CN110510724A - A kind of MnO2The method of O3 catalytic oxidation simulation oxalic acid waste water - Google Patents
A kind of MnO2The method of O3 catalytic oxidation simulation oxalic acid waste water Download PDFInfo
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- CN110510724A CN110510724A CN201910676156.4A CN201910676156A CN110510724A CN 110510724 A CN110510724 A CN 110510724A CN 201910676156 A CN201910676156 A CN 201910676156A CN 110510724 A CN110510724 A CN 110510724A
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- China
- Prior art keywords
- oxalic acid
- waste water
- mno
- acid waste
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
Abstract
The present invention provides a kind of MnO2The method that oxalic acid waste water is simulated in O3 catalytic oxidation, includes the following steps: MnO2Catalyst is put into simulation oxalic acid waste water, is stirred, and ozone generator is opened after adsorption equilibrium and is aerated, and is sampled after catalysis reaction, sample will filter out MnO after syringe filter filters2The sample of catalyst measures COD concentration according to dichromate titration, calculates COD concentration removal rate.MnO of the present invention2The method that oxalic acid waste water is simulated in O3 catalytic oxidation uses MnO2High to simulation oxalic acid wastewater treatment COD removal efficiency with the oxalic acid in ozone combined degradation waste water, effect is good.
Description
Technical field
The invention belongs to O3 catalytic oxidation fields, more particularly, to a kind of MnO2Oxalic acid waste water is simulated in O3 catalytic oxidation
Method.
Background technique
Oxalic acid (OA) is a kind of simplest binary acid in nature, is widely present in water body environment and soil environment.Grass
With metal complexing or chelation can occur for acid, be a kind of important industrial chemicals, waste water be mainly derived from medicine, chemical industry,
The fields such as weaving.Oxalic acid is one of persistent organic pollutants during ozone oxidation, and it is final to directly affect organic pollutant
Mineralization degree.Therefore, the processing method for studying oxalic acid waste water is very necessary.
Ozone high grade oxidation technology can remove the substance for being difficult to aoxidize in water body, without secondary pollution and easy to operate, In
It has a wide range of applications in water treatment field.Since independent ozone oxidation has selectivity to the degradation of pollutant, cause to one
A little small organic molecules (monoaldehyde, aldehydic acid, monocarboxylic acid, dicarboxylic acids etc.) can not be degradable.Catalytic ozonation is
A kind of emerging oxidation technology enhances the decomposition of ozone and the generation degradation target contaminant raising of hydroxyl radical free radical by catalyst
Mineralization degree, and the efficiency of O3 catalytic oxidation is higher than the efficiency of independent ozone oxidation.It is useless that oxalic acid is simulated in O3 catalytic oxidation
The selection of catalyst is most important in water.
Summary of the invention
In view of this, the present invention is directed to propose a kind of MnO2The method that oxalic acid waste water is simulated in O3 catalytic oxidation, to simulation
The degradation efficiency of oxalic acid waste water is high, and effect is good.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of MnO2The method that oxalic acid waste water is simulated in O3 catalytic oxidation, includes the following steps: MnO2Catalyst is put into mould
It in quasi- oxalic acid waste water, is stirred, ozone generator is opened after adsorption equilibrium and is aerated, sampled after catalysis reaction, sample warp
After crossing syringe filter filtering, MnO will be filtered out2The sample of catalyst measures COD concentration according to dichromate titration, calculates
COD concentration removal rate.
Further, the MnO2The dosage of catalyst is 0.15-0.7g/L.
Preferably, the MnO2The dosage of catalyst is 0.5g/L.
Further, the concentration of the simulation oxalic acid waste water mesoxalic acid is 500mg/L.
Further, the adsorption time of the adsorption equilibrium is 20-40min.
Preferably, the adsorption time of the adsorption equilibrium is 30min.
Further, the catalysis time of the catalysis reaction is 30-45min.
Preferably, the catalysis time of the catalysis reaction is 30min.
Further, the ozone output of the ozone generator is 10g/h.
Compared with the existing technology, MnO of the present invention2The method that oxalic acid waste water is simulated in O3 catalytic oxidation has following
Advantage:
MnO of the present invention2The method that oxalic acid waste water is simulated in O3 catalytic oxidation uses MnO2It is useless with ozone combined degradation
Oxalic acid in water, high to simulation oxalic acid wastewater treatment COD removal efficiency, effect is good.
Detailed description of the invention
Fig. 1 is the removal efficiency time history plot of the COD of embodiment 5 and comparative example 1；
Fig. 2 is the removal efficiency figure of the COD of embodiment 1-4.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
Below with reference to examples and drawings, the present invention will be described in detail.
