CN109384300A - Catalytic ozonation method - Google Patents
Catalytic ozonation method Download PDFInfo
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- CN109384300A CN109384300A CN201710667516.5A CN201710667516A CN109384300A CN 109384300 A CN109384300 A CN 109384300A CN 201710667516 A CN201710667516 A CN 201710667516A CN 109384300 A CN109384300 A CN 109384300A
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- catalytic ozonation
- ozone
- secondary clarifier
- clarifier effluent
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
- C02F2201/007—Modular design
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The present invention provides a kind of catalytic ozonation methods, the catalytic ozonation is carried out using device for catalyzing and oxidating ozone, the device for catalyzing and oxidating ozone includes passing through the sequentially connected apparatus of oxygen supply of pipeline, ozone generator, catalytic ozonation reactor and absorption plant, wherein, the catalytic ozonation reactor is cylindrical tube, including the micropore aerator being arranged from the bottom up and packing layer, secondary clarifier effluent is injected in the catalytic ozonation reactor, catalysis oxidation is carried out under aeration condition, wherein, the COD concentration of the secondary clarifier effluent is 60-100mg/L, filler in described filler layer is ozone oxidation catalyst, and the volume ratio of the filler and the secondary clarifier effluent is 0.5-1:1, the aeration efficiency of the micropore aerator meets: the COD of the secondary clarifier effluent The mass concentration ratio of mass concentration and ozone is 1:0.2-1.
Description
Technical field
The invention belongs to catalytic ozonation technical field more particularly to a kind of catalytic ozonation methods.
Background technique
With the development of industry, more and more industrial wastewaters enter sewage network, while the city based on industrial wastewater
Sewage treatment plant, city and the sewage treatment plant of industrial park are more and more.In recent years, Environmental Protection Situation is more and more severeer, to city dirt
The effluent quality of water treatment plant requires to be increasingly stringenter, and Effluent criteria from level-one B to level-one A, even want by economically developed region
It finds out water and reaches four standard of class earth's surface.Wherein COD (COD) Cr standard is increased to 50mg/L from 60mg/L, and is increased to
30mg/L.Industrial wastewater removes the COD of a large amount of bio-degradables in the treatment facility of on-site, into pipe network
COD is mainly with soluble nondegradable, in addition, the metabolite (humus etc.) of biochemical degradation is also mostly that solubility can not drop
The COD of solution, these soluble non-degradable COD (referred to as " nbsCOD ") will carry out huge pressure to mark work belt is proposed, thus just
There are more and more sewage plants to increase advanced treatment units, how advanced treatment unit realizes the economy of nbsCOD and steady removal
As a urgent problem needed to be solved.
One of critical process of the high-level oxidation technology as nbsCOD in deeply treating wastewater is imperative, and conventional is advanced
Oxidation technology mainly has ozone oxidation, Fenton's reaction, catalytic wet oxidation etc..Existing Fenton process, wet raw noodles,
Although wastewater treatment efficiency can be improved to a certain extent, exist dosage is big, operating cost is high, there are secondary pollution,
The disadvantages of troublesome in poeration.In addition, Fenton's reaction is there are large labor intensity, that processing cost is high, sludge is more, corrosivity is big etc. is many scarce
Point, and for low strength COD poor processing effect (water outlet COD is relatively inaccessible to 50mg/L or less), it is high-strength under the requirement of low cost
The high-level oxidation technology of degree can not be accomplished, such as Fenton, catalytic wet oxidation, overcritical etc..Especially as nbsCOD in water
Excessive concentration when, the high-level oxidation technologies such as Fenton process, method for dosing medicine are difficult to realize 30mg/L COD index below.
Ozone oxidation due to have many advantages, such as it is easy to operate, without medicament addition, it is without secondary pollution, without sludge generate and by
The favor of water dirt researcher, market need vigorous.Using ozone oxidation, being reduced to 48mg/L from 58mg/L to be discharged COD is
Example, operating cost is about 0.25 yuan or so, and operating cost is low.However, further increasing with Effluent criteria, for example implement ground
Four class water quality standard of table, COD require to be lower than 30mg/L, at this point, the cost is relatively high, COD removal rate is relatively low.But mesh
Preceding ozone oxidation effect is not unable to satisfy above-mentioned requirements also, and therefore, urgent need develops a kind of catalytic ozonation technique.
