CN107032540A - One kind improves LaFeO3The method for removing organic pollutants efficiency - Google Patents
One kind improves LaFeO3The method for removing organic pollutants efficiency Download PDFInfo
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- CN107032540A CN107032540A CN201710326499.9A CN201710326499A CN107032540A CN 107032540 A CN107032540 A CN 107032540A CN 201710326499 A CN201710326499 A CN 201710326499A CN 107032540 A CN107032540 A CN 107032540A
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
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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
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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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
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Abstract
LaFeO is improved the invention discloses one kind3The method for removing organic pollutants efficiency, the LaFeO used3Nano-photocatalyst combination ozone enhanced photocatalysis technology efficiently removes organic pollutants in water body, LaFeO3The narrow energy band of itself can absorb most visible ray in sunshine, can produce substantial amounts of light induced electron and hole pair, the present invention makes ozone and LaFeO by the introducing of ozone3Reaction, can be obviously improved LaFeO3Middle light induced electron and the separative efficiency and its photocatalytic activity in hole pair, this photochemical catalyst and catalytic reaction technology are applied to that in water environment processing cost can be reduced, secondary pollution is avoided, while extending LaFeO3As the application of photochemical catalyst, and LaFeO3Photochemical catalyst, which has good stability and repeated, utilizes feature.During ozone enhanced photocatalysis, due to the strong electrophilic performance of ozone, light induced electron can be largely captured, the separative efficiency in electronics and hole pair is improved, generate more OH, and then improve catalytic activity.
Description
Technical field
The invention belongs to water process research field, and in particular to one kind improves LaFeO3Remove organic pollutants efficiency
Method.
Background technology
Ozone enhanced photocatalysis as one kind in high-level oxidation technology, with it efficiently, the advantage that has a wide range of application and receive
The attention of people.However, the visible light-responded photochemical catalyst of exploitation is used to ozone enhanced photocatalysis technology handle difficult degradation in water body
Organic pollution is conducive to improving solar energy utilization rate, it is to avoid the high cost of ultraviolet source, the shortcoming of big energy consumption, Neng Gouji
The practical ranges of big expansion ozone enhanced photocatalysis.Therefore, the stable visible-light response nano photocatalysis of exploitation chemical property
It is significant that agent is used for ozone enhanced photocatalysis.
LaFeO3As the narrow energy carrying semiconductor material of one kind, with good visible light-responded property and photochemical stability.
Under visible light illumination, LaFeO3Can effectively produce substantial amounts of electron-hole pair, but be limited to electron hole it is seriously compound and
Weak oxide reducing power and most persistent organic pollutants can not be removed in water body and degradation efficiency is low, therefore, will
LaFeO3Simple can not meet actual demand for photochemical catalytic oxidation water treatment procedure.
The content of the invention
It is an object of the invention to provide a kind of method of oxidation removal Organic Pollutants In Water under visible ray, to overcome
The deficiencies in the prior art.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
One kind improves LaFeO3The method for removing organic pollutants efficiency, specifically includes following steps：
1), first by LaFeO3Add in the water containing organic pollution and carry out dark reaction and stir；
2), after dark reaction, by illumination and ozone is passed through at 20-30 DEG C.
Further, step 1) in, by LaFeO3Add and pass through after containing in organic pollutant wastewater photo catalysis reactor
Ultrasound, be stirred until homogeneous it is scattered.
Further, by the water after stirring, lasting stirring is not less than 30min in dark situation.
Further, step 2) in, at 20-30 DEG C to water body in by illumination and be passed through ozone.
Further, the water containing organic pollution carries out temperature control by condenser pipe.
Further, step 2) in, by ozone reactor into the water containing organic pollution with 30mL/min-
200mL/min speed is passed through the ozone that concentration is 14.2mg/L and continues 1h.
Further, concentration is passed through with 60mL/min speed into the water containing organic pollution by ozone reactor
Continue 1h for 14.2mg/L ozone.
Further, step 2) in, using xenon source, xenon source λ>420nm.
