CN115301243B - 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 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 57
- 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 41
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 34
- 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 30
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 29
- 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 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 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
- 239000007788 liquid Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 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 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 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
- 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
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 19
- 230000015556 catabolic process Effects 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000002386 leaching Methods 0.000 abstract 2
- 238000010309 melting process Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229910052622 kaolinite Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 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
- 230000009286 beneficial effect Effects 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
- 150000001768 cations Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 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 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-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
- 238000013329 compounding Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 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
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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 column agent, montmorillonite as a carrier, perovskite as an active component, and adopts a solid melting method to prepare a supported catalyst, namely, perovskite active component PrFe is prepared firstly x Co 1‑x O 3 The method comprises the steps of carrying out a first treatment on the surface of the PrFe is then melted using a solid state melting process x Co 1‑x O 3 Loaded on the column support montmorillonite. Compared with the traditional pillared montmorillonite catalyst, the supported perovskite catalyst disclosed by the invention has the advantages of larger specific surface area, smaller metal ion leaching amount, higher catalytic activity, less metal ion leaching and higher recycling value, can be used for degrading salicylic acid wastewater by a catalytic wet hydrogen peroxide oxidation method, is environment-friendly and safe in the whole degradation process, mild in condition, less in byproduct generation and good in degradation effect.
Description
Technical Field
The invention relates to the field of wastewater treatment, relates to a catalyst and a preparation method thereof, and in particular 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 if the pharmaceutical wastewater is not treated properly, serious threat to human beings and environment can be caused. Because of the greater harmfulness of pharmaceutical wastewater, strict wastewater discharge standards are implemented in various places, and the treatment of pharmaceutical wastewater is increasingly emphasized. Salicylic acid is also called p-hydroxybenzoic acid (2-Hydroxybenzoic Acid, abbreviated as 2-HA), is a common component in pharmaceutical wastewater, if the wastewater containing salicylic acid is ingested by human body, damage to gastrointestinal tract and kidney functions can be caused, and the pharmaceutical wastewater is treated very necessarily, and common methods comprise an adsorption method, a membrane separation technology, an electrolysis method and a photocatalysis method, wherein the adsorption method is widely applied due to the advantages of simple operation, low cost, high removal rate and the like.
Montmorillonite is the main component of bentonite, and can also be called montmorillonite, microcrystalline kaolinite and the like, and silicon oxygen tetrahedra and aluminum oxygen octahedra form a lamellar structure of montmorillonite. The montmorillonite has large specific surface area, high mechanical strength, porosity and porous interlayer, and exchangeable cations exist between the layers, so that polycations formed during the hydrolysis of metal oxide can be exchanged with the cations between the layers to lead the layers to be spread, and polycations inserted between the montmorillonite layers can stably exist by means of electrostatic force and Van der Waals force, thereby maintaining the porous structure of the montmorillonite and increasing the interlayer spacing of the montmorillonite, so that the montmorillonite has larger specific surface area and more active sites.
However, the traditional supported montmorillonite catalyst is easy to block and inactivate the pore channel structure of the catalyst along with the progress of the reaction, and the active components are easy to dissolve, so that the catalytic activity is reduced, and secondary pollution is caused.
