CN115301243A - Supported perovskite catalyst, preparation method and application thereof - Google Patents
Supported perovskite catalyst, preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 58
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 41
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 30
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 28
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 24
- 239000002351 wastewater Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
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- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
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- 238000003760 magnetic stirring Methods 0.000 claims description 5
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 10
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- 238000012360 testing method Methods 0.000 description 3
- LODHFNUFVRVKTH-ZHACJKMWSA-N 2-hydroxy-n'-[(e)-3-phenylprop-2-enoyl]benzohydrazide Chemical compound OC1=CC=CC=C1C(=O)NNC(=O)\C=C\C1=CC=CC=C1 LODHFNUFVRVKTH-ZHACJKMWSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- -1 calcium-based Chemical compound 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 230000003907 kidney function Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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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
- 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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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0081—Preparation by melting
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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 discloses a supported perovskite catalyst, a preparation method and application thereof. The preparation method of the invention uses aluminum chloride as a pillaring agent, montmorillonite as a carrier and perovskite as an active component and adopts a solid melting method to prepare the supported catalyst, namely, firstly, the perovskite active component PrFe is prepared x Co 1‑x O 3 (ii) a Then PrFe is melted by solid melting method x Co 1‑x O 3 Loaded on the pillared montmorillonite. Compared with the traditional pillared montmorillonite catalyst, the supported perovskite catalyst disclosed by the invention has the advantages of larger specific surface area, less metal ion elution amount, higher catalytic activity, less metal ion elution and the likeThe method has high recycling value, can be used for degrading the salicylic acid wastewater by a catalytic wet hydrogen peroxide oxidation method, has the advantages of environmental protection, safety, mild condition, less byproduct generation and good wastewater degradation effect in the whole degradation process.
Description
Technical Field
The invention relates to the field of wastewater treatment, relates to a catalyst and a preparation method thereof, and particularly relates to a supported perovskite catalyst, a preparation method and application thereof.
Background
The pharmaceutical wastewater has the characteristics of large COD value, strong toxicity, difficult thorough degradation and the like, and can cause serious threat to human beings and the environment if not treated well. Because the harmfulness of pharmaceutical wastewater is high, strict wastewater discharge standards are implemented everywhere, and the treatment of pharmaceutical wastewater is more and more emphasized. Salicylic Acid, also known as 2-Hydroxybenzoic Acid (2-HA), is a common component in pharmaceutical wastewater, and the salicylic Acid-containing wastewater, if ingested by a human body, may cause damage to gastrointestinal tract and renal function, and is necessary for treating pharmaceutical wastewater.
Montmorillonite is the main component of bentonite, and can also be called montmorillonite, microcrystalline kaolinite and the like, and the silicon-oxygen tetrahedron and the aluminum octahedron form the lamellar structure of montmorillonite. The montmorillonite has large specific surface area, high mechanical strength, looseness and porosity, and exchangeable cations exist among layers, so that the interlayer can be expanded by exchanging polycations formed in the hydrolysis of metal oxides with the cations among the layers, and the inserted polycations among the montmorillonite can stably exist by means of electrostatic force and van der waals force, so that the porous structure of the montmorillonite is maintained, the interlayer spacing of the montmorillonite is increased, and the montmorillonite has larger specific surface area and more active sites.