Summary of the invention
The purpose of the present invention is to provide a kind of catalytic ozonation methods, it is intended to solve existing catalytic ozonation effect
The problem of being unable to satisfy COD Effluent criteria.
The invention is realized in this way a kind of catalytic ozonation method, the catalytic ozonation uses ozone catalytic
Oxidation unit carries out, and the device for catalyzing and oxidating ozone includes by the sequentially connected apparatus of oxygen supply of pipeline, ozone generator, smelly
Oxygen catalyst oxidation reactor and absorption plant, wherein the catalytic ozonation reactor is cylindrical tube, including from the bottom up
The micropore aerator and packing layer of setting inject secondary clarifier effluent in the catalytic ozonation reactor, in aeration condition
Lower carry out catalysis oxidation, wherein the COD concentration of the secondary clarifier effluent is 60-100mg/L, and the filler in described filler layer is
Ozone oxidation catalyst, and the volume ratio of the filler and the secondary clarifier effluent is 0.5-1:1, the exposure of the micropore aerator
Gas efficiency meets: the mass concentration ratio of the COD mass concentration of the secondary clarifier effluent and ozone is 1:0.2-1.
The catalytic ozonation method of offer of the invention is to be provided based on specific using device for catalyzing and oxidating ozone
Middle method for testing can achieve very high catalytic efficiency by modulation process parameter, so that the COD after catalytic ozonation is dense
Degree can drop to 30mg/L.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of device for catalyzing and oxidating ozone provided in an embodiment of the present invention.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
A kind of catalytic ozonation method, the catalytic ozonation is carried out using device for catalyzing and oxidating ozone, described smelly
Oxygen catalytic oxidizing equipment include by the sequentially connected apparatus of oxygen supply of pipeline, ozone generator, catalytic ozonation reactor and
Absorption plant, wherein the catalytic ozonation reactor is cylindrical tube, including the micropore aerator that is arranged from the bottom up and
Secondary clarifier effluent is injected in the catalytic ozonation reactor, catalysis oxidation is carried out under aeration condition by packing layer,
In, the COD concentration of the secondary clarifier effluent is 60-100mg/L, and the filler in described filler layer is ozone oxidation catalyst, and
The volume ratio of the filler and the secondary clarifier effluent is 0.5-1:1, and the aeration efficiency of the micropore aerator meets: described two
The COD mass concentration of sinking pool effluent and the mass concentration ratio of ozone are 1:0.2-1.
In the embodiment of the present invention, as shown in Figure 1, the device for catalyzing and oxidating ozone includes passing through the sequentially connected confession of pipeline
Oxygen device, ozone generator, catalytic ozonation reactor and absorption plant, wherein the catalytic ozonation reactor is
Cylindrical tube, including the micropore aerator being arranged from the bottom up and packing layer, catalytic ozonation is reacted in the micropore gas explosion
It is carried out above device, the micropore aerator provides the ozone uniformly discharged for catalytic ozonation.
The embodiment of the present invention, the treatment sewage provided are secondary clarifier effluent, and the COD concentration of the secondary clarifier effluent is
60-100mg/L.Filler in described filler layer is ozone oxidation catalyst, in order to improve catalytic effect, more preferably support type
Catalyst.Further, it is studied repeatedly by inventor, the volume ratio of the filler and the secondary clarifier effluent is 0.5-1:1,
The aeration efficiency of the micropore aerator meets: the COD mass concentration of the secondary clarifier effluent and the mass concentration ratio of ozone are
1:0.2-1, at this point, catalytic ozonation effect is preferable, COD mass concentration can be down in the water outlet after catalytic ozonation
30-50mg/L at least reduces 40mg/L than the COD mass concentration of the secondary clarifier effluent, has the effect of preferable removal COD
Fruit.The volume ratio of most preferred embodiment the most, the filler and the secondary clarifier effluent is 0.8:1, the exposure of the micropore aerator
Gas efficiency meets: when the mass concentration ratio of the COD mass concentration of the secondary clarifier effluent and ozone is 1:1, having optimal urge
Change effect, COD mass concentration can be even lower down to 30mg/L in the water outlet after catalytic ozonation.
