CN106140137A - Microwave catalysis degradation of organic waste water catalyst and the method processing organic wastewater - Google Patents
Microwave catalysis degradation of organic waste water catalyst and the method processing organic wastewater Download PDFInfo
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- CN106140137A CN106140137A CN201610482600.5A CN201610482600A CN106140137A CN 106140137 A CN106140137 A CN 106140137A CN 201610482600 A CN201610482600 A CN 201610482600A CN 106140137 A CN106140137 A CN 106140137A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
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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
- C02F1/302—Treatment of water, waste water, or sewage by irradiation with microwaves
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/38—Organic compounds containing nitrogen
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The present invention provides a kind of microwave catalysis degradation of organic waste water catalyst, and catalyst includes that metal-oxide, described metal-oxide are the metal-oxide of bismuth-containing.The catalyst of the present invention can fully absorb microwave and the generation electron hole pair that is excited, hydrone in organic wastewater is combined with strong electrophilic hole thus the hydroxyl radical free radical isoreactivity oxygen species that produces act as the oxidant of degradation reaction, it is achieved the efficient degradation of organic wastewater.The present invention also provides for the processing method of a kind of organic wastewater, comprises the following steps: step A, mixed homogeneously with organic wastewater by catalyst；Step B, insert in microwave equipment, degrade under microwave exposure, be cooled to the waste liquid after room temperature i.e. obtains degraded.The processing method of the present invention is applicable to all waste water that the concentration of nitrophenols is 100 500mg/L, practical；Microwave exposure state modulator is convenient, and exposure time is short, and degradation rate can reach 99.2%, meets efficient demand.
Description
Technical field
The present invention relates to technical field of waste water processing, be specifically related to a kind of microwave catalysis degradation of organic waste water catalyst and
The method processing organic wastewater.
Background technology
Along with industrial expansion, environmental pollution is also on the rise, especially water environment pollution.
The shortcomings such as organic wastewater has that murder by poisoning is high, colourity deep, complicated component and bio-refractory, therefore, if these have
Machine waste water flows in rivers,lakes and seas, and water body can be caused heavily contaminated, thus the life that the serious threat mankind etc. are biological.
Many aromatic compounds in industrial wastewater are classified as priority pollutant by EPA and control in list, this
A little pollutant are essentially from the industries such as synthetic dyestuffs, pharmacy, petrochemical industry, fine chemistry industry, wherein nitrophenols extremely derivatives class
Pollutant have respiratory system and central nervous system's toxic, and biochemical degradation rate is low, and traditional processing method is difficult to meet
Pollutant catabolic gene requirement, Details as Follows: (1) physisorphtion, and having can not be fundamentally by the defect of contaminant degradation；(2)
Biological decolouring method, has time-consuming length and pollutant are difficult to degradable defect；(3) sonication, has time-consuming long and effect
The defect that rate is the highest；(4) photocatalytic degradation method, the waste water being only suitable for low colourity low concentration processes, and the longest, can not meet existing
Real demand；(5) microwave-assisted or strengthening photocatalytic method, energy consumption is high, and equipment is complicated, the most fundamentally improves the photocatalysis of routine
Method；(6) microwave and inorganic oxidizer common point logos, processing cost is high, uneconomical.
In sum, it is badly in need of seeking a kind of efficient, safe and environment-friendly, economic method processing organic wastewater existing to solve
There is problem present in technology.
Summary of the invention
Present invention aim at providing a kind of microwave catalysis degradation of organic waste water catalyst, concrete technical scheme is as follows:
A kind of microwave catalysis degradation of organic waste water catalyst, catalyst includes metal-oxide, described metal-oxide
Metal-oxide for bismuth-containing.
In above technical scheme preferably, the metal-oxide of described bismuth-containing is α-Bi2O3。
In above technical scheme preferably, described α-Bi2O3Manufacture method be: after bismuth nitrate is fully ground, in temperature
Roasting 2-8 hour under conditions of being 200 DEG C-800 DEG C, i.e. obtains catalyst α-Bi after being down to room temperature2O3。
In above technical scheme preferably, the temperature of described roasting is 450 DEG C-550 DEG C, and roasting time is 3-5 hour.
