CN101423261A - Method and device for degradation of contaminant by microwave reinforcement catalytic wet-type oxidation - Google Patents
Method and device for degradation of contaminant by microwave reinforcement catalytic wet-type oxidation Download PDFInfo
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- CN101423261A CN101423261A CNA2007100475886A CN200710047588A CN101423261A CN 101423261 A CN101423261 A CN 101423261A CN A2007100475886 A CNA2007100475886 A CN A2007100475886A CN 200710047588 A CN200710047588 A CN 200710047588A CN 101423261 A CN101423261 A CN 101423261A
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Abstract
The invention discloses a microwave enhanced catalytic wet-typed oxidation method of mild and rapid reaction conditions, and high-effective pollutant degradation. The method can make use of the high thermal efficiency function of the microwave and cause the reaction to be carried out at the mild conditions close to moderate temperature and pressure by adding the oxide of variable valence transition state metal. Compared with the traditional catalytic wet-typed oxidation method which needs high temperature (180-315 DEG C) and high-voltage (2-25MPa) reaction conditions, the microwave enhanced catalytic wet-typed oxidation reaction can be carried out at the temperature of 50-80 DEG C and under the pressure of 0.2-0.5MPa; the removal rate for the total organic pollutants (TOC) of the pollutants can reach over 90 percent; the reaction time is 1/4-1/6 of the required time of the traditional catalytic wet-typed oxidation method at the same temperature and pressure; and simultaneously, the invention also designs a special treatment device which uses the method. The method is not only rapid and high effective, but also has the advantages of green oxidation and wide prospect.
Description
Technical field
The invention belongs to the green technology process field, be mainly used in the processing of pollutant effluents.
Background technology
Along with the development of industrial economy, organic pollutant presents the characteristics that make new advances: kind is many, complex structure, toxicity big, the difficult for biological degradation composition is many, concentration is high.Explore the efficient catalyzed oxidation technology of handling poisonous and harmful, bio-refractory pollutent, be the focus of home and abroad environment area research always.
Catalytic Wet Oxidation technology (Catalytic Wet Oxidation, abbreviation CWO) pollutent for many bio-refractories has good degradation effect, so be widely used in the processing of various industrial sewage such as coking chemical waste water, phenolic wastewater, waste water from dyestuff, paper waste, this technology is compared with other traditional chemical sewage oxidation treatment technology, has outstanding advantage such as efficient height, non-secondary pollution.But the greatest problem that this technology exists is: oxidation reaction condition requires harsh, must under high temperature (180-315 ℃) and high pressure (2-25MPa) condition, carry out, this makes this The Application of Technology and popularization be greatly limited, therefore, how to reduce the degradation technique requirement, impel reaction to realize seeming particularly important at mild conditions.
At present, as a kind of transmission medium and heating energy source, microwave has been widely used in every field, as carbothermic reduction, microwave-assisted drying and dehydration, the microwave auxiliary extraction etc. of microwave high-temperature heating, the polishing of microwave-assisted ore, microwave-assisted metal oxide.Simultaneously, microwave technology is introduced in fields such as environmental purification, Pollutant Treatment gradually, as oil removal of impurities, purifying air, regeneration of activated carbon reaction, sewage disposal etc., compares traditional heating mode, and the microwave technology heating efficiency is higher.At present, microwave technology is used for the catalytic wet air oxidation Research on degradation still belongs to the starting stage, the greatest problem of existence is that degradation temperature and pressure are still higher, does not more have sophisticated microwave degradation device.In existing research, because catalyzer is gac or metallic iron etc., a little less than the absorption to microwave, microwave only plays the effect of quick raising system temperature, castering action to catalyst activity is very little, can't realize the catalyst activation of lesser temps, so degradation condition is still very high.
Summary of the invention
The objective of the invention is to solve the problem that conventional catalyst wet oxidation technology exists needs the harsh reaction conditions of High Temperature High Pressure, impel this advanced oxidation degradation technology to be able under mild conditions, realize, further improve the degradation rate and the degradation efficiency of this method simultaneously near normal temperature and pressure.
