CN103011332A - Method and device for catalytically treating organic pollutants in water by laser - Google Patents
Method and device for catalytically treating organic pollutants in water by laser Download PDFInfo
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- CN103011332A CN103011332A CN2012105296135A CN201210529613A CN103011332A CN 103011332 A CN103011332 A CN 103011332A CN 2012105296135 A CN2012105296135 A CN 2012105296135A CN 201210529613 A CN201210529613 A CN 201210529613A CN 103011332 A CN103011332 A CN 103011332A
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Abstract
The invention relates to a method and a device for catalytically treating organic pollutants in water by laser. A photoreaction tube is made of a quartz material and is wound with electromagnetic coils outside; air is fed into the lower part of a photoreactor by an air pump; a laser generator emits laser which is refracted to the photoreaction tube by a beam splitter to irradiate the organic pollutants and catalysts; alternating current is provided to the electromagnetic coils; reaction solution passes through a liquid inlet, the photoreactor and a liquid outlet in sequence; and air is pressed into the photoreactor by the air pump and is discharged from an air outlet. The particle size of a composite magnetic material synthesizing nangold is 5 to 100 nm, the core of the composite magnetic material is ferroferric oxide, and the shell of the composite magnetic material is gold. The wavelength of incident laser is 200 to 550 nm. According to the method and the device for catalytically treating organic pollutants in water by laser, the organic pollutants in water can be effectively degraded, the prepared catalyst is stable and good in catalytic activity, and the magnetic nano composite material can be recycled quickly by magnetic field and can be recycled continuously.
Description
Technical field
The invention belongs to environment protection and Pollution abatement technical field, relate to a kind of nanometer gold of utilizing and under laser excitation, produce surface plasmon resonance effect, the electric charge dipole polarization occurs, method and the apparatus for photoreaction of efficient Quick Oxidation reduction organic pollutants.
Background technology
The surround lighting catalysis technique is the advantages such as device structure is simple, reaction conditions is gentle, operational condition is easy to control, oxidation capacity is strong, non-secondary pollution because having, and the semiconductor catalyst commonly used such as the nano titanium oxide (TiO that use
2) have the advantages such as chemical stability is high, nontoxic and inexpensive, make the surround lighting catalysis technique become one of focus of organic pollutant degradation experiment and application research in the water treatment.Along with developing rapidly of nanotechnology, especially the monochromaticity, low scattering and the high strength characteristics that have because of characteristics such as having good electroconductibility, small-size effect, surface and easily modify and be easy to be recycled and laser of noble metal nano particles, laser and nanometer gold be also day by day development in the basic and applied research in photocatalysis technology field.
At present, focus mostly in UV-light and visible light about the use of surround lighting catalysis technical field inner light source, carry out the photocatalytic degradation pollutent by using suitable photocatalyst.But ordinary light source has produced the efficiency of light energy utilization low because of high scattering and the pyrogenic effect of light, the shortcoming that the luminous energy loss is large.At present, domestic also not with laser and noble metal nanometer material in conjunction with the report that is applied to remove organic pollutants.
Summary of the invention
The technical problem to be solved in the present invention is: develop a kind of method and the apparatus for photoreaction that can rapidly and efficiently process organic pollutants, overcome the shortcoming that the ordinary light source efficiency of light energy utilization is low, the luminous energy loss is large in the existing light-catalyzed reaction process, by in conjunction with low scattering and the monochromaticity characteristics of utilizing surface plasmon resonance effect and the laser of nanometer gold, improve the photodegradation speed of pollutent.
The technical solution adopted for the present invention to solve the technical problems is as follows:
A kind of laser catalyzed degradation organic pollutants device comprises laser generator, optical splitter, light power meter, photoresponse pipe, valve, solenoid, under meter, pneumatic pump and pipeline; It is characterized in that photoresponse pipe 4 made by quartz material, the outside solenoid 7 that twines, the photoreactor bottom passes into air by pneumatic pump 10; Laser generator 1 Emission Lasers, by optical splitter 2 with laser refraction in photoresponse pipe 4, irradiation organic pollutant and catalyzer; The solenoid indirect current; Reaction soln is successively by fluid inlet 11, photoreactor 4 and liquid outlet 12; Air is pressed in the photoreactor 4 by pneumatic pump 10, and 6 discharges from the air outlet.