Disclosure of Invention
Aiming at the defects existing 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 adsorption effect of the supported pillared montmorillonite catalyst in the prior art is poor due to the fact that the pore structure is easy to be used.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the supported perovskite catalyst takes aluminum chloride as a column agent, takes montmorillonite as a carrier, takes perovskite as an active component, adopts a solid melting method to prepare the supported catalyst, and specifically comprises the following steps:
step S1: adding sodium montmorillonite powder into aluminum chloride solution to obtain mixed feed liquid A;
step S2: sequentially adding polyethylene glycol and sodium hydroxide into the mixed material liquid A under the conditions of water bath heating and magnetic stirring to obtain mixed material liquid B;
step S3: heating the mixed material liquid B in a water bath, magnetically stirring, continuously stirring at room temperature, and aging at room temperature to obtain layered liquid C;
step S4: centrifuging, washing, drying and grinding the layering liquid C, and roasting to obtain aluminum column montmorillonite;
step S5: mixing ferric nitrate, praseodymium nitrate, cobalt nitrate and citric acid according to a certain proportion, dissolving and dispersing by ultrasonic to obtain mixed solution D, heating the mixed solution D in water bath, drying, grinding, crushing and roasting to obtain perovskite active component PrFe x Co 1- x O 3 ；
Step S6: mixing, grinding and roasting aluminum pillared montmorillonite and perovskite active components 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, in the step S1, the concentration of the aluminum chloride solution is 0.39-0.42 mol/L, and the mass ratio of the aluminum chloride to the sodium montmorillonite in the mixed feed liquid A is 1: (0.62-0.63).
Further, the step S2 specifically includes: the mixed material liquid A is stirred for 10 to 12 minutes in a water bath with the temperature of 70 to 80 ℃, and then 2.4 to 2.6mL of polyethylene glycol and 7 to 7.5mL of sodium hydroxide with the concentration of 0.4mol/L are added in sequence. 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).
Furthermore, in the step S3, the magnetic stirring time is 30-40 min, the water bath heating temperature is 70-80 ℃, and the room temperature aging time is 12-24 h.
Further, the step S4 specifically includes: washing the separated liquid C until no Cl exists - Drying at 70-80 deg.c for 20-24 hr, grinding to 80-100 mesh, and roasting at 400 + -10 deg.c for 1.5-2.5 hr.
Further, 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 dispersing 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 for 2-2.5 h at 500+ -10 ℃, and then roasting for 4-4.5 h at 700+ -10 ℃.
Further, the grinding time in the step S6 is 10-15 min, and then roasting is carried out for 2-3 h in a muffle furnace at 200-220 ℃.
The invention also protects the supported perovskite catalyst prepared by the preparation method.
The invention also protects an application of the supported perovskite catalyst for treating the salicylic acid-containing wastewater.
Furthermore, the adding amount of the supported perovskite catalyst in each 140-160 mL of salicylic acid wastewater is 0.04-0.05 g, the salicylic acid concentration is 100+/-1 mg/L, the pH=4.8-5.2, meanwhile, the adding amount 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:
according to the preparation method disclosed by the invention, the supported perovskite catalyst is directly synthesized by taking aluminum chloride as a column agent, montmorillonite as a carrier and perovskite as an active component by adopting a solid melting method, so that the preparation flow is simple and the cost is low.
The supported perovskite catalyst prepared by the method has good stability, less metal ion dissolution and higher recycling value.
The supported perovskite catalyst prepared by the method can be used for catalyzing the wet hydrogen peroxide oxidation method to degrade the salicylic acid wastewater, and the whole degradation process is environment-friendly, safe, mild in condition, less in byproduct generation and good in degradation effect of the wastewater.
The following examples illustrate the invention in further detail.
Drawings
FIG. 1 is an SEM image of supported perovskite catalysts synthesized according to examples 1 to 4 of the invention;
FIG. 2 is a FT-IR spectrum of supported perovskite catalysts synthesized according to examples 1 to 4 of the invention;
FIG. 3 is an N-type representation of supported perovskite catalysts synthesized according to examples 1-4 of the invention 2 Adsorption-desorption isotherms;
FIG. 4 is a UV-vis spectrum of supported perovskite catalysts synthesized in examples 1-4 of the invention;
FIG. 5 is an XRD pattern of supported perovskite catalysts synthesized according to examples 1 to 4 of the present invention.
Detailed Description
The following specific embodiments of the present invention are given according to the above technical solutions, and it should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solutions of the present application fall within the protection scope of the present invention.
All devices and apparatuses used in the present invention are known in the art, and, unless specifically stated otherwise, for example, in the present invention: the drying device is a drying device known in the art.