The embodiment of the present invention is red, and the filler is ozone oxidation catalyst based on Alumina Foam Ceramics carrier, is based on
At least one of the ozone oxidation catalyst of active gamma-aluminium oxide carrier, ozone oxidation catalyst based on absorbent charcoal carrier.
Preferred catalyst, catalyst load effect is good, can efficiently remove the nbsCOD in sewage, catalytic ozonation 60min,
The removal rate of nbsCOD may be up to 72%, higher by 30% or more than the COD removal rate of O3 contacted oxidation.
Specifically, as a kind of preferred situation, the ozone oxidation catalyst based on Alumina Foam Ceramics carrier is
The metal oxide of Alumina Foam Ceramics load, wherein the metal oxide is ferriferous oxide, Cu oxide, ruthenium oxidation
At least one of object, cerium oxide, cobalt/cobalt oxide, Mn oxide, nickel oxide.
In the embodiment of the present invention, the Alumina Foam Ceramics play catalytic action as catalyst carrier, for loading
Metal oxide, there is porous, large specific surface area, not swollen do not split holding original state after mechanical strength is big, hygroscopicity is strong and water suction
The advantages of.Preferably, the porosity of the Alumina Foam Ceramics carrier is 75%-90%, and aperture 0.5-1.5mm compares table
Area is 80-150m2/ g, compression strength 0.5-3MPa.Preferred Alumina Foam Ceramics carrier, has biggish hole
Rate, high mechanical property, suitable diameter and specific surface area therefore can be under the premise of guaranteeing support strength, and it is suitable to provide
Metal oxide load capacity, be conducive to that ozone oxidation catalyst is stable, equably removes nbsCOD in sewage, improve
COD removal rate；Simultaneously as metal oxide is evenly dispersed in the apparent gap of the Alumina Foam Ceramics, therefore can be with
The usage amount of catalyst is reduced, and then reduces cost.
In the embodiment of the present invention, the load capacity of the metal oxide has certain shadow to the nbsCOD in removal sewage
It rings.Preferably, based on by described by the quality of the ozone oxidation catalyst of Alumina Foam Ceramics carrier for 100%, the gold
The load capacity for belonging to oxide is 1-10%, and the ozone oxidation catalyst obtained at this time has preferable removal effect to nbsCOD.
If the load capacity of the metal oxide is too low, the relative amount of catalyst is lower, and the effect for removing nbsCOD is relatively poor,
COD removal rate reduces；If the load capacity of the metal oxide is excessively high, it is be easy to cause metal sintering, duct blocking, to reduce
Catalytic activity influences the removal of nbsCOD.
In ozone oxidation catalyst provided in an embodiment of the present invention, the metal oxide that can remove nbsCOD includes oxidation
The ceramic carrier supported metal oxide of aluminum foam, wherein the metal oxide is ferriferous oxide, Cu oxide, ruthenium oxidation
At least one of object, cerium oxide, cobalt/cobalt oxide, Mn oxide, nickel oxide.Specifically, the ferriferous oxide preferably three
Aoxidize two iron, the preferred manganese dioxide of Mn oxide.
As a particular preferred embodiment, the ozone oxidation catalyst based on Alumina Foam Ceramics carrier is oxygen
Change the ceramic carrier supported di-iron trioxide of aluminum foam, and with the ozone oxidation catalysis based on Alumina Foam Ceramics carrier
The quality of agent is 100% meter, and the load capacity of the di-iron trioxide is 3%.The preferred ozone oxidation catalyst, can efficiently go
Except nbsCOD in sewage, the removal rate of catalytic ozonation 60min, nbsCOD are up to 73% or more, than the blank under parallel condition
Control at least improves 35%.
As another particular preferred embodiment, the ozone oxidation catalyst based on Alumina Foam Ceramics carrier is
The carrier loaded manganese dioxide of Alumina Foam Ceramics, and with the ozone oxidation catalysis based on Alumina Foam Ceramics carrier
The quality of agent is 100% meter, and the load capacity of the manganese dioxide is 5%.The preferred ozone oxidation catalyst, can efficiently remove
The removal rate of nbsCOD in sewage, catalytic ozonation 60min, nbsCOD are up to 78% or more, than the blank pair under parallel condition
According at least raising 40%.
