CN1259255C - Reactor for efficient removing organic pollutanti in water by catalysis and ozonization - Google Patents
Reactor for efficient removing organic pollutanti in water by catalysis and ozonization Download PDFInfo
- Publication number
- CN1259255C CN1259255C CN 03150149 CN03150149A CN1259255C CN 1259255 C CN1259255 C CN 1259255C CN 03150149 CN03150149 CN 03150149 CN 03150149 A CN03150149 A CN 03150149A CN 1259255 C CN1259255 C CN 1259255C
- Authority
- CN
- China
- Prior art keywords
- reactor
- water
- alachlor
- reaction
- catalytic ozonation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The present invention provides a reactor for removing organic pollutants from water through catalytic ozonation. The reactor is composed of a glass reaction column, an ozone gas inlet pipe, a quartz sand multi-hole gas distributing system, a catalyst column and a constant temperature control system. Ozone gas with certain concentration is led into the reaction column in which organic pollutants with certain concentration are placed in advance; compared with the removal of organic pollutants through single ozone oxidation, the removal of organic pollutants through mineralization is realized at a higher degree under the combined action of the ozone gas and a catalyst. When the treatment of catalytic ozonation is carried out on herbicide alachlor as target organic pollutants, more than 98% of alachlor is removed after the treatment of catalytic ozonation is carried out for 30 minutes, and the TOC removing rate reaches 90% after the treatment is carried out for 180 minutes. The reactor can control the treatment time of catalytic ozonation, the catalyst can be repeatedly used for multiple times after catalyst regeneration while the treatment effects are not influenced, and the metal digestion amount is smaller than 2 ppb in the use process so that secondary pollution to the treated water is not caused.
Description
Technical field
The present invention relates to a kind of O3 catalytic oxidation and remove the reactor of organic pollutant in the water, specifically is certain density ozone gas to be evenly distributed to one by a porous air distribution plate water-filled loaded Cu/Al arranged
2O
3In the reactor that the honeycomb ceramic body of catalyzer exists, at Cu/Al
2O
3Organism under the catalysis in the oxidizing water.
Background technology
In source water, underground water, surface water and trade effluent, all contain various Persistent organic pollutants to some extent, as various Insecticides (tech) ﹠ Herbicides (tech)s, sterilant and macromole soil ulmin, small molecules organic carboxyl acid etc., utilize existing water technology to be difficult to they thorough removals.In addition, Cl
2, ClO
2Deng forming a series of by products that still have toxicity and internal secretion interferon activity after the method for oxidation processing, the water after handling is caused secondary pollution; Because O
3Have stronger oxidisability, instability, become oxygen after the decomposition, so ozonize is a kind of water technology of safety.Studies have shown that independent ozone oxidation can effectively remove multiple Persistent organic pollutants, but under different pH conditions O
3Oxidizing reaction has extremely strong selectivity, and can not be CO with the thorough mineralising of most of material
2And H
2O, these materials still exist with the form that contains aromatic ring organism or small molecules organic carboxyl acid, can not thoroughly eliminate its pollution to water.The UV/O that developed recently gets up
3Method and TiO
2Persistent organic pollutants in the photocatalysis method treating water have been proved to be good effect, but because it has relatively high expectations powder TiO to reactor
2The separation difficulty of catalyzer in the water after the photocatalysis treatment, and processing cost is higher, therefore is difficult to be applied to actual water technology.Therefore, simple, efficiently, treatment process is the key that ozonize contains Persistent organic pollutants water cheaply.Studies have shown that and adopt a kind of Cu/Al
2O
3The process of catalyst ozonize Persistent organic pollutants can obtain higher TOC clearance, the organic intermediate product that produces in the ozone oxidation process can both be removed largely as containing phenyl ring organism and small molecules organic carboxyl acid (oxalic acid, acetate, propionic acid etc.) etc. separately, makes the ozone oxidation of Persistent organic pollutants in the water remove thorough more, complete.
Summary of the invention
The objective of the invention is: solve the problem that independent ozone oxidation can not be removed some organism permineralization in the water, overcome existing powder TiO
2The defective of heterogeneous catalysis ozonize cost height, separation difficulty is invented the reactor that Persistent organic pollutants in the water are removed in a kind of efficient catalytic ozonize, improves the utilization ratio of ozone in water, reaches higher mineralization of organic material efficient.
