mentioned catalytic ozonation system, aeration head 21 is that titanium is aerated stick, and the aeration head 21 is mounted on a rotation
On axis.When working normally, the hydraulic shear of 21 outer surface of aeration head is greatly enhanced, and it is contaminated both to have reduced surface
Possibility, and improve mass transfer rate.
Above-mentioned yet another form, as shown in Fig. 2, being provided with aeration in bubble-free high-concentration ozone water preparing device 5
The fixed device 20 of head enters bubble-free high-concentration ozone water through the aeration head 24 of its end by capillary 23 containing ozone gas 10
It is smelly to form the supply catalysis of high-concentration ozone water 15 with the water 11 for entering bubble-free high-concentration ozone water preparing device 5 for preparation facilities 5
Oxygen oxidation reaction tank 6；The aeration head 24 of 23 end of capillary is fixed on the fixed device 20 of aeration head, the fixed dress of the aeration head
20 are set as shown in Fig. 2, it is provided with along reactor tank 6 in different height on the cross towards different directions in crux
Aeration head 24, as shown in figure 3, Fig. 3 is fixed on for the aeration head 24 inside the bubble-free high-concentration ozone water preparing device 5 in ten
Structure enlargement diagram on the fixed device of the aeration head of cabinet frame shape；This structure setting for setting up aeration head in each side can
Liquid is set to form circulation, that is, realizing makes internal water when entering bubble-free high-concentration ozone water preparing device 5 containing ozone gas 10
Form circulation stirring (as shown in Figure 3).
In above-mentioned catalytic ozonation system, contain ozone gas into bubble-free high-concentration ozone water preparing device 5
10 temperature is 0-10 DEG C, and the temperature into the water 11 of bubble-free high-concentration ozone water preparing device 5 is 0-5 DEG C.
In above-mentioned catalytic ozonation system, pass through gas booster pump 9 and liquid respectively containing ozone gas 10 and water 11
Booster pump 8 enters bubble-free high-concentration ozone water preparing device 5 after being pressurized and mixes, and forms high-concentration ozone water 15 at low temperature,
Ozone concentration in high-concentration ozone water 15 is about 50~500mg/L, the outlet pressure of gas booster pump 9 and liquid booster pump 8
It is 0.3-0.8MPa.
Catalytic ozonation generallys use liquid oxygen in the advanced treating application of industrial wastewater and produces ozone skill at present
Art, but liquid oxygen carburetor is in winter, the especially winter of China the north most area, due to freezing when outside air temperature is low,
Frosting and lead to evaporating capacity wretched insufficiency, even summer can also waste a large amount of energy cooling capacity.Therefore the present invention considers to improve
Vaporizer is improved to low energy consumption refrigerating plant of the invention, using the cooling capacity energy that vaporization generates come to containing ozone gas and reflux
Water cools down, while guaranteeing vaporization of liquid oxygen amount, not only improves improve the solubility of ozone in water in this way, and can reach energy conservation
Purpose.
For this purpose, the present inventor is also provided with a low energy consumption refrigerating plant 2, low energy consumption in above-mentioned catalytic ozonation system
Temperature containing ozone gas 10 is cooled to 0-10 DEG C by refrigerating plant 2.
In above-mentioned catalytic ozonation system, by the cooling of low energy consumption refrigerating plant 2 containing ozone gas 10 through gas
Booster pump 9 enters bubble-free high-concentration ozone water preparing device 5 after being pressurized.
In order to save water resource, in above-mentioned catalytic ozonation system, water 11 is anti-from O3 catalytic oxidation
The recirculation water on 6 top of tank is answered, the reflux coolant-temperature gage of 6 top of O3 catalytic oxidation reactor tank discharge is generally 5-40 DEG C.Then it uses
The reflux on 6 top of low energy consumption refrigerating plant self-catalysis in 2 future ozone oxidation reaction tank is water-cooled to 0-5 DEG C.By low energy consumption system
The water 11 after cooling of device for cooling 2 enters bubble-free high-concentration ozone water preparing device 5 after the pressurization of liquid booster pump 8.
