CN111420686B - F. S, zr and Al co-doped TiO 2 Preparation of photocatalyst and efficiency of degrading acrylonitrile industrial wastewater by using sunlight catalysis - Google Patents
F. S, zr and Al co-doped TiO 2 Preparation of photocatalyst and efficiency of degrading acrylonitrile industrial wastewater by using sunlight catalysis Download PDFInfo
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- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 38
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011941 photocatalyst Substances 0.000 title claims description 15
- 230000000593 degrading effect Effects 0.000 title claims description 5
- 239000010842 industrial wastewater Substances 0.000 title description 3
- 238000006555 catalytic reaction Methods 0.000 title description 2
- 239000002351 wastewater Substances 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000000741 silica gel Substances 0.000 claims abstract description 7
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 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
- 238000001354 calcination Methods 0.000 claims abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 12
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- 238000000034 method Methods 0.000 claims description 8
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- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
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- 230000032683 aging Effects 0.000 claims description 2
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- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
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- 239000001301 oxygen Substances 0.000 abstract description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 2
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- 230000009286 beneficial effect Effects 0.000 abstract 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical class O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
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- -1 comprises adsorption Chemical compound 0.000 description 3
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 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
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- 238000003917 TEM image Methods 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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- 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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- 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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Abstract
The invention relates to a preparation method of a F, S, zr, al co-doped modified titanium dioxide composite oxide catalyst for photocatalytic degradation of acrylonitrile practical wastewater COD (chemical oxygen demand) under simulated and natural sunlight condition irradiation, which meets the national emission standard. The invention firstly provides the optimized F-doped TiO by the sol-gel method 2 Based on the preparation method of the catalyst, namely, zirconium nitrate pentahydrate and thiourea are used as precursors to carry out S, zr and Al co-doping. F. S, zr and Al co-doped modified TiO 2 The catalyst has obvious synergistic effect, the light response range of the catalyst is widened, the strength of acid sites on the surface of a sample is high, the light scattering caused by the uneven appearance and pore structure formed by adding silica gel is beneficial to light absorption, and the improvement of the photocatalytic activity is important, wherein the addition of Zr and Al obviously improves the stability of the whole catalyst system. The optimum ratio of Ti, F, S, zr, al is 1:0.5-5:1-10:0.1-2%, and the proper calcining temperature and calcining time are 350-500 deg.C and 1-3h respectively. The catalyst is repeated for 4 times, and the COD can still be reduced from about 89 to below 42 mg/L.
Description
Technical Field
The invention relates to a composite oxide catalyst for photocatalytic degradation of acrylonitrile actual wastewater, in particular to a photocatalyst for photocatalytic degradation of acrylonitrile industrial wastewater in an aqueous phase, which is prepared by dispersing fluorine, sulfur, zirconium and aluminum co-doped modified titanium dioxide by silica gel and a preparation method thereof, and belongs to the technical field of environmental protection.
Background
Acrylonitrile (CH) 2 =ch-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 ten thousand 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 wastewater from acrylonitrile production is composed of a large amount of highly toxic compounds, and the wastewater from acrylonitrile not only damages the water ecosystem, but also has great harm to human health. However, due to the great demand for acrylonitrile in the market, the use of acrylonitrile is unavoidable in a short time, and a plan for effectively treating acrylonitrile wastewater is urgently required. At present, the treatment of acrylonitrile mainly comprises adsorption, incineration, recovery, activated sludge and the like. The method has high cost, insufficient removal, harsh working conditions and difficult effective control of pollution of the acrylonitrile wastewater. The most difficult contaminant to treat in acrylonitrile wastewater is a polymer. It is mainly derived from low molecular polymers or copolymers of nitriles. These polymers are often present in water in colloidal or dissolved form, are difficult to hydrolyze and to use by microorganisms, and cannot be practically removed. Acrylonitrile wastewater is generally considered the most difficult organic wastewater to treat.
The photocatalyst oxidation is that the catalyst is irradiated by light to absorb light energy, generates electron transition to generate electron hole pairs, directly oxidizes and reduces pollutants adsorbed on the surface to generate hydroxyl free radicals with strong oxidability, and oxidizes the pollutants. Due to its abundant resources and low carbon production, the sunCan be one of the best alternative energy sources. At present, research and development of solar energy utilization systems have been greatly progressed, and the most studied semiconductor catalytic material is TiO 2 TiO in the ultraviolet light range of 300nm to 390nm 2 The photocatalytic activity of the catalyst is very high, and the catalyst can still keep very high photocatalytic activity after repeated recycling, and the TiO 2 Can thoroughly mineralize target pollutants into water and carbon dioxide without causing secondary pollution to the environment, and in addition, tiO 2 Has great stability in chemical, thermodynamic and mechanical properties, etc., so that it is widely used in the field of environmental purification.