For solving the harsh problem of degradation condition that conventional catalyst wet oxidation technology exists, the present invention combines with the Catalytic Wet Oxidation technology by microwave, and by suitable variable valency metal oxide catalyst, makes DeR to realize under mild conditions.Because adopt the type of heating of microwave " from inside to outside " to replace the direct intensification type of heating of tradition " from outside to inside ", simultaneously, metal oxide catalyst can absorb the energy of microwave transfer, has strengthened catalyst activity, has improved the degradation property of system.Microwave heating has clear superiority to the performance that strengthens the variable valency metal oxide catalyst: on the one hand, it is faster to the absorption of microwave energy that metal oxide catalyst is compared solution, very fast intensification under microwave action, with liquid phase formation temperature gradient, the situation lower at liquidus temperature is issued to activation, makes DeR be carried out under this condition; On the other hand, metal oxide catalyst can reach very high temperature in the short period of time under microwave action, forms catalysis " focus ", and catalytic activity significantly strengthens, and quickens H
2O
2Decomposition reaction, thereby the degradation property of raising system.
The present invention for the catalytic wet air oxidation specialized designs that realizes the microwave-assisted heating a kind of device, comprise microwave generating apparatus, reaction unit, protector, temperature and pressure control device, rotary-tray.The principal character of this device is reactor and temperature and pressure control device.Reactor adopts polytetrafluoroethylmaterial material to make, and is difficult for by chemical substance corrosion in the waste water and has heatproof pressing performance, is divided into reaction tank and reaction tank lid; Be provided with the catalytic reaction bed in the reaction tank, be used to sprawl the oxide catalyst particle that appraises at the current rate, can carry out solid water simultaneously again and separate.For the ease of the control reaction, need to install temperature and pressure transmitter and control securing system, be convenient to online detected temperatures and pressure, and prevent that temperature and pressure is too high.For the degraded sample is heated evenly, rotary-tray is installed at the device orlop.
The present invention prepares copper oxide granule type catalyzer.At first, prepare the copper oxide nanoparticle, again it is mixed with polymeric dispersant, obtain viscous paste, then slurry is injected the spherical ceramic mould, get the granule type metal oxide catalyst through super-dry, roasting by the rapid precipitation method.This catalyzer not only has nano-metal-oxide to H
2O
2The strong catalytic performance of decomposition reaction, and because particle size is bigger, be easy to separate after reaction finishes.
The method of above-mentioned degradation of contaminant by microwave reinforcement catalytic wet-type oxidation, specifically: according to Catalytic Wet Oxidation reaction configuration reactant, and the adding catalyzer, adopt microwave radiation to replace traditional heating mode, oxidative degradation pollutent under near the mild conditions of normal temperature and pressure.
Method wherein as mentioned above: catalyzer is the oxide compound of transiting state metal of appraising at the current rate, and comprises CuO, F
2O
3, MnO
2
Method is wherein as mentioned above: catalyzer is an oxide nano-particles, catalyzer be particle diameter between 10-30nm, the particle diameter of sintered particles is between 0.5-1cm.
Method wherein as mentioned above: the amount ratio of catalyzer and reaction system total amount is between 0.3/ ‰-0.8/ ‰.
Method wherein as mentioned above: after catalyzed reaction finishes, by catalytic bed in the reactor catalyst solid is separated with waste water, reclaim catalyzer.
Method wherein as mentioned above: temperature of reaction is between 50-80 ℃, and pressure is between 0.2-0.5MPa, and the reaction times is between 5-50min.
Method wherein as mentioned above: pollutent is the aromatics pollutent; The aromatics pollutent comprises phenol, para-chlorophenol.
Method wherein as mentioned above: microwave output power is between 200-600W, and operating frequency is between 2000-3000MHz.