Contain ozone gas 10 to provide, be also provided with an ozone generator 3 in catalytic ozonation system of the invention,
Contain ozone gas 10 to generate.The temperature containing ozone gas 10 that ozone generator 3 generates is usually 25-40 DEG C.
In above-mentioned catalytic ozonation system, what ozone generator 3 generated is filled containing ozone gas 10 by low energy consumption refrigeration
It sets 2 and is cooled to predetermined temperature.
The raw material of ozone generator 3 is usually pure oxygen gas, for this purpose, catalytic ozonation system of the invention further includes one
Liquid oxygen storage tank 1 is sequentially connected with low energy consumption refrigerating plant 2, ozone generator 3；Liquid oxygen 12 passes through low energy consumption in liquid oxygen storage tank 1
The gasification of refrigerating plant 2 is gas source of the purity oxygen 3 as ozone generator 3.
In above-mentioned catalytic ozonation system, the effect of low energy consumption refrigerating plant 2 is the liquid that will be exported in liquid oxygen storage tank 1
The recirculation water containing 6 top of ozone gas 10 and O3 catalytic oxidation reactor tank for generating ozone generator 3 while gasification
11 coolings, structure can be calculated by thermodynamics method according to the thermic load at scene and be designed, the preferably double heat exchange of structure
Install star fin structure on the outside of pipe additional, inner tube is containing 11 channel of ozone gas 10 or recirculation water, and outer tube is 15 channel of liquid oxygen, star
Fin is the heat exchange area in order to increase air side.In operation, the flow velocity containing ozone gas 10 is controlled, so that it is through too low
The residence time of energy consumption refrigerating plant 2 and pipeline is 1-10min.
The present invention also provides a kind of method for carrying out catalytic ozonation using above-mentioned catalytic ozonation system, features
It is, the liquid oxygen 12 from liquid oxygen storage tank 1 is vaporized by low energy consumption refrigerating plant 2, forms oxygen, and ozone supply generator 3
Ozone is generated, the ozone of generation and the recirculation water from 6 top of O3 catalytic oxidation reactor tank all enter low energy consumption refrigerating plant
2, ozone is cooled to odor at low temperature 10, and recirculation water is cooled into low temperature reflux water 11, and odor at low temperature 10 passes through gas booster pump 9
Enter bubble-free high-concentration ozone water preparing device 5 after pressurization, low temperature reflux water 11 enters nothing after being pressurized by liquid booster pump 8
Bubble high-concentration ozone water preparing device 5, the two pressurize in bubble-free high-concentration ozone water preparing device 5 be mixed to form it is highly concentrated
Ozone Water 15 is spent, high-concentration ozone water 15 enters the generation diameter of O3 catalytic oxidation reactor tank 6 by jet stream release 16 and is less than
50 microns of fine gas bubbles, it is anti-that waste water to be processed from bottom enters O3 catalytic oxidation by 14 promotions of pump after pretreatment
Tank 6 is answered, the high-concentration ozone water 15 of the fine gas bubbles form with diameter less than 50 microns is sufficiently mixed, and is gone under the action of catalyst
Except hardly degraded organic substance in waste water.
Catalytic ozonation system of the invention is suitable for the processing of various organic wastewaters, is particularly suitable for coal chemical industry, essence
Refine the advanced treating for the organic wastewater that the industries such as work, petrochemical industry, pharmacy, organic agricultural chemicals, printing and dyeing generate.
The invention has the following beneficial effects:
1, the present invention uses bubble-free high-concentration ozone water preparing device under cryogenic, and waste water and ozone are mixed shape
It is sent into catalytic oxidation tank at high-concentration ozone water, forms fine gas bubbles, while making residence time of the ozone in waste water
Long, the rate of decay is slow, more abundant with the contact of useless Organic substance in water and catalyst, at the same using high concentration dissolved oxygen with contain
The mineral reaction of hydroxyl ferrous oxide generates hydroxyl radical free radical, and the generation rate of various free radicals is higher, significantly more efficient can go
Except the organic pollutant poisonous and harmful, difficult to degrade in water body, the results showed that, system of the invention is apparently higher than at traditional ozone
Science and engineering skill is to the removal efficiency of organic matter, also superior to existing catalytic ozonation technology to the removal efficiency of organic matter；
2, the present invention rationally using internal system recycle energy cooling capacity come to the water containing ozone gas and dissolved ozone into
Row cooling, had not only reached the condition requirement of present invention process, but also realized energy-saving, created economic benefit.