However, with the traditional supported pillared montmorillonite catalyst, along with the reaction, the pore structure of the catalyst is easily blocked and thus inactivated, and active components are easily dissolved out, so that the catalytic activity is reduced, and secondary pollution is caused.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a supported perovskite catalyst, a preparation method and application thereof, so as to solve the technical problem that the supported pillared montmorillonite catalyst in the prior art is poor in adsorption effect due to the fact that the pore channel structure is easy to cause.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a supported perovskite catalyst takes aluminum chloride as a pillaring agent, montmorillonite as a carrier and perovskite as an active component and adopts a solid melting method to prepare the supported perovskite catalyst, which comprises the following steps:
step S1: adding sodium-based montmorillonite powder into an aluminum chloride solution to obtain a mixed feed liquid A;
step S2: under the conditions of water bath heating and magnetic stirring, sequentially adding polyethylene glycol and sodium hydroxide into the mixed material liquid A to obtain mixed material liquid B;
and step S3: heating the mixed feed liquid B in a water bath, magnetically stirring, continuously stirring at room temperature, and aging at room temperature to obtain a layering liquid C;
and step S4: centrifuging, washing, drying, grinding and roasting the layering liquid C to obtain aluminum pillared montmorillonite;
step S5: dissolving and mixing ferric nitrate, praseodymium nitrate, cobalt nitrate and citric acid in proportion, performing ultrasonic dispersion to obtain a mixed feed liquid D, heating the mixed feed liquid D in a water bath, drying, grinding, crushing and roasting to obtain a perovskite active component PrFe x Co 1- x O 3 ；
Step S6: mixing, grinding and roasting the aluminum pillared montmorillonite and the perovskite active component to obtain a supported perovskite catalyst;
wherein the mass ratio of the perovskite active component to the aluminum pillared montmorillonite is 1 (1-4).
The invention also has the following technical characteristics:
specifically, the concentration of the aluminum chloride solution in the step S1 is 0.39-0.42 mol/L, and the mass ratio of the aluminum chloride to the sodium-based montmorillonite in the mixed feed liquid A is 1: (0.62-0.63).
Further, step S2 specifically includes: the mixed feed liquid A is stirred in a water bath at the temperature of 70-80 ℃ for 10-12 min, and then 2.4-2.6 mL of polyethylene glycol and 7-7.5mL of sodium hydroxide at the concentration of 0.4mol/L are added in sequence. Wherein the mass ratio of the sodium-based montmorillonite powder to the polyethylene glycol to the sodium hydroxide is 1: (6.34-6.36): (0.23-0.25).
Furthermore, the magnetic stirring time in the step S3 is 30-40 min, the water bath heating temperature is 70-80 ℃, and the room temperature aging time is 12-24 h.
Further, step S4 specifically includes: the layering solution C is washed to be Cl-free - Then drying for 20-24 h at 70-80 ℃, grinding to 80-100 meshes, and roasting for 1.5-2.5 h at 400 +/-10 ℃.
Furthermore, in the step S5, the molar ratio of praseodymium nitrate, cobalt nitrate, ferric nitrate and citric acid is 1: (0.3-0.7): (0.3-0.7): (1.99-2.01), ultrasonic dispersion time is 40-45 min, water bath heating temperature is 70-80 ℃, water bath heating time is 50-60 min, drying temperature is 100-105 ℃, drying time is 20-24 h, and grinding to 80-100 meshes; firstly, roasting at 500 +/-10 ℃ for 2-2.5 h, and then roasting at 700 +/-10 ℃ for 4-4.5 h.
Furthermore, the grinding time in the step S6 is 10-15 min, and then the mixture is roasted in a muffle furnace at 200-220 ℃ for 2-3 h.
The invention also provides a supported perovskite catalyst prepared by the preparation method.
The invention also protects the application of the supported perovskite catalyst for treating the salicylic acid-containing wastewater.
Furthermore, the dosage of the supported perovskite catalyst in per 140-160 mL of salicylic acid wastewater is 0.04-0.05 g, the concentration of salicylic acid is 100 +/-1 mg/L, the pH = 4.8-5.2, meanwhile, the dosage of hydrogen peroxide with the volume fraction of 30% is 0.20-0.22 mL, and the reaction time is 2.5-3 h.
Compared with the prior art, the invention has the beneficial technical effects that:
the preparation method directly synthesizes the supported perovskite catalyst by taking aluminum chloride as a pillaring agent, montmorillonite as a carrier and perovskite as an active component and adopting a solid melting method, and has the advantages of simple preparation process and low cost.
The supported perovskite catalyst prepared by the method has the advantages of good stability, less metal ion dissolution and higher recycling value.