Compared with prior art, the present invention has following beneficial technique effect：
A kind of raising LaFeO of the invention3The method for removing organic pollutants efficiency, the LaFeO used3Nanometer light
Catalyst combination ozone enhanced photocatalysis technology efficiently removes organic pollutants in water body, with ozone concentration consumption is few, mineralization degree
It is high, the characteristics of stability is strong, LaFeO3The narrow energy band of itself can absorb most visible ray in sunshine, can produce big
The light induced electron of amount and hole pair, the present invention make ozone and LaFeO by the introducing of ozone3Reaction, can be obviously improved LaFeO3
Middle light induced electron and the separative efficiency and its photocatalytic activity in hole pair, this photochemical catalyst and catalytic reaction technology are applied to
Processing cost can be reduced in water environment, secondary pollution is avoided, while extending LaFeO3As the application of photochemical catalyst,
And LaFeO3Photochemical catalyst, which has good stability and repeated, utilizes feature.During ozone enhanced photocatalysis, due to ozone
Strong electrophilic performance, can largely capture light induced electron, improve the separative efficiency in electronics and hole pair, generate more OH, enter
And improve catalytic activity.Therefore, by LaFeO3For ozone enhanced photocatalysis, it can be reached as photochemical catalyst, applied to industrial real
The purpose trampled.
Brief description of the drawings
Fig. 1 is LaFeO3Be passed through under different ozone amount ozone catalytics in visible ray, LaFeO3Under visible light catalytic, P25 receives
M- degradation efficiency graph of a relation when under rice photochemical catalyst catalysis.
Fig. 2 is m- degradation rate graph of a relation when being individually passed through the independent ozone oxidation of ozone amount under illumination/dark condition.
Fig. 3 is LaFeO3The degraded circulation experiment datagram of the optimal throughput visible ray ozone enhanced photocatalysis of nano material.
Embodiment
The present invention is described in further detail below：
One kind improves LaFeO3The method for removing organic pollutants efficiency, specifically includes following steps：
1), first by LaFeO3Add in the waste water containing organic pollution and carry out dark reaction and stir；
2), after dark reaction, by illumination and ozone is passed through at 20-30 DEG C.
Step 1) in, by LaFeO3Add the photo catalysis reactor containing organic pollutant wastewater in after by ultrasound, stir
Mix to dispersed, then persistently stirred in dark situation and be not less than 30min；
Step 2) in, the water containing organic pollution carries out temperature control by condenser pipe, makes to keep containing organic pollution water
At 20-30 DEG C.
Step 2) in, by ozone generator into the water containing organic pollution with 30mL/min-200mL/min speed
Degree is passed through the ozone that concentration is 14.2mg/L, continues 1h.
Step 2) in, using xenon source, xenon source λ>420nm.
Embodiment 1：
Compound concentration is added to photocatalysis for 10mg/L 2,4- dichlorphenoxyacetic acid solution 100mL and answered in device, Ran Houjia
Enter 0.1g LaFeO3Nano-photocatalyst, continues through ultrasound to dispersed in dark situation, then persistently stirs 30min, so
Xenon source is opened afterwards 1h is continued using the 30mL/min ozone for being passed through ozone concentration as 14.2mg/L simultaneously at 20 DEG C, it is seen that light
Sampled in During Illumination at interval of 10min, take supernatant liquor to test different using ultraviolet-uisible spectrophotometer after centrifugation
Concentration (the λ of 2,4 dichlorophenoxyacetic acid in supernatantmax=283nm) and calculate clearance.
Embodiment 2：
Compound concentration is added to photocatalysis for 10mg/L 2,4 dichlorophenoxyacetic acid solution 100mL and answered in device；Then plus
Enter 0.1g LaFeO3Nano-photocatalyst, continues through ultrasound to dispersed in dark situation, then persistently stirs 30min, so
Xenon source is opened afterwards 1h is continued using the 60mL/min ozone for being passed through ozone concentration as 14.2mg/L simultaneously at 20 DEG C, it is seen that light
Sampled in During Illumination at interval of 10min, take supernatant liquor to test different using ultraviolet-uisible spectrophotometer after centrifugation
Concentration (the λ of 2,4 dichlorophenoxyacetic acid in supernatantmax=283nm) and calculate clearance.
