CN102992444A - Method for degrading organic wastewater by adopting active carbon-based microwave catalyst - Google Patents
Method for degrading organic wastewater by adopting active carbon-based microwave catalyst Download PDFInfo
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- CN102992444A CN102992444A CN2012105704416A CN201210570441A CN102992444A CN 102992444 A CN102992444 A CN 102992444A CN 2012105704416 A CN2012105704416 A CN 2012105704416A CN 201210570441 A CN201210570441 A CN 201210570441A CN 102992444 A CN102992444 A CN 102992444A
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Abstract
The invention relates to a method for degrading wastewater by adopting an active carbon-based microwave catalyst through catalytic oxidation under the microwave radiation. According to the technical scheme, the method comprises the steps of: using active carbon as a catalyst, or loading one or more metal oxides on the active carbon as a catalyst, then placing the catalyst in the organic wastewater, and degrading the organic wastewater by adopting the microwave radiation. The method provided by the invention can be used for continuously treating the wastewater through the microwave immobilizing catalyst. The method has the advantages of simpleness and easiness in operation, low investment and operation cost, small occupation area, thorough degradation, large range of concentration of degradable organic wastewater, and no secondary pollution, and is suitable for treating organic wastewater in industries such as printing and dyeing, papermaking, chemical engineering and pharmacy.
Description
Technical field
The present invention relates to a kind of method of absorbent charcoal based microwave catalyst degradation of organic waste water.
Background technology
Along with expanding economy, environmental pressure is also day by day heavy, especially water body environment.Environmental pollution is to a global significant challenge.Organic waste water colourity is dark, bio-refractory, complicated component.These organic pollutants flow in the water body, and water resources is subject to serious pollution, and human body is had potential danger.Since 1976, the aromatics in the trade effluent has appeared in the EPAs principal pollutant inventory.One of most important subclass waste water from dyestuff has caused very large attention in the pollutent.Process various waste water from dyestuff, be considered to one of the main task polluted that controls environment in the whole world.Because most organic compound contains phenyl ring and naphthalene nucleus usually, they can not be decomposed by traditional biological and chemical method easily.These compounds are considered to toxic pollutant, and they have potential danger to the mankind's health, must process it before discharge of wastewater.Therefore developing a kind of efficient, economic method of wastewater treatment is imminent.
The method that is used at present degradation of organic waste water mainly contains physisorphtion, biological decolouring method, ultrasound polyethylene-reducing solution, photocatalytic degradation method, microwave assisted photocatalysis edman degradation Edman, microwave and inorganic oxidizer oxidation style.Biological process, the treatment time is long, the pollutent in can not degradable waste water, absorption method can not degradation of contaminant, and just the state with them shifts, and photocatalysis degradation is only suitable for the processing of low-concentration organic waste water, and the treatment time is long.The ultrasonic degradation treatment time is long, and degradation efficiency is low.The microwave assisted photocatalysis edman degradation Edman its essence is with the mode of microwave-assisted and strengthens light-catalysed effect, does not still break away from photochemical catalysis fully, to a certain extent, but Reaction time shorten, but can not process high concentrated organic wastewater.
Microwave is a kind of energy that is comprised of Electric and magnetic fields, is a kind of hertzian wave, and wavelength is at 1mm-100cm, and frequency is 300MHz-300GMHz..In recent years, microwave exposure is at food sterilisation, and organic synthesis has obtained in the processing of analysis and extraction and environmental pollution seeing more and more widely and used.Microwave and inorganic oxidizer oxidation style, very large to the consumption of oxygenant, cause processing cost high, and the utilization ratio of oxygenant is low.
Summary of the invention
Long in order to overcome the treatment time that exists in the prior art, degradation efficiency is low, the high in cost of production problem, the present invention proposes a kind of method and a kind of new new microwave catalyst that is used for degradation of organic waste water of new degradation of organic waste water, adopt Catalyst And Method of the present invention, can effectively solve problems of the prior art, and scale is processed continuously, is easy to suitability for industrialized production.
