CN111420686A - F. S, Zr and Al codoped TiO2Preparation of photocatalyst and efficiency of catalytic degradation of acrylonitrile industrial wastewater by sunlight - Google Patents
F. S, Zr and Al codoped TiO2Preparation of photocatalyst and efficiency of catalytic degradation of acrylonitrile industrial wastewater by sunlight Download PDFInfo
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 17
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 14
- 239000011941 photocatalyst Substances 0.000 title claims description 16
- 230000015556 catabolic process Effects 0.000 title description 8
- 238000006731 degradation reaction Methods 0.000 title description 8
- 230000003197 catalytic effect Effects 0.000 title description 7
- 239000010842 industrial wastewater Substances 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002351 wastewater Substances 0.000 claims abstract description 25
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000000741 silica gel Substances 0.000 claims abstract description 7
- 230000031700 light absorption Effects 0.000 claims abstract description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 6
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 6
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000149 argon plasma sintering Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000499 gel Substances 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 claims 1
- 239000002019 doping agent Substances 0.000 claims 1
- 239000004570 mortar (masonry) Substances 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 52
- 239000002253 acid Substances 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004088 simulation Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 13
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- -1 comprises adsorption Chemical compound 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- 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
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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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- 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
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- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention relates to a preparation method of an F, S, Zr and Al co-doped modified titanium dioxide composite oxide catalyst for photocatalytic degradation of COD (chemical oxygen demand) of acrylonitrile actual wastewater under the conditions of simulation and natural sunlight, wherein the COD meets the national emission standard. The invention firstly provides an optimized sol-gel method F-doped TiO2Based on the catalyst preparation method, zirconium nitrate pentahydrate and thiourea are used as precursors to carry out S, Zr and Al co-doping. F. S, Zr and Al codoped modified TiO2The synergistic effect of the catalyst has obvious advantages, the photoresponse range of the catalyst is widened, the strength of acid sites on the surface of a sample is high, the uneven appearance and the pore structure formed by adding the silica gel cause light scattering, the light absorption is facilitated, and the improvement of the photocatalytic activity plays a roleThe optimum ratio of Ti, F, S, Zr and Al is 1: 0.5-5%: 1-10%: 0.1-2%, the appropriate calcination temperature and calcination time are 350-500 deg.C and 1-3h respectively, the catalyst can still reduce COD from about 89 to below 42 mg/L after 4 times of repetition.
Description
Technical Field
The invention relates to a composite oxide catalyst for photocatalytic degradation of actual acrylonitrile wastewater, in particular to a photocatalyst for photocatalytic degradation of acrylonitrile industrial wastewater in a water phase, which is prepared by dispersing fluorine, sulfur, zirconium and aluminum codoped modified titanium dioxide in silica gel and a preparation method thereof, and belongs to the technical field of environmental protection.
Background
Acrylonitrile (acrylonitrile, CH)2CH-CN, abbreviated as AN) acrylonitrile is AN important raw material (ABS) resin for producing acrylic fiber, nitrile rubber, acrylamide, acrylonitrile-butadiene styrene. Global acrylonitrile production capacity exceeds 500 million tons per year. China and the united states are the largest two acrylonitrile producing countries in the world. Unfortunately, current acrylonitrile production processes produce at least one ton of wastewater when producing one ton of acrylonitrile. More seriously, the acrylonitrile production wastewater is composed of a large amount of highly toxic compounds, and the acrylonitrile wastewater not only destroys an aqueous ecosystem, but also has great harm to human health. However, the use of acrylonitrile is inevitable for a short time due to the great demand for acrylonitrile on the market, and a plan for effectively treating acrylonitrile waste water is urgently required. At present, the treatment of acrylonitrile mainly comprises adsorption, incineration, recovery, activated sludge and the like. The method has the advantages of high cost, insufficient removal and harsh working conditions, and is difficult to effectively control the pollution of the acrylonitrile wastewater. The most difficult contaminant to treat in acrylonitrile wastewater is polymer. It is mainly derived from low molecular polymers or copolymers of nitriles. These polymers are usually present in water in colloidal or dissolved form, are difficult to hydrolyze and are used by microorganisms, and cannot be practically removed. Acrylonitrile waste water is generally considered the most difficult organic waste water to treat.