The supported perovskite catalyst prepared by the invention can be used for catalyzing the degradation of salicylic acid wastewater by a wet hydrogen peroxide oxidation method, the whole degradation process is environment-friendly and safe, the condition is mild, byproducts are less generated, and the degradation effect of the wastewater is good.
The present invention will be explained in further detail with reference to examples.
Drawings
FIG. 1 is an SEM image of a supported perovskite catalyst synthesized in examples 1 to 4 of the present invention;
FIG. 2 is an FT-IR spectrum of a supported perovskite catalyst synthesized in examples 1 to 4 of the present invention;
FIG. 3 shows N of supported perovskite catalysts synthesized in examples 1 to 4 of the present invention 2 Adsorption-desorption isotherms;
FIG. 4 is a UV-vis spectrum of a supported perovskite catalyst synthesized in examples 1 to 4 of the present invention;
FIG. 5 is an XRD pattern of the supported perovskite catalysts synthesized in examples 1 to 4 of the present invention.
Detailed Description
The present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention.
It should be noted that all the devices and apparatuses used in the present invention can be adopted in the devices and apparatuses known in the art without specific description, for example, in the present invention: the drying apparatus is a drying apparatus known in the art.
The definitions or concepts to which the invention relates are illustrated below:
montmorillonite (also known as montmorillonite or microcrystalline kaolinite) is a natural mineral of silicate, and is the main mineral component of bentonite ore. Monoclinic system, multi-site microcrystals, aggregates in the form of soil, spheres, etc. White, slightly grayish, yellowish, greenish, bluish when containing impurities, earthy luster or dull luster, and slippery feel. After adding water, the volume can expand several times and become paste. The volume of the product shrinks after heated dehydration. Has strong adsorption capacity and cation exchange performance, and is mainly produced in the weathering crust of volcanic tuff. Montmorillonite (including calcium-based, sodium-calcium-based, and magnesium-based montmorillonite) is peeled, dispersed, purified, modified, ultra-fine graded, and organically combined, has average wafer thickness of less than 25nm, and can be used as bleaching agent and adsorbent filler.
In a specific embodiment of the present invention, functional group information in a sample was measured using an IRTf definition-1S type Fourier Infrared spectrometer manufactured by Shimadzu corporation; n was carried out by using NOVE 2200e type specific surface area and pore size distribution meter manufactured by Quantachrome corporation, USA 2 Adsorption/desorption test, mainly used for measuring nitrogen adsorption/desorption isotherm and structural parameters of the sample; observing the morphology of the catalyst by using a SIGMA type scanning electron microscope of a Carl Zeiss company, and simultaneously obtaining the element content and the distribution condition of a sample; an ultraviolet-visible spectrum analyzer model UV-2600 by Shimadzu corporation was used to measure the ultraviolet-visible spectrum of the catalyst, scanning at 200-800 nm using barium sulfate as a test reference. A SmartLab SE type X-ray diffractometer from Rigaku corporation was used to analyze the crystal phase structure, composition, and the like of the sample.
Example 1
The embodiment provides a preparation method of a supported perovskite catalyst, which takes aluminum chloride as a pillaring agent, montmorillonite as a carrier and perovskite as an active component and adopts a solid melting method to prepare the supported catalyst, and the preparation method specifically comprises the following steps:
step S1: adding 500mg of sodium-based montmorillonite powder into 15mL of aluminum chloride solution with the concentration of 0.4 mol/L; obtaining mixed feed liquid A;
step S2: stirring the mixed material liquid A in a water bath at 80 ℃ for 10min, then adding 2.5mL of polyethylene glycol, and then adding 7.5mL of 0.4mol/L sodium hydroxide solution to obtain a mixed material liquid B;
and step S3: heating the mixed material liquid B in a water bath at 60 ℃ and magnetically stirring for 30min, then stirring for 30min at normal temperature, and aging for 12h at room temperature to obtain a layering liquid C;
and step S4: drying the precipitate obtained by centrifugally washing the layering liquid C at 80 ℃ for 20h, grinding to 100 meshes, and roasting at 400 ℃ for 2h to obtain the aluminum pillared montmorillonite;
step S5: dissolving and mixing ferric nitrate, praseodymium nitrate, cobalt nitrate and citric acid in proportion, and carrying out ultrasound for 30min, wherein the molar ratio of the praseodymium nitrate to the cobalt nitrate to the ferric nitrate to the citric acid is 1:0.7:0.3:2, heating the perovskite powder in a water bath at 90 ℃ for 30min, drying the perovskite powder at 100 ℃ for 24 hours, grinding and crushing the perovskite powder, roasting the perovskite powder at 500 ℃ for 2 hours, and roasting the perovskite powder at 700 ℃ for 4 hours to obtain a perovskite active component; the molar ratio of Co to Fe = 1.