Below with reference to specific preferred embodiment, the present invention is described in further detail, and the embodiment is to this hair
Bright explanation and it is non-limiting.
Embodiment 1 is referring to Fig. 1, and liquid oxygen 12 is 3 conduct of purity oxygen by the gasification of low energy consumption refrigerating plant 2 in liquid oxygen storage tank 1
The gas source of ozone generator 3；Ozone generator 3, which generates, contains ozone gas 10, and gas temperature freezes at 25-40 DEG C through low energy consumption
After device 2 cools down, reach 0-10 DEG C；Pass through tank upper outlet through treated the effluent part of O3 catalytic oxidation reactor tank 6 to return
It is cooling to flow to low energy consumption refrigerating plant 2, waste water water temperature reaches 0-5 after low energy consumption refrigerating plant 2 is cooling at 5-40 DEG C or so
℃；Containing after ozone gas 10 and recirculation water 11 are pressurized by gas booster pump 9 and liquid booster pump 8 respectively after cooling enters nothing
Bubble high-concentration ozone water preparing device 5 uniformly mixes in bubble-free high-concentration ozone water preparing device 5, forms high concentration
Ozone Water 15；High-concentration ozone water 15 enters generation diameter in O3 catalytic oxidation reactor tank 6 by jet stream release 16 and is less than
50 microns of fine gas bubbles；It is promoted by pump 14 from 6 bottom of O3 catalytic oxidation reactor tank and is entered by pretreated waste water 18
Reactor tank is sufficiently mixed with high-concentration ozone water 15, a large amount of free radicals is generated under the effect of catalyst 17, in free radical and ozone
Oxidation go down water removal in organic pollutant, removal organic pollutant ratio be O3: Δ COD=0.4-1.5；Through
The tail gas being discharged at the top of O3 catalytic oxidation reactor tank enters vent ozone destructor 7 and is handled.Wherein, recirculation water 11 and contain ozone
Temperature of the gas 10 when entering bubble-free high-concentration ozone water preparing device 5 is 0 DEG C, gas booster pump 9 and liquid pressurization
The outlet pressure of pump 8 is 0.3MPa.
Certain coke-oven plant's secondary biochemical effluent is handled using system and method for the invention, the COD concentration in waste water is
150mg/L-300mg/L handles above-mentioned waste water using system described in Fig. 1, and the mineral bed course selected is containing nontronite
Layer, the catalyst carrier selected is γ-Al2O3, supported copper and cerium active component thereon, the COD concentration in treated waste water is
50mg/L-80mg/L, average removal rate is in 70-80%.