The catalyst of the application present invention, has the advantages that (1) catalyst includes metal-oxide, described metal
Oxide is the metal-oxide of bismuth-containing so that catalyst can fully absorb microwave and the generation electron-hole pair that is excited, organic
Hydrone in waste water is combined with strong electrophilic hole thus the hydroxyl radical free radical isoreactivity oxygen species that produces act as degraded
The oxidant of reaction, it is achieved the efficient degradation of organic wastewater；(2) metal-oxide of described bismuth-containing is α-Bi2O3, raw material is easy
Obtaining, and it uses traditional solid phase roasting method to prepare, mature preparation process, technological parameter is easily controlled.
The second object of the present invention is to provide a kind of method using above-mentioned catalyst treatment organic wastewater, specifically includes
Following steps:
Step A, catalyst is mixed homogeneously with organic wastewater obtain mixed material；
Step B, step A gained mixed material is inserted in microwave equipment, degrade under microwave exposure, be cooled to room
Temperature i.e. obtains the waste liquid after degraded.
In above technical scheme preferably, the organic wastewater in described step A is the waste water containing nitrophenols.
In above technical scheme preferably, in described step A: in organic wastewater, the concentration of nitrophenols is 100-500mg/L；
When process is the organic wastewater 100mL of 100mg/L containing nitrophenols concentration, the consumption of catalyst is 3-9g.
In above technical scheme preferably, in described step B, the power of microwave exposure is 100-800 watt, during microwave exposure
Between be 1-7 minute.
In above technical scheme preferably, in described step B, the power of microwave exposure is 600 watts, and microwave irradiation time is 5
Minute；In described step A: in organic wastewater, the concentration of nitrophenols is 100mg/L；Processing containing nitrophenols concentration is 100mg/L's
During organic wastewater 100mL, the consumption of catalyst is 5g.
The method using the present invention to process organic wastewater, has the effect that (1) treatment of Organic Wastewater step is simplified, place
Reason apparatus structure is simplified, it is simple to industrial operation；(2) the present invention is especially suitable for the organic wastewater containing nitrophenols, it is adaptable to
The concentration of nitrophenols is all waste water of 100-500mg/L, applied widely；Processing containing nitrophenols concentration is having of 100mg/L
During machine waste water 100mL, the consumption of catalyst is 3-9g, and catalyst amount is few, low cost；(3) microwave exposure state modulator is convenient,
Exposure time is short, and degradation rate can reach 99.2%, meets efficient demand.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.
Below with reference to figure, the present invention is further detailed explanation.
Accompanying drawing explanation
The accompanying drawing of the part constituting the application is used for providing a further understanding of the present invention, and the present invention's is schematic real
Execute example and illustrate for explaining the present invention, being not intended that inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is processing before organic wastewater and process the X-ray of organic wastewater rear catalyst and spreading out of the preferred embodiment of the present invention 1
Penetrate the comparison diagram of collection of illustrative plates and standard card (JCPDS#14-0699).
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the invention are described in detail, but the present invention can limit according to claim
Multitude of different ways that is fixed and that cover is implemented.
Embodiment 1:
A kind of processing method of the organic wastewater containing nitrophenols, first prepare a certain amount of catalyst, microwave equipment,
One ultraviolet spectrophotometer, a desk centrifuge and containing the organic wastewater 100mL that nitrophenols concentration is 100mg/L.
Catalyst uses α-Bi2O3, its preparation method specifically: after bismuth nitrate is fully ground, be 550 DEG C in temperature
Under the conditions of roasting 5 hours, i.e. obtain catalyst α-Bi after being down to room temperature2O3。
Step A, the catalyst of 0.1g is mixed homogeneously with organic wastewater obtain mixed material；
Step B, step A gained mixed material is inserted in microwave equipment, degrade under microwave exposure, be cooled to room
Temperature i.e. obtains the waste liquid after degraded, and wherein: the power of microwave exposure is 600 watts, the time of microwave exposure is 5min.
