CN100540481C - A kind of method for the treatment of polyvinyl alcohol waste water by catalytic oxidizing process - Google Patents
A kind of method for the treatment of polyvinyl alcohol waste water by catalytic oxidizing process Download PDFInfo
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- CN100540481C CN100540481C CNB2005101002490A CN200510100249A CN100540481C CN 100540481 C CN100540481 C CN 100540481C CN B2005101002490 A CNB2005101002490 A CN B2005101002490A CN 200510100249 A CN200510100249 A CN 200510100249A CN 100540481 C CN100540481 C CN 100540481C
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- waste water
- polyvinyl alcohol
- treatment
- cod
- oxidizing process
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Abstract
The invention discloses a kind of method for the treatment of polyvinyl alcohol waste water by catalytic oxidizing process, solved the problem that polyvinyl alcohol waste water is difficult to handle.Technical scheme may further comprise the steps: the polyvinyl alcohol trade effluent is carried out pre-treatment; Carry out pretreated water reuse Fenton reagent and carry out catalytic oxidation treatment above-mentioned, particular content is to add FeSO in waste water
4Solution and H
2O
2, H wherein
2O
2/ FeSO
4Mol ratio be (15-20): 1.Can make COD in polyvinyl alcohol (PVA) waste water by this method
CrClearance reach 85.1%, reached the Industrial Wastewater Treatment control criterion substantially, and, because reaction conditions do not have particular requirement to temperature, can realize that at normal temperatures catalytic oxidation speed is fast; In addition, Fenton reagent is a kind of efficient and environment-friendly type reagent, and no coupling product produces, and can not pollute environment.
Description
Technical field
The present invention relates to a kind of method for the treatment of polyvinyl alcohol waste water by catalytic oxidizing process.
Background technology
Polyvinyl alcohol (PVA) is the textile industry important chemical material, belongs to the polymer substance of difficult for biological degradation.In dyeing and printing process, the destarch operation mainly is to remove the slurry that is added in the fabrication processes on the fine gauze, make avidity is better arranged between fabric fibre and dyestuff, because PVA is used in cotton blended fabric starching at present more, therefore contain a large amount of PVA in the desized wastewater, since the organic content height in the PVA waste water, its COD
CrContent reaches 3000-4000mg/L, adopts traditional materialization, biochemical method to be difficult to degraded.
At present, the main both at home and abroad materialization ultrafiltration concentration method that adopts is recycled polyvinglalcohol floating pulp waste water, and still, this method of wastewater treatment cost height is only limited to the waste water high to polyvinyl alcohol concentration; The pure strain that also has the screening adopted to decompose polyvinyl alcohol is inoculated processing, but complex process, not easy to operate is difficult to apply.
Summary of the invention
Technical problem to be solved by this invention is to provide the method for the treating polyvinyl alcohol waste water by catalytic oxidizing process that a kind of technological operation is simple, efficient is high.
For solving the problems of the technologies described above, technical scheme provided by the present invention is: a kind of method for the treatment of polyvinyl alcohol waste water by catalytic oxidizing process is provided, and it adopts the homogeneous catalysis oxidation style, may further comprise the steps:
(1), measures the COD that needs to handle waste water
Cr
(2), press H
2O
2/ COD
Cr(g/g) in waste water, add Fenton reagent, i.e. FeSO
4Solution and H
2O
2,
H wherein
2O
2/ FeSO
4Molar ratio be (15-20): 1.
Further improvement in the technical proposal is described H
2O
2/ COD
Cr(g/g) be 1.25-2.25.
Described H
2O
2Concentration be 25%-30%.
H
2O
2/ FeSO
4Molar ratio be 20: 1.
As required waste water is carried out pre-treatment.
Described pretreated waste water ph scope is 4.0-7.0.
Described pretreated waste water optimal ph scope is 5.0-6.0.
The time of described wastewater treatment is 3 to 10 minutes at normal temperatures.
The temperature of the time of described wastewater treatment with the waste water that needs to handle is inversely proportional to.
The invention has the beneficial effects as follows: the present invention can make COD in polyvinyl alcohol (PVA) waste water by Fenton reagent method
CrClearance reach 85.1%, reached the Industrial Wastewater Treatment control criterion substantially, and, because reaction conditions do not have particular requirement to temperature, can realize that at normal temperatures catalytic oxidation speed is fast; In addition, Fenton reagent is a kind of efficient and environment-friendly type oxygenant, and no coupling product produces, and can not pollute environment.Present method is that a kind of cost is low, efficient is high, can effectively administers the technique for treating industrial wastewater of polyvinyl alcohol.
