CN105540819A - Method for treating organic wastewater difficult to degrade by preparing ozone catalyst through modifying carrier - Google Patents
Method for treating organic wastewater difficult to degrade by preparing ozone catalyst through modifying carrier Download PDFInfo
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- CN105540819A CN105540819A CN201610066943.3A CN201610066943A CN105540819A CN 105540819 A CN105540819 A CN 105540819A CN 201610066943 A CN201610066943 A CN 201610066943A CN 105540819 A CN105540819 A CN 105540819A
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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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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
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- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Environmental & Geological Engineering (AREA)
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- Treatment Of Water By Oxidation Or Reduction (AREA)
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Abstract
The invention provides a method for treating organic wastewater difficult to degrade by preparing an ozone catalyst through modifying a carrier and belongs to methods for treating the organic wastewater difficult to degrade. The method comprises the following steps: (1) carrying out activating treatment on the carrier: washing purchased active carbon with de-ionized water and then boiling the active carbon with boiled water for about 2 hours; washing the active carbon to be neutral and drying; (2) modifying the carrier: carrying out ultrasonic modification on the carrier; (3) preparing the catalyst: preparing the load type catalyst by adopting an impregnation-precipitation method; impregnating the modified active carbon into a manganese nitrate solution and impregnating and dropwise dropping a sodium hydroxide solution into a shaking table; vibrating, filtering and precipitating in the shaking table and drying; after cooling, putting the catalyst into a dryer; (4) combining ozone oxidization to remove the organic wastewater difficult to degrade: carrying out catalytic ozonization on 100mg/L of phenol wastewater and combining a removing capability of phenol to select an optimal catalyst modification manner. The method provided by the invention has the advantages that by changing surface characteristics and pore structures of the active carbon through ultrasounds, the loading capability of the catalyst is strengthened and an effect for treating of organic matters difficult to degrade is remarkable.
Description
Technical field
The present invention relates to a kind of method processing organic wastewater with difficult degradation thereby, particularly a kind of support modification prepares the method for ozone catalyst process organic wastewater with difficult degradation thereby.
Background technology
Organic wastewater with difficult degradation thereby refers to that to be decomposed by the microorganisms hourly velocity very slow, decompose halfway organism (also comprising some organic meta-bolites), having the features such as toxicity is large, complicated, chemical oxygen demand are high, biodegradability is poor, is focus and the difficult point of current water prevention and cure of pollution research.In recent years, adopt the research of such waste water of advanced oxidation processes process more, because it can produce the extremely strong hydroxyl radical free radical of oxidation capacity, effectively can decompose poisonous, bio-refractory organic pollutants, even thoroughly mineralising, has the advantage that oxidisability is strong, operational condition is easy to control.Wherein, ozone oxidation effectively destroys the feature such as unsaturation, non-secondary pollution because having, be subject to the favor of numerous investigator, and heterogeneous catalysis ozonation technique, improving catalyzed oxidation usefulness, reduce catalyst loss, improve catalyzer work-ing life etc. in outstanding advantages, become the new focus of ozonation technology research.
In the selection of heterogeneous ozone catalytic agent carrier, especially in the majority with the gac that relative low price, hole are comparatively flourishing.In order to the carrying capacity of fortifying catalytic agent, the surface property having investigator to inquire into from changing gac is started with, and gac is carried out to the modes such as sour modification, alkali modification, oxidation modification, improves the performance of catalytic ozonation organic wastewater with difficult degradation thereby to a certain extent.But as the gac of porous material, can be used for adsorbing and the avtive spot of supported catalyst compared to surface, the specific surface area that huge internal void has and avtive spot will can not be ignored, and the research of this partial content relates to less at present.
Summary of the invention
The object of the invention is to provide a kind of support modification that can significantly improve catalytic ozonation organic wastewater with difficult degradation thereby processing power to prepare the method for ozone catalyst process organic wastewater with difficult degradation thereby.