The definitions or concepts to which the present invention relates are described below:
montmorillonite (english name montmorillonite) is also known as kaolinite, microcrystalline kaolinite, a natural mineral of silicate, which is the main mineral component of bentonite. Monoclinic system, multi-site crystallites, aggregates in the form of earth, pellets, etc. White light grey, light yellow, light green, light blue when containing impurities, soil luster or no luster, and smooth feeling. The volume of the paste can be expanded by several times after water is added, and the paste becomes pasty. The volume is contracted after heated and dehydrated. 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, magnesium-based montmorillonite) is subjected to stripping dispersion, purification modification, superfine classification, special organic compounding, and average wafer thickness less than 25nm, and can be used as bleaching agent and adsorbent filler.
In a specific embodiment of the invention, IRTfinity-1S Fourier infrared spectrometer manufactured by Shimadzu corporation is used to determine the functional group information in the sample; n was performed by using NOVE 2200e specific surface area and pore size distribution instrument manufactured by Quantachrome Co., ltd 2 The adsorption/desorption test is mainly used for measuring nitrogen adsorption/desorption isotherms and structural parameters of the sample; observing the morphology of the catalyst by using a SIGMA scanning electron microscope of Carl Zeiss company, and obtaining the element content and distribution of the sample; a UV-visible diffuse spectrum analyzer, model UV-2600, manufactured by Shimadzu corporation, was used to measure the UV-visible spectrum of the catalyst, using barium sulfate as a test reference, and scanning was performed at 200-800 nm. A SmartLab SE type X-ray diffractometer from Rigaku corporation was used to analyze the crystalline phase structure and composition of the sample, etc.
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 specifically comprises the following steps:
step S1: 500mg of sodium montmorillonite powder is added into 15mL of aluminum chloride solution with the concentration of 0.4 mol/L; obtaining a mixed material liquid A;
step S2: stirring the mixed material liquid A for 10min at 80 ℃ in a water bath, then adding 2.5mL of polyethylene glycol, and then adding 7.5mL of sodium hydroxide solution with the concentration of 0.4mol/L to obtain mixed material liquid B;
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 layered liquid C;
step S4: drying the precipitate obtained by centrifugal washing of the layering liquid C at 80 ℃ for 20 hours, grinding to 100 meshes, and roasting at 400 ℃ for 2 hours to obtain aluminum column montmorillonite;
step S5: mixing ferric nitrate, praseodymium nitrate, cobalt nitrate and citric acid in proportion, and performing ultrasonic treatment for 30min, wherein the mol 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 mixture in a water bath at 90 ℃ for 30min, drying the mixture at 100 ℃ for 24h, grinding and crushing the mixture, roasting the mixture at 500 ℃ for 2h, and roasting the mixture at 700 ℃ for 4h to obtain a perovskite active component; the molar ratio of Co to Fe was = 1:0.43.
As a preferable mode of this embodiment, in this step, praseodymium nitrate: (cobalt nitrate+iron nitrate) =1: (0.99-1.01), (praseodymium nitrate+cobalt nitrate+iron nitrate): citric acid = 1: (0.95-1.05), ferric nitrate: cobalt nitrate=1: (0 to 2.33).
Step S6: mixing a certain amount of aluminum pillared montmorillonite and perovskite active components 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 salicylic acid solution at a concentration of 100mg/L and 0.05g of 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. The three-necked flask was placed in a magnetic stirring water bath, the temperature was adjusted and magnetically stirred for 30min, then 0.21mL of H was added 2 O 2 The COD value and absorbance value of the solution were recorded starting from this point. During the CWPO reaction, all glass syringes were used to sample and filter at different time periods and the data relating to the wastewater was measured.
The prepared supported perovskite catalyst is subjected to performance analysis experiments, and the results show that the COD removal rate reaches 67.7%, and the degradation rate of salicylic acid reaches 85.84%.