The air outlet of device exceeds approximately 5cm-10cm than the filter membrane of liquid outlet, and inlet mouth is than the approximately low 2cm-5cm of fluid inlet.
Pipeline at fluid inlet and liquid outlet is provided with valve 5, can carry out batch type to pollutent and process.
Of the present invention with laser catalyzed degradation organic pollutants method, step is as follows:
(1) particle diameter of synthesis of nano gold composite magnetic is 5-100nm, and the composite magnetic kernel is Z 250, and shell is gold;
(2) add the nanometer gold composite magnetic in reactor, open laser generator, the laser wavelength of incidence scope is between 200nm-550nm, and pulse-repetition is 1-100Hz;
(3) open solenoid switch, open pressure lock, pass into the water body that contains pollutent, by valve sewage is carried out batch type and process.
Wherein, nanometer gold composite magnetic preparation method is: commercially available nano gold sol is mixed with amidized ferriferrous oxide nanometer material after 24 hours as seed particles, after ultrapure water cleans, change in the Glass Containers, then add the 21.4ml ultrapure water, under the rapid stirring state, the chlorauric acid solution that adds 50 μ l 0.05M, the sodium citrate solution of 500 μ l 75mM, the last sodium borohydride that adds rapidly 250 μ l 100mM stirs, until color no longer changes.
Regulate the thickness of golden shell by control chlorauric acid solution concentration or seed concentration.
The present invention compared with prior art has advantages of:
The method of the present invention organic pollutants of can effectively degrading is such as dyestuff and chlorophenol;
Method of the present invention is compared under the ordinary light source condition, has higher unit energy utilization ratio and speed of reaction, without pyrogenic effect;
The catalyzer of method preparation of the present invention is stable, and catalytic activity is good, and the magnetic Nano composite magnetic can reclaim fast through magnetic field sustainable recycle;
Method of the present invention is less demanding, and method is simple and easy, and is easy to operate;
Method condition of the present invention is controlled, and the nanometer particle size size is controlled, can mate to greatest extent laser.
Description of drawings
The reaction unit figure of Fig. 1 laser catalytic treatment of the present invention organic pollutant;
Figure 25 32nm laser catalyzed degradation methylene radical blueprint;
Figure 33 55nm laser catalyzed degradation methylene radical blueprint;
Figure 42 66nm laser catalyzed degradation 2,4,5-Trichlorophenol figure.
Embodiment
Introduce in detail the present invention below in conjunction with specific embodiments.But following embodiment only limits to explain the present invention, and protection scope of the present invention should comprise the full content of claim, and by following examples, those skilled in the art namely can realize the full content of claim of the present invention.
The device of laser catalyzed degradation organic pollutants as shown in Figure 1, installation composition mainly comprises laser generator, optical splitter, light power meter, photoresponse pipe, valve, solenoid, under meter, pneumatic pump and pipeline etc.; The function of wherein said laser generator 1 provides ps pulsed laser and ns pulsed laser; Wherein said photoresponse pipe 4 is made by quartz material, the outside solenoid 7 that twines, and the photoreactor bottom passes into air by pneumatic pump 10.The effect that passes into air is to promote contaminant degradation as the electron capture agent, the effect of external electromagnetic coil provides magnetic field reactant is stirred, promote the dissolving of electron capture agent, strengthen electric charge dipole polarization intensity, promote light-catalyzed reaction, can also realize the recovery to the nanometer gold composite magnetic simultaneously.In whole photoreaction system, laser generator 1 Emission Lasers, by optical splitter 2 with laser refraction in photoresponse pipe 4, irradiation organic pollutant and catalyzer.The solenoid indirect current.Reaction soln is successively by fluid inlet 11, photoreactor 4 and liquid outlet 12.Air is pressed in the photoreactor 4 by pneumatic pump 10, and 6 discharges from the air outlet.Air outlet 6 exceeds approximately 5cm-10cm than the filter membrane 8 of liquid outlet, and inlet mouth is than the approximately low 2cm-5cm of fluid inlet.The effect of valve 5 is pollutent to be carried out batch type process.