As a preferable scheme of this embodiment, in this step, the ratio of praseodymium nitrate: (cobalt nitrate + iron nitrate) =1: (0.99 to 1.01), (praseodymium nitrate + cobalt nitrate + iron nitrate): citric acid =1: (0.95 to 1.05), iron nitrate: cobalt nitrate =1: (0-2.33).
Step S6: mixing a certain amount of aluminum pillared montmorillonite and perovskite active component in a mortar, grinding for 10min to obtain black powder with single and uniform color, and roasting at 220 ℃ for 2h to obtain the supported perovskite catalyst.
Performance analysis experiments:
150mL of a 100mg/L salicylic acid solution and 0.05g catalyst were added to a three-necked flask using NaOH solution and dilute H 2 SO 4 The solution was adjusted to pH =5.0. Placing the three-necked flask in a magnetic stirring water bath, adjusting different temperatures, magnetically stirring for 30min, and adding 0.21mL H 2 O 2 Solution, recording starting from this timeCOD value and absorbance value. Samples were taken at different time intervals and filtered during the CWPO reaction using an all glass syringe and relevant data of the wastewater was measured.
The performance analysis experiment of the prepared supported perovskite catalyst shows that the COD removal rate reaches 67.7 percent and the degradation rate of salicylic acid reaches 85.84 percent.
Example 2
The preparation method of the supported perovskite catalyst of this example is the same as that of example 1.
In this example, cobalt nitrate is not added to the mixed feed liquid D, the molar ratio of praseodymium nitrate, ferric nitrate and citric acid is 1.
The performance analysis experiment of the prepared supported perovskite catalyst shows that the COD removal rate reaches 62.7 percent and the degradation rate of salicylic acid reaches 80.3 percent.
Example 3
The preparation method of the supported perovskite catalyst of this example is the same as that of example 1.
The example also provides an application of the supported perovskite catalyst in treatment of salicylic acid wastewater, wherein the ratio of Co to Fe =1 (0.99-1.01) in the example, and other implementation steps and the dosage of the medicine are the same as those in the example 1.
The performance analysis experiment of the prepared supported perovskite catalyst shows that the COD removal rate reaches 40.34 percent and the degradation rate of salicylic acid is 41.41 percent.
Example 4
The preparation method of the supported perovskite catalyst of this example is the same as that of example 1.
The embodiment also provides the application of the supported perovskite catalyst in treating salicylic acid wastewater, wherein the ratio of Co to Fe =1 (2.3-2.4) in the embodiment, and other implementation steps and the dosage of the medicines are the same as those in the embodiment 1.
Performance analysis experiments are carried out on the prepared supported perovskite catalyst, and the results show that the COD removal rate reaches 50.34%, and the degradation rate of salicylic acid reaches 75.72%.
Comparative example 1
The preparation method and the molar ratio of Co to Fe of the supported perovskite catalyst of the comparative example are the same as those of example 1.
In this comparative example, the amount of catalyst added was 0.025g, and the procedure was otherwise as in example 1.
The results of performance analysis experiments show that the COD removal rate is 67.27 percent, and the salicylic acid degradation rate is 83.23 percent.