Structure of reactor of the present invention as shown in drawings.Loaded Cu/Al
2O
3Ceramic honeycomb catalyst 4, ozone reaction post 5 in recirculated water constant temperature system 6; The ozone gas that ozonizer produces is uniformly distributed in the reaction column by quartz sand porous air distribution plate 3 through inlet pipe 1, and tolerance is by intake valve 2 controls; Organism in ozone gas and the water fully reacts; Remaining ozone gas enters device for absorbing tail gas through escape pipe 9, can control air output by the adjusting of intake valve 2 and air outlet valve 8 as required; Sample is regularly taken out by thief hole 7 and analyzes alachlor concentration and TOC.
The ozone reaction post of this reactor is a diameter 30mm, the glass column of high 200mm, and the bottom is fixed with quartz sand porous air distribution plate (aperture 10 μ m), then is that load has Cu/Al on the air distribution plate
2O
3The honeycomb ceramic body of catalyzer (diameter 29mm, high 100mm).Ozone fully contacts with organism and catalyzer in the slit of honeycomb ceramic body by the porous air distribution plate, finishes the catalytic ozonation reaction.
Because the solubleness of ozone gas in water is subjected to Temperature Influence bigger, variation of temperature also can influence O greatly
3Mass transfer in water, and then can influence O largely
3The organic reaction process of oxidative degradation.Therefore, in the present invention, considered the influence of temperature to the catalytic ozonation reaction.The present invention adopts a thermostatic circulation bath to keep homo(io)thermism in the treating processes, makes processing can reach the stable treated effect within the predetermined time under identical condition of water quality.
This reactor also can be selected stainless steel for use, and distribution device uses titanium porous air distribution plate (aperture 10 μ m) to replace thereupon, tightly is fixed in the bottom of reactor with flange.Can make the ozone gas physical efficiency more even, soluble in water more expeditiously, and then ozone gas, water and catalyzer are contacted more fully, improve the efficient of catalytic ozonation reaction.Reactor diameter 70mm, high 300mm, reactor loam cake also are connected with the reactor cylinder with flange, make to be reflected under the airtight condition and carry out.Remaining ozone gas enters device for absorbing tail gas by the air outlet and carries out the tail gas absorption.
The operating process of reactor of the present invention is as follows: with ultrapure water reactor is washed several times continuously, and continue logical O in empty reactor
3About 10 minutes, remove the organic or inorganic impurity that remains on the reactor with oxidation, in order to avoid in the process of catalytic ozonation, consume O
3With alachlor is that representative target organic pollutant carries out the catalytic ozonation removal, preparing certain density alachlor solution joins in the reaction column, reactor is airtight, the reactor air valve is adjusted to required size, open ozonizer, control certain ozone flow and concentration, this moment is constantly zero as the catalytic ozonation reaction, takes a sample constantly in different reactions and analyzes.Catalytic ozonation reaction after 30 minutes alachlor can remove after about 98%, 180 minute the alachlor more than 90% and can be removed by permineralization.
Remain O in the treating processes in the water
3The measuring method of concentration is as follows: extract in an amount of reactor from the thief hole place with the syringe that finite concentration Indigo reagent is housed in advance and be dissolved with O
3Water, mix immediately, in the colorimetric estimation of 600nm place.
Characteristics of the present invention are as follows:
1, adopts quartz sand porous air distribution plate, both do not had the organism stripping, ozone gas evenly is distributed in the solution effectively, improved the utilization ratio of ozone.
2, working method is simple, facility compact, easy handling.
3, various parameters are controlled easily, can be as required conditioned reaction parameter at any time, and can be by the required tolerance of several different methods control reaction.
4, the catalytic effect of catalytic ozonation process is remarkable, can realize that the permineralization of Persistent organic pollutants in the water is removed.
5, Cu/Al
2O
3The metal stripping of solid catalyst is minimum, can not cause secondary pollution to processed water.
6, Cu/Al
2O
3Can use for several times continuously behind the solid catalyst high temperature regeneration and do not reduce catalytic effect.
7, the simple and easy investment of reactor is low, handles rear catalyst and processed water natural separation.
8, this reactor is treated the no particular restriction of pH value for the treatment of water, can be acidity, neutrality or alkaline, and the gained treatment effect all is better than the independent ozone Oxidation Treatment under the same condition of water quality.
9, this reactor also can be selected stainless steel for use, distribution device uses titanium porous air distribution plate (aperture 10 μ m) to replace thereupon, can make the ozone gas physical efficiency more even, soluble in water more expeditiously, and then ozone gas, water and catalyzer are contacted more fully, improve the efficient of catalytic ozonation reaction.