The present invention adopts following technical scheme to realize:
A kind of method that adopts absorbent charcoal based microwave catalyst degradation of organic waste water, wherein absorbent charcoal based microwave catalyst is mixed with organic waste water, adopt microwave that organic waste water is carried out irradiation, described absorbent charcoal based microwave catalyst is the gac that gac or load have metal or metal oxide.
The method of the absorbent charcoal based microwave catalyst degradation of organic waste water of above-mentioned employing, wherein said metal is one or more in titanium, iron, cobalt, nickel, copper, magnesium, molybdenum, bismuth, the tungsten, and described metal oxide is one or more in the oxide compound of metal titanium, iron, cobalt, nickel, copper, magnesium, molybdenum, bismuth, tungsten.
The method of the absorbent charcoal based microwave catalyst degradation of organic waste water of above-mentioned employing, wherein the metal of load or metal oxide are the 1-10% of quality of activated carbon on gac.
The method of the absorbent charcoal based microwave catalyst degradation of organic waste water of above-mentioned employing, wherein said gac is processed through removal of impurities.
The method of the absorbent charcoal based microwave catalyst degradation of organic waste water of above-mentioned employing, wherein said remove impurity with active carbon processing comprises washes gac, boils drying step.
The method of the absorbent charcoal based microwave catalyst degradation of organic waste water of above-mentioned employing, wherein organic waste water is Methyl Orange in Wastewater, the concentration of Methyl Orange in Wastewater is 10-500mg/L.
The method of the absorbent charcoal based microwave catalyst degradation of organic waste water of above-mentioned employing, wherein the mass ratio of organism and microwave catalyst is 1: 2-440.
The method of the absorbent charcoal based microwave catalyst degradation of organic waste water of above-mentioned employing, wherein the power of microwave exposure is 200-800 watt, the time of microwave exposure is 2-30 minute.
The method of the absorbent charcoal based microwave catalyst degradation of organic waste water of above-mentioned employing wherein is filled in microwave catalyst composition microwave catalysis reaction bed in the microwave reaction pipe, and waste water is processed continuously.
The method of the absorbent charcoal based microwave catalyst degradation of organic waste water of above-mentioned employing, wherein the microwave catalysis reaction bed contains at least two sections microwave reaction pipes.
Adopt technical scheme of the present invention, can greatly improve degradation efficiency, and the treatment time greatly shorten, operation is simple, investment and running cost are low, floor space is few, and degraded is thorough, and the concentration range of degradable organic waste water is wide, scale is processed continuously, be easy to suitability for industrialized production, non-secondary pollution is applicable to print and dye, the processing of organic waste water in the industry such as papermaking, chemical industry, pharmacy.
Embodiment
The analytical procedure that adopts in the embodiment is: utilize ultraviolet spectrophotometer at the 270nm place absorbancy of solution to be measured, strength of solution and absorbancy are proportional as can be known by (formula 1), therefore can draw strength of solution, and calculate the solution degradation rate according to (formula 2).
A=αCL （1）
Wherein, A: optical density α: molar absorptivity, Lg-1cm-1; C: the concentration of solution, gL-1; L: absorber thickness, cm.
Wherein, C
0, C
tBe respectively tropeolin-D initial soln concentration and reacted concentration, mgL
-1
The microwave catalyst that uses in the specific embodiment of the invention is: gac, TiO
2-AC, CuO/AC.
TiO
2The preparation of-AC microwave catalyst: a certain amount of butyl (tetra) titanate is joined in the dehydrated alcohol that rapid stirring, continue to stir 30min, add a certain amount of methyl ethyl diketone, after the restir 30min, drip the mixing solutions of dehydrated alcohol and deionized water and concentrated nitric acid, after the dropping, stirring at low speed 2h, add the pretreated gac of 20g, stir 2h, putting into the ultrasonic 3h of ultrasonic cleaning machine.At this moment the gel with gained leaves standstill 24h, 80 ℃ of dry 20h.450 ℃ of calcining 2h.Namely get required loaded catalyst.