Embodiment 3：
Compound concentration is added to photocatalysis for 10mg/L 2,4 dichlorophenoxyacetic acid solution 100mL and answered in device；Then plus
Enter 0.1g LaFeO3Nano-photocatalyst, continues through ultrasound to dispersed in dark situation, then persistently stirs 30min, so
Xenon source is opened afterwards 1h is continued using the 90mL/min ozone for being passed through ozone concentration as 14.2mg/L simultaneously at 20 DEG C, it is seen that light
Sampled in During Illumination at interval of 10min, take supernatant liquor to test different using ultraviolet-uisible spectrophotometer after centrifugation
Concentration (the λ of 2,4 dichlorophenoxyacetic acid in supernatantmax=283nm) and calculate clearance.
Embodiment 4：
Compound concentration is added to photocatalysis for 10mg/L 2,4 dichlorophenoxyacetic acid solution 100mL and answered in device；Then plus
Enter 0.1g LaFeO3Nano-photocatalyst, continues through ultrasound to dispersed in dark situation, then persistently stirs 30min, so
Xenon source is opened afterwards, and 1h is continued using the 200mL/min ozone for being passed through ozone concentration as 14.2mg/L simultaneously at 20 DEG C, it is seen that
Sampled in light During Illumination at interval of 10min, take supernatant liquor to be tested not using ultraviolet-uisible spectrophotometer after centrifugation
With the concentration (λ of 2,4 dichlorophenoxyacetic acid in supernatantmax=283nm) and calculate clearance.
Embodiment 5
Compound concentration is added to photocatalysis for 10mg/L 2,4 dichlorophenoxyacetic acid solution 100mL and answered in device；Then plus
Enter 0.1g LaFeO3Nano-photocatalyst, continues through ultrasound to dispersed in dark situation, then persistently stirs 30min, so
Xenon source is opened afterwards 1h is continued using the 30mL/min ozone for being passed through ozone concentration as 14.2mg/L simultaneously at 30 DEG C, it is seen that light
Sampled in During Illumination at interval of 10min, take supernatant liquor to test different using ultraviolet-uisible spectrophotometer after centrifugation
Concentration (the λ of 2,4 dichlorophenoxyacetic acid in supernatantmax=283nm) and calculate clearance.
Embodiment 6
Compound concentration is added to photocatalysis for 10mg/L 2,4 dichlorophenoxyacetic acid solution 100mL and answered in device；Then plus
Enter 0.1g LaFeO3Nano-photocatalyst, continues through ultrasound to dispersed in dark situation, then persistently stirs 30min, so
Xenon source is opened afterwards 1h is continued using the 60mL/min ozone for being passed through ozone concentration as 14.2mg/L simultaneously at 30 DEG C, it is seen that light
Sampled in During Illumination at interval of 10min, take supernatant liquor to test different using ultraviolet-uisible spectrophotometer after centrifugation
Concentration (the λ of 2,4 dichlorophenoxyacetic acid in supernatantmax=283nm) and calculate clearance.
Embodiment 7
Compound concentration is added to photocatalysis for 10mg/L 2,4 dichlorophenoxyacetic acid solution 100mL and answered in device；Then plus
Enter 0.1g LaFeO3Nano-photocatalyst, continues through ultrasound to dispersed in dark situation, then persistently stirs 30min, so
Xenon source is opened afterwards 1h is continued using the 90mL/min ozone for being passed through ozone concentration as 14.2mg/L simultaneously at 30 DEG C, it is seen that light
Sampled in During Illumination at interval of 10min, take supernatant liquor to test different using ultraviolet-uisible spectrophotometer after centrifugation
Concentration (the λ of 2,4 dichlorophenoxyacetic acid in supernatantmax=283nm) and calculate clearance.
