CN113477242A - Oily sludge/bismuth vanadate composite photocatalyst, and preparation method and application thereof - Google Patents
Oily sludge/bismuth vanadate composite photocatalyst, and preparation method and application thereof Download PDFInfo
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- CN113477242A CN113477242A CN202110725790.XA CN202110725790A CN113477242A CN 113477242 A CN113477242 A CN 113477242A CN 202110725790 A CN202110725790 A CN 202110725790A CN 113477242 A CN113477242 A CN 113477242A
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- oily sludge
- photocatalyst
- active material
- composite photocatalyst
- bivo
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- 239000010802 sludge Substances 0.000 title claims abstract description 161
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 135
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 30
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 30
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229940124530 sulfonamide Drugs 0.000 claims abstract description 52
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011149 active material Substances 0.000 claims abstract description 36
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 12
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 12
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- 239000000463 material Substances 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
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- 239000011521 glass Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 11
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
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- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
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- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 2
- 229960004306 sulfadiazine Drugs 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- 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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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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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
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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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- 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
- C02F2101/40—Organic compounds containing sulfur
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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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Abstract
The invention discloses a preparation method of an oily sludge/bismuth vanadate composite photocatalyst, which comprises the following steps: step one, oil stainActivating mud; step two, preparing the photocatalyst, namely weighing polyether P123, adding sufficient ethanol, and stirring until the polyether P123 is completely dissolved; adding ammonium metavanadate and bismuth nitrate pentahydrate according to the proportion, and stirring until the ammonium metavanadate and the bismuth nitrate pentahydrate are completely dissolved to obtain a mixed solution; transferring the oil-containing sludge active material subjected to acid leaching treatment and drying to a mixed solution, and adjusting the pH value to 7; heating in water bath and stirring; cooling, transferring into a high-pressure reaction kettle, and reacting under a certain hydrothermal condition; then naturally cooling to room temperature, centrifuging, washing with water and alcohol to neutrality, and drying to obtain oily sludge/BiVO4A composite photocatalyst is provided. The invention also discloses an oily sludge/bismuth vanadate composite photocatalyst and application thereof. The invention can realize the full utilization of the oily sludge, changes waste into valuable, and the prepared photocatalyst can effectively degrade sulfanilamide.
Description
Technical Field
The invention relates to a photocatalyst, in particular to an oily sludge/bismuth vanadate composite photocatalyst, a preparation method and application thereof, and belongs to the technical field of sewage treatment materials.
Background
In recent years, medical treatment technologies are developed, sulfanilamide is used as the earliest and most frequently used artificially synthesized medical substance, sulfanilamide antibiotics are often detected in a large amount of public water supply systems, and sulfanilamide wastewater attracts more and more attention due to the characteristics of high salinity, difficult degradation and the like. However, the organic matter content in the sulfonamide wastewater is large, and the sulfonamide wastewater is difficult to biodegrade, so that the treatment difficulty is increased. Therefore, the photocatalysis technology is a novel physicochemical treatment technology, and the photocatalyst has the advantages of high selectivity, high degradation efficiency, energy conservation, capability of completely degrading pollutants, no secondary pollution and the like, thereby having good prospect in the treatment technology of polluted wastewater.
Bismuth vanadate (BiVO)4) One of the subjects of intense research in the field of photocatalytic materials in recent years is to exhibit n-type semiconductor properties, have a perovskite-like structure, have a narrow band gap of 2.3 to 2.4eV, and have strong light response at 520nm of visible light. It is composed ofThe organic fertilizer has the advantages of wide sources of the composition elements, good chemical and thermal stability, good stability in aqueous solution, no toxicity, environmental friendliness and capability of effectively utilizing solar energy to achieve the purpose of degrading organic matters. And BiVO is studied by Yuhan Yao et al4The research of the photocatalyst material on sulfadiazine with high concentration shows that BiVO4Has good effect on sulfadiazine under certain conditions. But phase-pure BiVO4The photocatalytic activity is not high, and the defects of low catalytic efficiency, low conductivity and the like caused by weak adsorption capacity and easy recombination of electron-hole pairs exist. To address these problems, researchers have turned their attention to synthetic composites.
Oily sludge is typically produced during the process of crude oil extraction, transportation, storage, etc. According to statistics, the annual output of the global oily sludge exceeds 6000 million tons, and the cumulative output exceeds 10 hundred million tons. On one hand, the oily sludge has important recycling value, and on the other hand, if the oily sludge is not treated properly, toxic and harmful substances in the sludge can cause serious pollution to the environment. The preparation of the oily sludge into an active material and the further research into the preparation of the photocatalyst are a great development direction for the resource utilization of the oily sludge.
Disclosure of Invention
The invention aims to provide a method for preparing an oily sludge active material by fully utilizing the oily sludge active material, which loads BiVO on the oily sludge active material4A method for preparing the oily sludge/bismuth vanadate composite photocatalyst.
The invention is realized by the following steps:
a preparation method of an oily sludge/bismuth vanadate composite photocatalyst comprises the following steps:
step one, activation of oily sludge
Adding oily sludge to 2mol/L of zinc chloride (ZnCl)2) In the solution, the solid-to-liquid ratio is kept to be 1: 2.5g/ml, soaking for 24h, placing in a 115 ℃ oven to be semi-dried, then placing in a nitrogen atmosphere tube furnace, heating at a rate of 10 ℃/min to a target temperature of 300 ℃ to 800 ℃, and pyrolyzing for 3h after the target temperature is reached. After the reaction is completely and naturally cooled to room temperature, the materials after the reaction are respectively cleaned by ethanol and distilled water, and the surfaces of the materials are cleaned to be attachedCentrifuging the activator and the excess impurities, drying at 80 ℃, crushing the dried material by a crusher and sieving by a 100-mesh sieve. Obtaining the oily sludge active material.