Referring to fig. 2, liquid oxygen 12 is 3 conduct of purity oxygen by the gasification of low energy consumption refrigerating plant 2 to embodiment 2 in liquid oxygen storage tank 1
The gas source of ozone generator 3；Ozone generator 3, which generates, contains ozone gas 10, and gas temperature freezes at 25-38 DEG C through low energy consumption
After device 2 cools down, reach 0-8 DEG C；It is flowed back through treated the effluent part of O3 catalytic oxidation reactor tank 6 by tank upper outlet
Cooling to low energy consumption refrigerating plant 2, waste water water temperature reaches 0-5 DEG C after low energy consumption refrigerating plant 2 is cooling at 5-35 DEG C or so；
Containing after ozone gas 10 and recirculation water 11 are pressurized by gas booster pump 9 and liquid booster pump 8 respectively into no gas after cooling
High-concentration ozone water preparing device 5 is steeped, is uniformly mixed in bubble-free high-concentration ozone water preparing device 5, in capillary end
Aeration head 24 is set on all angles direction in each height and is fixed on the fixed device 20 of aeration head, makes containing ozone gas
The internal water of body forms circulation stirring, that is, forms the high-concentration ozone water 15 of circulation shape；High-concentration ozone water 15 is released by jet stream
It puts device 16 and enters generation fine gas bubbles of the diameter less than 50 microns in O3 catalytic oxidation reactor tank 6；By pretreated waste water
18 enter reactor tank from 6 bottom of O3 catalytic oxidation reactor tank by 14 promotion of pump, are sufficiently mixed with high-concentration ozone water 15,
The effect of catalyst 17 is lower to generate a large amount of free radicals, goes down the organic pollutant in water removal in free radical and ozonidation,
The ratio for removing organic pollutant is O3: Δ COD=0.6-1.25；Tail gas through being discharged at the top of O3 catalytic oxidation reactor tank
It is handled into vent ozone destructor 7.Wherein, recirculation water 11 and containing ozone gas 10 enter bubble-free high-concentration ozone water system
Temperature when standby device 5 is 4 DEG C, and the outlet pressure of gas booster pump 9 and liquid booster pump 8 is 0.8MPa.
Certain coke-oven plant's secondary biochemical effluent is handled using system and method for the invention, the COD concentration in waste water is
150mg/L-300mg/L handles above-mentioned waste water using system described in Fig. 2, and the mineral bed course selected is containing rock bridgeite
Layer, the catalyst carrier selected is γ-Al2O3, Supported Manganese and cerium active component thereon, the COD concentration in treated waste water is
50mg/L-70mg/L, average removal rate is in 75-85%.
Comparative example 1 uses method and system substantially the same manner as Example 1, only saves low energy consumption refrigerating plant 2, saves
Bubble-free high-concentration ozone water preparing device 5 and booster pump 8,9 save jet stream release in O3 catalytic oxidation reactor tank 6
Device, using normal pressure and 20 DEG C of common blister aeration method, test result shows that average removal rate is in 30-40%.
Comparative example 2 uses the method and system essentially identical with comparative example 1, only before O3 catalytic oxidation reactor tank 6
Increase micro-nano bubble generator, so as to generate bubble of the diameter less than 50 microns, using normal pressure and 20 DEG C of microbubble
Aeration method, test result show that average removal rate is in 50-55%.
Although it is not intended to limit the present invention, Ren Heben it should be noted that the present invention discloses preferred embodiment
Field those of ordinary skill, under conditions of not departing from the spirit and principles in the present invention, various changes can be made and adjustment, these
Change and adjusts within the scope of the present invention.
Claims (10)
1. a kind of catalytic ozonation system comprising O3 catalytic oxidation reactor tank (6), the O3 catalytic oxidation reactor tank
(6) bottom is provided with jet stream release (16), and high-concentration ozone water (15) enters catalysis ozone oxygen by jet stream release (16)
Change reactor tank (6), forms fine gas bubbles；Enter O3 catalytic oxidation reactor tank (6) by pretreated waste water (18), and it is subtle
The high-concentration ozone water (15) of bubble form mixes；Filled with mineral bed course (4) and catalysis in O3 catalytic oxidation reactor tank (6)
Agent (17)；O3 catalytic oxidation reactor tank (6) upper layer is equipped with vortex generator (22).
2. catalytic ozonation system according to claim 1, hydroxyl ferrous oxide is contained in the mineral bed course (4).
3. catalytic ozonation system according to claim 1 or 2 further includes bubble-free high-concentration ozone water preparation dress
It sets (5), is provided with aeration head (21) in bubble-free high-concentration ozone water preparing device (5), (10) containing ozone gas pass through installation
Aeration head (21) on the rotary shaft enters bubble-free high-concentration ozone water preparing device (5), and bubble-free high concentration is smelly with entering
The water (11) of oxygen water preparation apparatus (5) forms high-concentration ozone water (15) supply O3 catalytic oxidation reactor tank (6).