Embodiment 8
Compound concentration is added to photocatalysis for 10mg/L 2,4 dichlorophenoxyacetic acid solution 100mL and answered in device；Then plus
Enter 0.1g LaFeO3Nano-photocatalyst, continues through ultrasound to dispersed in dark situation, then persistently stirs 30min, so
Xenon source is opened afterwards, and 1h is continued using the 200mL/min ozone for being passed through ozone concentration as 14.2mg/L simultaneously at 30 DEG C, it is seen that
Sampled in light During Illumination at interval of 10min, take supernatant liquor to be tested not using ultraviolet-uisible spectrophotometer after centrifugation
With the concentration (λ of 2,4 dichlorophenoxyacetic acid in supernatantmax=283nm) and calculate clearance.
Embodiment 9
Compound concentration is added to photocatalysis for 10mg/L 2,4 dichlorophenoxyacetic acid solution 100mL and answered in device；Then plus
Enter 0.1g LaFeO3Nano-photocatalyst, continues, through ultrasound, stirring 30min, then to open xenon source 30 in dark situation
Carry out reacting lasting 1h at DEG C, it is seen that sample at interval of 10min in light During Illumination, take supernatant liquor to use after centrifugation purple
Outer visible spectrophotometer tests the concentration (λ of 2,4 dichlorophenoxyacetic acid in different supernatantsmax=283nm) and calculate removal
Rate.
Embodiment 10
Compound concentration is added to photocatalysis for 10mg/L 2,4 dichlorophenoxyacetic acid solution 100mL and answered in device；Then plus
Enter 0.1gP25 nano-photocatalysts, continue in dark situation through ultrasound to dispersed, then persistently stir 30min, then beat
Open xenon source to carry out reacting lasting 1h at 30 DEG C, it is seen that sample, taken after centrifugation at interval of 10min in light During Illumination
Supernatant liquor tests the concentration (λ of 2,4 dichlorophenoxyacetic acid in different supernatants using ultraviolet-uisible spectrophotometermax=
283nm) and calculate clearance.
As shown in figure 1, respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 9, embodiment 10 are one
In hour in the clearance of pollution organic pollutants, Fig. 1, LaFeO3Under catalyst respectively with 30mL/min, 60mL/min,
90mL/min, 200mL/min are passed through ozone amount and are designated as respectively：30-O3/ Vis, 60-O3/ Vis, 90-O3/ Vis, 200-O3/Vis；
As seen from the figure, LaFeO is being added3In the case of concentration is passed through as 14.2mg/L ozone using 60mL/min after organic pollutants
Removal efficiency highest, and from curve map, adding LaFeO3While 1h concentration is passed through as 14.2mg/ using 60mL/min
The final clearance of organic pollution in L ozone, water tends to 100%, and only adds LaFeO3In the case of reaction 1h in water
The final clearance of organic pollution tend to 3%, it can be seen that, LaFeO of the present invention3Nano-photocatalyst combines smelly
Oxygen photocatalysis technology efficiently removes Organic Pollutants In Water, with the spy that ozone usage is few, mineralization degree is high, stability is strong
Point.
Fig. 2 carries out ozone oxidation to be individually passed through ozone 1h with different rates, wherein being designated as respectively under dark and visible ray：
O3/ Dark and O3/ Light, as can be seen from Figure, in the case of independent ozone oxidation, when being passed through ozone amount for 60mL/min,
Removal efficiency is most fast, and highest has only reached 52%, much not as good as LaFeO3Clearance of the catalyst under ozone oxidation is high.
Prepared LaFeO as seen from Figure 33Photochemical catalyst, for visible ray ozone enhanced photocatalysis, when ozone amount is 60mL/
Photochemical catalyst during min can still keep good removal activity after circulating four times, show LaFeO3Photochemical catalyst has
Good stability utilizes feature with repeatable.
Claims (8)
1. one kind improves LaFeO3The method for removing organic pollutants efficiency, specifically includes following steps：
1), first by LaFeO3Add in the water containing organic pollution and carry out dark reaction and stir；
2), after dark reaction, by illumination and ozone is passed through at 20-30 DEG C.