Embodiment 1
A kind of MnO2The method that oxalic acid waste water is simulated in O3 catalytic oxidation includes the following steps: the simulation for configuring 500mg/L
Oxalic acid waste water is in the reactor of 1L, by 0.167g/L MnO2Catalyst is put into simulation oxalic acid waste water, is stirred, and is adsorbed
Ozone generator is opened after balance 30min to be aerated, ozone output 10g/h, sample after catalysis reaction 30min, sample warp
After crossing syringe filter filtering, MnO will be filtered out2The sample of catalyst measures COD concentration according to dichromate titration, calculates
COD concentration removal rate.
Embodiment 2
A kind of MnO2The method that oxalic acid waste water is simulated in O3 catalytic oxidation includes the following steps: the simulation for configuring 500mg/L
Oxalic acid waste water is in the reactor of 1L, by 0.334g/L MnO2Catalyst is put into simulation oxalic acid waste water, is stirred, and is adsorbed
Ozone generator is opened after balance 30min to be aerated, ozone output 10g/h, sample after catalysis reaction 30min, sample warp
After crossing syringe filter filtering, MnO will be filtered out2The sample of catalyst measures COD concentration according to dichromate titration, calculates
COD concentration removal rate.
Embodiment 3
A kind of MnO2The method that oxalic acid waste water is simulated in O3 catalytic oxidation includes the following steps: the simulation for configuring 500mg/L
Oxalic acid waste water is in the reactor of 1L, by 0.5g/L MnO2Catalyst is put into simulation oxalic acid waste water, is stirred, and absorption is flat
Ozone generator is opened after weighing apparatus 30min to be aerated, ozone output 10g/h, sample after catalysis reaction 30min, sample passes through
After syringe filter filtering, MnO will be filtered out2The sample of catalyst measures COD concentration according to dichromate titration, calculates COD
Concentration removal rate.
Embodiment 4
A kind of MnO2The method that oxalic acid waste water is simulated in O3 catalytic oxidation includes the following steps: the simulation for configuring 500mg/L
Oxalic acid waste water is in the reactor of 1L, by 0.668g/L MnO2Catalyst is put into simulation oxalic acid waste water, is stirred, and is adsorbed
Ozone generator is opened after balance 30min to be aerated, ozone output 10g/h, sample after catalysis reaction 30min, sample warp
After crossing syringe filter filtering, MnO will be filtered out2The sample of catalyst measures COD concentration according to dichromate titration, calculates
COD concentration removal rate.
Embodiment 5
A kind of MnO2The method that oxalic acid waste water is simulated in O3 catalytic oxidation includes the following steps: the simulation for configuring 500mg/L
Oxalic acid waste water is in the reactor of 1L, by 0.167g/L MnO2Catalyst is put into simulation oxalic acid waste water, is stirred, and is adsorbed
Ozone generator is opened after balance 45min to be aerated, ozone output 10g/h, sample after catalysis reaction 45min, sample warp
After crossing syringe filter filtering, MnO will be filtered out2The sample of catalyst measures COD concentration according to dichromate titration, calculates
COD concentration removal rate.
Comparative example 1
A kind of method of ozone oxidation simulation oxalic acid waste water, includes the following steps: the simulation oxalic acid waste water for configuring 500mg/L
It in the reactor of 1L, opens ozone generator and is aerated, sampled after ozone output 10g/h, catalysis reaction 90min, sample
Product measure COD concentration according to dichromate titration, calculate COD concentration removal rate.
As shown in Figure 1, compared in embodiment 5 and comparative example 1, independent ozone oxidation, MnO2Catalyst Adsorption and MnO2It urges
Agent and O3 catalytic oxidation are to the removal efficiency for simulating oxalic acid waste water COD.As can be seen from the figure: independent ozone simulates oxalic acid
The COD removal efficiency of waste water is only 4.94%, and removal efficiency is lower.0.167g/LMnO is added2Catalyst, COD when adsorption equilibrium
Removal efficiency reaches 20.83%, independent MnO2Catalyst has certain suction-operated to simulation oxalic acid waste water.0.167g/LMnO2
When O3 catalytic oxidation oxalic acid waste water, COD removal efficiency is increased to 44.44%, illustrates MnO2Catalyst has catalytic action, MnO2
Catalyst and ozone can cooperate with the degradation for promoting oxalic acid.
As shown in figure 1, with adsorption time from 0 increase to 20min when, 0.167g/LMnO2Catalyst is to simulation oxalic acid waste water
COD removal efficiency is increased.0.167g/LMnO when 20 to 40min2Catalyst reaches adsorption equilibrium, simulates oxalic acid waste water COD
Removal efficiency is basically unchanged.Ozone is passed through after 40min, with the increase in reaction time, MnO2Catalyst and ozone come into full contact with,
Hydroxyl radical free radical is generated, simulation oxalic acid waste water COD removal efficiency gradually increases.MnO when 70-90min2Catalyst and ozone cooperative
The COD removal efficiency of degradation simulation oxalic acid waste water is basically unchanged.In view of factors such as costs, thus select adsorption time for
30min, catalysis reaction time are 30min.