Ozone oxidation catalyst provided in an embodiment of the present invention based on Alumina Foam Ceramics carrier, Alumina Foam pottery
Ceramic carrier intensity is high, and has porous structure, is conducive to disperse ozone gas, to improve ozone oxidation efficiency.In addition, using
For the Alumina Foam Ceramics as carrier, readily replaceable, assembling is easy to operate.It described will be carried based on Alumina Foam Ceramics
When the ozone oxidation catalyst of body is used for the catalytic ozonation of trade effluent, the nbsCOD in sewage can be efficiently removed, it is smelly
The removal rate of oxygen catalysis oxidation 60min, nbsCOD may be up to 72%, higher by 30% or more than the COD removal rate of O3 contacted oxidation.
In addition, under conditions of same catalytic efficiency, the ozone oxygen provided in an embodiment of the present invention based on Alumina Foam Ceramics carrier
Change catalyst, price is lower by 50% or more than the catalyst average price of mainstream producer currently on the market；In ozone high grade oxidation
In equipment use ozone oxidation catalyst of the present invention, removal efficiency under the same conditions, it is possible to reduce ozone injected volume, run
Cost reduces by 10% or more.
As another preferred situation, the ozone oxidation catalyst based on the balloon borne body of active gama-alumina is activity
Gamma oxidation aluminium ball load metal oxide, wherein the metal oxide be ferriferous oxide, Cu oxide, ru oxide,
At least one of cerium oxide, cobalt/cobalt oxide, Mn oxide, nickel oxide.
In the embodiment of the present invention, the activity gamma oxidation aluminium ball plays catalytic action as catalyst carrier, for loading
Metal oxide, there is porous, large specific surface area, not swollen do not split holding original state after mechanical strength is big, hygroscopicity is strong and water suction
The advantages of.Preferably, the diameter of the active gamma oxidation aluminium ball is 4-6mm, specific surface area 200-300m2/g.It is preferred living
Property gamma oxidation aluminium ball, have suitable diameter and specific surface area therefore can provide conjunction under the premise of guaranteeing granule strength
The load capacity of suitable metal oxide is conducive to ozone oxidation catalyst stabilization, equably removes the nbsCOD in sewage, mentions
High COD removal rate；Simultaneously as metal oxide is evenly dispersed in the apparent gap of the active gamma oxidation aluminium ball, therefore can
To reduce the usage amount of catalyst, and then reduce cost.Furthermore it is preferred that active gamma oxidation aluminium ball use after can recycle benefit
With.
In the embodiment of the present invention, the load capacity of the metal oxide has certain shadow to the nbsCOD in removal sewage
It rings.Preferably, based on by described by the quality of the ozone oxidation catalyst of the balloon borne body of active gama-alumina for 100%, the gold
The load capacity for belonging to oxide is 1-10%, and the ozone oxidation catalyst obtained at this time has preferable removal effect to nbsCOD.
If the load capacity of the metal oxide is too low, the relative amount of catalyst is lower, and the effect for removing nbsCOD is relatively poor,
COD removal rate reduces；If the load capacity of the metal oxide is excessively high, it is be easy to cause metal sintering, duct blocking, to reduce
Catalytic activity influences the removal of nbsCOD.
In ozone oxidation catalyst provided in an embodiment of the present invention, the metal oxide that can remove nbsCOD includes activity
Gamma oxidation aluminium ball load metal oxide, wherein the metal oxide be ferriferous oxide, Cu oxide, ru oxide,
At least one of cerium oxide, cobalt/cobalt oxide, Mn oxide, nickel oxide.Specifically, the ferriferous oxide preferably three aoxidizes
Two iron, the preferred manganese dioxide of Mn oxide.
As a particular preferred embodiment, the ozone oxidation catalyst based on the balloon borne body of active gama-alumina is
The di-iron trioxide of active gamma oxidation aluminium ball load, and with the ozone oxidation catalysis based on the balloon borne body of active gama-alumina
The quality of agent is 100% meter, and the load capacity of the di-iron trioxide is 3%.The preferred ozone oxidation catalyst, can efficiently go
Except nbsCOD in sewage, the removal rate of catalytic ozonation 60min, nbsCOD are up to 80% or more, than the blank under parallel condition
Control improves 35%.