Embodiment
The method of a kind for the treatment of polyvinyl alcohol waste water by catalytic oxidizing process of the present invention, it adopts Fenton reagent method, i.e. homogeneous catalysis oxidation style, to the polyvinyl alcohol in the trade effluent (Polyvinyl alcohol PVA) handles, and this method may further comprise the steps:
(1), measures the COD that needs to handle waste water
Cr
(2), press H
2O
2/ COD
Cr(g/g) in waste water, add Fenton reagent, i.e. Fe
2+Solution and H
2O
2,
H wherein
2O
2/ Fe
2+Molar ratio be (15-20): 1.
Described H
2O
2/ COD
Cr(g/g) be 1.25-2.25.
In step 1, the polyvinyl alcohol trade effluent is carried out pre-treatment, promptly regulate the pH value of polyvinyl alcohol, in the present embodiment, the pH value of polyvinyl alcohol is 5.0.
Utilize Fenton reagent to carry out catalytic oxidation treatment in waste water, adding Fe
2+Solution and H
2O
2Fe wherein
2+Solution is FeSO
4Solution.
Following reaction promptly takes place:
Fe
2++H
2O
2→Fe
3++OH
-+.HO
Fe
2++H
2O
2→Fe
2++H
++HO
2.
Hydrogen peroxide (H
2O
2) since oxidisability by force, safely, be easy to get, its at certain catalyst (as Fe
2+, UV etc.) and other oxygenants (as O
3) effect under, can produce the stronger .OH of oxidisability (redox potential is 2.8V), oxidation operation is degraded, and because of the degradation production of hydrogen peroxide be water and oxygen, so can not produce new pollutent, so Fenton reagent is a kind of environment-friendly type reagent.The .HO that generates in the reaction process is one of the most active oxygenant, and oxidation capacity is only second to F
2
In one embodiment of the invention, add H
2O
2Concentration be 25%-30%, be preferably 27.5%.What added contains Fe
2+Solvent be FeSO
4Solution generates Fenton reagent.
Fenton reagent mixes mutually with the polyvinyl alcohol trade effluent, stirs at normal temperatures 1 minute, and catalytic oxidation got final product in 4 minutes.
In the present invention, FeSO
4Solution is used other instead and is contained Fe
2+Solution also can use, but effect is relatively poor.
In the present invention, H
2O
2/ Fe SO
4Mol ratio be (15-20): 1, but preferred, H
2O
2/ Fe SO
4Molar ratio is 20: 1.
In the present invention, described pretreated waste water ph scope is 4.0-7.0, and preferred pH value scope is 5.0-6.0.
In the present invention, the temperature of the time of described wastewater treatment with the waste water that needs to handle is inversely proportional to, and promptly temperature is high more, and the time of required processing waste water is short more, and the following treatment time of normal temperature is 4 minutes.
In one embodiment of the invention, comprise further the trade effluent behind catalyzing oxidizing degrading detected that Pai Fang step then, this step mainly are the COD that measures in the water sample
CrContent is to detect COD
CrClearance.
In the present invention, in preparation Fenton reagent and catalytic oxidation process, Fe
2+, H
2O
2Dosage, pH value, temperature and the reaction times in when reaction all to COD
CrClearance has certain influence.Below estimate its corresponding incidence relation by specific embodiment.
Table 1 has characterized H
2O
2Dosage is to COD
CrThe influence of clearance.Work as pH=5.0, normal temperature condition adds H
2O
2/ Fe
2+(mol/mol)=20: 1, react after 4 minutes, measure the COD of water sample
Cr, the result is as shown in table 1.
Table 1 H
2O
2Dosage is to COD
CrThe influence of clearance
| H 2O 2/COD Cr (g/g) | Water outlet COD Cr mg/L | COD CrClearance |
| 1.25 | 739.3 | 63.4％ |
| 1.50 | 480.8 | 76.2％ |
| 2.00 | 301.0 | 85.1％ |
| 2.50 | 278.8 | 86.2％ |
| 3.00 | 266.6 | 86.8％ |
This shows, when preparation Fenton reagent, H
2O
2Dosage and COD
CrClearance certain cognation is arranged.Along with H
2O
2/ COD
Cr(g/g) increase, COD
Cr(g/g) content reduces gradually, that is COD
CrClearance increases gradually.Yet, the experiment proved that, work as H
2O
2/ COD
Cr(g/g) value reaches at 2.00 o'clock, COD
CrClearance increase beginning slowly, therefore, from the H of Fenton reagent
2O
2The angle of utilization ratio is considered, should be selected to work as H
2O
2/ COD
Cr(g/g) 2.00 is best dosage.