Step two, preparation of photocatalyst
According to the weight ratio of polyether P123: ammonium metavanadate: the molar ratio of bismuth nitrate pentahydrate is 0.02-0.004: 0.8-1.5: weighing polyether P123 into a dry and clean beaker according to the proportion of 0.8-1.5, adding sufficient ethanol into the beaker, and stirring with a glass rod until the polyether P123 is completely dissolved; adding ammonium metavanadate and bismuth nitrate pentahydrate according to the proportion, and stirring until the ammonium metavanadate and the bismuth nitrate pentahydrate are completely dissolved to obtain a mixed solution;
carrying out ultrasonic treatment on the oily sludge active material in 2mol/L dilute nitric acid for 30min, wherein the mass ratio of the oily sludge active material to the dilute nitric acid is 1: and 10, carrying out centrifugal separation on the oily sludge active material subjected to acid leaching, washing with water to be neutral, completely drying in a muffle furnace at the temperature of 80 ℃, weighing a proper amount of the oily sludge active material, transferring the oily sludge active material to the mixed solution, controlling the loading amount of the final oily sludge to be 5-30% (namely the weight ratio of the final oily sludge active material to the bismuth vanadate is 5-30%), and adding a proper amount of NaOH solution to adjust the pH value to be 7. The mixture is covered and heated and stirred for 1h in a water bath at 50 ℃. After cooling, the mixed solution is transferred to a pressure reaction kettle for hydrothermal reaction for 12 hours at 120 ℃. Taking out, naturally cooling to room temperature, centrifugally separating, washing with distilled water and ethanol for 3 times respectively, and drying the sample in a crucible at 80 ℃ for 12h to obtain oily sludge/BiVO4A composite photocatalyst is provided.
The further scheme is as follows:
the oily sludge is sludge collected from oil field, and its main component is SiO2、SO3BaO, and also oil-type organic substances and other impurities.
The invention also provides an oily sludge/bismuth vanadate composite photocatalyst, which is prepared by the preparation method of the oily sludge/bismuth vanadate composite photocatalyst.
The invention also provides an application of the oily sludge/bismuth vanadate composite photocatalyst, which is used for treating sulfanilamide wastewater.
In the invention, ZnCl is adopted2As an activator, the activated sludge is impregnated into the oily sludge to act as a framework, and the material formed after the reaction is deposited on the framework. The invention adopts a tubular furnace to pyrolyze oily sludge, and aims to carry out thermal conversion treatment on organic substances in the activated oily sludge under the conditions of oxygen exclusion and high temperature to carry out cracking reaction, so that macromolecular polymers are converted into gas, oil, carbon and other micromolecular substances, and ZnCl is generated in the cracking process2Can promote the formation of a pore structure in a sludge pyrolysis product and form a large amount of abundant microporous structures in the material. High temperature pyrolysis followed by HNO3Purpose of treating oily sludge material: firstly, carrying out acid washing to remove ash impurities on the surface after roasting, and leaving an oily sludge active material; secondly, removing redundant ZnCl2The porous oily sludge active material is formed, and the photocatalytic effect of the oily sludge/bismuth vanadate composite photocatalytic material on target pollutants can be further improved. ZnCl compared with other activators2The activation effect of the method is milder, and the method is also highly efficient in pore-forming capability. And (3) continuing drying after pyrolysis to ensure that the oily sludge active material before the photocatalyst is prepared is completely in a dry state, and judging that oily sludge powder is dispersed and does not adhere according to judgment, wherein the oily sludge active material is dried for 2-5 hours generally.
The invention can realize the full utilization of the oily sludge and change waste into valuable. Meanwhile, the prepared oily sludge/bismuth vanadate composite photocatalyst can effectively degrade sulfanilamide, and has good practical significance and social value.
Drawings
FIG. 1 flow diagram for activation of oily sludge
FIG. 2 is a flow chart of photocatalyst preparation at different calcination temperatures
FIG. 3 is a flow chart of the preparation of composite photocatalyst with different doping amounts
FIG. 4 shows different calcination temperatures of photocatalyst XRD
FIG. 5 composite photocatalyst XRD with different loading amounts
FIG. 6 shows DRS spectra of photocatalysts at different calcination temperatures
FIG. 7 is a graph showing the energy band widths of photocatalysts at different calcination temperatures
FIG. 8 is a spectrum diagram of DRS of composite photocatalysts with different loads
FIG. 9 is a graph of the band width of composite photocatalysts with different loading amounts
FIG. 10 PL diagram of photocatalyst with different calcination temperatures
FIG. 11 PL diagram of composite photocatalysts with different loading amounts
FIG. 12 FTIR chart of photocatalysts at different calcination temperatures
FIG. 13 FTIR chart of composite photocatalyst with different loading amounts
FIG. 14 is a graph of different calcination temperatures of photocatalyst I-t
FIG. 15 is a graph of composite photocatalysts I-t with different loads
FIG. 16A-C impedance diagram of photocatalyst with different calcination temperatures
FIG. 17 is an AC impedance diagram of composite photocatalysts with different loading amounts
FIG. 18 shows the activity of photocatalysts at different calcination temperatures
FIG. 19 is a graph showing activity test of composite photocatalysts with different loadings
FIG. 20 is a graph showing the effect of pH on photocatalytic degradation
FIG. 21H2O2Effect diagram of dosage on photocatalytic degradation process
FIG. 22 is a graph showing the effect of the amount of photocatalyst added on the photocatalytic degradation process
FIG. 23 shows the effect of photocatalyst stability studies
FIG. 24 test results of photocatalyst active species
FIG. 25 shows the degradation effect of sulfonamide wastewater with different initial concentrations
FIG. 26 first order kinetic Linear equation
FIG. 27 two-stage kinetic Linear equation
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments.
A preparation method of an oily sludge/bismuth vanadate composite photocatalyst comprises the following steps:
step one, activation of oily sludge
Adding oily sludge to 2mol/L of zinc chloride (ZnCl)2) In solution (solid-to-liquid ratio 1: 2.5g/ml), soaking for 24h, placing in a 115 ℃ oven to be semi-dried, placing in a tube furnace, heating at a rate of 10 ℃/min, and continuously introducing nitrogen to maintain the inert atmosphere in the experimental process, wherein the target temperatures are respectively 300 ℃, 500 ℃, 700 ℃ and 800 ℃. Pyrolysis is carried out for 3h after the target temperature is reached. After the reaction is completely and naturally cooled to room temperature, the material after the reaction is washed by ethanol and distilled water, an activating agent and redundant impurities attached to the surface of the material are cleaned, the centrifugation is carried out, the drying is carried out at 80 ℃, the dried material is crushed by a crusher and is sieved by a 100-mesh sieve. Obtaining the oily sludge active material. The specific process is shown in figure 1.