The photocatalyst oxidation is that the catalyst is irradiated by light, absorbs light energy, generates electron transition and generates electron spaceThe hole pairs directly carry out oxidation reduction on the pollutants adsorbed on the surface to generate hydroxyl radicals with strong oxidizing property to oxidize the pollutants. Solar energy is one of the best alternative energy sources due to its abundant resources and low carbon production. At present, great progress has been made in the research and development of solar energy utilization systems, and the most studied semiconductor catalytic material is TiO2In the ultraviolet range of 300nm to 390nm, TiO2The photocatalytic activity of the TiO-based photocatalyst is very high, and the TiO-based photocatalyst can still keep very high photocatalytic activity after being recycled for many times2Can completely mineralize the target pollutant into water and carbon dioxide, does not cause secondary pollution to the environment, and in addition, TiO2Has great stability in the aspects of chemistry, thermodynamics, mechanical properties and the like, so the method is widely applied to the field of environmental purification.
TiO2The photocatalytic activity of (A) can be improved by adding silica gel to increase its specific surface area. In recent years, various reports have been made on the manner of supporting titanium dioxide, for example, TiO supported on activated carbon2Molecular sieve supported TiO2Glass bead-supported TiO2TiO supported on silica2. The mineralization capability of the catalyst to the degradation pollutants can be improved by utilizing the adsorption characteristic of the carrier. The activity of the supported catalyst is greatly improved compared with that of the unsupported titanium dioxide, because a synergistic effect can be formed between the titanium dioxide and the carrier. Wherein, the silicon dioxide has good adsorption performance and larger specific surface area. TiO supported on silica2The catalyst has the advantages of thermal stability and mechanical stability of silicon dioxide, is transparent, and can reduce light scattering, thereby effectively improving the degradation performance of the catalyst. Adding SiO2Can effectively control TiO2The crystal particles grow, the agglomeration phenomenon of the catalyst is effectively inhibited, and the catalyst obtains smaller particle size and higher specific surface area. TiO supported on silica gel2It also undergoes interfacial diffusion with silicon dioxide to form Si-O-Ti bonds. The formation of Si-O-Ti bond can inhibit anatase type TiO2Rutile type TiO2And (4) converting. Golden brightness, etcPeople find that the nano titanium dioxide can effectively degrade acrylonitrile in the water in an open reactor under the condition of sufficient and stable illumination. Pang D.D et al found that F-doped SiO using HF as the F source2Supported TiO2The composite photocatalyst shows the highest activity of degrading acrylonitrile. In situ infrared and NH3The results of TPD show that F-doping increases SiO2Supported TiO2The surface acid position number and the acid strength of the composite photocatalyst. When the molar ratio of HF to Ti is 1: 1 and TiO2When the load is 36%, under the irradiation of simulated sunlight, the removal rate of acrylonitrile can reach 66% in 6 min.
