CN104549279B - Microwave helps the preparation and application of Fenton-like degraded methyl orange dyeing waste water catalyst - Google Patents
Microwave helps the preparation and application of Fenton-like degraded methyl orange dyeing waste water catalyst Download PDFInfo
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- CN104549279B CN104549279B CN201410620523.6A CN201410620523A CN104549279B CN 104549279 B CN104549279 B CN 104549279B CN 201410620523 A CN201410620523 A CN 201410620523A CN 104549279 B CN104549279 B CN 104549279B
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Abstract
The invention discloses the preparation and application that a kind of microwave helps Fenton-like degraded methyl orange dyeing waste water catalyst.The technical scheme is that it is carbon source in LaNiO to use methane3The by-product impurities carbon that in-situ deposition prepares CNT on presoma is raw material, as carrier after purified processing, loads α iron oxide active components by infusion process, then this catalyst is put into methyl orange stimulated dye wastewater, adds appropriate H2O2, methyl orange is degraded using microwave irradiation.The catalyst of the present invention has good microwave absorbing property in itself, while energy and H2O2Coupling forms heterogeneous Fenton-like system, so that concerted catalysis oxidation processes contain Methyl Orange in Wastewater, high catalytic efficiency.The present invention carbon it is ferric oxide catalyst carried also have magnetic, make it easier to separation and recovery, it is reusable.
Description
Technical field
Fenton-like degraded methyl is helped the present invention relates to the treatment technology of organic wastewater with difficult degradation thereby, more particularly to a kind of microwave
The preparation and application of orange dyeing waste water catalyst.
Background technology
The organic wastewater with difficult degradation thereby of high-level oxidation technology (Advanced Oxidation Process, AOPs) processing in recent years
The common concern of people is received, wherein Fenton methods can aoxidize a variety of Recalcitrant chemicals, senior as water treatment field
The study hotspot of oxidation technology.Although Fenton methods have, reactivity is strong, oxidation efficiency is high, reaction condition is gentle and operation letter
Single the advantages of, but due to reaction must carry out in acid condition, H2O2Utilization ratio is low, Fe (II) is difficult to reuse and produced
Secondary pollution problems, constrain the large-scale application of Fenton methods.It is many to solve the problems that Fenton reagent is present
Researcher proposes a variety of embryonic stem-like cells.
Microwave irradiation is another new high-level oxidation technology, with without hysteresis effect, without thermograde,
The advantages of degraded is soon and palliating degradation degree is high, it is ideal to the treatment effect of organic wastewater using the technology.By microwave and class
Fenton technologies are combined, and are an effective way (Zheng Huaili, microwave assisted embryonic stem-like cells for improving Fenton-like efficiency
Catalysis oxidation decolored degradation dye, rhodamine B.Spectroscopy and spectrum analysis, 2009；Wang Kunping, microwave induced AC/Cu, AC/Fe
It is catalyzed heterogeneous Fenton reaction catalytic degradation percolate.Environmental project journal, 2012).But for the class of the process
Fenton catalyst researches are still extremely limited, microwave assisted embryonic stem-like cells heterogeneous catalyst few in number be typically all with
Aluminum oxide, titanium oxide and activated carbon are used as carrier.So far, domestic and foreign literature and patent there is no report to utilize CNT
The carbon impurity generated in preparation process is carrier, and load iron oxide helps class as multiphase type Fenton catalyst for microwave
Fenton reaction degraded dyeing waste waters.
The content of the invention
It is an object of the invention to provide the preparation that a kind of microwave helps Fenton-like degraded methyl orange dyeing waste water catalyst
Method, it is intended under microwave induced effect, improves the activity of the catalyst embryonic stem-like cells, so as to promote microwave and class
The extensive use that Fenton technologies are combined.
To achieve the above object, the present invention uses following technical scheme：
The by-product impurities carbon for using methane to prepare CNT for carbon source in-situ deposition is raw material, and purified rear be used as carries
Body, loads alpha-ferric oxide active component by infusion process, then this catalyst is put into methyl orange stimulated dye wastewater, plus
Enter appropriate H2O2, methyl orange is degraded using microwave irradiation.
The specific steps of above-mentioned catalyst preparation include：(1) with LaNiO3It is in situ heavy by carbon source of methane as presoma
Product prepares CNT, while by-product impurity carbon materials；(2) the 50mL nitration mixture (concentrated sulfuric acids are used:Concentrated nitric acid=3:1) purifying 1.5g is miscellaneous
Suction filtration is to neutrality after matter carbon material, and ultrasound 20h；(3) impurity carbon materials after purification are put into iron nitrate solution and impregnate 10
~20h；(4) 4h is dried at 100 DEG C, then in 2~5h of roasting at 300~500 DEG C.