Description of drawings
Accompanying drawing is the structural representation of reactor involved in the present invention.
Reference numeral:
1. inlet pipe; 2. intake valve; 3. porous air distribution plate; 4. catalyzer post; 5. ozone reaction post; 6. recirculated water constant temperature system; 7. thief hole; 8. air outlet valve; 9. escape pipe.
Embodiment
Embodiment 1:
In glass reactor, add alachlor solution 75ml, adjust O
3Each parameter of producer is to set(ting)value, with the flow velocity generation O of 40ml/min
3, treat that steady air current inserts the gas reactor inlet after 2 minutes, pick up counting, the airtight oxidizing reaction of carrying out, this moment is as 0 constantly.Carrying out catalytic ozonation under the following conditions handles:
Reaction target solution volume: 75ml
Reaction target solution concentration: alachlor: 100mg/L, TOC:60mg/L
Reaction target solution temperature: 20 ℃
Reaction soln system: 0.001M phosphate buffer soln
Solution initial pH value: 7.00
O
3Concentration: 12.2mg/L/min takes place
Catalytic material: catalyst fines is carried on the cylindric material that the ceramic honey comb surface forms
Alachlor and corresponding TOC clearance are as shown in table 1 after sampling time point: 10min, 30min, 60min, 120min, 180min, the processing.
Table 1 embodiment 1 handles back alachlor and TOC clearance
| Time (min) | 10 | 30 | 60 | 120 | 180 | |
| Alachlor clearance (%) | On-catalytic | 52.3 | 85.6 | 90.5 | 91.4 | 92.8 |
| Catalysis | 68.5 | 97.6 | 98.5 | 99.0 | 99.3 | |
| TOC clearance (%) | On-catalytic | 4.61 | 21.4 | 31.4 | 38.6 | 49.3 |
| Catalysis | 5.22 | 36.9 | 56.4 | 82.2 | 87.3 |
Embodiment 2:
In glass reactor, add alachlor solution 75ml, adjust O
3Each parameter of producer is to set(ting)value, with the flow velocity generation O of 40ml/min
3, treat that steady air current inserts the gas reactor inlet after 2 minutes, pick up counting, the airtight oxidizing reaction of carrying out, this moment is as 0 constantly.Carrying out catalytic ozonation under the following conditions handles:
Reaction target solution volume: 75ml
Reaction target solution concentration: alachlor: 100mg/L, TOC:60mg/L
Reaction target solution temperature: 20 ℃
Reaction soln system: 0.001M phosphate buffer soln
Solution initial pH value: 4.30
O
3Concentration: 12.2mg/L/min takes place
Catalytic material: catalyst fines is carried on the cylindric material that the ceramic honey comb surface forms
Alachlor and corresponding TOC clearance are as shown in table 2 after sampling time point: 10min, 30min, 60min, 120min, 180min, the processing.
Table 2 embodiment 2 handles back alachlor and TOC clearance
| Time (min) | 10 | 30 | 60 | 120 | 180 | |
| Alachlor clearance (%) | On-catalytic | 45.3 | 75.6 | 84.9 | 87.3 | 89.9 |
| Catalysis | 59.4 | 85.7 | 93.8 | 95.6 | 95.8 | |
| TOC clearance (%) | On-catalytic | 1.52 | 21.2 | 26.2 | 38.0 | 48.1 |
| Catalysis | 3.93 | 28.7 | 47.2 | 74.1 | 80.8 |
Embodiment 3:
In glass reactor, add alachlor solution 75ml, adjust O
3Each parameter of producer is to set(ting)value, with the flow velocity generation O of 40ml/min
3, treat that steady air current inserts the gas reactor inlet after 2 minutes, pick up counting, the airtight oxidizing reaction of carrying out, this moment is as 0 constantly.Carrying out catalytic ozonation under the following conditions handles:
Reaction target solution volume: 75ml
Reaction target solution concentration: alachlor: 100mg/L, TOC:60mg/L
Reaction target solution temperature: 20 ℃
Reaction soln system: 0.001M phosphate buffer soln
Solution initial pH value: 9.10
O
3Concentration: 12.2mg/L/min takes place
Catalytic material: catalyst fines is carried on the cylindric material that the ceramic honey comb surface forms
Alachlor and corresponding TOC clearance are as shown in table 3 after sampling time point: 10min, 30min, 60min, 120min, 180min, the processing.