Step two, preparation of photocatalyst
With bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) and ammonium metavanadate (NH)4VO3) Under the conditions of inorganic source, ethanol as solvent and polyether P123 as surfactant, the hydro-thermal synthesis method is adopted to prepare the oil-containing sludge/BiVO with different roasting temperatures4The following specific operations were carried out at normal temperature and pressure, as shown in FIGS. 2 and 3.
According to the weight ratio of polyether P123: ammonium metavanadate: the molar ratio of bismuth nitrate pentahydrate is 0.02-0.004: 0.8-1.5: weighing polyether P123 into a dry and clean beaker according to the proportion of 0.8-1.5, adding sufficient ethanol into the beaker, and stirring with a glass rod until the polyether P123 is completely dissolved; adding ammonium metavanadate and bismuth nitrate pentahydrate according to the proportion, and stirring until the ammonium metavanadate and the bismuth nitrate pentahydrate are completely dissolved to obtain a mixed solution;
carrying out ultrasonic treatment on the oily sludge active material prepared at different roasting temperatures in 2mol/L dilute nitric acid for 30min, wherein the mass ratio of the oily sludge active material to the dilute nitric acid is 1: and 10, carrying out centrifugal separation on the oily sludge active material subjected to acid leaching, washing the oily sludge active material to be neutral, completely drying the oily sludge active material in a muffle furnace at the temperature of 80 ℃, weighing a proper amount of the oily sludge active material, transferring the oily sludge active material to the mixed solution, and adding a proper amount of NaOH solution to adjust the pH value to be 7. Heating in a water bath with a cover and stirring for 1 h. Cooling, transferring the mixed solution to a 200ml pressure reaction kettle, and carrying out hydrothermal reaction at 120 DEG CAnd (4) 12 h. Taking out, naturally cooling to room temperature, centrifugally separating, washing with distilled water and ethanol for 3 times respectively, and then placing the sample into a crucible and drying at 80 ℃ for 12 h. Obtaining the oil-containing sludge/BiVO at different roasting temperatures4Active material, recorded as 300 ℃ oily sludge/BiVO 4500 ℃ oil-containing sludge/BiVO 4700 ℃ oil-containing sludge/BiVO 4800 ℃ oily sludge/BiVO4。
Selecting the roasting temperature with the best catalytic effect to obtain the oily sludge active material, and only changing the loading amounts of the oily sludge to be 5%, 10%, 20% and 30% respectively according to the steps to obtain the photocatalysts with different loading amounts of the oily sludge active material, namely 5% oily sludge/BiVO 410% oil-containing sludge/BiVO 420% oil-containing sludge/BiVO430% oil-containing sludge/BiVO4。
The following is a description of a part of the analytical method employed in the present invention.
1. Characterization by X-ray fluorescence Spectroscopy (XRF)
And (3) analyzing and detecting the element components and the content of the oily sludge by adopting an X-ray fluorescence spectrometer.
2. Characterization by X-ray diffraction (XRD)
The crystal structure of each photocatalyst is analyzed by a DX-1000 ray diffractometer, and the scanning step is as follows: 0.02 ° and a scanning range 2 θ of 0.5 ° to 10 °.
3. Specific surface area (BET) characterization
The specific surface area, pore volume and pore diameter of each photocatalyst were obtained using a model SSA-4200 pore specific surface analyzer.
4. Ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS) analysis
And measuring the relative reflectivity of the sample by adopting a UV2550 spectrophotometer to obtain a sample reflection spectrum within the wavelength range of 400-800 nm. And calculating the band gap energy values of different photocatalysts according to the Kubelka-Munk function.
5. Fourier Infrared (FTIR) characterization
Analyzing each photocatalyst by NicoleetiS 50 Fourier transform infrared spectroscopy, mixing and grinding the photocatalyst and KBr by adopting a KBr tabletting methodGrinding, pressing into tablets, and scanning with wave number range of 400-4000cm-1。
6. Photoluminescence Spectroscopy (PL) characterisation
The photoluminescence spectrum of each photocatalyst was obtained using an RF-5301PC molecular fluorescence spectrophotometer. The scanning range is 250 nm-450 nm.
7. Electrochemical characterization
A Chi660E electrochemical workstation is adopted to obtain a transient photocurrent response diagram (I-t) and an Electrochemical Impedance Spectroscopy (EIS) of the catalyst so as to analyze the catalytic mechanism of the catalyst.
The oily sludge/BiVO prepared by the invention4The performance of (2) is illustrated using photocatalytic experiments.
1. Activity test of each photocatalyst
A simulated sulfanilamide wastewater degradation experiment is carried out by using a XPA-7 type photocatalytic reaction device of a Nanjing xu river machine power plant. 30mg of photocatalyst materials prepared at different roasting temperatures of the oily sludge are added into a quartz test tube filled with 30ml of simulated sulfanilamide wastewater with the initial concentration of 30mg/L, and a certain amount of oxidant H is added2O2And after the photocatalyst is stirred for 1 hour in a dark mode in a photocatalyst instrument to achieve adsorption and desorption balance, starting a 350W xenon lamp light source, starting timing reaction after light intensity is stable, sampling every 1 hour, filtering by using a 0.22 mu m filter membrane, measuring residual concentration in the sulfanilamide wastewater by using high performance liquid chromatography, and further calculating the photodegradation efficiency of sulfanilamide so as to screen out the photocatalyst with the roasting temperature corresponding to the best photocatalytic activity.
And after the optimal roasting temperature is screened out, changing the load of the corresponding oily sludge, and carrying out photocatalytic reaction under the same conditions to obtain the optimal load of the corresponding oily sludge.