4. catalytic ozonation system according to claim 1 or 2 comprising bubble-free high-concentration ozone water prepare dress
It is fixed device (20) to set (5) interior aeration head that is provided with, passes through capillary (23) through end aeration head (24) containing ozone gas (10)
Into bubble-free high-concentration ozone water preparing device (5), with the water (11) for entering bubble-free high-concentration ozone water preparing device (5)
Form high-concentration ozone water (15) supply O3 catalytic oxidation reactor tank (6)；Capillary (23) end aeration head (24) is fixed
On aeration head fixed device (20), make when entering bubble-free high-concentration ozone water preparing device (5) containing ozone gas (10)
Internal water forms circulation stirring.
5. catalytic ozonation system according to claim 1-4 further includes ozone generator (3), liquid oxygen
Storage tank (1), low energy consumption refrigerating plant (2), wherein liquid oxygen storage tank (1), low energy consumption refrigerating plant (2) and ozone generator (3) according to
It is secondary to be connected；Liquid oxygen (12) is that purity oxygen (13) are used as ozone by low energy consumption refrigerating plant (2) gasification in liquid oxygen storage tank (1)
The gas source of device (3).
6. catalytic ozonation system according to claim 1-5, wherein the knot of low energy consumption refrigerating plant (2)
Structure is to install star fin structure on the outside of double heat exchanger tubes additional, and inner tube is to be containing ozone gas (10) or recirculation water (11) channel, outer tube
Liquid oxygen (15) channel；Low energy consumption refrigerating plant (2) is simultaneously generated ozone generator (3) using the cold energy of gasification liquid oxygen (12)
Recirculation water (11) cooling down containing ozone gas (10) and O3 catalytic oxidation reactor tank (6) top.
7. catalytic ozonation system according to claim 1-5, wherein O3 catalytic oxidation reactor tank (6)
Structure be Down-Up to be followed successively by water distribution gas distribution area, mineral bed course and catalyst fill area, vortex reaction zone, buffer area, collection
Water Efflux District and exhaust collection area.
8. catalytic ozonation system according to claim 7, wherein the O3 catalytic oxidation reactor tank (6) it is total
Height is 6m~9m, and the height in water distribution gas distribution area controls within 1m.
9. the catalytic ozonation system of any one of -8 institutes according to claim 1, wherein O3 catalytic oxidation reactor tank (6) is interior
Vortex reaction zone in be provided with multiple groups swirling device, every group is connected on axis by multiple circular vortex generators (22).
10. a kind of method for carrying out catalytic ozonation using the described in any item catalytic ozonation systems of claim 1-9,
It is characterized in that, the liquid oxygen (12) from liquid oxygen storage tank (1) is vaporized by low energy consumption refrigerating plant (2), oxygen is formed, and supply
Ozone generator (3) generates ozone, and the ozone of generation and the recirculation water at the top of O3 catalytic oxidation reactor tank (6) all enter
Low energy consumption refrigerating plant (2), ozone are cooled to odor at low temperature (10), and recirculation water is cooled into low temperature reflux water (11), low temperature
Ozone (10) enters bubble-free high-concentration ozone water preparing device (5) after being pressurized by gas booster pump (9), low temperature reflux water
(11) enter bubble-free high-concentration ozone water preparing device (5) after being pressurized by liquid booster pump (8), the two is highly concentrated in bubble-free
Pressurization is mixed to form high-concentration ozone water (15) in degree ozone water preparation device (5), and high-concentration ozone water (15) is released by jet stream
It puts device (16) and generates the fine gas bubbles of fine gas bubbles, especially diameter less than 50 microns into O3 catalytic oxidation reactor tank (6),
Enter O3 catalytic oxidation reactor tank (6) by pretreated waste water (18), the fine gas bubbles shape with diameter less than 50 microns
The high-concentration ozone water (15) of formula is sufficiently mixed, and high-concentrated ozone, which quickly aoxidizes the substance for being easy to ozone reaction in waste water, to be divided
Solution, supersaturated dissolved oxygen and remaining dissolubility ozone in high-concentration ozone water respectively with the mineral containing hydroxyl ferrous oxide
Layer and catalyst layer effect generate hydroxyl radical free radical, and organic matter difficult to degrade in waste water is decomposed removal.
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