CN115403195B - Method for treating organic wastewater by utilizing micro-nano dendritic zero-valent copper catalyst to activate molecular oxygen - Google Patents
Method for treating organic wastewater by utilizing micro-nano dendritic zero-valent copper catalyst to activate molecular oxygen Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000010949 copper Substances 0.000 title claims abstract description 70
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 239000002351 wastewater Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 20
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001882 dioxygen Inorganic materials 0.000 title claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 230000001105 regulatory effect Effects 0.000 claims abstract description 15
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 claims description 26
- 229960000282 metronidazole Drugs 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 8
- 230000003213 activating effect Effects 0.000 abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 14
- 238000003760 magnetic stirring Methods 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 239000004098 Tetracycline Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 6
- 229940012189 methyl orange Drugs 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 229960002180 tetracycline Drugs 0.000 description 6
- 229930101283 tetracycline Natural products 0.000 description 6
- 235000019364 tetracycline Nutrition 0.000 description 6
- 150000003522 tetracyclines Chemical class 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/722—Oxidation by peroxides
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- 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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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C02F2101/30—Organic compounds
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Abstract
A method for treating organic wastewater by utilizing micro-nano dendritic zero-valent copper catalyst to activate molecular oxygen belongs to the field of wastewater treatment, and particularly relates to a method for treating organic wastewater. The invention aims to solve the problems that the activity of the existing nano zero-valent copper catalyst for activating molecular oxygen is low, and the nano zero-valent copper catalyst is easy to agglomerate and oxidize. The method comprises the following steps: 1. preparing a micro-nano dendritic zero-valent copper catalyst; 2. and (3) regulating the pH value of the organic wastewater, adding the micro-nano dendritic zero-valent copper catalyst into the organic wastewater with the pH value regulated, and reacting under the stirring condition to obtain wastewater with the organic matters removed. The micro-nano dendritic zero-valent copper catalyst prepared by the invention has excellent capability of activating molecular oxygen to degrade organic pollutants, and can be improved by 60.13% compared with commercial micron-sized copper powder; the method for preparing the micro-nano dendritic zero-valent copper catalyst is simple and quick, the raw materials are cheap and easy to obtain, the application range is wide, and the method is H 2 O 2 High yield and is suitable for enlarged production.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a method for treating organic wastewater.
Background
Fenton/Fenton-like technology is an advanced oxidation technology and is considered to be one of the most promising methods for eliminating difficult-to-biodegrade organic pollutants. Based on H 2 O 2 In the activated Fenton/Fenton-like technology, H 2 O 2 Can be decomposed into oxygenHydroxyl radical (OH) with a potential of 2.8V, OH can degrade and even mineralize organic pollutants which are difficult to degrade by living beings. However, H 2 O 2 Is added in an amount far higher than the actual H involved in the reaction 2 O 2 Amount of H to 2 O 2 The utilization efficiency of (a) is lowered. In addition, high concentration H 2 O 2 In turn, presents a double challenge to the technology both in terms of safety and economy. Therefore, there is an urgent need to find a safe, readily available oxidizing agent to replace H 2 O 2 。
The inexpensive, harmless and most readily available oxidizing agent molecular oxygen has received great attention. However, in the normal state O 2 The spin directions of the two electrons on the HOMO orbit are parallel but are not matched, and the two electrons are in a spin triplet state, so that the property is quite stable, and the organic pollutants cannot be directly degraded. Thus, activated molecular oxygen generates H in situ 2 O 2 Is an ideal improvement way, and under the proper reaction conditions, H is slowly generated 2 O 2 And is immediately decomposed by the catalyst to generate active oxygen for degrading organic pollutants, so that H can be avoided 2 O 2 Unnecessary decomposition. But also can effectively solve H 2 O 2 Risk and economic challenges associated with production, transportation and storage.