TiO 2 The photocatalytic activity of (2) can be improved by adding silica gel to increase the specific surface area thereof. In recent years, many documents report on the manner of loading titanium dioxide, such as activated carbon-loaded TiO 2 Molecular sieve loaded TiO 2 Glass bead supported TiO 2 Silica supported TiO 2 . The mineralization capacity of the catalyst for degrading 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 property and larger specific surface area. Silica supported TiO 2 The catalyst has excellent thermal stability and mechanical stability of silicon dioxide, is a light transparent body, can reduce light scattering, and can effectively improve the degradation performance of the catalyst. SiO addition 2 Can effectively control TiO 2 The crystal particles grow up, so that the agglomeration phenomenon of the catalyst is effectively inhibited, and the catalyst has smaller particle size and higher specific surface area. TiO supported on silica gel 2 And also interfacial diffusion with silicon dioxide to form Si-O-Ti bonds. TiO, in which formation of Si-O-Ti bond can inhibit anatase form 2 To rutile type TiO 2 And (3) converting. The gold and the like find that the nano titanium dioxide can effectively degrade acrylonitrile in water distribution in an open reactor under the condition of sufficient and stable illumination. Pang D.D et al found that HF was used as the F source, doped with FHetero SiO 2 Loaded TiO 2 The composite photocatalyst shows the highest activity for degrading acrylonitrile. In situ infrared and NH 3 The results of TPD show that F doping improves SiO 2 Loaded TiO 2 The number of acid sites on the surface of the composite photocatalyst and the acid strength. When the mole ratio of HF to Ti is 1:1 and TiO 2 When the load amount is 36%, the removal rate of the acrylonitrile can reach 66% in 6min under the irradiation of simulated sunlight.
Modification of TiO by non-metallic element doping 2 One advantage of activity is that it enables the expansion of TiO 2 The visible light catalytic activity is not influenced at the same time. Semiconductor TiO 2 Medium metal ion Ti 4+ The d-orbital level of (2) determines the energy level of its conduction band, while the energy level of the valence band is determined by the nonmetallic ion O 2- Is determined by the p-orbital level of (c). The modification of the valence band is generally achieved because the space for increasing the valence band potential is larger than the space for decreasing the conduction band potential. Compared with the 2p orbit of O, the nonmetallic elements such as B, C, N, S and the like have p orbitals with higher energy, and when the elements replace O atoms, the valence band potential of the semiconductor titanium dioxide is improved to a certain extent, thereby reducing the semiconductor TiO 2 Is set in the band gap of the semiconductor device. However, in theory, the ions of the nonmetallic element can replace TiO only when the radii of the ions of the nonmetallic element and the O ions are very close 2 Oxygen ions in the crystal lattice of (a). Therefore, nonmetallic elements studied by scientists are mainly distributed in the vicinity of oxygen elements such as C, N, S, B and halogen elements. The fluorine atom has a smaller diameter than the oxygen atom, so that in theory, the fluorine atom can replace the oxygen atom in the titanium dioxide. Modified TiO in a large amount of fluorine doping 2 In the study of (2), fluorine can replace TiO 2 Oxygen ions in the crystal lattice can also be adsorbed on TiO 2 The surface of the particles. Doped with nitrogen to form TiO 2 Differently, fluorine doped modified TiO 2 The light absorption edge of the catalyst is not significantly changed because the potential of the 2p orbitals of fluorine is higher than that of TiO 2 Is low. Researchers have used hydrothermal synthesis of anatase TiO 2 The visible light catalytic activity of the catalyst was very high, and the authors found fluorineDoped TiO 2 After that, part of Ti 4+ Conversion to Ti 3+ Oxygen vacancies are formed, oxygen molecules on the surface of the catalyst are captured to generate superoxide radicals, and the activity of the catalyst is further improved. In addition to that, F-doped TiO 2 Can also increase TiO 2 Is a surface acidity of the steel sheet. F-doped TiO 2 After that, lewis and Bronsted acidic sites appear on the surface of the sample, and the Lewis and Bronsted acidic 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 organic matters with lone pair electrons.
Another effective way to increase catalysis and activity is to increase the number of acid sites on its surface. Photocatalytic activity has been demonstrated to increase with increasing acidic sites on the catalyst surface. Cui et al 1995 reported that TiO could be doped by metal oxides 2 To increase its surface acidity and photocatalytic activity. Wang et al 2006 report amorphous TiO 2 And sulfur compounds can synthesize sulfur-doped TiO at high temperature 2 Having an acidic site can act as a photocatalyst. However, few reports have reported the photocatalytic degradation of acrylonitrile using acidic and highly stable catalysts.