2. Effect of reaction conditions on photocatalytic reaction
(1) Effect of pH on photocatalytic degradation Process
Under the condition of obtaining the optimal roasting temperature and the optimal loading capacity, adjusting the pH values of 30ml of sulfanilamide wastewater with the initial concentration of 30mg/L to be 1, 3, 5, 7, 9, 11 and 13, and adding 30mg of optimal photocatalyst into the quartz test tube filled with sulfanilamide wastewater with different pH valuesAdding a certain amount of H2O2As an oxidizing agent, a photocatalytic reaction was performed in a photocatalyst apparatus to investigate the optimum pH value.
(2)H2O2Influence of dosage on photocatalytic degradation process
Selecting optimum photocatalyst and pH value, putting the photocatalyst into a quartz test tube filled with 30ml of sulfanilamide wastewater with initial concentration of 30mg/L, and adding 0.1%, 0.5%, 1%, 2% and 3% of H respectively2O2As an oxidant, a quartz tube filled with the mixed solution is placed in a photocatalysis instrument for photocatalytic reaction to search for the optimal H2O2Adding the amount.
(3) Effect of catalyst dosage on photocatalytic reaction
Under the optimal process conditions, the photocatalyst content of 0.5mg/L, 1mg/L, 2mg/L and 3mg/L are respectively added into a quartz test tube filled with 30ml of sulfanilamide wastewater with the initial concentration of 30 mg/L. And then carrying out a photocatalytic degradation experiment on the mixed solution to investigate the influence of the addition amount of the catalyst on the photocatalytic reaction.
3. Experiment of dynamics
Adding 1g/L optimal catalyst into sulfanilamide wastewater solutions with initial concentrations of 5mg/L, 15mg/L, 30mg/L, 50mg/L and 70mg/L respectively, carrying out photocatalytic reaction under the optimal process conditions, and carrying out sulfanilamide photodegradation kinetic analysis.
4. Active species test experiment
Under the optimal reaction conditions, 1mmol of NaHCO is added into the reaction system3Isopropyl alcohol (IPA) and p-Benzoquinone (BQ) (each H)+OH and O2 -Quencher) to investigate the major active species during the photocatalytic reaction.
5. Life test
And carrying out photocatalytic reaction under the optimal reaction condition, recovering the catalyst participating in the reaction when the reaction reaches balance, drying, adding the dried catalyst into the same amount of sulfanilamide wastewater solution, carrying out next photocatalytic reaction after constant volume is equal to the volume, and carrying out cyclic reaction for 5 times to explore the stability and the service life of the photocatalyst and lay a theoretical foundation for the practical application of the catalyst.
The analysis results of the specific embodiment of the invention are as follows:
1. XRF analysis of oil-containing sludge
TABLE 1 XRF analysis Table of oily sludge
The table above represents the XRF characterization of the oily sludge. The XRF analysis shows that the composition comprises the following components in percentage by mass:
SiO228.45％，Na2O 0.631％，SO317.54％，K2O 0.661％，SrO 0.376％，BaO 34.24％，MgO 1.31％，Fe2O34.07%, and other components such as Al2O3、P2O5、Cl、K2O、CaO、TiO2、Cr2O3、MnO、NiO、CuO、ZnO、As2O3、SrO、MoO3Etc., and part of the oil-type organic substances.
2. XRD analysis
To determine BiVO4And oily sludge/BiVO with different roasting temperatures and different loading amounts4The XRD test was performed on the composition of the structure of (1).
(1) Photocatalyst XRD (X-ray diffraction) at different roasting temperatures
As can be seen from FIG. 4, the synthesized oily sludge/BiVO4Shows high crystallinity, and some main diffraction peaks appear around 18.8 °, 30.62 °, 34.89 °, 46.94 °, 50.09 °, 52.97 °, 53.24 ° and 59.83 ° and correspond to (011), (112), (004), (020), (024), (224), (008), (323) and (411) crystal planes respectively, all of which are in common with monoclinic phase bismuth vanadate in standard diffraction card (JCPDS file No.14-0688)The characteristic peaks are consistent, and no diffraction peak of other impurities is detected, which indicates that the oily sludge/BiVO with higher purity is successfully prepared4Composite material and no or only few impurities.
Crystallinity problem all corresponding diffraction peak peaks are sharp and elongated as can be seen in fig. 4, illustrating the synthetic oil-containing sludge/BiVO4The composite material has high crystallization quality, and under the temperature gradient of 300-800 ℃, the diffraction peak is more obvious along with the temperature rise, which shows that the crystallinity of the sample rises, but the peak height shows a descending trend when the temperature exceeds 700 ℃, and the crystallinity also shows a descending trend along with the temperature rise, possibly because the roasting temperature is too high, the sample has a sintering phenomenon, so that the BiVO is caused4The sample structure changed and the laminate collapsed.
(2) Composite photocatalyst XRD with different loading amounts
From FIG. 5, it can be seen that the synthesized oily sludge/BiVO4Shows high crystallization, all crystal faces are consistent with the characteristic peak of monoclinic phase bismuth vanadate in a standard diffraction card (JCPDS file No.14-0688), and no diffraction peak of other impurities is detected, which indicates that the oily sludge/BiVO with higher purity is successfully prepared4A composite material.
The problem of crystallinity can be seen from the figure that all the corresponding diffraction peak peaks are sharp and slender, which indicates that the synthesized oily sludge/BiVO4The composite material has high crystallization quality, and the diffraction peak is more obvious along with the gradual increase of the loading amount, which indicates that the crystallinity of the sample is increased, but when the loading amount is more than 20 percent, the peak intensity is weakened, which indicates that the crystallinity is poor, and when the loading amount is too large, BiVO is inhibited4And (5) forming crystals.
3. BET analysis
(1) Photocatalyst BET of different calcination temperatures
TABLE 2 BET TABLE of photocatalysts of different calcination temperatures
If the catalyst is provided withThe larger specific surface area and the higher crystallinity have higher photocatalytic activity, and the larger specific surface area can provide more active centers for photocatalytic reaction, so that the surface adsorption amount is increased, and the capture capacity of photogenerated electrons and holes is improved; and the high crystallinity can reduce the recombination of photo-generated electrons and holes on the surface of the crystal grains. From Table 2, the hydrothermal preparation of a single BiVO4Specific surface area of only 2.5m2Perg, BiVO after load modification4Along with the increase of the roasting temperature, the specific surface area of the sample is obviously numerically reflected as firstly increasing and then reducing, wherein the specific surface area of the roasted material at 700 ℃ is the largest, which shows that the material can expose more reactive active sites in the process of photocatalytic reaction, can effectively accelerate the process of degrading sulfanilamide wastewater by photocatalysis, and improve the reaction rate of degradation reaction. And 800 ℃ compared with the single BiVO4The reason why the specific surface area is remarkably reduced may be that the composite material is sintered during firing, resulting in the agglomeration of the composite material and the reduction of the specific surface area.