The preparation of CuO/AC catalyzer: at first the carrier granule gac is boiled cleaning, drying 12h with deionized water; Adopt pickling process with the gac incipient impregnation at cupric nitrate (Cu (NO3) 2) solution, at room temperature leave standstill behind the 12h dry; Dried sample is placed roasting 2h in the retort furnace, namely get experiment required catalyzer (CuO/AC).
Embodiment 1
The microwave catalyst that uses is gac: measure the Methyl Orange in Wastewater of 100mL100mg/L in the Erlenmeyer flask of 500mL, add catalyzer 1.8g, after at microwave power being the catalyzed reaction 6min under the condition of 600W, get supernatant liquor, with its absorbancy of ultraviolet-visible luminosity instrumentation, calculating its degradation rate is that degradation rate is 87.5%.
Embodiment 2
The microwave catalyst that uses is gac: measure the Methyl Orange in Wastewater of 100mL100mg/L in the Erlenmeyer flask of 500mL, add catalyzer 1.8g, after at microwave power being the catalyzed reaction 8min under the condition of 600W, get supernatant liquor, with its absorbancy of ultraviolet-visible luminosity instrumentation, calculating its degradation rate is that degradation rate is 91.5%.
Embodiment 3
The microwave catalyst that uses is gac: measure the Methyl Orange in Wastewater of 100mL100mg/L in the Erlenmeyer flask of 500mL, add catalyzer 1.8g, after at microwave power being the catalyzed reaction 10min under the condition of 600W, get supernatant liquor, with its absorbancy of ultraviolet-visible luminosity instrumentation, calculating its degradation rate is that degradation rate is 95%.
Embodiment 4
The microwave catalyst that uses is gac: measure the Methyl Orange in Wastewater of 100mL100mg/L in the Erlenmeyer flask of 500mL, add catalyzer 1.8g, after at microwave power being the catalyzed reaction 12min under the condition of 600W, get supernatant liquor, with its absorbancy of ultraviolet-visible luminosity instrumentation, calculating its degradation rate is that degradation rate is 96.7%.
Embodiment 5
Use microwave catalyst to be TiO
2-AC: measure the Methyl Orange in Wastewater of 100mL100mg/L in the Erlenmeyer flask of 500mL, add catalyzer 1.8g, at microwave power be the catalyzed reaction 8min under the condition of 600W after, get supernatant liquor, with its absorbancy of ultraviolet-visible luminosity instrumentation, calculating its degradation rate is that degradation rate is 94.9%.
Embodiment 6
Use microwave catalyst to be TiO
2-AC: measure the Methyl Orange in Wastewater of 100mL100mg/L in the Erlenmeyer flask of 500mL, add catalyzer 1.8g, after at microwave power being the catalyzed reaction 12min under the condition of 600W, get supernatant liquor, with its absorbancy of ultraviolet-visible luminosity instrumentation, calculating its degradation rate is that degradation rate is 98.9%.
Embodiment 7
Use microwave catalyst to be TiO
2-AC: measure the Methyl Orange in Wastewater of 100mL50mg/L in the Erlenmeyer flask of 500mL, add catalyzer 1.8g, at microwave power be the catalyzed reaction 12min under the condition of 600W after, get supernatant liquor, with its absorbancy of ultraviolet-visible luminosity instrumentation, calculating its degradation rate is that degradation rate is 99.1%.
Embodiment 8
Use microwave catalyst to be TiO
2-AC: measure the Methyl Orange in Wastewater of 100mL250mg/L in the Erlenmeyer flask of 500mL, add catalyzer 1.8g, after at microwave power being the catalyzed reaction 12min under the condition of 600W, get supernatant liquor, with its absorbancy of ultraviolet-visible luminosity instrumentation, calculating its degradation rate is that degradation rate is 84.7%.
