WO2017201795A1 - 利用有机膜产生羟基自由基及去除水中有机污染物的方法 - Google Patents
利用有机膜产生羟基自由基及去除水中有机污染物的方法 Download PDFInfo
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- WO2017201795A1 WO2017201795A1 PCT/CN2016/087168 CN2016087168W WO2017201795A1 WO 2017201795 A1 WO2017201795 A1 WO 2017201795A1 CN 2016087168 W CN2016087168 W CN 2016087168W WO 2017201795 A1 WO2017201795 A1 WO 2017201795A1
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- Prior art keywords
- sheet material
- hydroxyl radicals
- hydroxyl radical
- nitrocellulose
- water
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- 239000012528 membrane Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 48
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 title claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 18
- 229920001220 nitrocellulos Polymers 0.000 claims abstract description 94
- 239000000020 Nitrocellulose Substances 0.000 claims abstract description 93
- 239000000463 material Substances 0.000 claims abstract description 38
- 230000001699 photocatalysis Effects 0.000 claims abstract description 27
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- OTVAEFIXJLOWRX-NXEZZACHSA-N thiamphenicol Chemical compound CS(=O)(=O)C1=CC=C([C@@H](O)[C@@H](CO)NC(=O)C(Cl)Cl)C=C1 OTVAEFIXJLOWRX-NXEZZACHSA-N 0.000 claims abstract description 13
- 229960003053 thiamphenicol Drugs 0.000 claims abstract description 13
- 238000006552 photochemical reaction Methods 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
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- 238000006864 oxidative decomposition reaction Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 238000005286 illumination Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000004435 EPR spectroscopy Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
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- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
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- 239000004408 titanium dioxide Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- QWLULCKKOHDCIE-UHFFFAOYSA-N 2,3-dimethyl-1-oxidopyridin-1-ium Chemical compound CC1=CC=C[N+]([O-])=C1C QWLULCKKOHDCIE-UHFFFAOYSA-N 0.000 description 1
- 0 CO*(C(C(*)C1*)C(*)OC1OC(C(*)C1*)C(*)OC1O)=N Chemical compound CO*(C(C(*)C1*)C(*)OC1OC(C(*)C1*)C(*)OC1O)=N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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Images
Classifications
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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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/20—Esters of inorganic acids, e.g. cellulose nitrate
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/061—Chiral polymers
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/39—
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- B01J35/59—
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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
-
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
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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
-
- 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
-
- 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
- C02F2101/345—Phenols
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/44—Time
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Definitions
- the application belongs to the field of photochemical technology and sewage treatment, and particularly relates to a method for generating hydroxyl radicals by using an organic film and removing organic pollutants in water.
- Hydroxyl radical is a kind of active oxygen radical, which has strong oxidizing property and oxidation-reduction potential of 2.80V, which is second only to fluorine atom, and can diffusely control the rate with most inorganic or organic substances.
- the reaction rate constant is generally greater than 10 8 mol L -1 s -1 .
- hydroxyl radicals are used in the degradation of organic pollutants and are the most important active intermediates in advanced oxidation process wastewater treatment processes.
- the chemical catalysis method generally adopts the Fenton reaction, and the hydrogen peroxide catalyzes the decomposition of hydrogen peroxide to generate hydroxyl radicals.
- the method is simple and easy, and relatively inexpensive, but a large amount of iron-containing sludge is generated when applied on a large scale, which is unchanged for subsequent processing; Ozone and hydrogen peroxide photolyze under the action of ultraviolet light, which can generate hydroxyl radicals, but need to add hydroxyl radical precursor ozone and hydrogen peroxide, and have more side reactions; photocatalytic generation of hydroxyl radicals by using semiconductor titanium dioxide particles as catalyst It is necessary to ensure that the catalyst is in suspension, and photocatalysis also needs to separate the photocatalyst, and the continuous operability is poor, and the dissolved oxygen has a great influence on the photocatalytic generation of hydroxyl radicals by titanium dioxide; the method of electrocatalyzing the generation of hydroxyl radicals to dissolved oxygen in water The catalytic component has higher requirements and the current efficiency is lower; the ray method has the problems of high cost and great harm to the human body.
