CN1312055C - Ozone high grade oxidation method for treating water - Google Patents
Ozone high grade oxidation method for treating water Download PDFInfo
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- CN1312055C CN1312055C CNB2005100096471A CN200510009647A CN1312055C CN 1312055 C CN1312055 C CN 1312055C CN B2005100096471 A CNB2005100096471 A CN B2005100096471A CN 200510009647 A CN200510009647 A CN 200510009647A CN 1312055 C CN1312055 C CN 1312055C
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- hydrogen peroxide
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- oxidation method
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Abstract
The present invention provides a novel high-grade ozone oxidizing method for treating water, which relates to a water treating method. The present invention is completed by the following steps: a. an alkaline solution whose concentration is from 10<-7> to 10<2>mol/L is mixed with an aqueous hydrogen peroxide solution to enable the pH value of the aqueous hydrogen peroxide solution to be between 7 and 14; b. the alkaline aqueous hydrogen peroxide solution is filled in water to be combined with ozone to oxidize organic substances in water. In the present invention, the adding quantity of hydrogen peroxide in an O3/H2O2 high-grade oxidizing method can be greatly reduced, the efficiency for removing organic substances in water can be obviously improved, the residual quantity of the hydrogen peroxide in water can be greatly reduced, and the problem that the residual hydrogen peroxide causes secondary pollution in the O3/H2O2 high-grade oxidizing method can be solved. The treating method has the advantages of simple operation, high operation efficiency, reliable work and wide popularization prospect.
Description
Technical field:
The present invention relates to a kind of water treatment method, be specifically related to a kind of novel ozone high grade oxidation method for treating water.
Background technology:
Development along with industrial and agricultural production, various factory effluents and sanitary sewage do not reach emission standard and just directly enter into water body, earth surface water source has been caused great harm, source quality also therefore and sharply descends, organic pollutant in the water body exists potential threat to human beings'health, particularly the persistence toxic organics long period stably is present in the water, utilizes traditional water treatment method limited to these high stability organic pollutant removal effects.Adopt high-level oxidation technology to come oxidation of organic compounds, have that speed of response is fast, non-selectivity, reaction conditions gentleness, can not produce the characteristics of secondary pollution, be considered to solve the effective means of organic contamination by the hydroxyl radical free radical that produces the hyperoxia voltinism.O
3/ H
2O
2Treatment process is a kind of the most extensive and effective advanced oxidization method that is applied in the drinking water treatment, and Japan began one's study in late 1970s, and the U.S. used it in the municipal sewage treatment in the eighties.Ozone itself has very strong oxidisability, and a lot of organism is had the removal effect, but relatively poor to organic oxidation effectivenesses such as some halohydrocarbon and agricultural chemicals, hydrogen peroxide is used in combination with ozone can improves oxidation efficiency greatly.O for example
3Very slow (its dynamic (dynamical) rate constant is 0.06～3M to the speed of oxidation chlorobenzene when pH=2
-1S
-1), but use O
3/ H
2O
2During the treatment process oxidation, degradation efficiency can improve greatly that (its dynamic (dynamical) rate constant is 4～5 * 10
9M
-1S
-1).O
3/ H
2O
2Treatment process also has good effect of removing to the agricultural chemicals monocrotophos, and clearance reaches more than 95% in the 20min.Studies show that O both at home and abroad
3/ H
2O
2It is more effective when seemingly organism can not react with UV-light in the method for economical and effective processing drinking water, the especially water the most in all advanced oxidation processes.But adopt O
3/ H
2O
2Treatment process degraded water pollutant, can there be residue H in water after processing
2O
2, cause water pollution once again, water quality is had side effects, and consume follow-up chlorine residue, influence sterilisation effect, thereby restricted O
3/ H
2O
2Applying aborning.
Summary of the invention:
The purpose of this invention is to provide a kind of sewage disposal or drinking water deep of being used for handles and has degradation of organic substances efficient height, an adding less a kind of novel ozone high grade oxidation method for treating water of hydrogen peroxide.It is finished by following steps: a, be 10 with concentration
-7～10
2The basic solution of mol/L mix with aqueous hydrogen peroxide solution make aqueous hydrogen peroxide solution the pH value between 7～14; B, the hydrogen peroxide alkaline aqueous solution is added to the water combines organism in the oxidation removal water with ozone.
The present invention has following beneficial effect: 1, traditional O that uses
3/ H
2O
2It is more to remain amount of hydrogen peroxide after the water treatment method existence of degraded water pollutant is handled in the water, causes the problem of water pollution once again, in order to address this problem the HO that the present invention utilizes hydrogen peroxide and alkali reaction to generate
2 -Promote that ozone is converted into the hydroxyl radical free radical with very strong oxidation capacity, strengthen the poisonous and hazardous organic pollutant of organic pollutant, particularly high stability (as agricultural chemicals, halogenated organic matters, nitro-compound etc.) in the water of decomposition.2, HO
2 -The preparation method hydrogen peroxide was mixed with certain density basic solution moment, make the pH value of aqueous hydrogen peroxide solution be alkalescence, pH value scope combines this alkaline hydrogen peroxide water solution then and removes high stability organism in the water between 7-14 with the ozone oxidation water treatment procedure.Concrete reaction mechanism of the present invention is as follows:
There is a dissociation equilibrium in hydrogen peroxide in the water:
At O
3/ H
2O
2In the HO that generates of above-mentioned reaction
2 -Ion is the inducer that free radical HO produces.
O
3+HO
2 -→·OH+O
2·
-+O
2
Free radical HO is in case following chain reaction just takes place in generation:
O
3+·OH→HO
2·+O
2
O
3+O
2·
-→O
3·
-+O
2
O
3·
-+H
2O→·OH+O
2+OH
-
Except above-mentioned reaction, also there are HO free radical and H
2O
2Reaction, but HO free radical and H
2O
2Reaction than above-mentioned reaction slowly many, so can be left in the basket.Have organic pollutants P in the solution, then reaction is:
P+HO → product or intermediate
In addition, the direct oxidation of organism P and ozone reaction is:
P+O
3→ product or intermediate
The end stopping of chain reaction is:
HO·+HO
2·→O
3+H
2O
Balance below also existing simultaneously:
The concentration of the HO free radical of the strong oxidizing property that in water treatment, plays a major role as can be seen from the above analysis and the HO in the aqueous solution
2 -Ionic concn has much relations, improves HO
2 -Ionic concn certainly will promote the generation of strong oxidizing property HO.3HO
2 -The preparation method after hydrogen peroxide was mixed with certain density basic solution moment, improve the pH value of aqueous hydrogen peroxide solution, thereby increased the dissociation degree of hydrogen peroxide in the water.4, with hydrogen peroxide alkaline aqueous solution combined with ozone and contaminated water thorough mixing, can promote organic pollutant degradation in the water, the present invention and existing O
3/ H
2O
2Advanced oxidation processes compare have the oxidation efficiency height, dosing is few, in the water medicament residual content few, to characteristics such as the side effect of water quality is little.5, the present invention also can make organic pollutant can access efficient degradation with the hydrogen peroxide alkaline aqueous solution by the porous material mixing tank or the film mixing tank is homodisperse joins in the water that contains organic pollutant.6, the present invention also can be with O
3/ H
2O
2High-level oxidation technology combines with heterogeneous, homogeneous catalyst, not only can improve HO
2 -To the adaptive faculty of water quality, improve clearance to organic pollutant, also can further reduce the hydrogen peroxide residual concentration, heterogeneous, homogeneous catalyst can decompose leading portion O
3/ H
2O
2Remaining hydrogen peroxide in the advanced oxidation process.7, the present invention has been owing to adopted the method for reconciling aqueous hydrogen peroxide solution pH value, makes O
3/ H
2O
2The process of removing hardly degraded organic substance has obtained reinforcement, has improved O significantly
3/ H
2O
2Remove the processing efficiency of Persistent organic pollutants, reduced the dosage of hydrogen peroxide, solved the hydrogen peroxide secondary pollution problem.8, treatment process of the present invention has the technology advanced person, and is simple to operate, operating efficiency height, reliable operation, advantage such as promotional value is wide.
Embodiment:
Embodiment one: the present invention relates to a kind of novel ozone high grade oxidation method for treating water, it is finished by following steps: a, be 10 with concentration
-7～10
2The basic solution of mol/L mixes with aqueous hydrogen peroxide solution, and the pH value that makes aqueous hydrogen peroxide solution is between 7～14; B, the hydrogen peroxide alkaline aqueous solution joined in the polluted water combine organism in the oxidizing water with ozone.
Embodiment two: the difference of present embodiment and embodiment one is: a step concentration is 10
-6The basic solution of mol/L mixes with aqueous hydrogen peroxide solution, and the pH value that makes aqueous hydrogen peroxide solution is 8.
Embodiment three: the difference of present embodiment and embodiment one is: a step concentration is 10
1The basic solution of mol/L mixes with aqueous hydrogen peroxide solution, and the pH value that makes aqueous hydrogen peroxide solution is 13.
Embodiment four: the difference of present embodiment and embodiment one is: a step concentration is 10
-2The basic solution of mol/L mixes with aqueous hydrogen peroxide solution, and the pH value that makes aqueous hydrogen peroxide solution is 10.5.
Embodiment five: present embodiment with the difference of embodiment one is: the basic solution of a step mixes in porous material mixing tank or film mixing tank with aqueous hydrogen peroxide solution; The hydrogen peroxide alkaline aqueous solution of b step adopts and is added to the water with the mode branch that adds, mixed and alternate carries out in pipeline; The porous material of described porous material mixing tank is a tetrafluoroethylene, and the mould material of described film mixing tank is pvdf membrane or poly tetrafluoroethylene or stainless steel membrane or titanium plate film or ceramic membrane.
Embodiment six: present embodiment with the difference of embodiment one is: the basic solution of a step mixes in porous material mixing tank or film mixing tank with aqueous hydrogen peroxide solution; The hydrogen peroxide alkaline aqueous solution of b step adopts and is added to the water in the mode that adds, mixed and alternate carries out respectively in each pond.This embodiment is applicable in the water treatment of big water factory.
Embodiment seven: the difference of present embodiment and embodiment five, embodiment six is: the hydrogen peroxide alkaline aqueous solution of b step is added to the water with porous material mixing tank or film mixing tank.Employing porous material mixing tank or film mixing tank can be with HO
2 -Be distributed to equably in the water and the organic pollutant effect.
Embodiment eight: present embodiment with the difference of embodiment one is: the hydrogen peroxide alkaline aqueous solution of b step is added to the water and combines organism in the oxidizing water with ozone, homogeneous catalyst or heterogeneous catalyst; Described heterogeneous catalyst is solid metal or metal oxide or loads on metal on the carrier; Described homogeneous catalyst is a metal ion.Select for use homogeneous catalyst or heterogeneous catalyst can improve clearance to organic pollutant.
Embodiment nine: the difference of present embodiment and embodiment one is: the hydrogen peroxide of a, step and basic solution force moment to be mixed into the hydrogen peroxide alkaline aqueous solution of high density with agitator in advance.
Claims (10)
1, a kind of novel ozone high grade oxidation method for treating water is characterized in that it is finished by following steps: a, be 10 with concentration
-7～10
2The basic solution of mol/L mixes with aqueous hydrogen peroxide solution, and the pH value that makes aqueous hydrogen peroxide solution is between 7～14; B, the hydrogen peroxide alkaline aqueous solution is added to the water combines organism in the oxidizing water with ozone.
2, a kind of novel ozone high grade oxidation method for treating water according to claim 1 is characterized in that a step concentration is 10
-6The basic solution of mol/L mixes with aqueous hydrogen peroxide solution, and the pH value that makes aqueous hydrogen peroxide solution is 8.
3, a kind of novel ozone high grade oxidation method for treating water according to claim 1 is characterized in that a step concentration is 10
1The basic solution of mol/L mixes with aqueous hydrogen peroxide solution, and the pH value that makes aqueous hydrogen peroxide solution is 13.
4, a kind of novel ozone high grade oxidation method for treating water according to claim 1 is characterized in that a step concentration is 10
-2The basic solution of mol/L mixes with aqueous hydrogen peroxide solution, and the pH value that makes aqueous hydrogen peroxide solution is 10.5.
5, a kind of novel ozone high grade oxidation method for treating water according to claim 1 is characterized in that the basic solution of a step mixes in porous material mixing tank or film mixing tank with aqueous hydrogen peroxide solution; The hydrogen peroxide alkaline aqueous solution of b step adopts and is added to the water with the mode branch that adds, mixed and alternate carries out in pipeline.
6, a kind of novel ozone high grade oxidation method for treating water according to claim 1 is characterized in that the basic solution of a step mixes in porous material mixing tank or film mixing tank with aqueous hydrogen peroxide solution; The hydrogen peroxide alkaline aqueous solution of b step adopts and is added to the water in the mode that adds, mixed and alternate carries out respectively in each pond.
7, a kind of novel ozone high grade oxidation method for treating water according to claim 1 is characterized in that the hydrogen peroxide alkaline aqueous solution of b step is added to the water with porous material mixing tank or film mixing tank.
8, a kind of novel ozone high grade oxidation method for treating water according to claim 1, the hydrogen peroxide alkaline aqueous solution that it is characterized in that the b step is added to the water and combines organism in the oxidizing water with ozone, homogeneous catalyst or heterogeneous catalyst.
9, a kind of novel ozone high grade oxidation method for treating water according to claim 8 is characterized in that described heterogeneous catalyst is solid metal or metal oxide or loads on metal on the carrier.
10, a kind of novel ozone high grade oxidation method for treating water according to claim 8 is characterized in that described homogeneous catalyst is a metal ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100096471A CN1312055C (en) | 2005-01-19 | 2005-01-19 | Ozone high grade oxidation method for treating water |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100096471A CN1312055C (en) | 2005-01-19 | 2005-01-19 | Ozone high grade oxidation method for treating water |
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| Publication Number | Publication Date |
|---|---|
| CN1657436A CN1657436A (en) | 2005-08-24 |
| CN1312055C true CN1312055C (en) | 2007-04-25 |
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ID=35007170
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|---|---|---|---|
| CNB2005100096471A Active CN1312055C (en) | 2005-01-19 | 2005-01-19 | Ozone high grade oxidation method for treating water |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717146B (en) * | 2009-12-03 | 2011-07-13 | 浙江工业大学 | Method for treating catalytic ozone oxidation water |
| CN102161536B (en) * | 2010-07-27 | 2012-11-21 | 王兵 | Advanced treatment method for fracturing flow-back fluid |
| CN105217871B (en) * | 2015-11-04 | 2017-10-10 | 四川师范大学 | Synthesize processing method and its application of the technique waste water of dinitrodiazophenol |
| CN106554114A (en) * | 2016-12-01 | 2017-04-05 | 中国人民解放军63605部队 | A kind of method of hydrogen peroxide ozone-ultraviolet line Combined Treatment uns-dimethylhydrazine sewage |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194626A (en) * | 1995-08-29 | 1998-09-30 | 韩国科学技术研究院 | Waste water treatment by catalytic oxidation |
| JP2000279973A (en) * | 1999-03-29 | 2000-10-10 | Kurita Water Ind Ltd | Oxidation treatment of organic matter-containing waste water |
| US6767472B2 (en) * | 1998-06-24 | 2004-07-27 | The University Of Akron | Catalytic fixed bed reactor systems for the destruction of contaminants in water by hydrogen peroxide and ozone |
-
2005
- 2005-01-19 CN CNB2005100096471A patent/CN1312055C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194626A (en) * | 1995-08-29 | 1998-09-30 | 韩国科学技术研究院 | Waste water treatment by catalytic oxidation |
| US6767472B2 (en) * | 1998-06-24 | 2004-07-27 | The University Of Akron | Catalytic fixed bed reactor systems for the destruction of contaminants in water by hydrogen peroxide and ozone |
| JP2000279973A (en) * | 1999-03-29 | 2000-10-10 | Kurita Water Ind Ltd | Oxidation treatment of organic matter-containing waste water |
Non-Patent Citations (1)
| Title |
|---|
| 废水中有机污染物高级氧化过程的降解 钟理，化工进展，第4卷 1998 * |
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| CN1657436A (en) | 2005-08-24 |
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Effective date of registration: 20191230 Address after: 017000 Hi-tech Industrial Park Incubator B Block 701, Erdos City, Inner Mongolia Autonomous Region Patentee after: Ordos City An Xintai Environmental Protection Technology Co., Ltd Address before: 150001 Harbin, Nangang, West District, large straight street, No. 92 Patentee before: Harbin Institute of Technology |