The operating method of organic wastewater degraded process is：Methyl orange simulated wastewater is fitted into reactor, added in right amount
H2O2It is placed in micro-wave oven, is irradiated under certain microwave power with after catalyst.After reaction terminates, UV, visible light spectrophotometric is used
Meter determines its absorbance at 460nm, and according to the removal efficiency of absorbance calculating methyl orange.
Compared with prior art, advantages and positive effects of the present invention are：
(1) the by-product impurities carbon that the present invention uses CNT preparation process prepares load alpha-ferric oxide and urged for carrier
Agent.The catalyst has good absorbing property, is applied to microwave and helps in embryonic stem-like cells system, class can be greatly improved
Fenton methods handle the ability of organic wastewater.
(2) catalyst of the present invention for microwave when helping Fenton to handle organic wastewater, in neutral conditions with regard to that can reach
Good removal effect, and suitable for containing various organic wastewaters.
(3) catalyst of the present invention is separated and recovered using external magnetic field after use, and repeat performance is good.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of the by-product impurities carbon of CNT preparation process, wherein containing part carbon nanometer
Pipe.
Fig. 2 is the stereoscan photograph of the carbon load alpha-ferric oxide catalyst prepared in embodiment 1.
Fig. 3 is the XRD spectrums of the carbon load alpha-ferric oxide catalyst prepared in embodiment 1.
Fig. 4 is that different disposal method is contrasted to methyl orange removal effect.
The effect photo and catalyst that Fig. 5 is helped after Fenton-like degraded methyl orange dyeing waste water for microwave are under external magnetic field
Separation situation.
Embodiment
Technical scheme is described in further detail with reference to the accompanying drawings and detailed description, the present invention
It is not limited to these embodiments.
Embodiment 1
It will be equipped with 100mgLaNiO3Quartz boat be put into the flat-temperature zone of horizontal tube reactor, in N2The lower slow heating of protection
20%CH is passed through after to 750 DEG C4/N2, react and stop logical CH after 2.0h4, in N2Protection is lower to cool, in quartz boat and reaction tube
By-product impurities carbon is collected between wall, its scanning electron microscope analysis is as shown in Figure 1.
1.5g carbon impurities are taken, with the 50mL nitration mixture (concentrated sulfuric acids configured:Concentrated nitric acid=3:1) it is purified, and surpassed
Suction filtration is to neutrality after sound 20h.Take 2.43gFe (NO3)3·9H2O adds in 20mL deionized waters the Fe for preparing 0.2mol/L3+It is molten
Liquid, be put into after purification carbon impurity dipping 20h, at 100 DEG C dry 4h, then in being calcined 2h at 400 DEG C, that is, obtain carbon carry α-
Ferric oxide catalyst, its scanning electron microscope analysis are as shown in Figure 2.
By this catalyst applied to the processing of methyl orange stimulated dye wastewater.Measure the methyl orange that 50mL concentration is 20mg/L molten
Liquid is placed in reactor, adds 0.1g catalyst and 1mLH2O2, regulation pH value is 7, is subsequently placed in micro-wave oven, in microwave power
Taken out to be irradiated under the conditions of 700W after 4min, magnetic separation takes supernatant to be cooled to room temperature, with ultraviolet-uisible spectrophotometer in 460nm
Place determines its absorbance.As a comparison, microwave cooperating H has also been investigated2O2Fenton-like method is helped to methyl with traditional heating (80 DEG C)
The degradation effect of orange.As shown in figure 4, microwave cooperating H2O2Fenton-like method is helped to the degradation ten of methyl orange with traditional heating
Divide limited, and under microwave irradiation, the removal efficiency of methyl orange is up to 96.1%.As seen from Figure 5, simulated wastewater is by degraded
Decolourize substantially afterwards.Under external magnetic field, catalyst is easy to separate from reaction system.
Embodiment 2
By this catalyst applied to the processing of methyl orange stimulated dye wastewater.The concentration of methyl orange is changed to 100mg/L, other
Part is same as Example 1, and the removal efficiency of methyl orange is 79.7%.