- the present invention provides a method of producing a hydroxyl radical using an organic film, characterized in that the method comprises:
- nitrocellulose sheet material as a photocatalytic material, irradiating the surface of the nitrocellulose sheet material with light having a wavelength of more than 280 nm to cause photochemical crystallization of the nitrocellulose sheet material
- the reaction produces hydroxyl radicals.
- the light source used is sunlight or a solar light having a wavelength greater than 280 nm.
- the nitrocellulose sheet material is a nitrocellulose membrane.
- the surface of the nitrocellulose sheet material is irradiated for a time of 60 minutes or more.
- the method further comprises adjusting the rate of production of hydroxyl radicals by adjusting the surface area of the membrane and the intensity of the light.
- the present invention provides a method for removing organic pollutants in water by using an organic film to generate hydroxyl radicals, characterized in that the method comprises:
- nitrocellulose sheet material as a photocatalytic material with a wavelength greater than 280 nm Irradiating the surface of the nitrocellulose sheet material to cause photochemical reaction of the surface of the nitrocellulose sheet material to generate hydroxyl radicals;
- the method is for removing phenol, bisphenol A and thiamphenicol in water.
- the light source used is sunlight or a solar light having a wavelength greater than 280 nm.
- the surface of the nitrocellulose sheet material is irradiated for a time of 60 minutes or more.
- the method further comprises adjusting the rate of production of hydroxyl radicals by adjusting the surface area of the membrane and the intensity of the light.
- the molecular structure of the nitrocellulose mentioned in the present invention is:
- the method for generating hydroxyl radicals uses a nitrocellulose membrane as a photocatalytic material, and the nitrocellulose membrane is placed in water or an aqueous solution, and the sun or a solar light having a wavelength greater than 280 nm is used as a light source for illumination.
- the nitrocellulose membrane is photochemically reacted to produce hydroxyl radicals.
- the rate of hydroxyl radical generation can be achieved by adjusting the surface area and light intensity of the membrane.
- the hydroxyl radicals generated can remove phenol, bisphenol A and Typical organic pollutants such as thiamphenicol.
- Nitrocellulose is inexpensive and widely used in inks, leather, plastic products and other fields. Nitrocellulose is the main material of the microporous membrane, and the film forming process is very mature. The invention is issued It is now possible to produce hydroxyl radicals under the illumination of nitrocellulose, which is used as a photocatalytic material to generate hydroxyl radicals under the irradiation of light with a wavelength greater than 280 nm. It has a good removal effect on organic pollutants and is expected to be applied to water treatment. field.
- the effect of UVB on the photocatalytic production of hydroxyl radicals on nitrocellulose membranes is extremely advantageous compared to other wavelengths, which is about eight times greater than the UVA effect. Therefore, it is preferred to use light-to-nitrocellulose in the UVB spectral range.
- the film is irradiated.
- the wavelength of the illumination source is selected to be 300-320 nm.
- the nitrocellulose membrane is formed into a wavy shape having a sinusoidal surface. Applicants have found that the nitrocellulose membrane of this structure has a significantly higher light utilization rate than conventional flat nitrocellulose membranes and higher than other shapes of cellulose membranes.
- the hydroxyl radical is generated on the surface of the nitrocellulose membrane, which is convenient for recycling and reuse, solves the problem that the recovery of the particulate catalyst is difficult, and the method of the invention can stably, continuously and uniformly generate hydroxyl radicals. , the controllable formation of hydroxyl radicals is achieved.
- the process of the invention does not require the introduction of any hydroxyl radical precursors, avoiding secondary contamination.
- the nitrocellulose membrane Due to the ultraviolet radiation in the ultraviolet region with a wavelength greater than 280 nm, the nitrocellulose membrane can generate hydroxyl radicals, which can directly use sunlight and reduce the cost of water treatment.
- nitrocellulose membrane is used to overcome the mutual shading problem of the particulate catalyst, the rate of generation of hydroxyl radicals can be adjusted by adjusting the membrane area.
- nitrocellulose is inexpensive and easy to be widely applied.