(2) Composite photocatalyst BET with different loading amounts
TABLE 3 BET table of composite photocatalysts with different loadings
From Table 3, it is clear that BiVO is not loaded with oily sludge4The specific surface area of the particles was only 2.5m2Perg, while the loading with oily sludge is 5%, 10%, 20% and 30% of oily sludge/BiVO4Respectively, BET specific surface areas of 2.8m2/g、2.4m2/g、14.0m2G and 13.4m2(ii) in terms of/g. Obviously, the specific surface area of the photocatalyst loaded with the oily sludge is larger than that of the BiVO not loaded with the oily sludge4The specific surface area of the granular sample does not exhibit a positive phase as the content of the oily sludge increasesWherein the supported amount is 20 percent than that of the unsupported synthetic BiVO4The specific surface area of the photocatalyst is improved by about 46.4 percent, so that the photocatalyst can be fully contacted with degraded substances, the active sites of the photocatalytic reaction are increased, and the photocatalytic performance of the photocatalyst is further improved, therefore, the photocatalyst is also an important factor with higher visible light catalytic activity.
4. UV-vis DRS assay
The absorption capacity of the photocatalyst to visible light is an important factor for determining the photocatalytic performance of the photocatalyst, so that UV-vis DRS diffuse reflection characterization is carried out on composite photocatalysts with different temperatures and different loads. BiVO by looking up data4Has an absorption edge of 520 nm.
(1) Photocatalyst UV-vis DRS with different roasting temperatures
As shown in fig. 6 to 7, all photocatalysts have an absorption effect on light in the ultraviolet band, and also exhibit a strong absorption effect on light in the visible light region. As can be seen from the figure, the 300 ℃ oily sludge/BiVO4The absorption edge of the composite material is about 530nm, and the oily sludge/BiVO is at 500 DEG C4The absorption edge of the composite material is about 540nm and the temperature of the composite material is 700 ℃ oily sludge/BiVO4The absorption edge of the composite material extends to 550nm, and the temperature of the composite material is 800 ℃ oily sludge/BiVO4The absorption edge of the composite material is about 520 nm. It can be seen that, with the increase of the loading amount, the absorption of the photocatalyst to visible light is further enhanced, and the activity of the photocatalyst is promoted to be correspondingly increased. And 700 ℃ oily sludge/BiVO4Compared with other photocatalysts with different roasting temperatures, the composite material has more red shift at the absorption edge, stronger visible light absorption capacity and wider absorption range. This shift in absorption edge may be due to the presence of surface defect sites (e.g., oxygen vacancies) in the crystal structure of the sample, which in turn may increase the absorption of visible light due to the increase in surface defect sites.
According to the Kubelka-Munk function, the band gap energy of different materials is calculated according to the ultraviolet and visible light diffuse reflection spectrum:
ahv＝A(hv-Eg)n/2 (1)
wherein each letter represents a meaning:
a is the absorption coefficient;
hvis the absorption coefficient;
a is a constant;
Egis a band gap;
the n of the bismuth vanadate semiconductor material is equal to 4.
The band gap energy values of the 4 composite materials are respectively 2.52eV, 2.50eV, 2.46eV and 2.50eV through calculation, and the oily sludge/BiVO at the temperature of 700 ℃ can be known4The forbidden band width of the composite material is narrowest, so that the aim of improving the photocatalytic performance can be fulfilled by strong response to visible light.
(2) Composite photocatalyst UV-vis DRS with different loads
As shown in fig. 8-9 and combined with the above analysis, it can be seen that materials of different loadings exhibit strong absorption of light in the visible region in addition to absorption of light in the ultraviolet region. However, it can be seen from the graph that the band width does not change significantly at the loading of 5% to 20%, indicating that the change in loading at this time is for BiVO4The light absorption properties of (a) are not much affected. Meanwhile, the absorption edge with a lower loading amount has a slight blue shift due to excessive oil-containing sludge, and the forbidden bandwidth is increased, because the introduction of the excessive oil-containing sludge can inhibit the performance of the photocatalyst, so that the photocatalyst cannot be completely illuminated, and the forbidden bandwidth is further increased.
5. PL characterization analysis
Photoluminescence spectroscopy (PL) is a means of characterizing the chemical and optoelectronic properties of a photocatalyst itself, and the recombination of photo-generated electrons and holes in a semiconductor photocatalyst can be judged by PL.
(1) Photocatalyst PL with different calcination temperatures
Photo-generated carriers (electrons e) generated when a photocatalyst is excited by light-And a cavity h+) When recombined, the fluorescent material emits fluorescence, and the lower the fluorescence emission intensity, the smaller the recombination probability of electrons and holes, the higher the photocatalytic activity. The lower diagram is the oily sludge/BiVO with different temperatures4PL of composite MaterialThe spectra, as can be seen from FIG. 10, of the prepared oily sludge/BiVO at 300 deg.C, 500 deg.C, 700 deg.C and 800 deg.C4The composite materials have wide emission bands between 275-400nm, the shapes of the spectra at different temperatures are basically the same, and characteristic peaks appear at 311nm, which is caused by the recombination effect of excited electrons and holes, and indicates that the photo-generated electrons and holes are easy to recombine. And PL peak positions of photocatalyst materials with different roasting temperatures are deviated, and different energy levels are formed in a conduction band due to quantum size effect, and composite luminescence is formed at the different energy levels, so that the PL peak positions are deviated.
As can be seen from FIG. 10, the peak at 700 ℃ is significantly lower than the peaks at other temperatures, indicating an oily sludge/BiVO at 700 ℃4The composite material can effectively reduce BiVO4The recombination rate of photo-generated electrons and holes; meanwhile, photoproduction electrons and holes on the surface can participate in oxidation reduction reaction more easily, so that the oily sludge/BiVO at 700 ℃ can be obtained4Compared with the photocatalyst prepared at other temperatures, the composite material has a complete crystal form and an ordered structure, and simultaneously shows higher photocatalytic performance.