The treatment unit of degradation of contaminant by microwave reinforcement catalytic wet-type oxidation comprises: reactor, temperature and pressure detection control apparatus, protector and rotary-tray; Reactor is divided into reaction tank and reaction tank lid, it is characterized in that: also comprise the microwave generating apparatus that is installed in the reactor outside, and be located at the catalytic reaction bed in the reaction tank, be used to sprawl granules of catalyst, be used for the solid water lock out operation simultaneously after reaction.
Device wherein as mentioned above: the protective sleeve of this reactor and temperature, pressure detection control device adopts polytetrafluoroethylmaterial material to be processed into.
The present invention has following advantage:
1. the present invention adopts microwave heating to replace the common heating mode, and carries out catalysis by suitable variable valency metal oxide compound, makes Catalytic Wet Oxidation be reflected under the gentle condition and realizes.The conventional catalyst wet oxidation reaction generally needs to carry out under high temperature (180-315 ℃) and high pressure (2-25MPa) condition, microwave reinforced Catalytic Wet Oxidation reaction of the present invention can be carried out under 50-80 ℃ of temperature and 0.2-0.5MPa pressure, near normal temperature and pressure, the reaction conditions gentleness.
2. catalyzer of the present invention is Cu, Fe, the Mn transiting state metal oxide particle that appraises at the current rate, and the technical oxide material for common obtains easily.After catalyzed reaction finishes, by catalytic bed in the reactor catalyst solid is separated with waste water, be difficult for running off.
3. the corpuscular transiting state metal oxide catalyst that appraises at the current rate is subjected to microwave action to form catalysis " focus " in reaction system, and catalytic activity strengthens, and makes the speed of contaminant degradation reaction and efficient all significantly improve.The total organic carbon of pollutent (TOC) clearance can reach more than 90%, the reaction times be the conventional catalyst wet oxidation process under uniform temp and pressure required time 1/4～1/6.
4. the method for microwave reinforced-variable valency metal oxide compound Catalytic Wet Oxidation is passed through catalyzing and decomposing H
2O
2, generate the hydroxyl radical free radical that has strong oxidizing property in a large number, make the final oxygenolysis of pollutent become CO
2And water, in degradation process, there are not other toxic and harmful or intermediate product discharging.Therefore, the inventive method is not only a kind of oxidation technology rapidly and efficiently, and has green oxidation processing advantage, has broad application prospects.
Description of drawings
Fig. 1 is the isolated plant synoptic diagram that microwave reinforced catalytic wet air oxidation is handled pollutent.
Embodiment
As shown in Figure 1, this isolated plant comprises microwave generating apparatus (1), reaction tank (6), reaction tank lid (4), temperature and pressure transmitter (2), control device (9), pipe lid (3), sleeve pipe (5), the rotary-tray (8) that is installed in the reaction tank outside.Reactor need adopt polytetrafluoroethylmaterial material to process, and is difficult for by chemical substance corrosion in the waste water and has heatproof pressing performance, is divided into reaction tank (6) and reaction tank lid (4); Be provided with catalytic reaction bed (7) in the reaction tank, be used to sprawl variable valency metal oxide catalyst particle, can carry out solid water simultaneously again and separate.For the ease of the control reaction, need to install temperature and pressure transmitter and control device; Sleeve pipe and casing cover are the protectors that prevents that temperature and pressure is too high; The rotary-tray device is used for making the degraded sample to be heated evenly.
(1) preparation of nanometer CuO particle.
At first, adopt the rapid chemical precipitator method to prepare nanometer CuO particle.At room temperature the 0.4g polyoxyethylene glycol is dissolved in the CuSO of the 0.1mol/L of 100mL
4In the aqueous solution, add the Na of the 0.1mol/L of 100mL fast
2CO
3The aqueous solution stirs, and question response is abundant, aging 20min, and suction filtration, drying is 2 days under 60 ℃, 250 ℃ of following roastings 3 hours, can reach nanometer CuO particle, and particle diameter is at 10-30nm.