On the one hand, the doping of Zr enters the TiO2 crystal lattice, and the overall stability is improved because Zr is very stable. On the other hand, zr also affects the growth direction of Ti during crystal growth to form force, so that the stability of crystal structure is improved and fluorine fixing effect is achieved. While Al has both the above effects, the former is stronger.
Disclosure of Invention
The photocatalytic process is carried out in the actual acrylonitrile wastewater, and because various interference ions exist in the actual wastewater in a large quantity, organic matters and inorganic components are very complex, the invention aims to solve the problems, and aims to provide the photocatalyst for efficiently and repeatedly degrading the acrylonitrile actual wastewater by photocatalysis, wherein 100-200 meshes of silicon dioxide is taken as a dispersing agent, hydrogen fluoride, zirconium nitrate, aluminum nitrate and thiourea are taken as doping precursors, the catalyst with a mesoporous structure and a large specific surface area is prepared, the acid strength and the light absorption capacity of the catalyst surface are improved by the composite doping of F, S in the catalyst, the photocatalytic activity and the anti-interference capacity are improved, and the durability of the catalyst is greatly improved by doping Zr and Al.
The invention also aims to provide a preparation method of the catalyst for the sunlight catalytic degradation of the acrylonitrile actual 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 present invention found through research that F-doped TiO 2 The catalyst has excellent effect on the actual wastewater degradation of the acrylonitrile, and compared with the dark adsorption quantity of organic matters, the catalyst has P25 TiO 2 The method is also greatly improved, and analysis shows that adsorption exists between the acid center on the surface of the catalyst and lone pair electrons in the organic matters 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 co-doping. In the preparation process of the sol-gel method, hydrogen fluoride, zirconium nitrate pentahydrate, aluminum nitrate and thiourea solution are used as doping precursors to be added into the catalyst, and then the fluorine doping catalyst is obtained by high-temperature calcination, the fluorine doping catalyst has more surface acid sites, and the addition of silica gel forms light scattering caused by uneven apparent morphology and pore structure, so that the light absorption is facilitated, the important effect is played for improving the photocatalytic activity, and the photocatalytic activity of the fluorine doping catalyst 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:
2-8mL of butyl titanate is dropwise added into 10-16mL of absolute ethyl alcohol and mixed with the absolute ethyl alcohol, so as to obtain a clear solution, namely solution A.
12-32mL of absolute ethyl alcohol, 2.3-5.3mL of glacial acetic acid, 15-35mg of thiourea, 429-449mg of zirconium nitrate pentahydrate, 13-18mg of aluminum nitrate, 0.2-1.5mL of hydrofluoric acid and 0.4-1.9mL of deionized water are sequentially added into a 150mL beaker, and the solution B is obtained after ultrasonic treatment for 2 min.
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 to form oily sol, and adding 100-200 mesh silica gel until gel is formed.
Aging the gel at room temperature (20-30deg.C) for about 8-12 hr, oven drying at 70-130deg.C, grinding the obtained dry powdered catalyst precursor, and calcining at 350-500deg.C for 1-3 hr in a tube furnace. Thus obtaining the doped modified SiO 2 Dispersed TiO 2 /SiO 2 A catalyst. The composition ratio of Ti to F to S to Zr to Al=1 to 1 to 0.5-5% to 1-10% to 0.1-2%.
TEM results (left panel) show that the catalyst is particles of about 30nm diameter, and the enlarged right panel shows more clearly that these particles are agglomerated from what appears to be smaller particles, and that square particles are present.
F. S, zr and Al co-doped modified TiO 2 /SiO 2 The activity evaluation of the photocatalyst selects organic pollutants in the acrylonitrile actual wastewater as target degradation products.
From the angles of research comparison and practical application, 350w of AHD350 type spherical xenon lamp and sunlight two light sources are respectively selected to treat the acrylonitrile practical wastewater.
Drawings
FIG. 1 is F-S-Zr-Al-TiO 2 /SiO 2 TEM image of the sample.
FIG. 2 shows the use of F-S-Zr-Al-TiO 2 /SiO 2 The catalyst is subjected to four reactions (three recovery and activation) to treat the COD (chemical oxygen demand) change curve of the actual wastewater of the acrylonitrile along with the simulated solar illumination time.
FIG. 3 shows the use of F-S-Zr-Al-TiO 2 /SiO 2 COD of the actual wastewater of the acrylonitrile treated by the catalyst for the first time is changed along with the simulation and natural illumination time.