Zero-valent metals such as iron, aluminum, copper, etc., have strong reducibility and have been shown to activate O 2 Generation of H 2 O 2 Can also catalyze H 2 O 2 Active oxygen is generated to degrade organic pollutants. Among them, zero-valent copper has the strongest ability to activate molecular oxygen to degrade pollutants. The nano zero-valent copper has larger specific surface area, so that the nano zero-valent copper has obviously better molecular oxygen activating performance than the micro zero-valent copper, but the nano zero-valent copper is easier to agglomerate and passivate in the use process, and the problems of poor transportation capability, reduced electron transfer and the like are caused. Aiming at the defect of nano zero-valent copper, the invention provides the following technical scheme for solving.
Disclosure of Invention
The invention aims to solve the problems that the activity of the existing nano zero-valent copper catalyst for activating molecular oxygen is low, and the nano zero-valent copper catalyst is easy to agglomerate and oxidize, and provides a method for treating organic wastewater by using the micro-nano dendritic zero-valent copper catalyst for activating molecular oxygen.
In the invention, the micro-nano dendritic zero-valent copper catalyst is used as a catalyst, and H is generated in situ by catalytic activation of oxygen (the oxygen source is air and oxygen dissolved in organic wastewater without additional oxygen inlet) 2 O 2 With Cu + Forming Fenton-like reaction and degrading organic matters in the organic wastewater.
A method for treating organic wastewater by utilizing micro-nano dendritic zero-valent copper catalyst to activate molecular oxygen comprises the following steps:
1. preparing a micro-nano dendritic zero-valent copper catalyst:
(1) CuSO is to 4 ·5H 2 O is dissolved in deionized water to obtain a copper sulfate solution; adding absolute ethyl alcohol into the copper sulfate solution, and uniformly stirring to obtain electrolyte;
(2) taking an annular graphite ring as an anode, taking polished copper wires as a cathode, and applying 0.23A/cm after connecting a power supply 2 ～0.50A/cm 2 Carrying out deposition for 10 s-20 s each time, carrying out total deposition for 10 times, collecting powder obtained on a cathode, washing sequentially by using deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying to obtain the micro-nano dendritic zero-valent copper catalyst;
2. adjusting the pH value of the organic wastewater, adding the micro-nano dendritic zero-valent copper catalyst into the organic wastewater with the pH value adjusted, starting a magnetic stirrer, and reacting under the stirring condition to obtain wastewater with the organic matters removed.
The invention has the advantages that:
(1) The invention provides a micro-nano dendritic zero-valent copper catalyst, which not only can ensure good dispersibility by utilizing a micro-structure, but also can increase the specific surface area by utilizing a nano-structure and improve the catalytic activity;
(2) The invention uses green easily available molecular oxygen as oxidant without adding H 2 O 2 Improve H 2 O 2 Is used for the utilization rate of the water,at the same time reduce H 2 O 2 Safety issues and costs incurred during production, transportation and storage;
(3) The micro-nano dendritic zero-valent copper catalyst prepared by the invention has excellent capability of activating molecular oxygen to degrade organic pollutants, and can be improved by 60.13% compared with commercial micron-sized copper powder;
(4) The Fenton-like technology for activating molecular oxygen, which is established by the invention, has wide applicability and good degradation capability on dyes, antibiotics, phenolic compounds and the like;
(5) H produced in situ according to the invention 2 O 2 The concentration of (2) is kept at about 600 mu mol/L in the whole process;
(6) The method for preparing the micro-nano dendritic zero-valent copper catalyst is simple and quick, the raw materials are cheap and easy to obtain, the application range is wide, and the method is H 2 O 2 High yield and is suitable for enlarged production.
Drawings
FIG. 1 is an X-ray diffraction pattern of a micro-nano dendritic zero valent copper catalyst prepared in example 1;
FIG. 2 is a scanning electron microscope image of the micro-nano dendritic zero valent copper catalyst prepared in example 1;
FIG. 3 is a transmission electron microscope image of the micro-nano dendritic zero valent copper catalyst prepared in example 1;
FIG. 4 is a graph showing the effect of micro-nano dendritic zero valent copper catalyst of example 2 on degrading metronidazole with commercial micron copper powder of comparative example 2, wherein mnZVC is the micro-nano dendritic zero valent copper catalyst prepared in example 1 and mZVC is commercial micron copper powder;
FIG. 5 is a graph showing the effect of the micro-nano dendritic zero valent copper catalyst prepared in example 1 on degrading metronidazole in the waste water of metronidazole with different pH values;
FIG. 6 is a graph showing the degradation effect of the micro-nano dendritic zero valent copper catalyst prepared in example 1 on different pollutants, wherein phenol is phenol, MO is methyl orange, rhB is rhodamine B, and TCH is tetracycline;
FIG. 7 shows H during the degradation of the micro-nano dendritic zero valent copper catalyst prepared in example 1 2 O 2 Is generated by the generation of (a)。
Detailed Description
The following examples further illustrate the invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit of the invention are intended to be within the scope of the present invention.