Embodiment 3
By this catalyst applied to the processing of methyl orange stimulated dye wastewater.Methyl orange concentration is 100mg/L, and exposure time increases
6min is added to, other conditions are same as Example 1, the removal efficiency of methyl orange is 95.4%.
Embodiment 4
By this catalyst applied to the processing of methyl orange stimulated dye wastewater.Methyl orange concentration is 100mg/L, and exposure time is
6min, regulation pH value is 4, and other conditions are same as Example 1, and the removal efficiency of methyl orange is 98.9%.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than is limited；Although with reference to foregoing reality
Apply example the present invention is described in detail, for the person of ordinary skill of the art, can still implement to foregoing
Technical scheme described in example is modified, or carries out equivalent substitution to which part technical characteristic；And these are changed or replaced
Change, the essence of appropriate technical solution is departed from the spirit and scope of claimed technical solution of the invention.
Claims (6)
1. a kind of microwave helps the preparation method of Fenton-like degraded methyl orange dyeing waste water catalyst, it is characterised in that use methane
The by-product impurities carbon that CNT is prepared for carbon source in-situ deposition is raw material, it is purified after as carrier, it is negative by infusion process
Carry alpha-ferric oxide active component.
2. the preparation method of catalyst according to claim 1, it is characterised in that comprise the following steps：
(1) with LaNiO3As presoma, CNT is prepared by carbon source in-situ deposition of methane, while by-product impurity carbon materials；
(2) it is 3 with the 50mL concentrated sulfuric acids and concentrated nitric acid volume ratio:Taken out after 1 nitration mixture purifying 1.5g impurity carbon materials, and ultrasound 20h
Filter to neutrality；
(3) impurity carbon materials after purification are put into 10~20h of dipping in iron nitrate solution；
(4) 4h is dried at 100 DEG C, then in 2~5h of roasting at 300~500 DEG C.
3. the preparation method of catalyst according to claim 1, it is characterised in that contain carbon nanometer in part in impurity carbon materials
Pipe.
4. the preparation method of catalyst according to claim 1, it is characterised in that removed by purifying in impurity carbon materials
Agraphitic carbon, while some oxygen-containing functional groups are produced on its surface, so as to be conducive to the load of alpha-ferric oxide.
5. the preparation method of catalyst according to claim 1, it is characterised in that carbon carrier and alpha-ferric oxide are all good
Absorbing material, iron oxide makes catalyst have magnetic.
6. microwave according to claim 1 helps the application of Fenton-like degraded methyl orange dyeing waste water catalyst, its feature
It is by microwave, H2O2Methyl orange degradation can be small organic molecule by the degraded system constituted with catalyst or mineralising is CO2With
H2O。
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| CN201410620523.6A CN104549279B (en) | 2014-11-06 | 2014-11-06 | Microwave helps the preparation and application of Fenton-like degraded methyl orange dyeing waste water catalyst |
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| CN104549279B true CN104549279B (en) | 2017-08-15 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228832A (en) * | 2011-05-06 | 2011-11-02 | 重庆理工大学 | Preparation method of solid acid Fenton catalyst for processing methyl orange waste water |
| CN102992444A (en) * | 2012-12-25 | 2013-03-27 | 湘潭大学 | Method for degrading organic wastewater by adopting active carbon-based microwave catalyst |
| CN103084216A (en) * | 2012-12-25 | 2013-05-08 | 湘潭大学 | Microwave catalyst for degrading organic wastewater and catalytic oxidation degradation method thereof |
| CN103203234A (en) * | 2013-04-23 | 2013-07-17 | 北京化工大学 | Preparation method of high-dispersion supported nano metal Fe-based catalyst |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228832A (en) * | 2011-05-06 | 2011-11-02 | 重庆理工大学 | Preparation method of solid acid Fenton catalyst for processing methyl orange waste water |
| CN102992444A (en) * | 2012-12-25 | 2013-03-27 | 湘潭大学 | Method for degrading organic wastewater by adopting active carbon-based microwave catalyst |
| CN103084216A (en) * | 2012-12-25 | 2013-05-08 | 湘潭大学 | Microwave catalyst for degrading organic wastewater and catalytic oxidation degradation method thereof |
| CN103203234A (en) * | 2013-04-23 | 2013-07-17 | 北京化工大学 | Preparation method of high-dispersion supported nano metal Fe-based catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 《磺化碳材料固载Fe~(2+)催化甲基橙降解反应》;曲振平等;《催化学报》;20090228;第30卷(第2期);制备方法一节 * |
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