Use centrifuge to separate the waste liquid after degraded to take supernatant, supernatant uses ultraviolet spectrometry light photometer
Survey its absorbance, i.e. can get the degradation rate of organic wastewater.Record the concrete side of the degradation rate of absorbance post analysis organic wastewater
Method is as follows:
Ultraviolet spectrophotometer is utilized at 317nm, the absorbance of reactant liquor (supernatant) to be measured, by formula 1.
Understand solution concentration to be directly proportional to absorbance, it therefore follows that the concentration of nitrophenols in reactant liquor, and 2. calculate according to formula
The degradation rate (the results detailed in Table 1) of pollutant in reactant liquor:
A=α CL is 1.；
Wherein: A is absorbance；α is molar absorption coefficient, and its unit is L g-1·cm-1；C is nitrophenols in reactant liquor
Concentration, its unit is g L-1；L is absorber thickness, and its unit is cm.
η=(C0-Ct)/C0× 100% 2.；
Wherein: η is degradation rate, C0, Ct be respectively nitrophenols initial concentration solution and reaction after concentration, both units are equal
For mg/L.
The present embodiment have also obtained the front X ray diffracting spectrum with reacted catalyst of reaction, and by itself and standard card
Contrasting, refer to Fig. 1, as can be seen from Figure 1, prepared catalyst is (the most unreacted α-Bi before degrading waste water reacts2O3, as
In Fig. 1 (a)), reaction after α-Bi2O3XRD figure spectrum (in Fig. 1 (b)) and α-Bi2O3Standard diagram (in Fig. 1 (c)) mate
(that represent at 111,200,220 3 marked in figure is α-Bi very well2O3Crystal face corresponding to three stronger diffraction maximums), from Fig. 1
Understand, before reaction, be strictly α-Bi with reacted catalyst2O3。
Embodiment 2-embodiment 12:
Embodiment 2-embodiment 12 difference from Example 1 is only that parameter listed by table 1, refers to table 1, and embodiment 2-
Embodiment 12 all uses detection method same as in Example 1 to check, the results detailed in Table 1.
Embodiment 1-embodiment 5 is that different catalysts consumption processes the impact of organic wastewater to microwave catalysis, can from table 1
Know, when the consumption of catalyst is increased to 7g (processing containing the organic wastewater 100mL that nitrophenols concentration is 100mg/L) by 3g, fall
Solution rate is brought up to 99.2% by 98.0%, and when continuing the consumption increasing catalyst, degradation rate does not significantly improve, main cause
Be: certain microwave quantum density (i.e. power) can only excite a certain amount of microwave catalyst to produce electron hole pair, thus
Can only degrade a certain amount of pollutant.From cost-effective consideration, the catalyst of 5-7g consumption is preferred scope.
Embodiment 3 6-embodiment 8 in conjunction with the embodiments has been investigated microwave irradiation time and microwave catalysis has been processed organic wastewater
Impact, as known from Table 1, when microwave irradiation time was extended to 7 minutes by 5 minutes, the change of its degradation rate is little, can ignore, this
Place's data main cause that decreases on the contrary is probably: during reaction 7min, the non-total reflux of reactant liquor of condensing reflux is to reactant
System, and cause reaction system concentration to increase；It is also possible that measurement error.
Embodiment 3 9-embodiment 11 in conjunction with the embodiments has been investigated microwave exposure power and microwave catalysis has been processed organic wastewater
Impact, as known from Table 1,600W and 800W is high power, when other conditions are suitable, all can reach bigger degradation rate, but poor
It not the most the biggest.When microwave power is risen to 800W by 600W, its effect is deteriorated, it may be possible between each embodiment reactant liquor
Individual variation, it is also possible to error that other factors cause or measurement error.
Technical solution of the present invention has been investigated in the combination of embodiment 3 and embodiment 12 to be had for high concentration and low concentration nitrophenols
The disposition of machine waste water, as shown in Table 1, the either organic wastewater of low concentration or the organic wastewater of high concentration, use this
The technical scheme of invention all can obtain high degradation rate, and (degradation rate of low concentration is 98.4%, and the degradation rate of high concentration is
98.1%), absolutely prove that the suitability of technical solution of the present invention is wide.