Embodiment 9
Use microwave catalyst to be TiO
2-AC: measure the Methyl Orange in Wastewater of 100mL100mg/L in the Erlenmeyer flask of 500mL, add catalyzer 0.6g, after at microwave power being the catalyzed reaction 12min under the condition of 600W, get supernatant liquor, with its absorbancy of ultraviolet-visible luminosity instrumentation, calculating its degradation rate is that degradation rate is 63.2%.
Embodiment 10
Use microwave catalyst to be TiO
2-AC: measure the Methyl Orange in Wastewater of 100mL100mg/L in the Erlenmeyer flask of 500mL, add catalyzer 2.2g, after at microwave power being the catalyzed reaction 10min under the condition of 600W, get supernatant liquor, with its absorbancy of ultraviolet-visible luminosity instrumentation, calculating its degradation rate is that degradation rate is 99.2%.
Embodiment 11
Use microwave catalyst to be TiO
2-AC: measure the Methyl Orange in Wastewater of 100mL100mg/L in the Erlenmeyer flask of 500mL, add catalyzer 1.8g, at microwave power be the catalyzed reaction 12min under the condition of 200W after, get supernatant liquor, with its absorbancy of ultraviolet-visible luminosity instrumentation, calculating its degradation rate is that degradation rate is 90%.
Embodiment 12
Use microwave catalyst to be TiO
2-AC: measure the Methyl Orange in Wastewater of 100mL100mg/L in the Erlenmeyer flask of 500mL, add catalyzer 1.8g, after at microwave power being the catalyzed reaction 12min under the condition of 800W, get supernatant liquor, with its absorbancy of ultraviolet-visible luminosity instrumentation, calculating its degradation rate is that degradation rate is 99.1%.
Embodiment 13
Use microwave catalyst to be TiO
2-AC: measure the Methyl Orange in Wastewater of 100mL250mg/L in the Erlenmeyer flask of 500mL, microwave power is 600W, and catalyst levels is 1.8g.Catalyzed reaction under microwave condition.Microwave exposure 28min, the degradation rate of organic waste water tropeolin-D are 99.5%.
Embodiment 14
Use microwave catalyst to be CuO-AC: measure the Methyl Orange in Wastewater of 100mL250mg/L in the Erlenmeyer flask of 500mL, microwave power is 600W, and catalyst levels is 1.8g.Catalyzed reaction under microwave condition.Microwave exposure 28min, the degradation rate of organic waste water tropeolin-D are 99.7%.
Embodiment 15
Use microwave catalyst to be CuO-AC: measure the Methyl Orange in Wastewater of 100mL250mg/L in the Erlenmeyer flask of 500mL, microwave power is 600W, and catalyst levels is 1.8g.Catalyzed reaction under microwave condition.Microwave exposure 28min, the degradation rate of organic waste water tropeolin-D are 99.5%.
Reference examples 1
Use microwave catalyst to be TiO
2-AC: measure the Methyl Orange in Wastewater of 100mL50mg/L in the Erlenmeyer flask of 500mL, catalyst levels is 1.8g.Do not having to adsorb 30min under the room temperature under the microwave condition, the absorption degradation rate of organic waste water tropeolin-D is no more than 20%.
The Data Comparison result of above-described embodiment and reference examples is referring to table 1
Table 1
Claims (10)
1. method that adopts absorbent charcoal based microwave catalyst degradation of organic waste water, it is characterized in that absorbent charcoal based microwave catalyst is mixed with organic waste water, adopt microwave that organic waste water is carried out irradiation, described absorbent charcoal based microwave catalyst is the gac that gac or load have metal or metal oxide.