As another particular preferred embodiment, the ozone oxidation catalyst based on the balloon borne body of active gama-alumina
For active gamma oxidation aluminium ball load manganese dioxide, and with it is described based on the balloon borne body of active gama-alumina ozone oxidation catalysis
The quality of agent is 100% meter, and the load capacity of the manganese dioxide is 5%.The preferred ozone oxidation catalyst, can efficiently remove
The removal rate of nbsCOD in sewage, catalytic ozonation 60min, nbsCOD are up to 78% or more, than the blank pair under parallel condition
According to raising 30%.
Ozone oxidation catalyst provided in an embodiment of the present invention based on the balloon borne body of active gama-alumina, it is dirty for industry
When the catalytic ozonation of water, the nbsCOD in sewage, the removal of catalytic ozonation 60min, nbsCOD can be efficiently removed
Rate may be up to 75%, higher by 30% or more than the COD removal rate of O3 contacted oxidation.In addition, under conditions of same catalytic efficiency,
Ozone oxidation catalyst provided in an embodiment of the present invention based on the balloon borne body of active gama-alumina, price is than currently on the market
The catalyst average price low 50% or more of mainstream producer；It is catalyzed in ozone high grade oxidation equipment using ozone oxidation of the present invention
Agent, removal efficiency under the same conditions, it is possible to reduce ozone injected volume, operating cost reduce by 10% or more.
As another preferred situation, the ozone oxidation catalyst based on activity carbon carrier is activated carbon loaded gold
Belong to oxide, wherein the metal oxide is ferriferous oxide, Cu oxide, ru oxide, cerium oxide, cobalt/cobalt oxide, manganese
At least one of oxide, nickel oxide.
In the embodiment of the present invention, the activated carbon is as catalyst carrier, for loading the metal oxygen for playing catalytic action
Compound, not swollen do not split keeps original state after having the advantages that porous, large specific surface area, mechanical strength are big, hygroscopicity is strong and absorbing water.
Preferably, the diameter of the activity carbon carrier is 0.5-3mm, specific surface area 450-700m2/g.Preferred activity carbon carrier,
With suitable diameter and specific surface area, therefore, it is capable of providing the load capacity of suitable metal oxide, is conducive to ozone oxygen
Change catalyst stabilization, equably remove the nbsCOD in sewage, improves COD removal rate；Simultaneously as metal oxide is described
The apparent gap of activity carbon carrier is evenly dispersed, therefore can reduce the usage amount of catalyst, and then reduce cost.In addition, excellent
It can be recycled after the activity carbon carrier use of choosing.
In the embodiment of the present invention, the load capacity of the metal oxide has certain shadow to the nbsCOD in removal sewage
It rings.Preferably, based on by described by the quality of the ozone oxidation catalyst of activity carbon carrier for 100%, the metal oxide
Load capacity be 1-10%, the ozone oxidation catalyst obtained at this time to nbsCOD have preferable removal effect.If the gold
The load capacity for belonging to oxide is too low, then the relative amount of catalyst is lower, and the effect for removing nbsCOD is relatively poor, COD removal
Rate reduces；If the load capacity of the metal oxide is excessively high, it is be easy to cause metal sintering, duct blocking, is lived to reduce catalysis
Property, influence the removal of nbsCOD.
In ozone oxidation catalyst provided in an embodiment of the present invention, the metal oxide that can remove nbsCOD includes activity
Carbon load metal oxide, wherein the metal oxide be ferriferous oxide, Cu oxide, ru oxide, cerium oxide,
At least one of cobalt/cobalt oxide, Mn oxide, nickel oxide.Specifically, the preferred di-iron trioxide of ferriferous oxide, described
The preferred manganese dioxide of Mn oxide.
As a particular preferred embodiment, the ozone oxidation catalyst based on activity carbon carrier is activated carbon loaded
Di-iron trioxide, and by it is described by the quality of the ozone oxidation catalyst of activity carbon carrier be 100% based on, it is described three oxidation
The load capacity of two iron is 3%.The preferred ozone oxidation catalyst can efficiently remove nbsCOD in sewage, catalytic ozonation
The removal rate of 60min, nbsCOD at least improve 50% up to 80% or more, than the blank control under parallel condition.
It is described negative for activated carbon based on the ozone oxidation catalyst of activity carbon carrier as another particular preferred embodiment
The manganese dioxide of load, and by it is described by the quality of the ozone oxidation catalyst of activity carbon carrier be 100% based on, the titanium dioxide
The load capacity of manganese is 5%.The preferred ozone oxidation catalyst can efficiently remove nbsCOD in sewage, catalytic ozonation
The removal rate of 60min, nbsCOD improve 50% up to 76% or more, than the blank control under parallel condition.