Table 3 embodiment 3 handles back alachlor and TOC clearance
| Time (min) | 10 | 30 | 60 | 120 | 180 | |
| Alachlor clearance (%) | On-catalytic | 63.7 | 89.5 | 92.5 | 94.1 | 95.3 |
| Catalysis | 70.5 | 98.2 | 98.7 | 99.2 | 99.5 | |
| TOC clearance (%) | On-catalytic | 5.05 | 23.2 | 37.7 | 48.9 | 58.4 |
| Catalysis | 10.3 | 40.6 | 66.9 | 86.8 | 89.7 |
By table 1-3 as can be known, no matter under acid, alkaline or neutrallty condition, at Cu/Al
2O
3Catalytic ozonation process under the catalyst action can both show than independent O
3Make better alachlor of time spent and TOC removal effect.
Embodiment 4:
In glass reactor, add alachlor solution 75ml, adjust O
3Each parameter of producer is to set(ting)value, with the flow velocity generation O of 40ml/min
3, treat that steady air current inserts the gas reactor inlet after 2 minutes, pick up counting, the airtight oxidizing reaction of carrying out, this moment is as 0 constantly.Carry out catalytic ozonation under the following conditions and handle (catalyzer is reused after using 500 ℃ of high temperature regenerations of several times continuously):
Reaction target solution volume: 75ml
Reaction target solution concentration: alachlor: 100mg/L, TOC:60mg/L
Reaction target solution temperature: 20 ℃
Reaction soln system: 0.001M phosphate buffer soln
Solution initial pH value: 7.00
O
3Concentration: 12.2mg/L/min takes place
Catalytic material: catalyst fines is carried on the cylindric material that the ceramic honey comb surface forms
Alachlor and corresponding TOC clearance are as shown in table 4 after sampling time point: 10min, 30min, 60min, 120min, 180min, the processing.
Table 4 embodiment 4 handles back alachlor and TOC clearance
| Time (min) | 10 | 30 | 60 | 120 | 180 |
| Alachlor clearance (%) | 68.3 | 97.2 | 98.3 | 89.8 | 99.0 |
| TOC clearance (%) | 5.03 | 35.4 | 55.9 | 81.7 | 87.1 |
As can be seen from Table 4, work as Cu/Al
2O
3Behind continuous use of catalyzer and the high temperature regeneration several times, still can show very strong katalysis.In addition from the metal stripping result that measures catalyzer this Cu/Al as can be known
2O
3Catalyzer metal stripping in use very little (less than 2ppb) illustrates catalyzer by the very firm carrier surface that is fixed in, and this has explained its lasting catalysis efficiency dry straightly.
Embodiment 5:
In glass reactor, add humic acids, oxalic acid, acetic acid mixed solution 75ml, adjust O
3Each parameter of producer is to set(ting)value, with the flow velocity generation O of 40ml/min
3, treat that steady air current inserts the gas reactor inlet after 2 minutes, pick up counting, the airtight oxidizing reaction of carrying out, this moment is as 0 constantly.Carrying out catalytic ozonation under the following conditions handles:
Reaction target solution volume: 75ml
Reaction target solution concentration: humic acids 20mg/L (DOC), oxalic acid and each 20mg/L of acetate
Reaction target solution temperature: 20 ℃
O
3Concentration: 12.2mg/L/min takes place
Catalytic material: catalyst fines is carried on the cylindric material that the ceramic honey comb surface forms
Corresponding TOC clearance is as shown in table 5 after sampling time point: 10min, 30min, 60min, 120min, 180min, the processing.
Table 5 embodiment 5 handles back TOC clearance
| Time (min) | 10 | 30 | 60 | 120 | 180 | |
| TOC clearance (%) | On-catalytic | 2.3 | 4.8 | 10.6 | 15.9 | 16.2 |
| Catalysis | 11.0 | 31.9 | 43.6 | 52.8 | 65.7 |
From the result of table 5 as can be seen: for extremely difficult humic acids, oxalic acid and the acetate of being removed by various method for oxidation mineralisings the water, this Cu/Al
2O
3The catalytic ozonation method shows remarkable advantages, the mixing TOC clearance of several materials can be improved approximately 50%, if through the sufficiently long catalytic ozonation time, TOC all should be able to be removed, reaches permineralization.