The object of the present invention is achieved like this: the method for this process organic wastewater with difficult degradation thereby: utilize ultrasonic change activated carbon surface characteristic and pore texture, enhancement activated carbon surfactivity site and internal void are to metal catalyst absorption and carrying capacity, reinforcement, catalysis and ozonization hardly degraded organic substance, concrete steps are as follows:
(1) activation treatment of carrier: by the gac washed with de-ionized water of buying, afterwards with boiling water boiling about 2 hours, then is washed till neutrality, 105 DEG C of dryings;
(2) modification of carrier: carrier is carried out supersonic modifying, the ultrasonic power selecting supersonic modifying is 75 ~ 150w, and ultrasonic frequency is 50 ~ 55Hz, and ultrasonic time is 30 ~ 90min, to surface property and the pore texture modification of gac;
(3) preparation of catalyzer: the method adopting dipping-precipitated phase to combine prepares loaded catalyst; Modified 5g gac is immersed in manganous nitrate (AR) solution of 100ml5%, at least 24h is flooded in 150 ~ 180r/min shaking table, slowly drip sodium hydroxide (AR) solution of 45ml1 ~ 3mol/l afterwards, and the 1 ~ 2h that vibrates in shaking table, filtering-depositing afterwards, and 105 ~ 120 DEG C of dry 12h in an oven, dried sample is dry 3h in 500 ~ 700 DEG C of retort furnaces, puts into moisture eliminator for subsequent use after cooling;
(4) combine ozone oxidation and remove target organic waste water: the phenolic waste water of 100mg/l is carried out catalytic ozonation, in conjunction with the removal ability of phenol, the catalyst effect selecting the modified preparation of ultrasonic about 60min under 150W, 53Hz condition is optimum; The solution PH of described catalytic ozonation is 9 ~ 11, and ozone dosage is 3 ~ 7mg/l.
Carrier selected by described step (1) is bar-shaped gac.
Described step (2) determines the ultrasonic optimal conditions to support modification: ultrasonic 60min under 150W, 53Hz condition.
Described step (3) load solution used is manganese nitrate solution.
The phenolic waste water concentration that described step (4) is chosen is 100mg/l, and solution PH is 10, and ozone dosage is 6.12mg/l.
Beneficial effect, owing to have employed above-mentioned support modification scheme, the bar-shaped gac cost of investment of selection is low and not easily run off, and after modification, the adsorption effect of gac to catalyzer obtains strengthening, and catalytic effect is obvious improvement compared with other method of modifying.Modification is carried out by the ultrasonic surface to carrier and pore characteristic, improve absorption and the carrying capacity of catalyzer, the analysis of high vacuum mode image collection+energy spectrum analysis surface analysis pattern (EDS) is utilized to show: non-supersonic modifying Supported Manganese element is 2.40%, and the content of modified manganese element is 3.95%, and there is reduction to a certain degree through the content of supersound process rear impurity element; After support modification, the effect of catalytic ozonation phenol has remarkable lifting: under the ultrasound condition of 150W, 53KHz, 60min, the clearance of 33min phenol can reach 85.78%, improve 34.11% than not modification, improve 11.73%, 14.22% and 22.75% respectively than alkali modification, Nitric Acid Modified and hydrochloric Acid Modification.The present invention is not only based on the change of activated carbon surface characteristic, more be conceived to the change of gac internal pore structure, play the huge internal void of gac to metal catalyst absorption and carrying capacity, under optimal conditions, the degradation property Be very effective of target organic waste water after combining with ozone oxidation.
Advantage: this is lower to the method cost of organic wastewater with difficult degradation thereby, utilize more general gac and its surface property of ultrasonic change and pore texture, modified gac obtains strengthening to the absorption of catalyzer and load effect, and catalytic ozonation hardly degraded organic substance effect is all significantly increased compared with unmodified and other method of modifying.
Accompanying drawing illustrates:
Fig. 1 a is the scanning electron microscope (SEM) photograph without supersonic modifying Supported Manganese of the present invention.
Fig. 1 b is the scanning electron microscope (SEM) photograph of supersonic modifying back loading manganese of the present invention.
Fig. 2 a be without the activated carbon supported manganese of supersound process after EDS can spectrogram.
Fig. 2 b be without the activated carbon supported manganese of supersound process after manganese element mapping.
Fig. 2 c is that the EDS after supersonic modifying after activated carbon supported manganese can spectrogram.
Fig. 2 d is the manganese element mapping after supersonic modifying after activated carbon supported manganese.
Fig. 3 is the catalytic ozonation design sketch of different carriers modification mode of the present invention.
Fig. 4 is the catalytic ozonation design sketch of different ultrasonic power modified support of the present invention.