(2) Composite photocatalyst PL with different load amounts
As shown in fig. 11, when the loading amount of the oily sludge is 20%, the fluorescence intensity of the corresponding photocatalyst is significantly lower than that of the corresponding photocatalyst when the loading amount of the oily sludge is 20%, which indicates that the catalytic activity of the corresponding photocatalyst is the best when the loading amount of the oily sludge is 20%. However, as the loading amount of the oily sludge is increased, namely 30%, the spectral intensity of PL is increased compared with that of 20%, which shows that the addition of the oily sludge inhibits the recombination of photo-generated electron-hole pairs of the photocatalyst, namely, as the loading amount of the oily sludge is increased, BiVO (BiVO) can be generated4The surface clustering can cover the original active site, so that the catalytic activity of the photocatalyst is influenced.
6. FTIR characterization analysis
In order to determine the types of active functional groups existing in the prepared photocatalyst, FTIR tests are carried out on the photocatalysts with different calcination temperatures and the oily sludge composite photocatalysts with different loading amounts, and the spectrum is as follows.
3450cm, as shown in FIGS. 12-13-1The absorption peaks are relatively wide and respectively correspond to a characteristic stretching vibration peak of-OH on the surface of the composite material and a bending vibration peak of H-O-H on the surface of the composite material due to physical water absorption. 1640cm-1The stretching vibration of (a) indicates a bending vibration of the organic impurities of the composite material. 1380cm-1The characteristic peak of stretching vibration as methyl appears at the stretching vibration peak of C ═ C corresponding to the saturated alkane C-H deformation vibration absorption peak or epoxy group. 761cm-1The absorption peak is BiVO4VO in (1)4 3-Stretching vibration of the group V. 1126cm-1The absorption peak at (A) is indicated to be due to the formation of Si-O bonds, 1050cm-1The peak appearing nearby is the stretching vibration peak of Si-O-Si; description of SiO in the oily sludge2Loaded to BiVO4The above causes the catalytic effect of the photocatalysis to change. And shows that the oily sludge and the bismuth vanadate are successfully compounded, which is consistent with the XRD and BET results.
7. Transient photocurrent response analysis
The separation of electrons and holes in the semiconductor material can generate a photocurrent, and the higher the photocurrent means that the higher the separation efficiency and the faster the transfer rate of the photogenerated electron-hole pairs, thereby showing higher catalytic efficiency.
(1) Transient photocurrent response of photocatalyst at different calcination temperatures
As is clear from fig. 14, the current values of all the composites increased under the light irradiation condition. When the current is stable, the light current intensity is 700 ℃ from high to low respectively>500℃>800℃>At 300 ℃. And the photocurrent intensity at 700 ℃ is about 3.5 times of 500 ℃, and 7 times of 300 ℃ and 800 ℃, which can show that the oily sludge/BiVO at 700 ℃ is4The composite material has higher separation efficiency and higher transfer rate of photogenerated electron-hole pairs, thereby having optimal photocatalytic performance.
(2) Transient photocurrent response of composite photocatalysts with different loads
As is clear from fig. 15, the current values of all the composites increased under the light irradiation condition. When the current is stable, the photocurrent intensity of different load amounts is respectively 20% > 10% > 30% > 5% from high to low. And the photocurrent intensity with 20% of load capacity is about 2 times of 10% of load capacity and 30% of load capacity, and 6 times of 5% of load capacity, which can show that the separation efficiency of the photo-generated electron-hole pairs of the photocatalyst with 20% of load capacity is higher, the transfer rate is faster, and the photocatalytic performance is optimal.
8. Electrochemical impedance analysis
(1) Electrochemical impedance of photocatalyst at different roasting temperatures
Fig. 16 shows that the arc radii are, in order from small to large: the temperature of 700 ℃ is less than 500 ℃ and less than 300 ℃ and approximately equal to 800 ℃, which shows that the resistance of the bismuth vanadate loaded with the oily sludge is reduced along with the temperature rise, and shows that the oily sludge/BiVO at the temperature of 700 ℃ is4The composite material has lower charge transfer resistance and higher charge transfer efficiency, so that more electron hole pairs can be generated, and more excellent photocatalytic activity is shown, which is consistent with a photocurrent characterization result. This is consistent with the results of transient photocurrents.
(2) Electrochemical impedance of composite photocatalyst with different loading amounts
Fig. 17 shows that the arc radii are, in order from small to large: 20% < 10% < 30% < 5%, and as the loading amount of the oily sludge increases from 5% to 20%, the resistance of the catalyst gradually decreases, which indicates that the charge transfer rate of the catalyst is proportional to the loading amount of the oily sludge, since the active material contained in the oily sludge has good conductivity, so that the resistance of the catalyst decreases. The resistance of the bismuth vanadate loaded with the oily sludge is reduced along with the increase of the loading amount. And the photocatalyst with the load of 20% has lower charge transfer resistance and higher charge transfer efficiency, so that more electron hole pairs can be generated, and more excellent photocatalytic activity is shown, which is consistent with a photocurrent characterization result. This is consistent with the results of transient photocurrents.
The photocatalyst prepared by the embodiment of the invention is researched on the conditions of the photocatalytic process, and the conditions are as follows:
1. photocatalyst Activity test
(1) Photocatalyst activity test at different calcination temperatures
The degradation effect of each photocatalyst prepared by different activation modes on sulfanilamide is shown in figure 18. As can be seen from FIG. 18, after the sulfanilamide wastewater is illuminated by visible light for 1 hour, the degradation rate of sulfanilamide can reach about 10%. With the increase of the illumination time, the degradation rate of sulfanilamide is ranked from large to small as follows: 700 ℃ is more than 500 ℃ and more than 800 ℃ is more than 300 ℃. The characterization analysis shows that the inorganic mineral crystalline state is partially converted into the amorphous state after the oily sludge is roasted, the chemical activity of the inorganic mineral crystalline state is greatly improved, the roasting temperature is increased, so that the photocatalyst has large specific surface area, the separation efficiency of the photo-generated electron-hole pair is high, the speed is high, the photo-generated electron-hole pair is not easy to recombine, and better photocatalytic activity is represented. However, above 800 ℃, the composite material is sintered during roasting, which results in agglomeration of the composite material and reduction of photocatalytic performance, and the result is the same as the characterization analysis.