Embodiment 6:
In volume is the glass reactor of 100ml, add alachlor solution 75ml, adjust O
3Each parameter of producer is to set(ting)value, with the flow velocity generation O of 40ml/min
3, treat that steady air current inserts the gas reactor inlet after 2 minutes, pick up counting, the airtight oxidizing reaction of carrying out, this moment is as 0 constantly.Carrying out catalytic ozonation under the following conditions handles:
Reaction target solution volume: 75ml
Reaction target solution concentration: alachlor: 100mg/L, TOC:60mg/L
Reaction target solution temperature: 20 ℃
Reaction soln system: 0.001M phosphate buffer soln
Solution initial pH value: 7.00
O
3Concentration: 12.2mg/L/min takes place
Catalytic material: granules of catalyst (dosage: 250mg/L)
Alachlor and corresponding TOC clearance are as shown in table 6 after sampling time point: 10min, 30min, 60min, 120min, 180min, the processing.
Table 6 embodiment 6 handles back alachlor and TOC clearance
| Time (min) | 10 | 30 | 60 | 120 | 180 | |
| Alachlor clearance (%) | On-catalytic | 52.3 | 85.6 | 90.5 | 91.4 | 92.8 |
| Catalysis | 66.5 | 96.7 | 96.9 | 97.8 | 98.0 | |
| TOC clearance (%) | On-catalytic | 4.61 | 21.4 | 31.4 | 38.6 | 49.3 |
| Catalysis | 4.91 | 30.8 | 45.2 | 68.3 | 72.4 |
As can be known from the results of Table 6, when catalyzer adds with graininess, also can obtain relatively significantly catalytic effect, but than will hanging down slightly that supported solid state is used.The shortcoming that particle adds is that the catalyst separating after handling is difficult.
Embodiment 7:
In volume is the stainless steel reactor of 1400ml, add alachlor solution 1200ml, adjust O
3Each parameter of producer is to set(ting)value, with the flow velocity generation O of 40ml/min
3, treat that steady air current inserts the gas reactor inlet after 2 minutes, pick up counting, the airtight oxidizing reaction of carrying out, this moment is as 0 constantly.Carrying out catalytic ozonation under the following conditions handles:
Reaction target solution volume: 1200ml
Reaction target solution concentration: alachlor: 100mg/L, TOC:60mg/L
Reaction target solution temperature: 20 ℃
Reaction soln system: 0.001M phosphate buffer soln
Solution initial pH value: 7.00
O
3Concentration: 12.2mg/L/min takes place
Catalytic material: catalyst fines is carried on the cylindric material that the ceramic honey comb surface forms
Alachlor and corresponding TOC clearance are as shown in table 7 after sampling time point: 10min, 30min, 60min, 120min, 180min, the processing.
Table 7 embodiment 7 handles back alachlor and TOC clearance
| Time (min) | 10 | 30 | 60 | 120 | 180 | |
| Alachlor clearance (%) | On-catalytic | 50.1 | 82.3 | 88.2 | 92.5 | 93.7 |
| Catalysis | 73.5 | 98.2 | 98.8 | 99.3 | 99.5 | |
| TOC clearance (%) | On-catalytic | 5.45 | 23.8 | 35.2 | 40.0 | 50.7 |
| Catalysis | 10.4 | 40.1 | 58.9 | 84.2 | 89.0 |
As can be known from the results of Table 7, in the reactor of stainless steel and amplification slightly, can obtain good catalytic ozonation treatment effect equally, and alachlor and TOC clearance be higher slightly than glass reactor also, this may be because titanium porous gas distribution system can obtain than littler, more even, the more stable bubble of quartz sand porous air distribution plate, and the gas-to-liquid contact area has been increased, improved processing efficiency.
Claims (3)
1. the reactor of organic pollutant in the water is removed in an efficient catalytic ozonize, it is characterized in that a kind of Cu/Al
2O
3Catalyzer is carried on the ceramic honey comb surface equably, and as the core of catalytic ozonation reaction, the catalytic ozonation that is carried out in reactor reaction can make the thorough mineralising of organic pollutant in the water.
2. according to the described reactor of claim 1, solid Cu/Al
2O
3But the catalyst fines single or multiple lift evenly is coated on honeycomb ceramic body or other porous solid carrier surface, and dissolving is few, does not come off, and ozonization is had strong katalysis.