Fig. 5 is the catalytic ozonation design sketch of different ultrasonic time modified support of the present invention.
Fig. 6 a is the scanning electron microscope (SEM) photograph without supersonic modifying gac of the present invention.
Fig. 6 b is the scanning electron microscope (SEM) photograph of gac after supersonic modifying of the present invention.
Embodiment
The method of this process organic wastewater with difficult degradation thereby: utilize ultrasonic directed change activated carbon surface characteristic and pore texture, enhancement activated carbon surfactivity site and internal void are to metal catalyst absorption and carrying capacity, reinforcement, catalysis and ozonization hardly degraded organic substance, concrete steps are as follows:
(1) activation treatment of carrier: by the gac washed with de-ionized water of buying, afterwards with boiling water boiling about 2 hours, then is washed till neutrality, 105 DEG C of dryings;
(2) modification of carrier: carrier is carried out supersonic modifying, the ultrasonic power selecting supersonic modifying is 70 ~ 150w, and ultrasonic frequency is 50 ~ 55Hz, and ultrasonic time is 30 ~ 90min, to surface property and the pore texture modification of gac;
(3) preparation of catalyzer: the method adopting dipping-precipitated phase to combine prepares loaded catalyst; Modified 5g gac is immersed in manganous nitrate (AR) solution of 100ml5%, at least 24h is flooded in 150 ~ 180r/min shaking table, slowly drip sodium hydroxide (AR) solution of 45ml1 ~ 3mol/l afterwards, and the 1 ~ 2h that vibrates in shaking table, filtering-depositing afterwards, and 105 ~ 120 DEG C of dry 12h in an oven, dried sample is dry 3 ~ 4h in 500 ~ 700 DEG C of retort furnaces, puts into moisture eliminator for subsequent use after cooling;
(4) combine ozone oxidation and remove target organic waste water: the phenolic waste water of 100mg/l is carried out catalytic ozonation, the removal ability in conjunction with phenol selects optimum improved catalysts; The solution PH of described catalytic ozonation is 9 ~ 11, and ozone dosage is 3 ~ 7mg/l.
Carrier selected by described step (1) is bar-shaped gac.
Described step (2) determines the ultrasonic optimal conditions to support modification: ultrasonic 60min under 150W, 53Hz condition, and utilizes scanning electron microscope and surface analyzer to characterize surface property, specific surface area and the pore volume pore diameter characteristics preparing rear catalyst.
Described step (3) load solution used is manganese nitrate solution.
The phenolic waste water concentration that described step (4) is chosen is 100mg/l, and solution PH is 10, and ozone dosage is 6.12mg/l.
For content of the present invention, Characteristic can be understood further, hereby enumerate concrete experimental program, and the present invention will be described in detail to coordinate chart.
Embodiment 1: a kind of support modification prepares the method for heterogeneous ozone catalyst intensive treatment organic wastewater with difficult degradation thereby, comprise the activation treatment of carrier, the modification of carrier, the preparation of catalyzer, associating ozone oxidation removal target waste water step, comprise following concrete steps:
(1) activation treatment of carrier: by the gac washed with de-ionized water of buying, afterwards with boiling water boiling about 2 hours, then is washed till neutrality, 105 DEG C of dryings.
(2) modification of carrier: supersonic modifying: the ultrasonic power selecting supersonic modifying is 75w, 112.5w, 150w, and ultrasonic frequency is 53Hz, and then the ultrasonic time selecting supersonic modifying is 30min, 40min, 50min, 60min, 75min, 90min; Under 150w ultrasound condition, to surface property and the pore texture modification of gac, table 1.
Table 1 supersonic modifying
Contrast with other surface modification modes: 1. sour modification: configure the dilute hydrochloric acid that 100ml massfraction is 2% simultaneously, take 10g gac and soak wherein, after flooding 5h at 45 DEG C, put into baking oven dry for standby; 2. alkali modification: configuration 100ml massfraction is the sodium hydroxide of 2%, takes 10g gac and soaks wherein, flood 5h, dry for standby in baking oven at 45 DEG C; 3. oxidation modification: gac is placed in the salpeter solution that 100ml massfraction is 5%, floods 2h and carries out modification at 60 DEG C, clean afterwards, dry at 105 DEG C with pure water.