Improvement of TiO by doping modification of non-metal elements2One advantage of activity is the ability to extend TiO2The visible light catalytic activity does not affect the catalytic activity of the catalyst ultraviolet light. Semi-conductive TiO2Medium metal ion Ti4+The d orbital energy level of (a) determines the energy level of its conduction band, while the energy level of the valence band is determined by the non-metal ion O2-Is determined by the p orbital level of. The modification of the valence band is generally performed because the space for increasing the potential of the valence band is larger than the space for decreasing the potential of the conduction band, and the valence band is relatively easy to realize. Compared with the 2p orbital of O, non-metallic elements such as B, C, N and S have higher energy p orbitals, and after the elements replace O atoms, the valence band potential of the semiconductor titanium dioxide is improved to a certain extent, thereby reducing the semiconductor TiO2The forbidden band width of (c). However, theoretically, only when the radius of the non-metal element ion is very close to that of the O ion, the non-metal element ion can replace the TiO2Oxygen ions in the crystal lattice of (1). Thus, the non-metallic elements studied by scientists are mainly distributed around the oxygen element, such as C, N, S, B and the halogen element. The fluorine atom has a smaller diameter than the oxygen atom, and therefore, theoretically, the fluorine atom can replace the oxygen atom in titanium oxide. Modification of TiO by doping with a large amount of fluorine2In the study (2), fluorine may be substituted for TiO2Oxygen ions in the crystal lattice can also be adsorbed on TiO2The surface of the particles. With nitrogen-doped TiO2Different, fluorine-doped modified TiO2The light absorption edge of the catalyst is not significantly altered because of the 2 of fluorinepotential ratio of p orbital TiO2The valence band potential of (2) is low. Researchers have synthesized anatase type TiO by hydrothermal method2The visible photocatalytic activity of the catalyst was very high, the authors found that TiO was doped with fluorine2Then, part of Ti4+Conversion to Ti3+Oxygen vacancies are formed, and oxygen molecules on the surface of the catalyst are captured to generate superoxide radicals, so that the activity of the catalyst is improved. In addition, F is doped with TiO2Can also increase TiO2The surface acidity of (2). F-doped TiO2Then, L ewis and Bronsted acid sites appear on the surface of the sample, and L ewis and Bronsted acid sites are good adsorption centers of oxygen molecules and molecules with lone pair electrons, so that F doping can effectively improve the degradation activity of the organic matters with the lone pair electrons.
Another way to effectively increase the catalytic and activity is to increase the number of surface acid sites. It has been demonstrated that photocatalytic activity increases with an increase in the number of acid sites on the surface of the catalyst. Cui et al 1995 reported that TiO could be doped by metal oxides2To increase its surface acidity and photocatalytic activity. Wang et al 2006 reported that there was an amorphous TiO2And sulfur compound at high temperature to synthesize sulfur-doped TiO2And the photocatalyst can be prepared by using the photocatalyst with acid sites. However, few reports have been made on the photocatalytic degradation of acrylonitrile using acidic and highly stable catalysts.
On one hand, the Zr is doped into TiO2 crystal lattice, and the overall stability is improved because Zr is very stable. On the other hand, Zr also influences the growth direction of Ti during the crystal growth process to form force, so that the stability of the crystal structure is improved, and the Zr also has the function of fixing fluorine. Al has both of the above two effects, and the former has a stronger effect.
Disclosure of Invention
The photocatalysis process is carried out in actual acrylonitrile wastewater, and because various interference ions exist in the actual wastewater, and organic matters and inorganic components are very complex, in order to solve the problems, the invention aims to provide the high-efficiency reusable photocatalyst for photocatalytic degradation of the actual acrylonitrile wastewater, 100-plus-200-mesh silicon dioxide is used as a dispersing agent, and hydrogen fluoride, zirconium nitrate, aluminum nitrate and thiourea are used as doping precursors to prepare the catalyst with the mesoporous structure and the large specific surface area, the composite doping of F, S in the catalyst improves the acid strength and the light absorption capacity of the surface of the catalyst, so that the photocatalytic activity and the anti-interference capacity are improved, and the doping of Zr and Al greatly improves the overall durability of the catalyst.
The invention also aims to provide a preparation method of the catalyst for the sunlight catalytic degradation of the actual acrylonitrile wastewater, and the silica gel-supported fluorine, sulfur, zirconium and aluminum-doped titanium dioxide composite oxide catalyst is prepared by a sol-gel method.