2. the method for the absorbent charcoal based microwave catalyst degradation of organic waste water of employing as claimed in claim 1, it is characterized in that described metal is one or more in titanium, iron, cobalt, nickel, copper, magnesium, molybdenum, bismuth, the tungsten, described metal oxide is one or more in the oxide compound of metal titanium, iron, cobalt, nickel, copper, magnesium, molybdenum, bismuth, tungsten.
3. the method for the absorbent charcoal based microwave catalyst degradation of organic waste water of employing as claimed in claim 1 is characterized in that the metal of load on gac or metal oxide are the 1-10% of quality of activated carbon.
4. the method for the absorbent charcoal based microwave catalyst degradation of organic waste water of employing as claimed in claim 1 is characterized in that described gac is through the removal of impurities processing.
5. the method for the absorbent charcoal based microwave catalyst degradation of organic waste water of employing as claimed in claim 4 is characterized in that described remove impurity with active carbon is processed and comprises gac is washed, and boils drying step.
6. the method for the absorbent charcoal based microwave catalyst degradation of organic waste water of employing as claimed in claim 1 is characterized in that organic waste water is Methyl Orange in Wastewater, and the concentration of Methyl Orange in Wastewater is 10-500mg/L.
7. the method for the absorbent charcoal based microwave catalyst degradation of organic waste water of employing as claimed in claim 1, the mass ratio that it is characterized in that organism and microwave catalyst is 1: 2-450.
8. the method for the absorbent charcoal based microwave catalyst degradation of organic waste water of employing as claimed in claim 1, the power that it is characterized in that microwave exposure is 200-800 watt, the time of microwave exposure is 2-30 minute.
9. the method for the absorbent charcoal based microwave catalyst degradation of organic waste water of employing as claimed in claim 1 is characterized in that microwave catalyst is filled in composition microwave catalysis reaction bed in the microwave reaction pipe, and waste water is processed continuously.
10. the method for the absorbent charcoal based microwave catalyst degradation of organic waste water of employing as claimed in claim 9 is characterized in that the microwave catalysis reaction bed contains at least two sections microwave reaction pipes.
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| CN103433047A (en) * | 2013-08-28 | 2013-12-11 | 无锡优胜美迪环保科技有限公司 | Preparation method for samarium oxide-modified supported iron oxide microwave catalyst and application for of same in sterilization and algae killing |
| CN103663609A (en) * | 2013-12-26 | 2014-03-26 | 湘潭大学 | Method for treating high-COD (chemical oxygen demand) organic wastewater through microwave catalytic oxidation |
| CN104437553A (en) * | 2014-12-29 | 2015-03-25 | 湘潭大学 | Microwave catalyst, preparation method and application thereof |
| CN104549279A (en) * | 2014-11-06 | 2015-04-29 | 青岛科技大学 | Preparation method and application of microwave-assisted Fenton catalyst for degrading methyl orange printing and dyeing wastewater |
| CN105060364A (en) * | 2015-07-31 | 2015-11-18 | 山东大学 | Organic wastewater in situ treatment fixed bed, and treatment apparatus and treatment method thereof |
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| CN107486150A (en) * | 2017-08-21 | 2017-12-19 | 吉林大学 | A kind of preparation method for being used to cooperate with the activated carbon of microwave degradation coking chemical waste water |
| CN107487810A (en) * | 2017-08-14 | 2017-12-19 | 北京金泽环境能源技术研究股份有限公司 | A kind of method of microwave irradiation organic wastewater |
| CN107986382A (en) * | 2017-12-07 | 2018-05-04 | 北京科瑞博远科技有限公司 | A kind of method of microwave irradiation high concentrated organic wastewater |
| CN108404927A (en) * | 2018-03-13 | 2018-08-17 | 湘潭大学 | The method of dye wastewater degradation catalyst, preparation method and degrading waste water |
| CN109012740A (en) * | 2018-08-22 | 2018-12-18 | 国家能源投资集团有限责任公司 | Molecular sieve catalyst, preparation method and application for microwave catalysis oxidation processing organic wastewater |
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