(3) preparation of catalyzer: the method adopting dipping-precipitated phase to combine prepares manganese type carbon base catalyst; Modified 5g gac is immersed in the manganese nitrate solution of 100ml5%, 24h is flooded in 180r/min shaking table, drip sodium hydroxide solution afterwards, stir 1h, filtering-depositing, and dry 12h in an oven, dried sample is dry 3h in 500 ~ 700 DEG C of retort furnaces, puts into moisture eliminator for subsequent use after cooling;
(4) ozone oxidation target organic waste water is combined: get 100mg/l phenolic waste water 1L, PH is regulated to be 10, ozone dosage is 6.12mg/l, in waste water, add 2g catalyzer carry out, test, sample at thief hole respectively when 0min, 5min, 10min, 15min, 20min, 25min, 30min, adopt visible spectrophotometer to measure phenol concentration, calculate the clearance of phenol.
As seen from Table 1, before and after support modification, specific surface area and hole are melted aperture and all be there occurs change, time in supersound process 30min, BET specific surface area, hole are melted aperture and are slightly declined, also remain ash content and the impurity of part in pretreated gac, further divested tiny group and the impurity of carrier surface by supersound process, make in its surface and hole more clean, micropore is displayed gradually, and aperture is reduced to some extent; During ultrasonic 60min, specific surface area increases, aperture is melted in hole has increase with regard to 30min than all, along with the proper extension of time, cavatition grow, its shock action makes partial pore break for mesopore, wherein mesopore plays conveying effect, dominate rate of adsorption, mesopore increase the adsorption enhancing gac, be convenient to active ingredient and better disperse and deposit; But during to 90min, specific surface area and hole are melted aperture and declined to some extent, this is hole wall due to intense impact action breaks down, and cause amount of activated charcoal mechanism to subside, partial hole is broken.Therefore, consider in this research and adopt ultrasonic time 60min to be optimum carrier modified condition.
In Fig. 3, Fig. 4 and Fig. 5, in figure, the ability of catalytic ozonation target waste water is known, supersonic modifying is carried out to absorbent charcoal carrier, removal proportional relation within the scope of the 75w-150w of this effects of ultrasonic power and target waste water, ultrasonic power be 150w, under ultrasonic frequency is 53Hz condition, change carrier ultrasonic time, result shows that the catalyzer prepared through 60min supersonic modifying is best to the degradation property of target organic.
Fig. 6 a and Fig. 6 b is of the present invention without supersonic modifying and the scanning electron microscope (SEM) photograph through supersonic modifying gac, can find out that the gac pore distribution without supersonic modifying is less, and it is seriously stacking, modified active carbon surface through ultrasonic 60min process is comparatively clean, there is certain gradation sense, hole is increased relatively, mostly is through hole, thus the ultrasonic object reaching the surperficial also pore-creating of cleaning is described.
Embodiment 2: in described method steps:
(2) modification of carrier: carrier is carried out supersonic modifying, the ultrasonic power selecting supersonic modifying is 75, and ultrasonic frequency is 53Hz, and ultrasonic time is 90min;
(3) preparation of catalyzer: the method adopting dipping-precipitated phase to combine prepares loaded catalyst; Modified 5g gac is immersed in manganous nitrate (AR) solution of 100ml5%, at least 24h is flooded in 150 ~ 180r/min shaking table, slowly drip sodium hydroxide (AR) solution of 45ml1 ~ 3mol/l afterwards, and the 1 ~ 2h that vibrates in shaking table, filtering-depositing afterwards, and 105 DEG C of dry 12h in an oven, dried sample is dry 4h in 500 DEG C of retort furnaces, puts into moisture eliminator for subsequent use after cooling;
(4) combine ozone oxidation and remove target organic waste water: the phenolic waste water of 100mg/l is carried out catalytic ozonation, the removal ability in conjunction with phenol selects optimum improved catalysts; The solution PH of described catalytic ozonation is 9, and ozone dosage is 7mg/l.
Other and embodiment 1 are together.