The parametric statistics table of table 1 embodiment 1-embodiment 12
Comparative example 1
Do not use microwave catalyst, individually with microwave exposure: measure the organic wastewater that nitrophenols concentration is 100mg/L
100mL is in the there-necked flask of 250mL, and under the microwave that power is 600 watts after irradiation 5min, centrifugation takes supernatant, uses
UV, visible light light splitting light luminosity measures its absorbance, and calculating its degradation rate is 27.70%, refers to table 2.
Comparative example 2
The microwave catalyst used is α-Bi2O3: measure organic wastewater 100mL that nitrophenols concentration is 100mg/L in
In the there-necked flask of 250mL, in oil bath pan heated at constant temperature 420min, centrifugation takes supernatant, with UV, visible light light splitting light light
Degree measures its absorbance, and calculating its degradation rate is 82.98%, refers to table 2.
Comparative example 3
The microwave catalyst used is α-Bi2O3: measure organic wastewater 100mL that nitrophenols concentration is 100mg/L in
In the there-necked flask of 250mL, in room temperature at 500W, wavelength be 400-700nm xenon lamp under irradiation 420min, centrifugation takes
Clear liquid, measures its absorbance with UV, visible light light splitting light luminosity, and calculating its degradation rate is 94.68%, refers to table 2.
Comparative example 4
Using existing photocatalytic method to process waste water, details are shown in Table 2, concrete grammar list of references: Lixia
Yang,Shenglian Luo,Yue Li,Yan Xiao,Qing Kang,and Qingyun Cai.High Efficient
Photocatalytic Degradation of p-Nitrophenol on a Unique Cu2O/TiO2p-n
Heterojunction Network Catalyst,Environ.Sci.Technol.2010,44,7641–7646。
This kind of concrete catalyst of method prepares length complicated, time-consuming, the feature such as inefficient.
Comparative example 5
Using existing ultrasonic method to process waste water, details are shown in Table 2, concrete grammar list of references: Kashyap
P.Mishra and Parag R.Gogate.Ultrasonic Degradation of p-Nitrophenol in the
Presence of Additives at Pilot Scale Capacity.Ind.Eng.Chem.Res.2012,51,1166–
1172。
The method has time-consuming length, energy consumption is high, depend on the features such as organic reagent.
Comparative example 6
Using existing absorption method to process waste water, details are shown in Table 2, concrete grammar list of references: Lizhong
Zhu,Baoliang Chen,and Xueyou Shen.Sorption of Phenol,p-Nitrophenol,and
Aniline to Dual-Cation Organobentonites from Water.Environ.Sci.Technol.2000,
34,468 475。
The method simply shifts pollutant, and undegraded.
Comparative example 7
Using existing microwave assisting method to process waste water, details are shown in Table 2, concrete grammar list of references: Longli
Bo,Xie Quan,Shuo Chen,Huimin Zhao,Yazhi Zhao.Degradation of p-nitrophenol in
aqueous solution by microwave assisted oxidation process through a granular
activated carbon fixed bed.Water.Res.40(2006)3061–3068。
The method microwave, as just supplementary means, adds energy consumption.
The parameter of table 2 comparative example 1-comparative example 7 and statistical effect table
Comparative example 8-comparative example 9
Comparative example's 8-comparative example 9 difference from Example 1 is only that parameter listed by table 1, refers to table 1, and
Detection method same as in Example 1 is all used to check, the results detailed in Table 1.