- Figure 1 shows the ESR qualitative analysis of photocatalytic hydroxyl radical generation on the surface of nitrocellulose membrane. fruit
- Figure 2 is a time-concentration curve of hydroxyl radicals under different membrane areas
- Figure 3 is a time-concentration curve of hydrolysis of nitrocellulose membrane to nitrate and nitrite
- Figure 4 is a comparison of the formation of hydroxyl radicals under illumination by nitrite, aqueous nitrate solution and nitrocellulose membrane;
- Figure 5 shows the photocatalytic generation of hydroxyl radicals on the surface of nitrocellulose membrane under nitrogen, oxygen and control conditions
- Figure 6 is a time-concentration curve of hydroxyl radical generation under different repetition times when the nitrocellulose membrane is reused
- Figure 7 shows the effect of spectral interval (A), light intensity (B), pH (C) and temperature (D) on hydroxyl radical generation.
- Figure 8 is a graph showing the relationship between the concentration of phenol, bisphenol A and thiamphenicol in the photocatalytic removal of phenol, bisphenol A and thiamphenicol in the nitrocellulose membrane under sunlight;
- Figure 9 shows the relationship between the concentration of phenol, bisphenol A and thiamphenicol in the photocatalytic removal of phenol, bisphenol A and thiamphenicol in water under sunlight.
- nitrocellulose membrane was cut into strips of 2 cm in length and 0.1 cm in width, inserted into a quartz sample tube, and inhaled 100 mM dimethyl pyridine N-oxide (DMPO) for in situ electron self-in- Rotational resonance spectrum analysis.
- DMPO dimethyl pyridine N-oxide
- the generation of hydroxyl radicals was monitored in real time with 180W solar light. The results are shown in Fig. 1.
- the background signal is basically a flat line.
- the characteristic signals of the hydroxyl radical and the DMPO adduct can be observed, and four peaks and peak height ratios appear.
- the measurement of the hydroxyl radical was carried out by means of electron spin resonance (ESR) after DMPO capture.
- ESR electron spin resonance
- the electron spin resonance experimental device consists of ESR (Germany Bruker EMX-plus 10/12) spectrometer and solar light (Megra, USA).
- the ESR experimental parameters are as follows: microwave frequency 9.8527 GHz; microwave power 20 mW; scanning range 3459-3559G ; scan step size 1G.
- the amount of hydroxyl radical production is linear with the increase of the area of the nitrocellulose membrane, indicating that the nitrocellulose membrane can quantitatively and stably generate hydroxyl radicals.
- the inventors conducted the same experiment on cellulose and cellulose acetate membranes. However, the formation of phenol was not observed in cellulose and cellulose acetate membrane under the same light conditions, indicating that the photocatalytic hydroxyl radical production of nitrocellulose membrane is closely related to the nitro group in nitrocellulose membrane.
- the nitrocellulose membrane is chemically structurally a nitrate of cellulose, which may be hydrolyzed to produce nitrate or nitrite. It is currently not possible to exclude the latter from generating hydroxyl radicals under illumination.
- a hydrolysis experiment of a nitrocellulose membrane was carried out. A ⁇ 47mm nitrocellulose membrane was placed in pure water and hydrolyzed at 35 ° C. The nitrate and nitrite produced by hydrolysis were determined by ion chromatography and compared with the blank and standard. The results are shown in the figure. 3 is shown.
- the nitrocellulose membrane can only be slightly hydrolyzed in water; compared with the standard, after 2 hours of hydrolysis, only 0.8 ⁇ M of nitrite and 2.3 ⁇ M of nitrate are formed in the solution.
- the formation of hydroxyl radicals under illumination of 0.8 ⁇ M nitrite and 2.3 ⁇ M nitrate solution under the same conditions was investigated and compared with the formation of hydroxyl radicals by nitrocellulose membrane. The results are shown in Fig. 4. It can be seen that the formation of hydroxyl radicals in the nitrocellulose membrane is mainly generated on the surface of the membrane, while the nitrate and nitrite produced by hydrolysis in the solution phase have substantially no effect.
- Example 4 Photocatalytic generation of hydroxyl radicals on the surface of nitrocellulose membrane under nitrogen and oxygen
- Fig. 7A shows that the effective spectral range of photocatalytic production of hydroxyl radicals by nitrocellulose membranes is UVA and UVB, and the ability of UVB to generate hydroxyl radicals is stronger than that of UVA.
- the visible region is basically ineffective.
- the method for measuring a hydroxyl radical is to react with benzene to form phenol to reflect the formation of a hydroxyl radical.
- Phenol was determined by high performance liquid chromatography (Agilent 1200, USA).