Characterized Fe
2+Dosage is to COD
CrThe influence of clearance.Work as pH=5.0, under the normal temperature condition, react after 4 minutes, measure the COD of water sample
Cr
When preparation Fenton reagent, Fe
2+Dosage and COD
CrClearance certain cognation is arranged.Work as H
2O
2/ Fe
2+(mol/mol) value is 20: 1-20: 1.5, and COD
CrClearance basicly stable, in most preferred embodiment of the present invention, H
2O
2/ Fe
2+(mol/mol) value be 20: 1 for best dosage.
Table 2 has characterized the pH value to COD
CrThe influence of clearance.Under normal temperature condition, add H
2O
2/ Fe
2+(mol/mol) value is 20: 1, H
2O
2/ COD
Cr(g/g)=2.00, the COD of water sample is measured in reaction after 4 minutes
Cr, the result is as shown in table 2.
Table 2 pH value is to COD
CrThe influence of clearance
| The pH value | Water outlet COD Cr mg/L | COD CrClearance |
| 3.0 | 458.5 | 77.3％ |
| 4.0 | 349.5 | 82.7％ |
| 5.0 | 301.0 | 85.1％ |
| 6.0 | 335.3 | 83.4％ |
| 7.0 | 379.8 | 81.2％ |
This shows that under these conditions, the pH value is to COD
CrThe influence of clearance is little, in most preferred embodiment of the present invention, and pH value=5.0 o'clock, COD
CrThe clearance effect is best.
Evaluation temperature changes COD
CrThe influence of clearance.When reaction conditions is: pH=5.0 adds H
2O
2/ Fe
2+(mol/mol) 20: 1, H
2O
2/ COD
Cr(g/g)=2.00, the COD of water sample is measured in reaction after 4 minutes
Cr, COD as a result
CrClearance fluctuates about 85.1%, and amplitude very little (fluctuation range is in 1%) illustrates that thus temperature variation is to COD
CrThe influence of clearance is very little, and in addition, variation of temperature does not influence the end reaction result, but speed of response is had a significant impact.Along with the rising of temperature, speed of response is accelerated gradually.At normal temperatures, reaching complete reaction needed more than 4 minutes, and in the time of 65 ℃, only needed 3 minutes.
In addition, table 3 has characterized the reaction times to COD
CrClearance also has certain influence.At pH=5.0, under the condition of normal temperature, add H
2O
2/ Fe
2+(mol/mol) 20: 1, H
2O
2/ COD
Cr(g/g)=2.00 o'clock, different reaction times sampling CO
Cr, the result is as shown in table 3.
Table 3 reaction times is to COD
CrThe influence of clearance
| Time (s) | Water outlet COD Cr mg/L | COD CrClearance |
| 120 | 880.7 | 56.4％ |
| 180 | 462.6 | 77.1％ |
| 240 | 301.0 | 85.1％ |
| 360 | 278.8 | 86.2％ |
| 480 | 266.6 | 86.8％ |
The result shows, along with the increase in reaction times, COD
CrClearance progressively increases, after being reacted to 4 minutes, and COD
CrClearance tends towards stability substantially, and therefore, optimum reacting time is 4 minutes.
Verified that by above embodiment the present invention adopts Fenton reagent by catalyzed oxidation art breading polyvinyl alcohol (PVA) waste water, Fe
2+, H
2O
2Dosage, the pH value in when reaction and reaction times to COD
CrClearance all has certain cognation, below preferred suitable reaction conditions:
H
2O
2/COD
Cr(g/g)＝1.5-2.00
H
2O
2/Fe
2+(mol/mol)＝(15-20)∶1
Reaction times is 3 to 10 minutes
PH value scope is 4.0-7.0
Can make COD in polyvinyl alcohol (PVA) waste water by Fenton reagent method
CrClearance reaches 85.1%, has reached the Industrial Wastewater Treatment control criterion substantially, and, because reaction conditions does not have particular requirement to temperature, can realize that at normal temperatures catalytic oxidation speed is fast; In addition, Fenton reagent is a kind of efficient and environment-friendly type reagent, and no coupling product produces, and can not pollute environment.