The first embodiment is as follows: the method for treating organic wastewater by using micro-nano dendritic zero-valent copper catalyst to activate molecular oxygen in the embodiment comprises the following steps:
1. preparing a micro-nano dendritic zero-valent copper catalyst:
(1) CuSO is to 4 ·5H 2 O is dissolved in deionized water to obtain a copper sulfate solution; adding absolute ethyl alcohol into the copper sulfate solution, and uniformly stirring to obtain electrolyte;
(2) taking an annular graphite ring as an anode, taking polished copper wires as a cathode, and applying 0.23A/cm after connecting a power supply 2 ～0.50A/cm 2 Carrying out deposition for 10 s-20 s each time, carrying out total deposition for 10 times, collecting powder obtained on a cathode, washing sequentially by using deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying to obtain the micro-nano dendritic zero-valent copper catalyst;
2. adjusting the pH value of the organic wastewater, adding the micro-nano dendritic zero-valent copper catalyst into the organic wastewater with the pH value adjusted, starting a magnetic stirrer, and reacting under the stirring condition to obtain wastewater with the organic matters removed.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the concentration of the copper sulfate solution in the step one (1) is 0.5mol/L to 1mol/L. The other steps are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the volume ratio of the absolute ethyl alcohol to the copper sulfate solution in the step one (1) is (7-8) 150. The other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: step one, washing for 3 times by sequentially using deionized water and absolute ethyl alcohol; the temperature of the vacuum drying in the step (2) is 60 ℃, and the time of the vacuum drying is 6 hours. The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: the volume ratio of the mass of the micro-nano dendritic zero-valent copper catalyst to the organic wastewater in the second step is (1 g-2 g): 1L. Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: and in the second step, the pH value of the organic wastewater is regulated to 2-5. Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: in the second step, the organic matters in the organic wastewater are one or more of metronidazole, phenol, methyl orange, rhodamine B and tetracycline. Other steps are the same as those of embodiments one to six.
Eighth embodiment: one difference between the present embodiment and the first to seventh embodiments is that: the concentration of the organic matters in the organic wastewater in the second step is 10 mg/L-30 mg/L. The other steps are the same as those of embodiments one to seven.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: the stirring speed in the second step is 1000r/min. Other steps are the same as those of embodiments one to eight.
Detailed description ten: the present embodiment differs from the first to ninth embodiments in that: the reaction time in the second step is 120min. The other steps are the same as those of embodiments one to nine.
The present invention will be described in detail with reference to examples.
Example 1: the method for preparing the micro-nano dendritic zero-valent copper catalyst comprises the following steps of:
(1) CuSO of a certain quality 4 ·5H 2 O is dissolved in 150mL of deionized water to obtain copper sulfate solution with the concentration of 0.5mol/LA liquid; adding 7.5mL of absolute ethyl alcohol into a copper sulfate solution with the concentration of 0.5mol/L, and uniformly stirring to obtain an electrolyte;
(2) taking an annular graphite ring as an anode, taking polished copper wires as a cathode, and applying 0.50A/cm after connecting a power supply 2 And (3) carrying out deposition for 20s each time, carrying out total deposition for 10 times, collecting powder obtained on the cathode, washing for 3 times by sequentially using deionized water and absolute ethyl alcohol respectively, and finally carrying out vacuum drying at 60 ℃ for 6 hours to obtain the micro-nano dendritic zero-valent copper catalyst.