Therefore, the catalyst with the best photocatalytic performance is finally determined to be oil-containing sludge/BiVO at 700 DEG C4A composite material.
(2) Activity test of composite photocatalyst with different loading amounts
From the above conclusions, the photocatalyst with the best catalytic performance is oil-containing sludge/BiVO at 700 DEG C4The degrading effect of the photocatalyst prepared by changing the loading amount of the oily sludge on the sulfanilamide wastewater is shown in figure 19. As can be seen from fig. 19, when the loading amount of the oily sludge is 20%, the degradation rate of the corresponding photocatalyst to the sulfanilamide wastewater is the highest, and the sulfanilamide wastewater is basically completely degraded after the photocatalytic reaction reaches 4 hours. The effect is obviously higher than that of other load composite photocatalysts, and the degradation rate of the sulfanilamide wastewater is sequenced from large to small as follows: 20% > 10% > 30% > 5%. With the load increased from 5% to 20%, the degradation rate of the photocatalyst to the sulfanilamide wastewater increases, further proving that the photocatalytic activity of bismuth vanadate can be enhanced by introducing the oily sludge, but when the load of the oily sludge is increased from 20% to 30%, the degradation rate of the corresponding catalyst to the sulfanilamide wastewater decreases on the contrary, which may be because the load of the oily sludge is excessive and covers part of active sites on the surface of the bismuth vanadate, and when visible light irradiates on the catalyst, the bismuth vanadate cannot be excited to generate photo-generated electrons, so that the photocatalytic activity of the bismuth vanadate decreases. This is in accordance with the above characterizationThe results of the analyses were identical.
Thus, 20% oil-containing sludge/BiVO, combined with characterization analysis4The composite material has high separation efficiency of photo-generated electron-hole pairs, high speed and difficult recombination, thereby showing the optimal photocatalytic activity. The optimum loading of the thermally activated oily sludge was thus finally determined to be 20%.
2. Study of optimized Process conditions
(1) Effect of pH on photocatalytic degradation Process
As can be seen from fig. 20, the pH of the solution has a great influence on the degradation rate of sulfanilamide, and the degradation effect is the best under acidic and neutral conditions, while the degradation effect is obviously reduced under alkaline conditions. The main reasons are: under acidic and neutral conditions, the method is favorable for the migration of photo-generated electrons to the surface of the photocatalyst, simultaneously inhibits the recombination of the photo-generated electrons and hole pairs, increases the number of active groups on the surface of the photocatalyst, but under alkaline conditions, BiVO4Due to adsorption of OH on the surface-So that the oily sludge/BiVO is at 700 DEG C4The composite material is provided with negative charges, so that the work function of photo-generated electrons is increased, the electrons are not beneficial to reaching the surface, and holes can be captured to block the decomposition reaction. Thus, using oil-containing sludge/BiVO4The composite material is suitable for treating the sulfanilamide wastewater under the acidic and neutral conditions, and the problem of cost is also considered, so that the research of the degradation reaction of the sulfanilamide wastewater under the natural pH value (namely pH value of 7) of the sulfanilamide wastewater is adopted in the research of the subject.
(2)H2O2Influence of dosage on photocatalytic degradation process
As can be seen from FIG. 21, in the oil-containing sludge/BiVO4H can be seen in the experiment of the influence of the composite material on degrading sulfanilamide wastewater2O2The influence on the compound is large, and the general trend shows that the compound is accompanied with H2O2The degradation rate of the sulfanilamide shows a trend of increasing first and then decreasing after the addition of the sulfanilamide. This is due to the fact that in the photocatalytic process, H2O2Can directly generate OH free radical and H under the condition of illumination2O2Is a better electron acceptor, and can reduceRecombination of the photo-generated electrons and holes. Thus at low concentrations of H2O2Under the condition of H2O2OH generated under the condition of illumination can fully participate in the photocatalytic reaction for degrading sulfanilamide. But with H2O2After the addition amount of (D) exceeds a certain amount, H2O2The absolute amount of OH decomposed increases and excess H2O2OH radicals are absorbed, which results in the following reaction equation: OH + H2O2→·O2H+H2O, production of O2The reactivity of the H free radical to organic matters is far lower than that of the OH free radical, so the degradation rate of the sulfanilamide wastewater shows a small reduction trend.
(3) Effect of photocatalyst dosage on photocatalytic degradation Process
As can be seen from FIG. 22, when the amount of the photocatalyst added was increased from 0.5mg/L to 3mg/L, the degradation rate of the sulfanilamide waste water increased from 39.8% of 0.5mg/L to 95.76% of 1mg/L, but when it reached 3mg/L, the degradation rate gradually decreased to 75.43%. This is because when the amount of added photocatalyst is small, the photons generated by the light source of the photocatalytic reaction cannot be completely converted into chemical energy, so the photon energy generated by the light source cannot be fully utilized, and more active species can be generated when the amount of photocatalyst is properly increased, thereby accelerating the reaction effect during photocatalytic degradation. At the same time, when the adding amount of the photocatalyst is too much, the effective light intensity in the photocatalytic reaction is weakened due to the shielding and scattering effect among the particles, so that the absorption effect of light can be influenced. Therefore, the optimum amount of photocatalyst to be added in the present invention is 1 mg/L.
(4) Photocatalyst stability study
Whether the catalyst is stable is an important index for measuring the value of the catalyst, in order to verify the stability of the catalyst, a circulating experiment for degrading sulfanilamide by photocatalysis is carried out, after each circulating reaction is finished, the same amount of sulfanilamide solution is added to the same volume, and the next round of circulating experiment is carried out after adsorption balance is achieved. Because the oily sludge obtained by roasting at the temperature of 700 ℃ in the research and the oily sludge/BiVO formed by compounding the oily sludge with the load of 20 percent4The photocatalyst showed very good photocatalytic performance, so the experiment was used to cycle the experimental results as shown in fig. 23. Oily sludge/BiVO at 700 DEG C4The composite material still has good degradation effect on the degradation rate of sulfanilamide after being recycled for 5 times, the degradation effect is basically the same and can reach more than 90 percent, the catalyst after being recycled for 5 times can still keep good photocatalytic activity, and the oily sludge/BiVO at 700 DEG C4The composite material has good stability.