Example 2
The preparation method of the supported perovskite catalyst of this example is the same as that of example 1.
In this embodiment, cobalt nitrate is not added in the mixed solution D, the molar ratio of praseodymium nitrate, ferric nitrate and citric acid is 1:1:2, and other implementation steps and drug amounts are the same as in embodiment 1.
The prepared supported perovskite catalyst is subjected to performance analysis experiments, and the results show that the COD removal rate reaches 62.7%, and the degradation rate of salicylic acid reaches 80.3%.
Example 3
The preparation method of the supported perovskite catalyst of this example is the same as that of example 1.
The embodiment also provides an application of the supported perovskite catalyst in treating salicylic acid wastewater, wherein Co is Fe=1 (0.99-1.01), and other implementation steps and drug dosage are the same as those of the embodiment 1.
The prepared supported perovskite catalyst is subjected to performance analysis experiments, and the results show that the COD removal rate reaches 40.34%, and the degradation rate of salicylic acid is 41.41%.
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 an application of the supported perovskite catalyst in treating salicylic acid wastewater, wherein Co is Fe=1 (2.3-2.4), and other implementation steps and drug dosage are the same as those of the embodiment 1.
The prepared supported perovskite catalyst is subjected to performance analysis experiments, 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 Co to Fe molar ratio of the comparative supported perovskite catalyst are the same as those of example 1.
In this comparative example, the catalyst was added in an amount of 0.025g, and the procedure of example 1 was otherwise carried out.
The results of the performance analysis experiments show that the COD removal rate is 67.27% and the salicylic acid degradation rate is 83.23%.
Comparative example 2
The preparation method and Co to Fe molar ratio of the comparative supported perovskite catalyst are the same as those of example 1.
In this comparative example, the catalyst was added in an amount of 0.075g, and the procedure of example 1 was otherwise carried out.
The results of the 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 Co to Fe molar ratio of the comparative supported perovskite catalyst are the same as those of example 1.
In this comparative example, the catalyst addition amount was 0.1g, and the procedure of example 1 was otherwise carried out.
The results of the performance analysis experiments show that the COD removal rate is 36.23% and the salicylic acid degradation rate is 42.16%.
As can be seen from the data in the above examples, when Co: fe=1 (0.42 to 0.44), the supported perovskite catalyst had the best effect of degrading salicylic acid wastewater, and had a COD removal rate of 67.7% and a salicylic acid degradation rate of 85.84%, because the increase in the Co doping amount resulted in an increase in oxygen vacancies, which in turn resulted in an increase in catalytic activity. The salicylic acid wastewater degradation effect is not ideal when the catalyst addition amount is too small, because less catalyst cannot provide enough active sites, resulting in H 2 O 2 Cannot generate enough HO, thereby influencing the degradation effect of the salicylic acid wastewater.
As can be seen from comparative examples 1 to 3, when the addition amount of the supported perovskite catalyst was increased to 0.100g, both the COD removal rate and the salicylic acid degradation rate were significantly reduced, because too much catalyst caused elution 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 up to 90.83%, the COD removal rate is up to 74.07%, and the degradation effect is good. The 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 catalyst dosage is 0.025-0.075g, and the COD removal rate and the salicylic acid degradation rate are maintained at high levels.
In addition, as can be observed from fig. 1, the morphology of the prepared supported perovskite catalyst under a scanning electron microscope is different by adopting different molar ratios of Co to Fe, wherein in fig. 1a, 1b, 1c and 1d, the molar ratio of Co to Fe is 0 (0.99-1.01), 1 (2.30-2.40), 1 (0.99-1.01) and 1 (0.42-0.44) respectively.