The inventor of the invention discovers that F is doped with TiO through research2The catalyst shows excellent effect on the actual wastewater degradation of acrylonitrile, and the dark adsorption amount of the catalyst compared with that of organic matters is P25 TiO2The method also has a relatively large improvement, and analysis shows that an adsorption effect exists between the acid center on the surface of the catalyst and the lone pair of electrons in the organic matter of the acrylonitrile wastewater.
In order to further improve the photocatalytic activity of the catalyst, the composite oxide catalyst provided by the invention adopts fluorine, sulfur and zirconium codoping. In the preparation process by using a sol-gel method, hydrogen fluoride, zirconium nitrate pentahydrate, aluminum nitrate and thiourea solution are added into a catalyst as a doping precursor, and then the mixture is calcined at high temperature to form the fluorine-doped catalyst, which has more surface acid sites, and the addition of silica gel forms uneven apparent morphology and light scattering caused by a pore structure, so that the light absorption is facilitated, the important effect on the improvement of the photocatalytic activity is achieved, and the photocatalytic activity can be greatly improved. Especially, the addition of Zr and Al greatly improves the stability of the catalyst.
The invention also provides a preparation method of the composite oxide photocatalyst, which comprises the following steps:
dropwise adding 2-8ml of butyl titanate into 10-16m L of absolute ethyl alcohol, and mixing to obtain a clear solution, namely solution A.
12-32m L of absolute ethyl alcohol, 2.3-5.3m L of glacial acetic acid, 15-35mg of thiourea, 449mg of 429-449mg of zirconium nitrate pentahydrate, 13-18mg of aluminum nitrate, 0.2-1.5m L of hydrofluoric acid and 0.4-1.9m L of deionized water are sequentially added into a 150m L beaker, and the solution B is obtained after 2min of ultrasonic treatment.
And dropwise adding the solution B into the solution A, sealing and stirring for 1-3h, opening and sealing, continuously stirring to form uniform water-like sol, continuously stirring for a period of time until oily sol is formed, and then adding 100-mesh and 200-mesh silica gel until gel is formed.
Aging the gel for about 8-12h at room temperature (20-30 ℃), drying in a drying oven at 70-130 ℃, uniformly grinding the obtained dry powdery catalyst precursor, and finally calcining for 1-3h in a tubular furnace at 350-500 ℃. Thus obtaining the doped modified SiO2Dispersed TiO2/SiO2A catalyst. The composition ratio of Ti to F to S to Zr to Al is 1 to 0.5-5 to 1-10 to 0.1-2.
The TEM results (left panel) show the catalyst as particles of about 30nm in diameter, and the enlarged right panel more clearly shows that these particles are made up of seemingly smaller agglomerates of particles, with square particles present.
F. S, Zr and Al codoped modified TiO2/SiO2The activity evaluation of the photocatalyst selects organic pollutants in the actual acrylonitrile wastewater as target degradation products.
From the research comparison and practical application angles, two light sources, namely a 350w AHD350 type spherical xenon lamp and a sunlight, are respectively selected to treat the acrylonitrile practical wastewater.
Drawings
FIG. 1 shows F-S-Zr-Al-TiO2/SiO2TEM images of the samples.
FIG. 2 shows the use of F-S-Zr-Al-TiO2/SiO2The COD of the actual acrylonitrile wastewater treated by the catalyst through four reactions (three times of recovery and activation) is along the change curve of the simulated solar illumination time.
FIG. 3 shows the use of F-S-Zr-Al-TiO2/SiO2The COD of the actual acrylonitrile wastewater treated by the catalyst for the first time is along the curve of the change of simulation and natural illumination time.
Detailed Description
The following examples are provided to illustrate the present invention and to demonstrate the advantageous effects thereof, but should not be construed as limiting the scope of the invention in any way.