Detailed Description
The realization and the excellent effects of the present invention are described below by way of specific examples, but the scope of the present invention should not be construed as being limited in any way.
Method for evaluating catalyst Activity:
the method comprises the following specific steps: the activity evaluation of the photocatalyst selects low-concentration acrylonitrile actual wastewater as a target degradation product, 150mL of actual wastewater is poured into a quartz reactor, 300mg of the photocatalyst is added, then the reactor is closed, after stirring in the dark for 35min to reach adsorption and desorption equilibrium, a xenon lamp is turned on to start illumination, 350w AHD350 type spherical xenon lamp light sources are selected as light sources, and two groups of 4mL wastewater suspension parallel samples are respectively taken out at 2h,6h,10h and 14h in the illumination process.
The detection method comprises the following steps: the determination of COD adopts a quick determination instrument of combined-bloom LH-5B-3B (V8) COD. The COD error is + -10%. Determination of COD of the sample: and immediately after sampling, filtering by a 0.45 mu m pore-size filter membrane, and determining the COD corresponding to the time.
Along with the extension of illumination time, the COD (chemical oxygen demand) reduction curves of the catalyst and the solution are shown as figure 2, the COD of the solution is reduced from 89 to about 25mg/L after 14h irradiation, and the COD can still reach about 42mg/L after 4 times of reaction, so that the basically complete degradation of the organic matters and the good stability of the catalyst are demonstrated.
Under the same method, the acrylonitrile actual wastewater is degraded to about COD=50mg/L through sufficient sunlight reaction under the sunlight irradiation.
Claims (2)
1. F, S, zr, al co-doped modified TiO for degrading acrylonitrile actual wastewater 2 /SiO 2 The preparation method of the photocatalyst is characterized by comprising the following steps:
step 1, dropwise adding 2-8mL of butyl titanate into 10-16mL of absolute ethyl alcohol, and mixing with the absolute ethyl alcohol to obtain a clear solution, namely a solution A;
step 2, sequentially adding 12-32mL of absolute ethyl alcohol, 2.3-5.3mL of glacial acetic acid, 15-35mg of thiourea, 429-449mg of zirconium nitrate pentahydrate, 13-18mg of aluminum nitrate, 0.2-1.5mL of hydrofluoric acid and 0.4-1.9mL of deionized water into a 150mL beaker, and performing ultrasonic treatment for 2min to obtain a solution B;
step 3, 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, and adding 100-200 mesh silica gel until gel is formed after oily sol is formed;
step 4, aging the gel at 20-30 ℃ for 8-12 hours, then drying in a drying oven at 70-130 ℃, uniformly grinding the obtained dry powdery catalyst precursor by an agate mortar, and finally calcining for 1-3 hours at 350-500 ℃ in a tubular furnace to obtain F, S, zr, al co-doped modified TiO 2 /SiO 2 A photocatalyst;
the ratio of Ti to F to S to Zr to Al=1 to 1 to (0.5-5%) to (1-10%) to (0.1-2%) in the photocatalyst.
2. The method of claim 1, wherein the fluorine precursor hydrofluoric acid is a commercially available 40% aqueous solution of hydrogen fluoride, the sulfur precursor thiourea is analytically pure thiourea, the zirconium precursor zirconium nitrate pentahydrate is analytically pure zirconium nitrate pentahydrate, and the aluminum precursor aluminum nitrate is analytically pure aluminum nitrate nonahydrate.
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| GB1523141A (en) * | 1974-07-22 | 1978-08-31 | Standard Oil Co | Process for the oxidation of olefins using catalysts containing various promoter elements |
| CN104923271A (en) * | 2014-03-20 | 2015-09-23 | 哈尔滨工业大学深圳研究生院 | Supported fluorine-doped and nitrogen-fluorine co-doped titanium dioxide for acrylonitrile photocatalytic degradation |
| CN108906112A (en) * | 2018-08-06 | 2018-11-30 | 上海工程技术大学 | A kind of method that flame combustion process prepares multi-element doping photocatalysis material of titanium dioxide |
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| US8791044B2 (en) * | 2010-04-30 | 2014-07-29 | The United States Of America As Represented By The Administrator Of The U.S. Environmental Protection Agency | Doped titanium dioxide as a visible and sun light photo catalyst |
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| GB1523141A (en) * | 1974-07-22 | 1978-08-31 | Standard Oil Co | Process for the oxidation of olefins using catalysts containing various promoter elements |
| CN104923271A (en) * | 2014-03-20 | 2015-09-23 | 哈尔滨工业大学深圳研究生院 | Supported fluorine-doped and nitrogen-fluorine co-doped titanium dioxide for acrylonitrile photocatalytic degradation |
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