Catalyst amounts directly affect the degradation rate of target contaminant, therefore have investigated catalyst amounts to simulation
The degradation of oxalic acid waste water.It is constant to simulate oxalic acid waste water initial concentration, is 500mg/L.As shown in Fig. 2, in embodiment 1-4, with
MnO2Catalyst amounts increase to 0.5g/L from 0.167g/L, and simulation oxalic acid waste water COD removal efficiency is improved from 44.44%
To 85.87%；However MnO2Catalyst amounts increase to 0.668g/L, and COD removal efficiency is down to 80.69%.With MnO2It urges
The COD removal rate presentation of the increase of agent dosage, simulation oxalic acid waste water first increases the trend reduced afterwards.Catalyst amounts
Increase, more ozone generate OH by catalysis, promote the degradation of oxalic acid.But catalyst amounts it is excessive when, COD removal
Efficiency decline, it may be possible to excessive MnO2Quenching effect is generated to OH.Therefore, MnO2Catalyst optimum dosage is 0.5g/L.
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
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of MnO2The method of O3 catalytic oxidation simulation oxalic acid waste water, characterized by the following steps: by MnO2It urges
Agent is put into simulation oxalic acid waste water, is stirred, and ozone generator is opened after adsorption equilibrium and is aerated, and is taken after catalysis reaction
Sample, sample will filter out MnO after syringe filter filters2The sample of catalyst is dense according to dichromate titration measurement COD
Degree calculates COD concentration removal rate.
2. MnO according to claim 12The method of O3 catalytic oxidation simulation oxalic acid waste water, it is characterised in that: described
MnO2The dosage of catalyst is 0.15-0.7g/L.
3. MnO according to claim 22The method of O3 catalytic oxidation simulation oxalic acid waste water, it is characterised in that: described
MnO2The dosage of catalyst is 0.5g/L.
4. MnO according to claim 12The method of O3 catalytic oxidation simulation oxalic acid waste water, it is characterised in that: described
The concentration for simulating oxalic acid waste water mesoxalic acid is 500mg/L.
5. MnO according to claim 12The method of O3 catalytic oxidation simulation oxalic acid waste water, it is characterised in that: described
The adsorption time of adsorption equilibrium is 20-40min.
6. MnO according to claim 52The method of O3 catalytic oxidation simulation oxalic acid waste water, it is characterised in that: described
The adsorption time of adsorption equilibrium is 30min.
7. MnO according to claim 12The method of O3 catalytic oxidation simulation oxalic acid waste water, it is characterised in that: described
The catalysis time of catalysis reaction is 30-45min.
8. MnO according to claim 72The method of O3 catalytic oxidation simulation oxalic acid waste water, it is characterised in that: described
The catalysis time of catalysis reaction is 30min.
9. MnO according to claim 12The method of O3 catalytic oxidation simulation oxalic acid waste water, it is characterised in that: described
The ozone output of ozone generator is 10g/h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891297A (en) * | 2010-07-19 | 2010-11-24 | 江南大学 | Ozonization water treatment method using manganese dioxide one-dimensional nano material as catalyst |
| CN103663794A (en) * | 2013-12-16 | 2014-03-26 | 西安建筑科技大学 | Chemical conversion and granulation coagulating method of refractory organics |
| CN104772137A (en) * | 2015-03-05 | 2015-07-15 | 华南理工大学 | Ceramsite catalyst with high manganese dioxide content for ozone catalysis, and preparation method and application thereof |
| CN106746226A (en) * | 2016-12-28 | 2017-05-31 | 北京清大国华环境股份有限公司 | A kind of processing method and processing device of F- T synthesis waste water |
-
2019
- 2019-07-25 CN CN201910676156.4A patent/CN110510724A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891297A (en) * | 2010-07-19 | 2010-11-24 | 江南大学 | Ozonization water treatment method using manganese dioxide one-dimensional nano material as catalyst |
| CN103663794A (en) * | 2013-12-16 | 2014-03-26 | 西安建筑科技大学 | Chemical conversion and granulation coagulating method of refractory organics |
| CN104772137A (en) * | 2015-03-05 | 2015-07-15 | 华南理工大学 | Ceramsite catalyst with high manganese dioxide content for ozone catalysis, and preparation method and application thereof |
| CN106746226A (en) * | 2016-12-28 | 2017-05-31 | 北京清大国华环境股份有限公司 | A kind of processing method and processing device of F- T synthesis waste water |
Non-Patent Citations (2)
| Title |
|---|
| TAO ZHANG等: "A non-acid-assisted and non-hydroxyl-radical-related catalytic ozonation with ceria supported copper oxide in efficient oxalate degradation in water", 《APPLIED CATALYSIS B》 * |
| 张建琳等: "介孔二氧化锰制备及其催化臭氧氧化草酸研究", 《大连理工大学学报》 * |
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