3. Research on photocatalytic reaction mechanism
(1) Testing of active species
To investigate the reactive groups that may be contained in the composite, NaHCO was added separately to the experiment3Isopropanol (IPA) and p-Benzoquinone (BQ) as h+OH and O2 -A quencher. As shown in figure 24, after 4 hours of reaction, the degradation rate of the composite material without any quenching agent reaches 97.4 percent, and a quenching agent NaHCO is added into the reaction system3Isopropyl alcohol (IPA) and p-Benzoquinone (BQ) have certain reduction effect on the degradation effect of sulfanilamide, so that the degradation rate of sulfanilamide wastewater is reduced to 27.41%, 34.1% and 94.29% respectively. Thus explaining h+Is the main reactive group, OH.
(2) Study of kinetics
In order to further investigate the photocatalytic degradation kinetic characteristics of the composite photocatalyst on the sulfanilamide wastewater, a kinetic model suitable for describing the photocatalytic reaction process is found, degradation experimental studies are carried out on the sulfanilamide wastewater with initial concentrations of 5mg/L, 15mg/L, 30mg/L, 50mg/L and 70mg/L respectively under the optimal reaction conditions, and the degradation effect is shown in the attached drawing 25.
And fitting the data by using quasi-first-order and quasi-second-order equations respectively. Wherein, the quasi-first and quasi-second order reaction equations can be expressed as:
wherein each letter represents a meaning:
c is mass concentration of the reactant at the time t, mg/L;
C0the initial concentration of reactants is mg/L;
k1is a quasi first order reaction rate constant, h-1；
k2Quasi-second order reaction rate constant, L.mg-1·h-1。
The kinetic curves plotted by equations (2) and (3) are shown in FIGS. 26-27, and the results of the linear fit are shown in Table 4.
As can be seen from Table 4, for the degradation rate of sulfanilamide, when the initial concentration is 5mg/L, 15mg/L, 30mg/L, 50mg/L, 700mg/L sulfanilamide wastewater, the correlation coefficients of the corresponding first-order kinetic linear equations of the process are 0.9979, 0.9973, 0.9909, 0.9973, 0.9949, respectively, and the correlation coefficients of the corresponding second-order kinetic linear equations are 0.7852, 0.7682, 0.7767, 0.7794, 0.7918, respectively; therefore, the first-order kinetic correlation coefficient obtained in the degradation process is obviously higher than the second-order kinetic correlation coefficient, so that the method accords with a first-order kinetic model.
TABLE 4 kinetic constants for sulfonamide wastewater degradation process
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (4)
1. A preparation method of an oily sludge/bismuth vanadate composite photocatalyst is characterized by comprising the following steps:
step one, activation of oily sludge
Adding oily sludge into 2mol/L zinc chloride solution, and keeping a solid-liquid ratio of 1: 2.5g/ml, soaking for 24h, placing in a 115 ℃ oven to be semi-dried, then placing in a nitrogen atmosphere tube furnace, heating at a rate of 10 ℃/min to a target temperature of 300 ℃ to 800 ℃, and pyrolyzing for 3h after the target temperature is reached; after the reaction is complete, naturally cooling to room temperature, respectively cleaning the reacted materials by using ethanol and distilled water, cleaning activating agents and redundant impurities attached to the surfaces, centrifuging, drying at 80 ℃, crushing the dried materials by using a crusher, and sieving by using a 100-mesh sieve; obtaining an oily sludge active material;
step two, preparation of photocatalyst
According to the weight ratio of polyether P123: ammonium metavanadate: the molar ratio of bismuth nitrate pentahydrate is 0.02-0.004: 0.8-1.5: weighing polyether P123 into a dry and clean beaker according to the proportion of 0.8-1.5, adding sufficient ethanol into the beaker, and stirring with a glass rod until the polyether P123 is completely dissolved; adding ammonium metavanadate and bismuth nitrate pentahydrate according to the proportion, and stirring until the ammonium metavanadate and the bismuth nitrate pentahydrate are completely dissolved to obtain a mixed solution;
carrying out ultrasonic treatment on the oily sludge active material in 2mol/L dilute nitric acid for 30min, wherein the mass ratio of the oily sludge active material to the dilute nitric acid is 1: 10, carrying out centrifugal separation on the oily sludge active material subjected to acid leaching treatment, washing the oily sludge active material to be neutral, completely drying the oily sludge active material in a muffle furnace at the temperature of 80 ℃, weighing a proper amount of the oily sludge active material, transferring the oily sludge active material to the mixed solution, controlling the final load capacity of the oily sludge to be 5-30%, and adding a proper amount of NaOH solution to adjust the pH value to be 7; covering the kettle, heating the kettle in water bath at 50 ℃, and stirring the kettle for 1 hour; cooling, transferring the mixed solution to a pressure reaction kettle, and carrying out hydrothermal reaction at 120 ℃ for 12 hours; taking out, naturally cooling to room temperature, centrifugally separating, washing with distilled water and ethanol for 3 times respectively, and drying the sample in a crucible at 80 ℃ for 12h to obtain oily sludge/BiVO4A composite photocatalyst is provided.
2. The preparation method of the oily sludge/bismuth vanadate composite photocatalyst according to claim 1, which is characterized by comprising the following steps of:
the oily sludge is sludge collected from oil field, and comprises SiO2、SO3BaO, oil-based organic matter.
3. An oily sludge/bismuth vanadate composite photocatalyst is characterized in that: the composite photocatalyst is prepared by the preparation method of the oily sludge/bismuth vanadate composite photocatalyst in claim 1 or 2.
4. The application of the composite photocatalyst for oily sludge/bismuth vanadate as claimed in claim 3, which is characterized in that: used for treating sulfanilamide wastewater.
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