In comparative example 8-comparative example 9, the preparation process of catalyst is: by acid acid bismuth and alumina powder or oxygen
Change iron powder and use the quality proportioning mix homogeneously of 2.1:1；After being fully ground；Roasting 5 hours at 550 DEG C, after being down to room temperature be
Obtain catalyst α-Bi2O3-Al2O3Or catalyst α-Bi2O3-Fe2O3。
From Tables 1 and 2, use prior art (comparative example 3-comparative example 7) that the highest degraded can be obtained
Rate, but when there is equipment complexity and energy consumption big (such as comparative example 7) or catalyst preparation complicated (such as embodiment 4) or process
Between long (comparative example 5 and comparative example 3) or the most fundamentally degraded defect such as (such as comparative example 6), be unsuitable for
Industrial applications.And using the method for comparative example 1 and comparative example 2 to carry out waste water process, its degradation rate is the most too late
Technical solution of the present invention gained degradation rate.By α-Bi2O3It is combined with other metallic compounds (referring to comparative example 8 and right
Than embodiment 9) α-Bi can be largely effected on2O3To wastewater degradation rate.
In summary, using technical scheme, both can obtain high degradation rate, having again the process time contracts significantly
Short, equipment is simple to operation, investment and operating cost low, floor space is few, degraded is thorough, the concentration range of degradable waste water is wide
Etc. feature, it is possible to serialization scale processes, it is easy to industrialized production, non-secondary pollution.Technical solution of the present invention is applicable to dye
The process of organic wastewater in the industries such as material, pharmacy, petrochemical industry, fine chemistry industry.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, that is made any repaiies
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (9)
1. a microwave catalysis degradation of organic waste water catalyst, it is characterised in that catalyst includes metal-oxide, described gold
Belonging to oxide is the metal-oxide of bismuth-containing.
Microwave catalysis degradation of organic waste water catalyst the most according to claim 1, it is characterised in that the gold of described bismuth-containing
Belonging to oxide is α-Bi2O3。
Microwave catalysis degradation of organic waste water catalyst the most according to claim 2, it is characterised in that described α-Bi2O3's
Manufacture method is: after being fully ground by bismuth nitrate, and roasting 2-8 hour under conditions of temperature is 200-800 DEG C, after being down to room temperature
Obtain catalyst α-Bi2O3。
Microwave catalysis degradation of organic waste water catalyst the most according to claim 3, it is characterised in that the temperature of described roasting
Degree is 450 DEG C-550 DEG C, and roasting time is 3-5 hour.
5. the method for the catalyst treatment organic wastewater used as described in claim 1-4 any one, it is characterised in that
Comprise the following steps:
Step A, catalyst is mixed homogeneously with organic wastewater obtain mixed material；
Step B, step A gained mixed material is inserted in microwave equipment, degrade under microwave exposure, be cooled to room temperature i.e.
Waste liquid after must degrading.
The method of process organic wastewater the most according to claim 5, it is characterised in that in described step A, organic wastewater is
Waste water containing nitrophenols.
The method of process organic wastewater the most according to claim 6, it is characterised in that in described step A: in organic wastewater
The concentration of nitrophenols is 100-500mg/L；When process is the organic wastewater 100mL of 100mg/L containing nitrophenols concentration, catalyst
Consumption is 3-9g.
The method of process organic wastewater the most according to claim 7, it is characterised in that microwave exposure in described step B
Power is 100-800 watt, and microwave irradiation time is 1-7 minute.
The method of process organic wastewater the most according to claim 8, it is characterised in that microwave exposure in described step B
Power is 600 watts, and microwave irradiation time is 5 minutes；In described step A: in organic wastewater, the concentration of nitrophenols is 100mg/L；
When process is the organic wastewater 100mL of 100mg/L containing nitrophenols concentration, the consumption of catalyst is 5g.
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| CN113233539A (en) * | 2021-04-09 | 2021-08-10 | 厦门大学 | Degradation method of high molecular organic compound under electron beam concerted catalysis and application of degradation method in sewage treatment |
| CN116116421A (en) * | 2023-03-02 | 2023-05-16 | 湘潭大学 | Method for degrading organic wastewater containing antibiotics by microwave catalysis and catalyst thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113233539A (en) * | 2021-04-09 | 2021-08-10 | 厦门大学 | Degradation method of high molecular organic compound under electron beam concerted catalysis and application of degradation method in sewage treatment |
| CN116116421A (en) * | 2023-03-02 | 2023-05-16 | 湘潭大学 | Method for degrading organic wastewater containing antibiotics by microwave catalysis and catalyst thereof |
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