Firstly, except for Co: fe=0, (0.99 to 1.01), i.e. the catalyst without Co doping, the layered structure of the pillared montmorillonite was observed for all other catalysts, which indicates that the perovskite active components in fig. 1b, 1c and 1d were all successfully supported on the pillared montmorillonite; secondly, as can be seen from fig. 1, when no Co element is doped, the catalyst surface is smoother and denser, and the pore channels are smaller, which is unfavorable for the sufficient contact with the reactant; finally, the active component of the catalyst surface increases with the increase of the molar ratio of Co to Fe, and has a tendency of directional adhesion, which indicates that the doping of Co is beneficial to improving the activity and specific surface area of the sample.
The FT-IR spectrum of the catalyst with different Co to Fe molar ratios is shown in FIG. 2, and is clearly observed in FIG. 2: co: fe=1 (2.30-2.40), co: fe=1 (0.99-1.01) and Co: fe=1 (0.42-0.44) supported perovskite catalysts were located at 1028cm -1 The characteristic peak belonging to Si-O-Si is obviously different from a Co: fe=0 (0.99-1.01) supported perovskite catalyst, which shows that the interlayer structure of the original montmorillonite can be damaged in a sample without doping Co atoms. When Co: fe=0 (0.99-1.01) in the supported perovskite catalyst, it was measured at 529cm -1 There is a more pronounced peak, whereas in the other 3 samples, the octahedral coordination of the Fe atoms was replaced by Co atoms, resulting in octahedral (FeO 6 ) The metal-oxygen bond (Fe-O) in the structure vibrates, resulting in it being at 529cm -1 The absorption peak is reduced. With the increase of Co: fe molar ratio, the characteristic peak of the supported perovskite catalyst sample has a certain blue shift, wherein the blue shift phenomenon of the supported perovskite catalyst of Co: fe=1 (0.42-0.44) is most obvious, which indicates that the groups of the supported perovskite catalyst are more stable, and the catalyst is favorable for maintaining the catalytic activity in the CWPO reaction process.
In addition, BET tests were performed on the prepared supported perovskite catalysts of different Co to Fe molar ratios, and the resulting structural parameters are shown in Table 1 below:
as can be seen from Table 1, the larger the Co to Fe molar ratio of the supported perovskite catalyst prepared as per example 1 of the present invention, the specific surface area (S BET ) The larger the active component is, the easier it is to disperse, wherein when Co: fe=1 (0.42 to 0.44), the specific surface area of the sample is the largest, being 112.289m 2 ·g -1 And, the total pore Rong Heping of this sample was all larger in pore size than the other samples.
FIG. 3 shows N of supported perovskite catalysts synthesized in examples 1 to 4 2 Adsorption-desorption isotherms as can be seen, the isotherms of all supported perovskite catalysts are of type iv, wherein the supported perovskite catalysts produced in each example correspond to two isotherms, the upper one of which is N 2 Desorption isotherm, the lower one is N 2 Adsorption isotherms, each set of adsorption-desorption isotherms had an H3-type hysteresis loop, indicating more mesopores in each sample catalyst. In the case of Co: fe=1 (0.42 to 0.44), the hysteresis adsorption phenomenon may occur at a relatively low pressure, unlike other samples, because the octahedral coordination structure of Fe atoms is destroyed due to Co doping, oxygen vacancies are increased, and lattice defects are formed, resulting in higher activity.
As shown in FIG. 4, the UV-vis spectra of the Co doped and undoped samples are very different. Wherein the sample of B-site doped metallic cobalt has an absorption band at 500nm and 530-650nm, the absorption band at 500nm is related to the doped metal, and the absorption band is mainly formed by charge transfer between metals, namely Co 2+ +Fe 3+ →Co 3+ +Fe 2+ . The absorption band at 530-650nm is mainly due to Co 3+ Caused by d-d transitions of (c). This suggests that Co doping can be towards PrFeO 3 New energy levels are introduced and the more Co doped, the more pronounced the absorption of the d-d transition.