2. a kind of raising LaFeO according to claim 13The method for removing organic pollutants efficiency, its feature exists
In step 1) in, by LaFeO3Add the photo catalysis reactor containing organic pollution water in after by ultrasound, be stirred until homogeneous
It is scattered.
3. a kind of raising LaFeO according to claim 23The method for removing organic pollutants efficiency, its feature exists
In by the water after stirring, lasting stirring is not less than 30min in dark situation.
4. a kind of raising LaFeO according to claim 13The method for removing organic pollutants efficiency, its feature exists
In step 2) in, at 20-30 DEG C to water body in by illumination and be passed through ozone.
5. a kind of raising LaFeO according to claim 43The method for removing organic pollutants efficiency, its feature exists
In the water containing organic pollution carries out temperature control by condenser pipe.
6. a kind of raising LaFeO according to claim 13The method for removing organic pollutants efficiency, its feature exists
In step 2) in, it is logical with 30mL/min-200mL/min speed into the water containing organic pollution by ozone reactor
Enter the ozone that concentration is 14.2mg/L and continue 1h.
7. a kind of raising LaFeO according to claim 63The method for removing organic pollutants efficiency, its feature exists
In being passed through concentration as the smelly of 14.2mg/L using 60mL/min speed into the water containing organic pollution by ozone reactor
Oxygen continues 1h.
8. a kind of raising LaFeO according to claim 13The method for removing organic pollutants efficiency, its feature exists
In step 2) in, using xenon source, xenon source λ>420nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107376926A (en) * | 2017-08-18 | 2017-11-24 | 中国科学院过程工程研究所 | A kind of Ca-Ti ore type ozone decomposition catalyst and its preparation method and application |
| CN111533235A (en) * | 2020-04-29 | 2020-08-14 | 南京中微纳米功能材料研究院有限公司 | Novel photocatalyst LaFeO3Method for catalytic degradation of ammonia nitrogen wastewater |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103263943A (en) * | 2013-05-14 | 2013-08-28 | 中南民族大学 | Preparation method of LaF3O3/SBA-15 and application |
| CN104058516A (en) * | 2014-05-30 | 2014-09-24 | 安徽国星生物化学有限公司 | Treatment method for phosphor-containing wastewater produced in glyphosate production process |
| CN106179369A (en) * | 2016-07-25 | 2016-12-07 | 牛和林 | Tool visible ray Fenton activity LaFeO3/ C carbon back perovskite semiconductor composite nano material and its preparation method and application |
| CN105688918B (en) * | 2016-01-18 | 2018-12-07 | 常州大学 | A kind of preparation method and applications of clay-perovskite composite material |
-
2017
- 2017-05-10 CN CN201710326499.9A patent/CN107032540A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103263943A (en) * | 2013-05-14 | 2013-08-28 | 中南民族大学 | Preparation method of LaF3O3/SBA-15 and application |
| CN104058516A (en) * | 2014-05-30 | 2014-09-24 | 安徽国星生物化学有限公司 | Treatment method for phosphor-containing wastewater produced in glyphosate production process |
| CN105688918B (en) * | 2016-01-18 | 2018-12-07 | 常州大学 | A kind of preparation method and applications of clay-perovskite composite material |
| CN106179369A (en) * | 2016-07-25 | 2016-12-07 | 牛和林 | Tool visible ray Fenton activity LaFeO3/ C carbon back perovskite semiconductor composite nano material and its preparation method and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107376926A (en) * | 2017-08-18 | 2017-11-24 | 中国科学院过程工程研究所 | A kind of Ca-Ti ore type ozone decomposition catalyst and its preparation method and application |
| CN107376926B (en) * | 2017-08-18 | 2020-02-11 | 中国科学院过程工程研究所 | Perovskite type ozonolysis catalyst and preparation method and application thereof |
| CN111533235A (en) * | 2020-04-29 | 2020-08-14 | 南京中微纳米功能材料研究院有限公司 | Novel photocatalyst LaFeO3Method for catalytic degradation of ammonia nitrogen wastewater |
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