Then, for the ease of the carrying of catalytic reaction bed, nanometer CuO particle preparation must be become shaped granule.Specifically: adopting poly carboxylic acid amine is dispersion agent, and with nanometer CuO mix particles, control fractional solid volume 30%-50% adjusts slurry pH=10 with the NaOH aqueous solution of 0.5mol/L.Then slurry is injected the spherical ceramic mould, drying at room temperature 24h in 600 ℃ of following roastings, obtains the CuO beaded catalyst again, and grain diameter is 0.5-1cm.
(2) microwave reinforced catalysis wet-type oxidation degradation phenol experiment
With deionized water phenol is mixed with the high density simulated wastewater that concentration is 1000mg/L; With mass concentration is 10 times of 30% hydrogen peroxide solution dilutions, obtains 3% hydrogen peroxide solution.The phenol degrading experiment is in the microwave generator (output rating: 400W of repacking, operating frequency: carry out 2450MHz), get high concentration phenol waste water 250mL respectively, 3% hydrogen peroxide 60mL, CuO beaded catalyst 0.120g joins in the reaction tank, and be dispersed on the reaction bed, cover the reaction tank lid, then reaction tank is put into sleeve pipe, screw casing cover, (transmitter has the tetrafluoroethylene jacket layer outward to connect the temperature and pressure transmitter, directly do not contact) with solution, be fixed on the rotary-tray, adjusting temperature by control device is 60 ℃, and pressure is 0.3MPa, starter gear carries out oxidative degradation then.Adopt TOC instrument (day island proper Tianjin company's T OC-VCPN type) that the solution of different degradation times is carried out TOC (total content of organic carbon) mensuration.The result shows that degradation time is that the TOC clearance of 0.5min, 5min, 15min sample reaches 45.6%, 83.5%, 90.8% respectively.Under identical degradation condition, adopt direct-fired conventional catalyst wet oxidation process to handle phenolic waste water, degradation time is that the TOC clearance of 0.5min, 5min, 15min sample is respectively 9.5%, 17.4%, 36.0%, is starkly lower than micro ware auxiliary catalysis wet oxidation method.
(1) preparation of CuO beaded catalyst.
With embodiment 1.
(2) microwave reinforced catalysis wet-type oxidation degradation para-chlorophenol experiment.
In the degradation experiment, the concentration of para-chlorophenol is 100mg/L, sampling amount is 250mL, 3% hydrogen peroxide add-on is 6mL, the add-on of CuO beaded catalyst is 0.100g, the degraded operation is identical with embodiment 1, and the result shows that degradation time is the TOC clearance difference 35.0%, 772%, 85.5% of 0.5min, 5min, 15min sample.
Claims (10)
1. the method for degradation of contaminant by microwave reinforcement catalytic wet-type oxidation, it is characterized in that: according to Catalytic Wet Oxidation reaction configuration reactant, and the adding catalyzer, adopt microwave radiation to replace traditional heating mode, oxidative degradation pollutent under near the mild conditions of normal temperature and pressure.
2. the method for claim 1 is characterized in that: catalyzer is the oxide compound of transiting state metal of appraising at the current rate, and comprises CuO, F
2O
3, MnO
2
3. method as claimed in claim 2 is characterized in that: catalyzer is a metal oxide nanoparticles, and nano particle diameter is 10-30nm, and the particle diameter of sintered particles is between 0.5-1cm.
4. as arbitrary described method among the claim 1-3, it is characterized in that: the amount ratio of catalyzer and reaction system total amount is between 0.3/ ‰-0.8/ ‰.
5. as arbitrary described method among the claim 1-3, it is characterized in that: after catalyzed reaction finishes, catalyst solid is separated with waste water, reclaim catalyzer by catalytic bed in the reactor.
6. as arbitrary described method among the claim 1-3, it is characterized in that: temperature of reaction is between 50-80 ℃, and pressure is between 0.2-0.5MPa, and the reaction times is between 5-50min.
7. as arbitrary described method among the claim 1-3, it is characterized in that: pollutent is the aromatics pollutent; The aromatics pollutent comprises phenol, para-chlorophenol.