Ozone oxidation catalyst provided in an embodiment of the present invention based on activity carbon carrier, the large specific surface area of active carbon,
It is strong to the accumulation ability of organic matter, it can be improved the degradation speed and efficiency of nbsCOD, prepared catalyst is a kind of efficient
Catalyst.Ozone oxidation catalyst provided in an embodiment of the present invention based on activity carbon carrier, the ozone for trade effluent are urged
When changing oxidation, the nbsCOD in sewage can be efficiently removed, the removal rate of catalytic ozonation 60min, nbsCOD may be up to
80%, it is higher by 50% or more than the COD removal rate of O3 contacted oxidation.In addition, the present invention is real under conditions of same catalytic efficiency
The ozone oxidation catalyst based on activity carbon carrier of example offer is applied, price is more flat than the catalyst of mainstream producer currently on the market
Equal price low 50% or more；Ozone oxidation catalyst of the present invention is used in ozone high grade oxidation equipment, it is identical in removal efficiency
Under conditions of, it is possible to reduce ozone injected volume, operating cost reduce by 20% or more.
In the embodiment of the present invention, it is preferred that the water inlet flow velocity of the secondary clarifier effluent is 5-100L/ hours, and described two
Residence time of the sinking pool effluent in the catalytic ozonation reactor is 20-60min, thus before guaranteeing catalytic effect
It puts, saves time cost.
In the embodiment of the present invention, the catalytic ozonation reactor is 1 catalytic ozonation reaction member or 2
The catalytic ozonation reaction member of more parallel, to realize more large batch of COD of sewage pilot scale processing.The embodiment of the present invention
The device for catalyzing and oxidating ozone of offer is the device for catalyzing and oxidating ozone for pilot scale, therefore, from producing save the cost itself
Angle is set out, and each device for catalyzing and oxidating ozone is equipped with an ozone generator, while for catalytic ozonation reaction member
Catalytic ozonation oxygen.It is further preferred that the quantity of the catalytic ozonation reaction member is 2-6, if described
The quantity of catalytic ozonation reaction member is excessive, and the ozone that ozone generator generates enters the ozone catalytic oxygen after pipeline
Change reaction member after, gas distribution effect is poor, catalytic ozonation it is ineffective.
It is described when the catalytic ozonation reactor contains two or more catalytic ozonation reaction members
Wire feeding in catalytic ozonation reaction member is identical, part is identical or different.
Preferably, the internal diameter of the catalytic ozonation reactor is 80-120mm, high 1000-1200mm.Further,
Reaction volume is preferably 5-20L in catalytic ozonation reaction member described in the embodiment of the present invention.In principle, meeting above-mentioned institute
Under conditions of the volume ratio for stating filler and the secondary clarifier effluent, reaction volume is the smaller the better.If reaction volume is excessive, it is based on one
Also uncertain factor a bit, causes catalytic oxidation effect poor.
As a most preferred embodiment, the volume ratio of the filler and the secondary clarifier effluent is 0.8:1, and the micropore is quick-fried
The aeration efficiency of gas device meets: the COD mass concentration of the secondary clarifier effluent and the mass concentration ratio of ozone are 1:0.5, described
The water inlet flow velocity of secondary clarifier effluent is 100L/ hours, and the secondary clarifier effluent is in the catalytic ozonation reactor
Residence time is 60min, to obtain the COD removal rate most having.
The catalytic ozonation method of the offer of the embodiment of the present invention is based on specifically using device for catalyzing and oxidating ozone
The middle method for testing provided can achieve very high catalytic efficiency by modulation process parameter, so that after catalytic ozonation
COD concentration can drop to 30mg/L.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of catalytic ozonation method, the catalytic ozonation is carried out using device for catalyzing and oxidating ozone, described smelly
Oxygen catalytic oxidizing equipment include by the sequentially connected apparatus of oxygen supply of pipeline, ozone generator, catalytic ozonation reactor and
Absorption plant, wherein the catalytic ozonation reactor is the cylindrical pipe of internal diameter 100mm, high 1000ml, including under
The micropore aerator and packing layer being up arranged, wherein the filler of described filler layer is three oxygen of active gamma oxidation aluminium ball load
Change two iron catalysts, and the load percentage composition of the di-iron trioxide is 3%, the COD concentration of the secondary clarifier effluent is
92.8mg/L, the filler loading are 4L, and the volume of the secondary clarifier effluent is 5L.