FIG. 1 is an X-ray diffraction pattern of a micro-nano dendritic zero valent copper catalyst prepared in example 1;
as shown in fig. 1: XRD proves that the main crystal phase of the prepared micro-nano dendritic zero-valent copper catalyst is zero-valent copper (PDF#04-0836), and the diffraction peaks respectively correspond to 3 diffraction peaks of (111), (200) and (220) crystal faces.
FIG. 2 is a scanning electron microscope image of the micro-nano dendritic zero valent copper catalyst prepared in example 1;
FIG. 3 is a transmission electron microscope image of the micro-nano dendritic zero valent copper catalyst prepared in example 1;
characterization of the morphology of the catalyst by SEM and TEM revealed that the catalyst was typically dendritic in morphology, with a primary structure length of about 2 μm and a secondary structure length of 200-500nm.
Example 2:
50mL of Metronidazole wastewater with the concentration of 30mg/L is prepared, and H with the concentration of 1mol/L is used 2 SO 4 The pH value of the metronidazole wastewater is regulated to be 3, 75mg of the micro-nano dendritic zero-valent copper catalyst prepared in the example 1 is added, magnetic stirring is started at room temperature, the reaction is carried out for 120min at the stirring speed of 1000r/min, and the degradation rate of the metronidazole is 92.39% after detection, as shown in figure 4.
Comparative example 2: 50mL of Metronidazole wastewater with the concentration of 30mg/L is prepared, and H with the concentration of 1mol/L is used 2 SO 4 The pH value of the solution is regulated to be 3, 75mg of commercial micron-sized copper powder is added, magnetic stirring is started at room temperature, the solution reacts for 120min at the stirring speed of 1000r/min, and the degradation rate of the metronidazole is detected to be 32.26%, as shown in fig. 4 and fig. 4Shown in fig. 5.
FIG. 4 is a graph showing the effect of micro-nano dendritic zero valent copper catalyst of example 2 on degrading metronidazole with commercial micron copper powder of comparative example 2, wherein mnZVC is the micro-nano dendritic zero valent copper catalyst prepared in example 1 and mZVC is commercial micron copper powder;
example 3:
50mL of Metronidazole wastewater with the concentration of 30mg/L is prepared, and H with the concentration of 1mol/L is used 2 SO 4 The pH value of the metronidazole wastewater is regulated to be 2, 75mg of the micro-nano dendritic zero-valent copper catalyst prepared in the example 1 is added, magnetic stirring is started at room temperature, the solution reacts for 120min at the stirring speed of 1000r/min, and the degradation rate of the metronidazole is 100% through detection, as shown in figure 5;
50mL of Metronidazole wastewater with the concentration of 30mg/L is prepared, and H with the concentration of 1mol/L is used 2 SO 4 The pH value of the metronidazole wastewater is regulated to be 4, 75mg of the micro-nano dendritic zero-valent copper catalyst prepared in the example 1 is added, magnetic stirring is started at room temperature, the reaction is carried out for 120min at the stirring speed of 1000r/min, and the degradation rate of the metronidazole is 50.62% through detection, which is shown in the figure 5;
50mL of Metronidazole wastewater with the concentration of 30mg/L is prepared, and H with the concentration of 1mol/L is used 2 SO 4 The pH value of the metronidazole wastewater is regulated to be 5, 75mg of the micro-nano dendritic zero-valent copper catalyst prepared in the example 1 is added, magnetic stirring is started at room temperature, the reaction is carried out for 120min at the stirring speed of 1000r/min, and the degradation rate of the metronidazole is 43.45% after detection, which is shown in figure 5.
Fig. 5 is a graph showing the effect of the micro-nano dendritic zero-valent copper catalyst prepared in example 1 on degrading metronidazole in the metronidazole wastewater with different pH values.