Method for evaluating catalyst activity:
the method specifically comprises the steps of selecting low-concentration acrylonitrile actual wastewater as a target degradation product for activity evaluation of a photocatalyst, pouring 150m L actual wastewater into a quartz reactor, adding 300mg of the photocatalyst, sealing the reactor, stirring in the dark for 35min to achieve adsorption and desorption balance, turning on a xenon lamp to start illumination, selecting a 350w AHD350 spherical xenon lamp light source as the light source, and taking two groups of 4m L wastewater suspensions as parallel samples in 2h, 6h, 10h and 14h in the illumination process.
The detection method comprises the steps of measuring COD by using a Union L H-5B-3B (V8) type COD rapid measuring instrument, measuring the COD error within +/-10%, and measuring the COD of a sample by filtering the sample by using a filter membrane with the aperture of 0.45 mu m immediately after sampling, wherein the value is the COD corresponding to the time.
Along with the prolonging of the illumination time, the COD in the catalyst and the solution is decreased according to a curve shown in figure 2, after 14 hours of irradiation, the COD in the solution is decreased from 89 to about 25 mg/L, and after 4 times of reaction, the COD still can reach about 42 mg/L, so that the basic complete degradation of organic matters and the good stability of the catalyst are demonstrated.
In the same way, the actual waste water of acrylonitrile is degraded to COD of about 50 mg/L by sufficient sunlight reaction.
Claims (5)
1. The composite oxide photocatalyst for degrading acrylonitrile waste water is prepared with silica gel of 100-mesh and 200-mesh as dispersant, hydrofluoric acid, zirconium nitrate pentahydrate, aluminum nitrate and thiourea as dopant precursor, and fluorine, sulfur, zirconium and aluminum co-doped for modification to obtain TiO with stable structure2A catalyst.
2. The method for preparing a composite oxide catalyst according to claim 1, comprising the steps of:
step 1, dropwise adding 2-8m L of butyl titanate into 10-16m L of absolute ethyl alcohol, and mixing to obtain a clear solution, namely solution A.
And 2, sequentially adding 12-32m L of absolute ethyl alcohol, 2.3-5.3m L of glacial acetic acid, 15-35mg of thiourea, 429-449mg of zirconium nitrate pentahydrate, 13-18mg of aluminum nitrate, 0.2L-1.5 m L of hydrofluoric acid and 0.4-1.9m L of deionized water into a 150m L beaker, and carrying out ultrasonic treatment for 2min to obtain a solution B.
And 3, dropwise adding the solution B into the solution A, stirring for 1-3h in a sealed manner, opening and sealing, continuously stirring to form uniform water-like sol, continuously stirring for a period of time until oily sol is formed, and then adding 100-mesh 200-mesh silica gel until gel is formed.
And 4, aging the gel for about 8-12 hours at room temperature (20-30 ℃), drying the gel for several hours in a drying oven at 70-90 ℃, uniformly grinding the obtained dry powdery catalyst precursor by using an agate mortar, and finally calcining the obtained product for 1-3 hours in a tubular furnace at 350-500 ℃ to obtain the modified silica gel-supported TiO doped with the four elements2A catalyst.
3. The method according to claim 2, wherein the fluorine precursor is a commercially available 40% aqueous hydrogen fluoride solution, the sulfur precursor is prepared from analytically pure thiourea, the zirconium precursor is analytically pure zirconium nitrate pentahydrate, and the aluminum precursor is analytically pure aluminum nitrate nonahydrate.
4. F element is used as a doping main body, S, Zr and Al element precursors with different contents are doped, and the proportion is properly adjusted (F: S: Zr: Al is 1: 0.5-5%: 1-10%: 0.1-2%).
5. The preparation method according to claim 2, wherein the method for efficiently photocatalytic degradation of acrylonitrile actual wastewater by the catalyst is characterized in that the co-doping of F, S, Zr and Al improves the acidity strength, light absorption capability and stability of the catalyst surface, and particularly, the addition of silica gel forms uneven appearance and light scattering caused by pore structure, which is beneficial to light absorption and plays an important role in improving the photocatalytic activity.
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