Claims (9)
1. the method for a treating polyvinyl alcohol waste water by catalytic oxidizing process is characterized in that comprising the steps:
(1), measures the COD that needs to handle waste water
Cr
(2), press H
2O
2/ COD
Cr(g/g) in waste water, add Fenton reagent, i.e. FeSO
4Solution and H
2O
2,
H wherein
2O
2/ FeSO
4Molar ratio be (15-20): 1.
2. the method for a kind for the treatment of polyvinyl alcohol waste water by catalytic oxidizing process according to claim 1 is characterized in that: described H
2O
2/ COD
Cr(g/g) be 1.25-2.25.
3. the method for a kind for the treatment of polyvinyl alcohol waste water by catalytic oxidizing process according to claim 1 and 2 is characterized in that: described H
2O
2Concentration be 25%-30%.
4. the method for a kind for the treatment of polyvinyl alcohol waste water by catalytic oxidizing process according to claim 1 is characterized in that: H
2O
2/ FeSO
4Molar ratio be 20: 1.
5. the method for a kind for the treatment of polyvinyl alcohol waste water by catalytic oxidizing process according to claim 1 is characterized in that: also comprise as required waste water is carried out pretreated step.
6. the method for a kind for the treatment of polyvinyl alcohol waste water by catalytic oxidizing process according to claim 5, it is characterized in that: described pretreated waste water ph scope is 4.0-7.0.
7, the method for a kind for the treatment of polyvinyl alcohol waste water by catalytic oxidizing process according to claim 6 is characterized in that: described pretreated waste water ph scope is 5.0-6.0.
8, according to the method for any one described a kind for the treatment of polyvinyl alcohol waste water by catalytic oxidizing process of claim 5 to 7, it is characterized in that: the time of described wastewater treatment is 3 to 10 minutes at normal temperatures.
9, according to the method for any one described a kind for the treatment of polyvinyl alcohol waste water by catalytic oxidizing process of claim 5 to 7, it is characterized in that: the temperature of the time of described wastewater treatment with the waste water that needs are handled is inversely proportional to.
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|---|---|---|---|
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|---|---|---|---|
| CNB2005101002490A CN100540481C (en) | 2005-10-03 | 2005-10-03 | A kind of method for the treatment of polyvinyl alcohol waste water by catalytic oxidizing process |
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| CN100540481C true CN100540481C (en) | 2009-09-16 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974165B (en) * | 2010-09-30 | 2012-03-21 | 南京工业大学 | Method for recovering PVA in waste water generated by water jet abrasive material |
| CN101955281B (en) * | 2010-09-30 | 2012-07-11 | 南京工业大学 | Method for processing waste water generated by water jet abrasives |
| CN103408184B (en) * | 2013-05-14 | 2015-08-12 | 清华大学 | Containing the treatment process of polyvinyl alcohol waste water |
| CN105540818A (en) * | 2016-02-29 | 2016-05-04 | 四川理工学院 | Method for treating polyvinyl alcohol wastewater through catalytic oxidation of hydrogen peroxide |
| CN106145467A (en) * | 2016-08-26 | 2016-11-23 | 南京白云化工环境监测有限公司 | A kind of device processed containing PVA high concentrated organic wastewater and technique |
| CN106966539A (en) * | 2017-04-27 | 2017-07-21 | 江南大学 | A kind of method of efficient degradation polyvinyl alcohol material |
| CN109502857A (en) * | 2017-09-15 | 2019-03-22 | 上海江柘环境工程技术有限公司 | A kind of processing equipment and its processing method of polyvinyl chloride centrifugation mother liquid waste water |
| CN109133419A (en) * | 2018-07-16 | 2019-01-04 | 东华大学 | A kind of efficient coagulation method of the pre-oxidation-for the desized wastewater containing polyvinyl alcohol |
-
2005
- 2005-10-03 CN CNB2005101002490A patent/CN100540481C/en not_active Expired - Fee Related
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Assignee: Guangzhou ChinaEver Environment Engineering Co., Ltd. Assignor: Liu Depei Contract record no.: 2010440020212 Denomination of invention: Method for treating polyvinyl alcohol waste water by catalytic oxidizing process Granted publication date: 20090916 License type: Exclusive License Open date: 20070411 Record date: 20101118 |
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