Example 4:
50mL of phenol wastewater with a concentration of 30mg/L was prepared, and H with a concentration of 1mol/L was used 2 SO 4 The pH value of the phenol wastewater is regulated to be 3 by the solution, 75mg of the micro-nano dendritic zero-valent copper catalyst prepared in the example 1 is added, magnetic stirring is started at room temperature, the stirring speed is 1000r/min for 120min, and the degradation rate of the phenol is 62.54% through detection; see fig. 6;
50mL of methyl orange wastewater with the concentration of 30mg/L is prepared, and H with the concentration of 1mol/L is used 2 SO 4 The pH value of the methyl orange wastewater is regulated to be 3, 75mg of the micro-nano dendritic zero-valent copper catalyst prepared in the example 1 is added, magnetic stirring is started at room temperature, the stirring speed is 1000r/min for 120min, and the degradation rate of the methyl orange is detected to be 100%; see fig. 6;
50mL of rhodamine B wastewater with the concentration of 30mg/L is prepared, and H with the concentration of 1mol/L is used 2 SO 4 The pH value of rhodamine B wastewater is regulated to be 3 by the solution, 75mg of the micro-nano dendritic zero-valent copper catalyst prepared in the example 1 is added, magnetic stirring is started at room temperature, the stirring speed is 1000r/min for 120min, and the degradation rate of rhodamine B is 100% by detection; see fig. 6;
50mL of tetracycline wastewater with the concentration of 30mg/L is prepared, and H with the concentration of 1mol/L is used 2 SO 4 The pH value of the tetracycline wastewater is regulated to be 3, 75mg of the micro-nano dendritic zero-valent copper catalyst prepared in the example 1 is added, magnetic stirring is started at room temperature, the stirring speed is 1000r/min for 120min, and the degradation rate of the tetracycline is 100% through detection; see fig. 6.
FIG. 6 is a graph showing the degradation effect of the micro-nano dendritic zero valent copper catalyst prepared in example 1 on different pollutants, wherein phenol is phenol, MO is methyl orange, rhB is rhodamine B, and TCH is tetracycline;
example 5:
50mL of Metronidazole wastewater with the concentration of 30mg/L is prepared, and H with the concentration of 1mol/L is used 2 SO 4 The pH value of the metronidazole wastewater is regulated to be 3, 75mg of the micro-nano dendritic zero-valent copper catalyst prepared in the example 1 is added, magnetic stirring is started at room temperature, the reaction is carried out at the stirring speed of 1000r/min, sampling is carried out at a specific moment, and H generated in situ in the reaction system is measured by an iodometry 2 O 2 See fig. 7;
FIG. 7 shows H during the degradation of the micro-nano dendritic zero valent copper catalyst prepared in example 1 2 O 2 Is generated.
As shown in FIG. 7, H 2 O 2 Is at a concentration throughout the reactionIs kept at a high level (600. Mu. Mol/L).
Claims (1)
1. The method for treating the organic wastewater by utilizing the micro-nano dendritic zero-valent copper catalyst to activate molecular oxygen is characterized by comprising the following steps of:
1. preparing a micro-nano dendritic zero-valent copper catalyst:
(1) CuSO of a certain quality 4 ·5H 2 O is dissolved in 150mL of deionized water to obtain copper sulfate solution with the concentration of 0.5 mol/L; adding 7.5mL of absolute ethyl alcohol into a copper sulfate solution with the concentration of 0.5mol/L, and uniformly stirring to obtain an electrolyte;
(2) taking an annular graphite ring as an anode, taking polished copper wires as a cathode, and applying 0.50A/cm after connecting a power supply 2 Carrying out deposition for 20s each time, carrying out co-deposition for 10 times, collecting powder obtained on a cathode, washing for 3 times by using deionized water and absolute ethyl alcohol in sequence, and finally carrying out vacuum drying for 6 hours at 60 ℃ to obtain the micro-nano dendritic zero-valent copper catalyst;
2. and (3) regulating the pH value of 50mL of metronidazole wastewater with the concentration of 30mg/L to be 2, adding 75mg of micro-nano dendritic zero-valent copper catalyst into the metronidazole wastewater with the pH value regulated, starting a magnetic stirrer, and reacting for 120min at the stirring speed of 1000r/min to obtain the wastewater with the metronidazole removed.
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| CN102839394A (en) * | 2012-09-17 | 2012-12-26 | 哈尔滨工业大学 | Method for rapidly preparing tree-like nano-iron with multi-level structure |
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| CN106984316A (en) * | 2017-05-15 | 2017-07-28 | 哈尔滨工业大学 | A kind of preparation method of the dendritic iron-copper of efficient out-phase class fenton catalyst micro-nano |
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