Embodiment 2
Difference from Example 1 is that catalyst loading is 2L, reaction time 40min.
Embodiment 3
Difference from Example 1 is that the filler of described filler layer is activated carbon supported manganese dioxide-catalyst, and
The load percentage composition of the manganese dioxide is 5%.
Embodiment 4
Difference from Example 3 is that catalyst loading is 3L, reaction time 50min.
Embodiment 5
Difference from Example 1 is that the filler of described filler layer is the manganese dioxide of Alumina Foam Ceramics load
With cobalt oxide composite catalyst, and the load percentage composition of the manganese dioxide is 3%, and the load percentage composition of cobalt oxide is
2%.
Sample of the embodiment 1-5 after treated by ozone is subjected to COD concentration determination, test result is as follows shown in table 1.
Table 1
Seen from table 1 above, catalytic ozonation method provided in an embodiment of the present invention has excellent catalytic ozonation
Effect.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (8)
1. a kind of catalytic ozonation method, which is characterized in that the catalytic ozonation using device for catalyzing and oxidating ozone into
Row, the device for catalyzing and oxidating ozone include passing through the sequentially connected apparatus of oxygen supply of pipeline, ozone generator, catalytic ozonation
Reactor and absorption plant, wherein the catalytic ozonation reactor is cylindrical tube, including the micropore being arranged from the bottom up
Secondary clarifier effluent is injected in the catalytic ozonation reactor, is catalyzed under aeration condition by aerator and packing layer
Oxidation, wherein the COD concentration of the secondary clarifier effluent is 60-100mg/L, and the filler in described filler layer is urged for ozone oxidation
Agent, and the volume ratio of the filler and the secondary clarifier effluent is 0.5-1:1, the aeration efficiency of the micropore aerator is full
Foot: the mass concentration ratio of the COD mass concentration of the secondary clarifier effluent and ozone is 1:0.2-1.
2. catalytic ozonation method as described in claim 1, which is characterized in that the filler is to be made pottery based on Alumina Foam
The ozone oxidation catalyst of ceramic carrier, the ozone oxidation catalyst based on active gamma-aluminium oxide carrier, based on absorbent charcoal carrier
At least one of ozone oxidation catalyst.
3. catalytic ozonation method as described in claim 1, which is characterized in that the water inlet flow velocity of the secondary clarifier effluent is
5-100L/ hours, and reaction time of the secondary clarifier effluent in the catalytic ozonation reactor is 20-60min.
4. catalytic ozonation method as described in any one of claims 1-3, which is characterized in that the catalytic ozonation is anti-
Answering device is the catalytic ozonation reaction member of 1 catalytic ozonation reaction member or 2 more parallels.
5. catalytic ozonation method as claimed in claim 4, which is characterized in that the catalytic ozonation reaction member
Quantity is 2-6.
6. catalytic ozonation method as claimed in claim 4, which is characterized in that in the catalytic ozonation reaction member
Wire feeding is identical, part is identical or different.
7. catalytic ozonation method as claimed in claim 4, which is characterized in that in the catalytic ozonation reaction member
Reaction volume 5-20L.
8. catalytic ozonation method as described in any one of claims 1-3, which is characterized in that the filler is heavy with described two
The volume ratio of pond water outlet is 0.8:1, and the aeration efficiency of the micropore aerator meets: the COD mass of the secondary clarifier effluent is dense
The mass concentration ratio of degree and ozone is 1:1, and the water inlet flow velocity of the secondary clarifier effluent is 100L/ hours, and the secondary settling tank goes out
Residence time of the water in the catalytic ozonation reactor is 60min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710667516.5A CN109384300A (en) | 2017-08-07 | 2017-08-07 | Catalytic ozonation method |
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| CN112919616A (en) * | 2021-02-18 | 2021-06-08 | 科盛环保科技股份有限公司 | High-efficient ozone catalytic oxidation reactor for advanced treatment of chemical industry park sewage tail water |
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