3. according to the described reactor of claim 1, it is characterized in that the quartz sand porous gas distribution system of reactor bottom or titanium porous air distribution plate are distributed in the reaction soln ozone gas more equably.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150149 CN1259255C (en) | 2003-07-21 | 2003-07-21 | Reactor for efficient removing organic pollutanti in water by catalysis and ozonization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150149 CN1259255C (en) | 2003-07-21 | 2003-07-21 | Reactor for efficient removing organic pollutanti in water by catalysis and ozonization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1576244A CN1576244A (en) | 2005-02-09 |
| CN1259255C true CN1259255C (en) | 2006-06-14 |
Family
ID=34579791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03150149 Expired - Fee Related CN1259255C (en) | 2003-07-21 | 2003-07-21 | Reactor for efficient removing organic pollutanti in water by catalysis and ozonization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1259255C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357193C (en) * | 2006-06-16 | 2007-12-26 | 中钢集团鞍山热能研究院 | Deep technique for treating charking wastewater |
| CN102267756B (en) * | 2010-06-04 | 2013-08-21 | 中国科学院过程工程研究所 | Waste water deep treatment method through heterogeneous catalysis and ozone oxidation, and apparatus thereof |
| CN103159316B (en) * | 2013-04-01 | 2014-09-03 | 北京科技大学 | Method for removing organic matters from water by photocatalytic ozonization |
| CN104071888B (en) * | 2014-06-10 | 2015-12-09 | 南京德磊科技有限公司 | A kind of swash plate catalytic tower |
| CN103708598B (en) * | 2014-01-02 | 2016-05-11 | 天津大学 | One is utilized method and the device of Polychlorinated biphenyls in Ni-Fe duplex metal nano granule degradation water environment |
| CN108423795A (en) * | 2018-03-29 | 2018-08-21 | 中国矿业大学(北京) | Efficiently catalyzing and oxidizing device |
| CN113104950A (en) * | 2020-07-15 | 2021-07-13 | 昆山中环科本科技发展有限公司 | External catalyst ozone catalytic reactor and process thereof |
| CN113788504B (en) * | 2021-09-30 | 2022-10-04 | 中国矿业大学 | Bismuth tungstate-based photocatalytic reactor and mineral processing wastewater degradation system |
-
2003
- 2003-07-21 CN CN 03150149 patent/CN1259255C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1576244A (en) | 2005-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1186119C (en) | Oxidizing catalyst and its preparation, regeneration process and usage in treating waste water | |
| CN1275883C (en) | Process for water supply deep treatment of catalyzing ozone oxydation by hydroxy ferric oxide as catalyst | |
| CN110075845B (en) | Iron-based catalyst for enhancing ozone oxidation of organic pollutants and preparation method thereof | |
| CN101386461A (en) | Processing system for implementing coking waste water reuse and processing method | |
| CN102491451A (en) | Device and method with ultrasonic ozone and ultraviolet synergized for water treatment | |
| CN1259255C (en) | Reactor for efficient removing organic pollutanti in water by catalysis and ozonization | |
| CN105174423B (en) | A kind of coal chemical industry biochemical tail water processing method | |
| CN1576243A (en) | Process for efficient removing organic pollutant in water by catalysis and ozonization | |
| JP2008302308A (en) | Photocatalyst and method for manufacturing thereof, method and apparatus for water treatment using thereof | |
| CN1262229A (en) | Suspension and photocatalytic oxidization process and equipment combined with membrane separator for treating water | |
| CN111747575A (en) | Chemical pharmaceutical wastewater organic matter adsorption-catalytic oxidation functional material and use method thereof | |
| CN111744361A (en) | Device for advanced treatment of pyridine waste gas | |
| CN2920980Y (en) | Apparatus for treating orgain sewage utilizing ozone/active carbon | |
| JPH10305287A (en) | Ozone catalytic reactor | |
| CN103214133B (en) | Graphene sewage purification combined device and sewage purification method thereof | |
| CN206858341U (en) | A kind of microwave radiation technology ozone enhanced photocatalysis sewage disposal system | |
| CN105984978B (en) | A kind for the treatment of process of wastewater from aquatic product process | |
| CN103910468A (en) | Treatment method of aquatic product processing waste water | |
| CN108246329A (en) | It is a kind of to mix N graphenes-cerium oxide composite catalyst and its application in acid refractory wastewater | |
| CN203399621U (en) | Device for removing earthy smell of aquatic water in recirculation water aquaculture system | |
| US5266540A (en) | Process for the regeneration of active carbon | |
| Liu et al. | OZONATION OF OXYTETRACYCLINE IN THE PRESENCE OF ACTIVATED CARBON SUPPORTED CERIUM OXIDE. | |
| JPH01284385A (en) | Process and apparatus for producing pure water and superpure water | |
| TWM479924U (en) | Photocatalyst filter composite structure for degrading organics in water | |
| CN111499061B (en) | Natural water body treatment method and device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060614 Termination date: 20180721 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |