CN102030432A - Method for treating sewage through catalytic oxidation - Google Patents
Method for treating sewage through catalytic oxidation Download PDFInfo
- Publication number
- CN102030432A CN102030432A CN2009101771763A CN200910177176A CN102030432A CN 102030432 A CN102030432 A CN 102030432A CN 2009101771763 A CN2009101771763 A CN 2009101771763A CN 200910177176 A CN200910177176 A CN 200910177176A CN 102030432 A CN102030432 A CN 102030432A
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- China
- Prior art keywords
- waste water
- accordance
- oxygenant
- catalytic oxidation
- complexing agent
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Abstract
The invention relates to a method for treating sewage through catalytic oxidation, which comprises the following steps of: introducing sewage to be treated into an oxidation reactor, controlling the pH value of the sewage to be less than 7, adding an oxidant, a catalyst and a complexant for performing a catalytic oxidation reaction, and separating sewage and waste residues obtained after the reaction. The complexant is an organic acid metal complexant. The addition of the complexant in the invention enables iron ions and the complexant to produce a complex compound so as to reduce the generation of iron hydroxide precipitates, and thus, more iron ions can participate in the catalytic oxidation process. The utilization efficiency of the catalyst is increased, the consumption of the catalyst can be reduced, and simultaneously, the generation of waste residues can be reduced.
Description
Technical field
The present invention relates to a kind of treatment by catalytic oxidation that is used for the sewage disposal aspect, in particular for handling the treatment by catalytic oxidation of used water difficult to degradate.
Background technology
For a long time, the processing of organic wastewater with difficult degradation thereby is the difficult point in the water technology always in the environment, also is the important difficult problem of puzzlement countries in the world environment circle.
The research that with the catalyzed oxidation is the high-level oxidation technology processing organic wastewater with difficult degradation thereby of representative has in recent years obtained significant progress.The mechanism of catalyzed oxidation is to combine with oxygenant with catalyzer, produces active extremely strong free radical (as OH) in reaction; By the adduction between free radical and the organic compound, replacement, transfer transport, scission of link etc., make the macromole hardly degraded organic substance oxidative degradation in the water body become to be easy to biodegradable small-molecule substance, even directly be degraded into CO again
2And H
2O is near permineralization.
Catalytic oxidation hydrogen peroxide commonly used is an oxygenant, and ferrous ion (being typically expressed as Fe (II)) is a catalyzer, and the mechanism of its free-radical generating is as follows:
Fe
2++H
2O
2→Fe
3++·OH+OH
-
Fe
3++H
2O
2→Fe
2++HO
2·+H
+
Fe
2++·OH→Fe
3++OH
-
Fe
3++HO
2·→Fe
2++O
2+H
+
·OH+H
2O
2→H
2O+HO
2·
HO
2·→·O
- 2+H
+
·O
- 2+H
2O
2→O
2+OH
-+·OH
Because it is simple to operate that the catalyzed oxidation technology has, react characteristics such as quick, thereby obtained extensive studies.But in actual applications, because a large amount of ferric ions (being typically expressed as Fe (III)) have formed ferric hydroxide precipitate in water, thereby influenced the reaction effect of catalyzed oxidation, for guaranteeing that reaction effect just need add a large amount of catalyzer, and increasing of catalyst amounts can cause more precipitation to generate.Catalyst amounts and waste residue output too much make the catalyzed oxidation Industrial Application of Technology be subjected to bigger restriction, thereby be necessary to improve treatment by catalytic oxidation with the dosage of minimizing catalyzer and the generation of waste residue, the catalyzed oxidation technology is more widely used industrial.
At present, document both domestic and external mainly concentrates on supplementary means coupling aspects such as catalyzed oxidation technology and light, electricity for the report of catalytic oxidation process for treating, for example:
A.CN1724420A proposes a kind of method for the treatment of high salt oil production waste water by suspension state photoelecric catalystic oxidation.
B.CN1328177C proposes a kind of method of wastewater treatment and device of photoelectrical chemical synergistic catalytic reaction.
Summary of the invention
The objective of the invention is to propose a kind of method of new catalytic oxidation treatment waste water,, the catalyzed oxidation technology is used more widely industrial obtaining with the dosage that reduces catalyzer in the catalytic oxidation treatment process and the generation of waste residue.
The method of catalytic oxidation treatment waste water provided by the invention comprises: pending waste water is entered in the oxidation reactor, the pH value of control waste water is less than 7, add oxygenant, catalyzer and complexing agent and carry out catalytic oxidation, waste water after separating reaction finishes and waste residue.
Particularly, the inventive method can may further comprise the steps: pending waste water is entered in the oxidation reactor, add acid and regulate the pH value of waste water less than 7, preferred 1-6, add oxygenant, catalyzer and complexing agent and carry out catalytic oxidation, add alkali in the waste water after reaction finishes and regulate the pH value to greater than 7, preferred 6-9, waste water is entered carry out in the settling bowl flocculating settling, directly discharge after the waste water after sedimentation finishes is discharged or be for further processing; And the waste residue that settles down is for further processing after discharging.The residence time of waste water is 20-60 minute in the oxidation reactor; The residence time of waste water is 30-240 minute in the settling tank.
Among the present invention, the ratio of the mass concentration of the organism in oxygenant and the waste water (COD) is 2: 1-1: 20, preferred 1: 1-1: 10; The mol ratio of oxygenant and reductive agent is 10: 1-1: 5, preferred 5: 1-1: 2; The mol ratio 1 of complexing agent and reductive agent: 10-3: 1, preferred 1: 5-2: 1.
The oxygenant that adopts among the present invention can be hydrogen peroxide, hypochlorite, ozone or persulphate, preferred hydrogen peroxide.
Catalyzer among the present invention is to go back the ortho states transition metal ion, can be selected from Fe
2+, Mn
2+, Ni
2+, Co
2+, Cd
2+, Cu
2+, Ag
+, Cr
3+And Zn
2+In one or more, preferred Fe
2+, can derive from ferrous sulfate, iron protochloride, the Iron nitrate one or more, preferably sulfuric acid is ferrous.
Complexing agent among the present invention is the organic acid metal complexing agent, can be selected from ethylenediamine tetraacetic acid (EDTA), acetate, oxalic acid, citric acid, the nitrilotriacetic acid(NTA) one or more, preferred ethylenediamine tetraacetic acid (EDTA), oxalic acid and citric acid.
It can be a kind of in sulfuric acid, hydrochloric acid or the nitric acid that the present invention regulates the used acid of pH value, preferably sulfuric acid.
It can be sodium hydroxide, potassium hydroxide, sodium bicarbonate or yellow soda ash that the present invention regulates the used alkali of pH value, preferred sodium hydroxide.
The adding of complexing agent can make iron ion and complexing agent generate complex compound among the present invention, reduce the generation of ferric hydroxide precipitate, thereby make more iron ion participate in catalytic oxidation process, improved the utilising efficiency of catalyzer, so just can reduce the consumption of catalyzer, can reduce the generation of waste residue simultaneously.
Compared with prior art, the present invention has following advantage:
1, reduces the quantity discharged of waste residue, reduced the cost of handling waste residue.
2, environment has been protected in the minimizing of waste sludge discharge amount, has good social benefit.
3, reduce the usage quantity of catalyzer in the catalytic oxidation process, saved resource.
Embodiment
The present invention is further detailed explanation below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
Handle certain refinery bio-chemical effluent, adopt H
2O
2Be oxygenant, Fe
2SO
4Be catalyzer, ethylenediamine tetraacetic acid (EDTA) is a complexing agent, and used soda acid is dense H
2SO
4And NaOH.Operational condition is defined as: H
2O
2The COD mass concentration ratio of/waste water 1: 4, H
2O
2With Fe
2+Molar concentration rate is 2: 1, complexing agent and Fe
2+Mol ratio be 1: 1; Oxidizing reaction pond pH is 5, and settling bowl pH is 6.5, and 30 minutes oxidizing reaction pond residence time, the settling bowl residence time is 1 hour.The data that adopt treatment by catalytic oxidation of the present invention and conventional catalyst oxidation treatment method to handle waste water relatively see Table 1.The result of table 1 shows employing method processing of the present invention waste water, and waste residue and catalyzer usage quantity obviously reduce.
Table 1 is handled refinery's bio-chemical effluent
| Treatment process | Waste sludge discharge amount (kg/t waste water) | Catalyst amounts (kg/t waste water) |
| The conventional catalyst oxidation style | 20 | 0.9 |
| Embodiment 1 | 10 | 0.3 |
(waste residue weight is by 98% water content meter)
Embodiment 2
Handle certain chemical plant high-concentration waste water, adopt H
2O
2Be oxygenant, Fe
2SO
4Be catalyzer, oxalic acid is complexing agent, and used soda acid is dense H
2SO
4And NaOH.Operational condition is defined as: H
2O
2The COD mass concentration ratio of/waste water 1: 8, H
2O
2With Fe
2+Molar concentration rate is 1: 1, complexing agent and Fe
2+Mol ratio be 1: 2; Oxidizing reaction pond pH is 6, and settling bowl pH is 6.5, and 40 minutes oxidizing reaction pond residence time, the settling bowl residence time is 1 hour, and the data that adopt treatment by catalytic oxidation of the present invention and conventional catalyst oxidation treatment method to handle waste water relatively see Table 2.The result of table 2 shows employing method processing of the present invention waste water, and waste residue and catalyzer usage quantity significantly reduce.
Table 2 is handled chemical plant wastewater
| Treatment process | Waste sludge discharge amount (kg/t waste water) | Catalyst amounts (kg/t waste water) |
| The conventional catalyst method for oxidation | 45 | 2.0 |
| Embodiment 2 | 15 | 0.5 |
(waste residue weight is by 98% water content meter)
Embodiment 3
Handle certain factory's brine waste, the employing clorox is an oxygenant, Fe
2SO
4Be catalyzer, citric acid is a complexing agent, and used soda acid is dense H
2SO
4And NaOH.Operational condition is defined as: H
2O
2The COD mass concentration ratio of/waste water 1: 5, oxygenant and Fe
2+Molar concentration rate is 3: 1; Complexing agent and Fe
2+Mol ratio be 1: 2; Oxidizing reaction pond pH is 4, and settling bowl pH is 6.5; 30 minutes oxidizing reaction pond residence time, the settling bowl residence time is 1 hour, and the data that adopt treatment by catalytic oxidation of the present invention and conventional catalyst oxidation treatment method to handle waste water relatively see Table 3.The result of table 3 shows employing method processing of the present invention waste water, and waste residue and catalyzer usage quantity significantly reduce.
Table 3 processing plant brackish water waste water
| Treatment process | Waste sludge discharge amount (kg/t waste water) | Catalyst amounts (kg/t waste water) |
| The conventional catalyst method for oxidation | 35 | 2.5 |
| Embodiment 3 | 8 | 0.7 |
(waste residue weight is by 98% water content meter)
Embodiment 4
Handle certain factory's circulation sewer, employing ozone is oxygenant, Fe
2SO
4Be catalyzer, acetate is complexing agent, and used soda acid is dense H
2SO
4And NaOH.Operational condition is defined as: H
2O
2The COD mass concentration ratio of/waste water 1: 6, oxygenant and Fe
2+Molar concentration rate is 4: 1; Complexing agent and Fe
2+Mol ratio be 1: 3; Oxidizing reaction pond pH is 6, and settling bowl pH is 7; 30 minutes oxidizing reaction pond residence time, the settling bowl residence time is 1 hour, and the data that adopt treatment by catalytic oxidation of the present invention and conventional catalyst oxidation treatment method to handle waste water relatively see Table 3.The result of table 3 shows employing method processing of the present invention waste water, and waste residue and catalyzer usage quantity significantly reduce.
Table 4 processing plant recirculated water sewer
| Treatment process | Waste sludge discharge amount (kg/t waste water) | Catalyst amounts (kg/t waste water) |
| The conventional catalyst method for oxidation | 2.2 | 1.3 |
| Embodiment 3 | 6 | 0.5 |
(waste residue weight is by 98% water content meter)
Embodiment 5
Handle the defective externally discharged waste water in certain oil field, adopt H
2O
2Be oxygenant, Fe
2SO
4Be catalyzer, nitrilotriacetic acid(NTA) is a complexing agent, and used soda acid is dense H
2SO
4And NaOH.Operational condition is defined as: H
2O
2The COD mass concentration ratio of/waste water 1: 9, oxygenant and Fe
2+Molar concentration rate is 5: 1; Complexing agent and Fe
2+Mol ratio be 1: 4; Oxidizing reaction pond pH is 5, and settling bowl pH is 6.5; 30 minutes oxidizing reaction pond residence time, the settling bowl residence time is 1 hour, and the data that adopt treatment by catalytic oxidation of the present invention and conventional catalyst oxidation treatment method to handle waste water relatively see Table 5.The result of table 5 shows employing method processing of the present invention waste water, and waste residue and catalyzer usage quantity significantly reduce.
Table 4 processing plant recirculated water sewer
| Treatment process | Waste sludge discharge amount (kg/t waste water) | Catalyst amounts (kg/t waste water) |
| The conventional catalyst method for oxidation | 2.1 | 1.2 |
| Embodiment 3 | 5 | 0.4 |
(waste residue weight is by 98% water content meter).
Claims (13)
1. the method for a catalytic oxidation treatment waste water, comprise: pending waste water is entered in the oxidation reactor, the pH value of control waste water is less than 7, add oxygenant, catalyzer and complexing agent and carry out catalytic oxidation, waste water after separating reaction finishes and waste residue, said complexing agent are the organic acid metal complexing agents.
2. in accordance with the method for claim 1, it is characterized in that, regulate the pH value in the waste water after reaction finishes greater than 7, waste water is entered carry out flocculating settling in the settling bowl, directly discharge after waste water after sedimentation finishes is discharged or be for further processing, the waste residue that settles down is for further processing after discharging.
3. in accordance with the method for claim 1, it is characterized in that oxygenant is hydrogen peroxide, hypochlorite, ozone or persulphate.
4. in accordance with the method for claim 1, it is characterized in that catalyzer is to go back the ortho states transition metal ion.
5. according to claim 1 or 4 described methods, it is characterized in that catalyzer is selected from Fe
2+, Mn
2+, Ni
2+, Co
2+, Cd
2+, Cu
2+, Ag
+, Cr
3+And Zn
2+In one or more.
6. in accordance with the method for claim 1, it is characterized in that said complexing agent is selected from one or more in ethylenediamine tetraacetic acid (EDTA), acetate, oxalic acid, citric acid and the nitrilotriacetic acid(NTA).
7. in accordance with the method for claim 1, it is characterized in that the ratio of the organic mass concentration in oxygenant and the waste water is 2: 1-1: 20.
8. in accordance with the method for claim 1, it is characterized in that the ratio of the organic mass concentration in oxygenant and the waste water is 1: 1-1: 10.
9. in accordance with the method for claim 1, it is characterized in that the mol ratio of oxygenant and reductive agent is 10: 1-1: 5.
10. in accordance with the method for claim 1, it is characterized in that the mol ratio of oxygenant and reductive agent is 5: 1-1: 2.
11. in accordance with the method for claim 1, it is characterized in that the mol ratio of complexing agent and reductive agent is 1: 10-3: 1.
12. in accordance with the method for claim 1, it is characterized in that the mol ratio of complexing agent and reductive agent is 1: 5-2: 1.
13. in accordance with the method for claim 1, it is characterized in that, in the oxidation reactor, regulate the pH value 1-6 of waste water, regulate pH value 6-9 in the waste water after reaction finishes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101771763A CN102030432A (en) | 2009-09-28 | 2009-09-28 | Method for treating sewage through catalytic oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101771763A CN102030432A (en) | 2009-09-28 | 2009-09-28 | Method for treating sewage through catalytic oxidation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102030432A true CN102030432A (en) | 2011-04-27 |
Family
ID=43883957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101771763A Pending CN102030432A (en) | 2009-09-28 | 2009-09-28 | Method for treating sewage through catalytic oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102030432A (en) |
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| CN102583812A (en) * | 2011-12-27 | 2012-07-18 | 欧派斯环保科技（北京）有限公司 | Method and system for treating polymer-containing oil field oil production wastewater |
| CN102795736A (en) * | 2011-05-25 | 2012-11-28 | 四川环能德美科技股份有限公司 | Deep treatment method for anion exchange resin regeneration waste solution |
| CN103159271A (en) * | 2013-04-03 | 2013-06-19 | 济南瑞东实业有限公司 | Industrial sewage treating agent and preparation method thereof |
| CN103708647A (en) * | 2013-12-27 | 2014-04-09 | 同济大学 | Deep treatment method for industrial wastewater through natural pyrite catalyzed H2O2 oxidation |
| CN104445764A (en) * | 2014-11-24 | 2015-03-25 | 青岛青科金诺环境工程技术有限公司 | Catalysis-ozone oxidation treatment method and device for salt-containing degradation-resistant organic wastewater |
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| CN102583812B (en) * | 2011-12-27 | 2013-08-07 | 欧派斯环保科技（北京）有限公司 | Method and system for treating polymer-containing oil field oil production wastewater |
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Application publication date: 20110427 |