Comparative example 2
The preparation method and the molar ratio of Co to Fe of the supported perovskite catalyst of the comparative example are the same as those of example 1.
In this comparative example, the amount of catalyst added was 0.075g, and the procedure was otherwise as in example 1.
The results of performance analysis experiments show that the COD removal rate is 62.38%, and the salicylic acid degradation rate is 81.69%.
Comparative example 3
The preparation method and the molar ratio of Co to Fe of the supported perovskite catalyst of the comparative example are the same as those of example 1.
In this comparative example, the amount of the catalyst added was 0.1g, and the other steps were the same as in example 1.
The results of performance analysis experiments show that the COD removal rate is 36.23% and the salicylic acid degradation rate is 42.16%.
From the data in the above examples, it can be seen that when Co: fe =1 (0.42-0.44), the supported perovskite catalyst has the best degradation effect on salicylic acid wastewater, the COD removal rate reaches 67.7%, and the salicylic acid degradation rate reaches 85.84%, because the increase of Co doping amount leads to the increase of oxygen vacancy, and thus the catalytic activity is increased. When the catalyst dosage is too small, the degradation effect of the salicylic acid wastewater is not ideal, because less catalyst can not provide enough active sites, resulting in H 2 O 2 Sufficient HO can not be generated, thereby having influence on the degradation effect of the salicylic acid wastewater.
As can be seen from comparative examples 1 to 3, when the amount of the supported perovskite catalyst added was increased to 0.100g, both the COD removal rate and the salicylic acid degradation rate were significantly reduced because too much catalyst caused the dissolution of metal ions, resulting in a decrease in the COD removal rate of the wastewater after the reaction; when the addition amount of the supported perovskite catalyst is 0.050g, the degradation rate of salicylic acid is as high as 90.83%, the COD removal rate is as high as 74.07%, and the degradation effect is good at the moment. The above data show that when the molar ratio of Co to Fe is 0 (0.99-1.01), 1 (0.42-0.44) and 1 (2.30-2.40), the COD removal rate and the salicylic acid degradation rate are maintained at high levels when the amount of the catalyst is 0.025-0.075 g.
In addition, as can be seen from FIG. 1, the morphology of the prepared supported perovskite catalyst under a scanning electron microscope has some differences by using different molar ratios of Co to Fe, wherein in FIG. 1a, FIG. 1b, FIG. 1c and FIG. 1d, the molar ratios of Co to Fe are respectively 0 (0.99-1.01), 1 (2.30-2.40), 1 (0.99-1.01) and 1 (0.42-0.44).
Firstly, the layered structure of pillared montmorillonite is observed in all catalysts except for Co: fe =0 (0.99-1.01), namely catalysts without Co doping, which shows that the perovskite active components in FIG. 1b, FIG. 1c and FIG. 1d are successfully loaded on the pillared montmorillonite; secondly, as can be seen from fig. 1, when there is no Co element doped, the surface of the catalyst is smooth and compact, and the pore channel is small, which is not favorable for full contact with the reactant; finally, the active component on the surface of the catalyst increases with the increase of the molar ratio of Co to Fe and has a directional attachment tendency, which shows that the doping of Co is beneficial to improving the activity and the specific surface area of a sample.
The FT-IR spectra of the catalysts with different Co: fe molar ratios are shown in FIG. 2, and can be clearly observed in FIG. 2: the supported perovskite catalysts of Co Fe =1 (2.30-2.40), co Fe =1 (0.99-1.01) and Co Fe =1 (0.42-0.44) are positioned at 1028cm -1 The molecular structure of the montmorillonite is a characteristic peak belonging to Si-O-Si, which is obviously different from a supported perovskite catalyst with Co: fe =0 (0.99-1.01), and the result shows that the interlayer structure of the original montmorillonite can be damaged in a sample without doping Co atoms. When Co is Fe =0 (0.99-1.01) in the supported perovskite catalyst, the thickness is 529cm -1 Has a more obvious peak, and in other 3 samples, the perovskite activity is caused by the octahedral coordination of Co atoms replacing Fe atomsOctahedron (FeO) in the component 6 ) The metal-oxygen bond (Fe-O) in the structure vibrates, causing it to vibrate at 529cm -1 A decrease in absorption peak. With the increase of the molar ratio of Co to Fe, a certain blue shift occurs on the characteristic peak of the supported perovskite catalyst sample, wherein the blue shift of the supported perovskite catalyst with Co to Fe =1 (0.42-0.44) is most obvious, which indicates that the group of the supported perovskite catalyst is more stable and is beneficial to maintaining the catalytic activity in the CWPO reaction process.