The preparation method is as follows: the particle diameter of (1) synthesis of nano gold composite magnetic is 5-100nm, and the composite magnetic kernel is Z 250, and shell is gold; Its preparation method is that commercially available nano gold sol is mixed with amidized ferriferrous oxide nanometer material after 24 hours as seed particles, after ultrapure water cleans, change in the Glass Containers, then add the 21.4ml ultrapure water, under the rapid stirring state, the chlorauric acid solution that adds 50 μ l 0.05M, the sodium citrate solution of 500 μ l 75mM, the last sodium borohydride that adds rapidly 250 μ l 100mM, ceaselessly stir, until color no longer changes, can regulate by control chlorauric acid solution concentration or seed concentration the thickness of golden shell.(2) add the nanometer gold composite magnetic in reactor, open laser generator, the laser wavelength of incidence scope is between 200nm-550nm, and pulse-repetition is 1-100Hz; (3) open solenoid switch, open pressure lock, pass into the water body that contains pollutent, by valve sewage is carried out batch type and process.
Implementation is as follows:
Example 1
The implementation case is utilized the method and apparatus of laser catalytic treatment organic pollutants of the present invention, for the treatment of dyestuff methylene blue in the water.Strobe pulse optical maser wavelength is 532nm, and pulse-repetition is 10Hz, and nanometer gold magnetic composite mass concentration is 11.6mg/L, without focusing on parallel radiation, uses UV-VIS method and HLPC method to detect percent of decolourization and the degradation rate of dyestuff.In the implementation case, when reaction substrate methylene blue concentration was 4mg/L, percent of decolourization and degradation rate behind the reaction 15min reached respectively 94% and 91%.As shown in Figure 2.
Example 2
The implementation case is utilized the method and apparatus of laser catalytic treatment organic pollutants of the present invention, for the treatment of dyestuff methylene blue in the water.Strobe pulse optical maser wavelength is 355nm, and pulse-repetition is 10Hz, and nanometer gold magnetic composite mass concentration is 11.6mg/L, without focusing on parallel radiation, uses the UV-VIS method to detect the percent of decolourization of dyestuff.In the implementation case, when reaction substrate methylene blue concentration was 4mg/L, the percent of decolourization behind the reaction 15min reached 90%.As shown in Figure 3.
Example 3
The implementation case is utilized the method and apparatus of laser catalytic treatment organic pollutants of the present invention, for the treatment of Trichlorophenol in the water.Strobe pulse optical maser wavelength is 266nm, and pulse-repetition is 10Hz, and nanometer gold magnetic composite mass concentration is 11.6mg/L, without focusing on parallel radiation, uses the GC method to detect the degradation rate of 2,4,5-Trichlorophenol.In the implementation case, when 2,4,5-Trichlorophenol concentration was 50mg/L, the degradation rate behind the reaction 40min reached 85%.As shown in Figure 4.
Claims (6)
1. a laser catalyzed degradation organic pollutants device is characterized in that: comprise laser generator, optical splitter, light power meter, photoresponse pipe, valve, solenoid, under meter, pneumatic pump and pipeline; It is characterized in that the photoresponse pipe made by quartz material, the outside solenoid that twines, the photoreactor bottom passes into air by pneumatic pump; The laser generator Emission Lasers, by optical splitter with laser refraction in the photoresponse pipe, irradiation organic pollutant and catalyzer; The solenoid indirect current; Reaction soln is successively by fluid inlet, photoreactor and liquid outlet; Air is pressed in the photoreactor by pneumatic pump, and discharges from the air outlet.
2. device as claimed in claim 1 is characterized in that the air outlet exceeds approximately 5cm-10cm than the filter membrane of liquid outlet, and inlet mouth is than the approximately low 2cm-5cm of fluid inlet.
3. device as claimed in claim 1 is characterized in that being provided with valve at the pipeline of fluid inlet and liquid outlet, is pollutent to be carried out batch type process.