Embodiment 3: in described method steps:
(2) modification of carrier: carrier is carried out supersonic modifying, the ultrasonic power selecting supersonic modifying is 150w, and ultrasonic frequency is 53Hz, and ultrasonic time is 30min;
(3) preparation of catalyzer: the method adopting dipping-precipitated phase to combine prepares loaded catalyst; Modified 5g gac is immersed in manganous nitrate (AR) solution of 100ml5%, at least 24h is flooded in 150 ~ 180r/min shaking table, slowly drip sodium hydroxide (AR) solution of 45ml1 ~ 3mol/l afterwards, and the 1 ~ 2h that vibrates in shaking table, filtering-depositing afterwards, and 120 DEG C of dry 12h in an oven, dried sample is dry 3h in 700 DEG C of retort furnaces, puts into moisture eliminator for subsequent use after cooling;
(4) combine ozone oxidation and remove target organic waste water: the phenolic waste water of 100mg/l is carried out catalytic ozonation, the removal ability in conjunction with phenol selects optimum improved catalysts; The solution PH of described catalytic ozonation is 11, and ozone dosage is 3mg/l.
Other and embodiment 1 are together.
Claims (5)
1. a support modification prepares the method for ozone catalyst process organic wastewater with difficult degradation thereby, it is characterized in that: the method for this process organic wastewater with difficult degradation thereby: utilize ultrasonic change activated carbon surface characteristic and pore texture, enhancement activated carbon surfactivity site and internal void are to metal catalyst absorption and carrying capacity, reinforcement, catalysis and ozonization hardly degraded organic substance, concrete steps are as follows:
(1) activation treatment of carrier: by the gac washed with de-ionized water of buying, afterwards with boiling water boiling about 2 hours, then is washed till neutrality, 105 DEG C of dryings;
(2) modification of carrier: carrier is carried out supersonic modifying, the ultrasonic power selecting supersonic modifying is 75 ~ 150w, and ultrasonic frequency is 50 ~ 55Hz, and ultrasonic time is 30 ~ 90min, to surface property and the pore texture modification of gac;
(3) preparation of catalyzer: the method adopting dipping-precipitated phase to combine prepares loaded catalyst; Modified 5g gac is immersed in manganous nitrate (AR) solution of 100ml5%, at least 24h is flooded in 150 ~ 180r/min shaking table, slowly drip sodium hydroxide (AR) solution of 45ml1 ~ 3mol/l afterwards, and the 1 ~ 2h that vibrates in shaking table, filtering-depositing afterwards, and 105 ~ 120 DEG C of dry 12h in an oven, dried sample is dry 3 ~ 4h in 500 ~ 700 DEG C of retort furnaces, puts into moisture eliminator for subsequent use after cooling;
(4) combine ozone oxidation and remove target organic waste water: the phenolic waste water of 100mg/l is carried out catalytic ozonation, the removal ability in conjunction with phenol selects optimum improved catalysts; The solution PH of described catalytic ozonation is 9 ~ 11, and ozone dosage is 3 ~ 7mg/l.
2. a kind of support modification according to claim 1 prepares the method for ozone catalyst process organic wastewater with difficult degradation thereby, it is characterized in that: the carrier selected by described step (1) is bar-shaped gac.
3. a kind of support modification according to claim 1 prepares the method for ozone catalyst process organic wastewater with difficult degradation thereby, it is characterized in that: described step (2) for determining the ultrasonic optimal conditions to support modification, and characterizes the catalyzer after preparation.
4. a kind of support modification according to claim 1 prepares the method for ozone catalyst process organic wastewater with difficult degradation thereby, it is characterized in that: described step (3) load solution used is manganese nitrate solution, loaded with heavy metals manganese.
5. a kind of support modification according to claim 1 prepares the method for ozone catalyst process organic wastewater with difficult degradation thereby, it is characterized in that: the phenolic waste water concentration that described step (4) is chosen is 100mg/l, solution PH is 9 ~ 11, and ozone dosage is 3 ~ 7mg/l.
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| CN106215932A (en) * | 2016-07-27 | 2016-12-14 | 哈尔滨工业大学（威海） | A kind of novel ozone catalyst and preparation method thereof |
| CN106423060A (en) * | 2016-10-13 | 2017-02-22 | 天津城建大学 | Preparation method of modified activated carbon for adsorbing dye |
| CN107537459A (en) * | 2017-08-01 | 2018-01-05 | 云南省贵金属新材料控股集团有限公司 | A kind of preparation method for handling bio-refractory industrial organic waste water catalyst |
| CN108686648A (en) * | 2018-04-13 | 2018-10-23 | 浙江清华长三角研究院 | A kind of preparation method and application of carried active carbon ozone catalyst |
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