FIG. 5 is a graph of X for samples of different Co to Fe molar ratiosRD map, as can be seen from FIG. 5: with increasing Co/Fe molar ratio, the fraction at 2θ=32.4° belongs to PrFeO 3 Is sharper and has some splitting due to PrFeO 3 Part of B-site metal atoms Fe in the perovskite crystal are replaced by Co atoms, so that lattice distortion and torsion occur, the crystal structure is asymmetric, and then lattice defects are increased. And Co: fe=0 (0.99-1.01) the characteristic peak of the catalyst 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: co is Fe=1 (0.42-0.44), the characteristic peak of the catalyst is highest, the peak signal of the catalyst is strongest, the catalyst has more lattice defects, and the catalytic performance is better, which is consistent with the experimental result of performance, namely, when Co is Fe=1 (0.42-0.44), the supported perovskite catalyst has the best effect of degrading salicylic acid wastewater.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (6)
1. A preparation method of a supported perovskite catalyst is characterized by comprising the following steps of
Aluminum chloride is used as a column agent, montmorillonite is used as a carrier, perovskite is used as an active component, and a solid melting method is adopted to prepare a supported catalyst, which specifically comprises the following steps:
step S1: adding sodium montmorillonite powder into aluminum chloride solution to obtain mixed feed liquid A;
step S2: under the conditions of heating in water bath and magnetic stirring, sequentially adding polyethylene glycol and sodium hydroxide into the mixed material liquid A to obtain mixed material liquid B;
step S3: heating the mixed material liquid B in a water bath, magnetically stirring, continuously stirring at room temperature, and aging at room temperature to obtain layered liquid C;
step S4: centrifuging, washing, drying and grinding the layering liquid C, and roasting to obtain aluminum column montmorillonite;
step S5: mixing ferric nitrate, praseodymium nitrate, cobalt nitrate and citric acid according to a certain proportion, dissolving and dispersing by ultrasonic to obtain mixed solution D, heating the mixed solution D in water bath, drying, grinding, crushing and roasting to obtain perovskite active component PrFe x Co 1-x O 3 ；
Step S6: mixing, grinding and roasting aluminum pillared montmorillonite and perovskite active components 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 concentration of the aluminum chloride solution is 0.39-0.42 mol/L, and the mass ratio of the aluminum chloride to the sodium montmorillonite in the mixed feed liquid A is 1: (0.62 to 0.63);
stirring the mixed material liquid A in a water bath at 70-80 ℃ for 10-12 min, and then sequentially adding 2.4-2.6 mL of polyethylene glycol and 7-7.5 mL of 0.4mol/L sodium hydroxide, 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);
in the step S5, the mol 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 dispersing 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 for 2-2.5 h at 500+ -10 ℃, and then roasting for 4-4.5 h at 700+ -10 ℃.
2. The method for preparing a 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.
3. The method for preparing a supported perovskite catalyst as claimed in claim 1, wherein step S4 specifically comprises: washing the separated liquid C until no Cl exists - Drying at 70-80 deg.c for 20-24 hr, grinding to 80-100 mesh, and roasting at 400 + -10 deg.c for 1.5-2.5 hr.
4. The method for preparing a supported perovskite catalyst as claimed in claim 1, wherein the grinding time in the step S6 is 10 to 15 minutes, and then the catalyst is baked in a muffle furnace at 200 to 220 ℃ for 2 to 3 hours.
5. A supported perovskite catalyst prepared by the preparation method as claimed in any one of claims 1 to 4.
6. Use of the supported perovskite catalyst of claim 5 for treating salicylic acid-containing wastewater;
the adding amount of the supported perovskite catalyst in each 140-160 mL of salicylic acid wastewater is 0.04-0.05 g, the salicylic acid concentration is 100+/-1 mg/L, the pH=4.8-5.2, meanwhile, the adding amount of hydrogen peroxide with the volume fraction of 30% is 0.20-0.22 mL, and the reaction time is 2.5-3 h.
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