4. with laser catalyzed degradation organic pollutants method, be characterised in that:
(1) particle diameter of synthesis of nano gold composite magnetic is 5-100nm, and the composite magnetic kernel is Z 250, and shell is gold;
(2) add the nanometer gold composite magnetic in reactor, open laser generator, the laser wavelength of incidence scope is between 200nm-550nm, and pulse-repetition is 1-100Hz;
(3) open solenoid switch, open pressure lock, pass into the water body that contains pollutent, by valve sewage is carried out batch type and process.
5. method as claimed in claim 4, it is characterized in that nanometer gold composite magnetic preparation method is: commercially available nano gold sol is mixed with amidized ferriferrous oxide nanometer material after 24 hours as seed particles, after ultrapure water cleans, change in the Glass Containers, then add the 21.4ml ultrapure water, under the rapid stirring state, the chlorauric acid solution that adds 50 μ l 0.05M, the sodium citrate solution of 500 μ l 75mM, the last sodium borohydride that adds rapidly 250 μ l 100mM stirs, until color no longer changes.
6. method as claimed in claim 4 is characterized in that regulating by control chlorauric acid solution concentration or seed concentration the thickness of golden shell.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104925897A (en) * | 2015-07-03 | 2015-09-23 | 江苏师范大学 | Magnetic field inductive type photocatalytic reactor and degradation use method therefor |
| CN105218689A (en) * | 2015-11-06 | 2016-01-06 | 河南工业大学 | A kind of laser treatment prepares the device of modified starch |
| CN105850991A (en) * | 2016-01-29 | 2016-08-17 | 华电电力科学研究院 | Preparation method for amino composite magnetic nano bacteria remover |
| CN106268860A (en) * | 2016-08-16 | 2017-01-04 | 盐城师范学院 | A kind of Au/Fe3o4nano load catalyst and its preparation method and application |
| CN107601780A (en) * | 2017-10-30 | 2018-01-19 | 成都新柯力化工科技有限公司 | A kind of method using laser treatment ammonia nitrogen in sewage organic matter |
| CN111505072A (en) * | 2020-04-15 | 2020-08-07 | 浙江大学 | Portable laser catalysis detection device and method |
| CN111533342A (en) * | 2020-05-12 | 2020-08-14 | 广德华东电子电路发展有限公司 | Photocatalytic device for organic wastewater |
| CN114349108A (en) * | 2021-12-16 | 2022-04-15 | 四川大学 | Method for degrading organic matters in wastewater based on laser catalysis |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104925897A (en) * | 2015-07-03 | 2015-09-23 | 江苏师范大学 | Magnetic field inductive type photocatalytic reactor and degradation use method therefor |
| CN105218689A (en) * | 2015-11-06 | 2016-01-06 | 河南工业大学 | A kind of laser treatment prepares the device of modified starch |
| CN105850991A (en) * | 2016-01-29 | 2016-08-17 | 华电电力科学研究院 | Preparation method for amino composite magnetic nano bacteria remover |
| CN106268860A (en) * | 2016-08-16 | 2017-01-04 | 盐城师范学院 | A kind of Au/Fe3o4nano load catalyst and its preparation method and application |
| CN107601780A (en) * | 2017-10-30 | 2018-01-19 | 成都新柯力化工科技有限公司 | A kind of method using laser treatment ammonia nitrogen in sewage organic matter |
| CN107601780B (en) * | 2017-10-30 | 2018-09-14 | 中国石油大学(华东) | A method of utilizing laser treatment ammonia nitrogen in sewage organic matter |
| CN111505072A (en) * | 2020-04-15 | 2020-08-07 | 浙江大学 | Portable laser catalysis detection device and method |
| CN111533342A (en) * | 2020-05-12 | 2020-08-14 | 广德华东电子电路发展有限公司 | Photocatalytic device for organic wastewater |
| CN114349108A (en) * | 2021-12-16 | 2022-04-15 | 四川大学 | Method for degrading organic matters in wastewater based on laser catalysis |
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Application publication date: 20130403 |