8. as arbitrary described method among the claim 1-3, it is characterized in that: microwave output power is between 200-600W, and operating frequency is between 2000-3000MHz.
9. the treatment unit of degradation of contaminant by microwave reinforcement catalytic wet-type oxidation comprises: reactor, temperature and pressure detection control apparatus, protector and rotary-tray; Reactor is divided into reaction tank and reaction tank lid, it is characterized in that: also comprise the microwave generating apparatus that is installed in the reactor outside, and be located at the catalytic reaction bed in the reaction tank, be used to sprawl granules of catalyst, be used for the solid water lock out operation simultaneously after reaction.
10. as device as described in the claim 9, it is characterized in that: this reactor, protector adopt polytetrafluoroethylmaterial material to be processed into.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103359810A (en) * | 2012-03-30 | 2013-10-23 | 中国石油化工股份有限公司 | Wastewater treatment method |
| CN103739035A (en) * | 2014-01-06 | 2014-04-23 | 山东大学 | Rapid microwave treatment method of dye wastewater |
| CN104857897A (en) * | 2014-02-20 | 2015-08-26 | 通恒环保科技(上海)有限公司 | Catalytic wet oxidation apparatus reactor |
| CN105174423A (en) * | 2015-07-16 | 2015-12-23 | 南京工业大学 | Coal chemical and biochemical tail-water treatment method |
| CN107055892A (en) * | 2017-03-07 | 2017-08-18 | 南京工业大学 | The method that various metals compounding micro ware auxiliary catalysis aoxidizes brewing wastewater biochemical tail water |
| CN108975448A (en) * | 2018-10-11 | 2018-12-11 | 北京石油化工学院 | Magnetron built-in microwave strengthens heterogeneous catalysis/adsorbent fluidization bed waste water treatment system |
| CN110065991A (en) * | 2019-04-28 | 2019-07-30 | 山东大学 | A kind of technology of efficient process organic wastewater-microwave catalysis wet oxidation method |
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2007
- 2007-10-30 CN CNA2007100475886A patent/CN101423261A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103359810A (en) * | 2012-03-30 | 2013-10-23 | 中国石油化工股份有限公司 | Wastewater treatment method |
| CN103739035A (en) * | 2014-01-06 | 2014-04-23 | 山东大学 | Rapid microwave treatment method of dye wastewater |
| CN103739035B (en) * | 2014-01-06 | 2016-01-20 | 山东大学 | A kind of Rapid microwave treatment method of waste water from dyestuff |
| CN104857897A (en) * | 2014-02-20 | 2015-08-26 | 通恒环保科技(上海)有限公司 | Catalytic wet oxidation apparatus reactor |
| CN105174423A (en) * | 2015-07-16 | 2015-12-23 | 南京工业大学 | Coal chemical and biochemical tail-water treatment method |
| CN107055892A (en) * | 2017-03-07 | 2017-08-18 | 南京工业大学 | The method that various metals compounding micro ware auxiliary catalysis aoxidizes brewing wastewater biochemical tail water |
| CN107055892B (en) * | 2017-03-07 | 2020-10-09 | 南京工业大学 | Method for microwave-assisted catalytic oxidation of biochemical tail water of brewing wastewater by compounding of multiple metals |
| CN108975448A (en) * | 2018-10-11 | 2018-12-11 | 北京石油化工学院 | Magnetron built-in microwave strengthens heterogeneous catalysis/adsorbent fluidization bed waste water treatment system |
| CN108975448B (en) * | 2018-10-11 | 2023-10-13 | 北京石油化工学院 | Magnetron built-in microwave reinforced multiphase catalysis/adsorption fluidized bed sewage treatment system |
| CN110065991A (en) * | 2019-04-28 | 2019-07-30 | 山东大学 | A kind of technology of efficient process organic wastewater-microwave catalysis wet oxidation method |
| CN110065991B (en) * | 2019-04-28 | 2021-09-14 | 山东大学 | Microwave catalytic wet oxidation method for efficiently treating organic wastewater |
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Open date: 20090506 |