- the separation column was Zorbax SB-C18 (150 mm ⁇ 4.6 mm, 5 ⁇ m); the detector was a fluorescence detector with excitation and emission wavelengths of 260 and 310 nm, respectively;
- the phase was 40% aqueous acetonitrile (v/v), the pH was adjusted to about 2 to 3 with hydrochloric acid, and the mobile phase flow rate was 1 ml/min.
- Example 7 (Nitrogen lamp and sunlight nitrocellulose membrane catalyzed removal of organic pollutants in water)
- the illumination time of the nitrocellulose membrane is greater than or equal to 60 minutes, and the Applicant has found that if the nitrocellulose membrane is continuously illuminated, the hydroxyl is after 60 minutes.
- the rate of generation of radicals is about three times that of hydroxyl radicals in 60 minutes, and if the light is continued after the middle stops, the rate of generation of hydroxyl radicals returns to the normal rate.
- the nitrocellulose membrane and sewage are preheated prior to illumination, and the rate of hydroxyl radical generation at 35 ° C is about twice that of 20 °C.
- the larger the membrane area the faster the rate of generation of hydroxyl radicals. Therefore, in order to improve the treatment effect of the pollutants, the contact area between the membrane and the sewage should be increased as much as possible.
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- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
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Abstract
Description
Claims (10)
- 一种利用有机膜产生羟基自由基的方法,其特征是,所述方法包括:1)、制备硝酸纤维素片状材料;2)、将所述硝酸纤维素片状材料置于水溶液中;3)、以所述硝酸纤维素片状材料为光催化材料,通过波长大于280nm的光对所述硝酸纤维素片状材料的表面进行照射,使所述硝酸纤维素片状材料发生膜表面光化学反应产生羟基自由基。
- 根据权利要求1所述的利用有机膜产生羟基自由基的方法,其特征在于,在对所述硝酸纤维素片状材料进行照射时,所用的光源为太阳光或者波长大于280nm的太阳灯。
- 根据权利要求1所述的利用有机膜产生羟基自由基的方法,其特征在于,所述硝酸纤维素片状材料为硝酸纤维素膜。
- 根据权利要求1所述的利用有机膜产生羟基自由基的方法,其特征在于,对所述硝酸纤维素片状材料的表面进行照射的时间大于等于60分钟。
- 根据权利要求1所述的利用有机膜产生羟基自由基的方法,其特征在于,所述方法还包括通过调节膜表面积和光强来调节羟基自由基的产生速率。
- 一种利用有机膜产生羟基自由基去除水中有机污染物的方法,其特征在于,所述方法包括:1)、制备硝酸纤维素片状材料;2)、将所述硝酸纤维素片状材料置于含水和有机污染物的液体中;3)、以所述硝酸纤维素片状材料为光催化材料,通过波长大于280nm 的光对所述硝酸纤维素片状材料的表面进行照射,使所述硝酸纤维素片状材料发生膜表面光化学反应产生羟基自由基;4)、利用所产生的羟基自由基对液体中的有机污染物进行氧化分解。
- 根据权利要求6所述的利用有机膜产生羟基自由基去除水中有机污染物的方法,其特征在于,所述方法用于去除水中的苯酚、双酚A和甲砜霉素。
- 根据权利要求6所述的利用有机膜产生羟基自由基去除水中有机污染物的方法,其特征在于,在对所述硝酸纤维素片状材料进行照射时,所用的光源为太阳光或者波长大于280nm的太阳灯。
- 根据权利要求6所述的利用有机膜产生羟基自由基去除水中有机污染物的方法,其特征在于,对所述硝酸纤维素片状材料的表面进行照射的时间大于等于60分钟。
- 根据权利要求6所述的利用有机膜产生羟基自由基去除水中有机污染物的方法,其特征在于,所述方法还包括通过调节膜表面积和光强来调节羟基自由基的产生速率。
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US8038938B2 (en) * | 2007-01-31 | 2011-10-18 | Universidad Católica de la Santisima Concepción | Photocatalytic reactor and process for treating wastewater |
CN101863548A (zh) * | 2010-07-07 | 2010-10-20 | 中国地质大学(北京) | 一种去除水中有机物的装置及方法 |
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CN106082388A (zh) | 2016-11-09 |
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