In addition, BET tests were performed on the prepared supported perovskite catalysts with different molar ratios of Co to Fe, and the resulting structural parameters are shown in table 1 below:
as can be seen from Table 1, the larger the molar ratio of Co to Fe, the larger the specific surface area (S) of the supported perovskite catalyst prepared in example 1 of the invention BET ) The larger the size, the easier the active component is dispersed, wherein the specific surface area of the sample is the largest at 112.289m when Co: fe =1 (0.42-0.44) 2 ·g -1 And, the total pore volume and the average pore diameter of this sample were both greater than those of the other samples.
FIG. 3 shows N of supported perovskite catalysts synthesized in examples 1 to 4 2 Adsorption-desorption isotherms, it can be seen from the figure that the isotherms of all the supported perovskite catalysts are of type iv, wherein the supported perovskite catalyst prepared in each example corresponds to two isotherms, one of which is N 2 Desorption isotherm, the lower one being N 2 Adsorption isotherms, each set of adsorption-desorption isotherms having an H3-type hysteresis loop, indicate that each sample catalyst has more mesopores. Among them, when Co is Fe =1 (0.42 to 0.44), a delayed adsorption phenomenon may occur at a low relative pressure, which is different from other samples because doping with Co destroys the octahedral coordination structure of Fe atoms, increases oxygen vacancies, and further forms lattice defects, resulting in high activity.
As shown in FIG. 4, the UV-vis spectra of Co-doped and Co-undoped samples are very different. The sample with the B-site doped metal cobalt has absorption bands at 500nm and 530-650nm respectively, the absorption band at 500nm is related to the doped metal, and the absorption band is mainly formed by charge transfer between the metal and the metal, namely Co 2+ +Fe 3+ →Co 3+ +Fe 2+ . The absorption band at 530-650nm is mainly due to Co 3+ Is caused by the d-d transition of (a). This indicates that Co can be doped into PrFeO 3 New energy levels are introduced and the more Co doping, the more pronounced the absorption of the d-d transition.
FIG. 5 is an XRD pattern of samples of different Co: fe molar ratios, as can be seen in FIG. 5: belongs to PrFeO at 2 theta =32.4 DEG with increasing Co/Fe molar ratio 3 The characteristic peak of (A) is sharper and a certain split occurs, because of PrFeO 3 Partial B-site metal atoms Fe in the perovskite crystal are replaced by Co atoms, and then the lattice is distorted, and torsion and asymmetry of the crystal structure occur, so that lattice defects are increased. And the characteristic peak of the Co: fe =0 (0.99-1.01) catalyst at the position belonging to the montmorillonite has no obvious fluctuation, which indicates that the structure of the montmorillonite can be damaged. It can also be seen from the figure that: the characteristic peak of the Co: fe =1 (0.42-0.44) is the highest, the peak signal of the catalyst is the strongest and has more lattice defects, and the catalytic performance is better, which is consistent with the performance experiment result, namely, when the Co: fe =1 (0.42-0.44), the supported perovskite catalyst has the best degradation effect on salicylic acid wastewater.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications all fall within the protection scope of the present invention.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A preparation method of a supported perovskite catalyst is characterized in that aluminum chloride is used as a pillaring agent, montmorillonite is used as a carrier, perovskite is used as an active component, and a solid melting method is adopted to prepare the supported perovskite catalyst, and specifically comprises the following steps:
step S1: adding sodium-based montmorillonite powder into an aluminum chloride solution to obtain a mixed feed liquid A;
step S2: under the conditions of water bath heating and magnetic stirring, sequentially adding polyethylene glycol and sodium hydroxide into the mixed feed liquid A to obtain mixed feed liquid B;
and step S3: heating the mixed material liquid B in a water bath, magnetically stirring, continuing stirring at room temperature, and aging at room temperature to obtain a layered liquid C;
and step S4: centrifuging, washing, drying, grinding and roasting the layering liquid C to obtain aluminum pillared montmorillonite;
step S5: dissolving and mixing ferric nitrate, praseodymium nitrate, cobalt nitrate and citric acid in proportion, performing ultrasonic dispersion to obtain a mixed feed liquid D, heating the mixed feed liquid D in a water bath, drying, grinding, crushing and roasting to obtain a perovskite active component PrFe x Co 1-x O 3 ；
Step S6: mixing, grinding and roasting the aluminum pillared montmorillonite and the perovskite active component to obtain a supported perovskite catalyst;
wherein the mass ratio of the perovskite active component to the aluminum pillared montmorillonite is 1 (1-4).
2. The method for preparing the supported perovskite catalyst according to claim 1, wherein the concentration of the aluminum chloride solution is 0.39 to 0.42mol/L, and the mass ratio of the aluminum chloride to the sodium-based montmorillonite in the mixed feed liquid A is 1: (0.62-0.63).
3. The preparation method of the supported perovskite catalyst according to claim 1, wherein the mixed material liquid A is stirred in a water bath at 70-80 ℃ for 10-12 min, and then 2.4-2.6 mL of polyethylene glycol and 7-7.5 mL of 0.4mol/L of sodium hydroxide are sequentially added, wherein the mass ratio of the sodium montmorillonite powder to the polyethylene glycol to the sodium hydroxide is 1: (6.34-6.36): (0.23-0.25).
4. The preparation method of the supported perovskite catalyst according to claim 1, wherein the magnetic stirring time in the step S3 is 30-40 min, the water bath heating temperature is 70-80 ℃, and the room temperature aging time is 12-24 h.
5. The method for preparing a supported perovskite catalyst according to claim 1, wherein the step S4 specifically comprises: the layering solution C is washed to be Cl-free - Then drying for 20-24 h at 70-80 ℃, grinding to 80-100 meshes, and roasting for 1.5-2.5 h at 400 +/-10 ℃.
6. The method for preparing a supported perovskite catalyst according to claim 1, wherein in step S5, the molar ratio of praseodymium nitrate, cobalt nitrate, iron nitrate and citric acid is 1: (0.3-0.7): (0.3-0.7): (1.99-2.01), ultrasonic dispersion time is 40-45 min, water bath heating temperature is 70-80 ℃, water bath heating time is 50-60 min, drying temperature is 100-105 ℃, drying time is 20-24 h, and grinding to 80-100 meshes; firstly, roasting at 500 +/-10 ℃ for 2-2.5 h, and then roasting at 700 +/-10 ℃ for 4-4.5 h.
7. The process for preparing a supported perovskite catalyst as claimed in claim 1, wherein the grinding time in step S6 is 10 to 15min, followed by calcination in a muffle furnace at 200 to 220 ℃ for 2 to 3h.
8. A supported perovskite catalyst produced by the production method as claimed in any one of claims 1 to 7.
9. Use of a supported perovskite catalyst as defined in any one of claims 1 to 7 for the treatment of salicylic acid containing wastewater.
10. The use according to claim 9, wherein the supported perovskite catalyst is added in an amount of 0.04-0.05 g per 140-160 mL of salicylic acid wastewater, the salicylic acid concentration is 100 ± 1mg/L, the pH = 4.8-5.2, and the hydrogen peroxide with the volume fraction of 30% is added in an amount of 0.20-0.22 mL, and the reaction time is 2.5-3 h.
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