CN114558584A - Catalyst for advanced sewage treatment and preparation method thereof - Google Patents
Catalyst for advanced sewage treatment and preparation method thereof Download PDFInfo
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- CN114558584A CN114558584A CN202210234860.6A CN202210234860A CN114558584A CN 114558584 A CN114558584 A CN 114558584A CN 202210234860 A CN202210234860 A CN 202210234860A CN 114558584 A CN114558584 A CN 114558584A
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- temperature
- wastewater treatment
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000010865 sewage Substances 0.000 title description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000003756 stirring Methods 0.000 claims abstract description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 44
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000006261 foam material Substances 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 36
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- 238000003980 solgel method Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 19
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- 150000001621 bismuth Chemical class 0.000 claims abstract description 12
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 40
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 239000004642 Polyimide Substances 0.000 claims description 25
- 229920001721 polyimide Polymers 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 230000010355 oscillation Effects 0.000 claims description 20
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 18
- 229920005575 poly(amic acid) Polymers 0.000 claims description 15
- 239000006260 foam Substances 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 8
- 150000002603 lanthanum Chemical class 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical group [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000003842 bromide salts Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 230000009467 reduction Effects 0.000 abstract description 10
- 239000004952 Polyamide Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 3
- 229920002647 polyamide Polymers 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 20
- 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 description 16
- 239000011941 photocatalyst Substances 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241000877463 Lanio Species 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OLBRKKJBIBPJSE-UHFFFAOYSA-N bismuth;bromo hypobromite Chemical class [Bi].BrOBr OLBRKKJBIBPJSE-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008816 organ damage Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals 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
- 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
-
- 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
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of wastewater purification, and particularly relates to a catalyst for advanced wastewater treatment and a preparation method thereof. The preparation method adopts a sol-gel method to prepare LaNi(1‑x)FexMoyO3(ii) a Wherein x is 0.02-0.04, and y is 0.01-0.03; then polyamide acid and LaNi(1‑x)FexMoyO3Adding into water, adding triethylamine, stirring, and dispersing uniformly to obtain water dispersion; pouring the aqueous dispersion prepared in the step (1) into a mould, and carrying out vacuum freeze drying and thermal imidization to obtain a composite foam material; then preparing an ethylene glycol solution containing cetyl trimethyl ammonium bromide, bromine salt and bismuth salt, stirring for 2-4 h, adding the prepared composite foam material into the solution, and transferring to a hydrothermal reactionAnd (3) preserving the temperature of the kettle at 120-160 ℃ for 18-28 h, centrifuging, washing, and drying to obtain the catalyst for advanced wastewater treatment. The photocatalytic material is used for photocatalytic reduction of Cr (VI) in wastewater, can effectively reduce the content of Cr (VI) in the wastewater, and is an ideal material for treating Cr (VI) wastewater.
Description
Technical Field
The invention belongs to the technical field of wastewater purification. More particularly, relates to a catalyst for advanced wastewater treatment and a preparation method thereof.
Background
Heavy metals have been used by humans for thousands of years, and over the last few years, the rapid development of industry and population has also led to an increasing exposure of people to heavy metals, which has led to a range of health effects. Of all the toxic heavy metal ions, hexavalent chromium cr (vi) is a common surface and groundwater contaminant. Is widely applied to the chemical industries of leather manufacturing, electroplating, printing and dyeing, polishing and the like. Because it has acute toxicity, strong carcinogenicity and high solubility in water to most organisms, Cr (VI) in water and drinking water can cause a series of health problems such as cancer, distortion and organism organ damage, and the effective removal of Cr (VI) in water is a technical problem to be solved at present.
In terms of removing cr (vi), there are mainly cation and anion exchange resins, chemical precipitation, membrane filtration, adsorption, biological methods, and photocatalytic reduction. However, none of the current methods is well-established to completely overcome the problems of pollution abatement costs, process complexity, environmental damage and removal efficiency. Among them, the photocatalytic reduction method is a green and low-cost method, but its efficiency is to be improved.
The preparation method comprises the steps of preparing polyimide supramolecules by a dimethylformamide and ethylene glycol mixed solvent induced hydrothermal crystallization method, applying the polyimide supramolecules to reduction of Cr (VI) in wastewater for the first time, and analyzing influences of different operating parameters on Cr (VI) photoreduction efficiency. The results show that: the low pH value, the coexistence of small molecular organic acid, the high irradiation intensity and the dosage of the catalyst can promote the reaction, and particularly, the addition of the citric acid and the mandelic acid can improve the reaction rate by multiple times.
Preparation of LaNi from Zeiole et al by sol-gel method1-x MnxO3(x ═ 0, 0.2, 0.4, 0.6, 0.8, 1.0) perovskite-type oxide photocatalytic material. The results show that Mn doping shifts the diffraction peak to a low angle, causing lattice expansion, resulting in LaNi1-xMnxO3The crystal grain size is increased; mn after doping4+/Mn3+The ratio of the peak area of the photocatalyst to the peak area of the Oads/Olatt is increased, so that the oxidation capacity, the interface electron transfer rate and the number of surface adsorbed oxygen of the catalyst are improved, and the photocatalytic activity of the catalyst is further improved; when the doping amount of Mn is 40 percent, the obtained LaNi0.6Mn0.4O3The photocatalyst has optimal photocatalytic performance, the degradation rate of methyl orange after 120min of visible light irradiation reaches 99.46%, and the degradation rate can still reach 86.97% after five times of cyclic utilization, which shows thatLaNi0.6Mn0.4O3Has better stability and recycling property.
BiOBr is a ternary compound of a multicomponent metal oxyhalide family, has unique electrical property, magnetism, optical property and luminescence property, has a band gap of about 2.9eV, has a high absorption coefficient in a visible light-near infrared spectrum range, and is a photocatalyst with practical application value, CN109550508A discloses a preparation method and application of a modified bismuth oxybromide nano material, and the specific surface area is increased on the basis of changing the morphology of BiOBr through regulating and controlling the synthesis conditions of BiOBr, so that the adsorption capacity of the BiOBr on Cr (VI) in water is enhanced, the contact area of the photocatalyst and pollutants is increased, and the photocatalytic reduction of Cr (VI) by the BiOBr is further improved. The photocatalyst has a proper forbidden band width, can absorb visible light, can promote the rapid transfer of photoproduction electron holes, reduces the recombination of the electron holes, and further improves the photocatalytic efficiency; when the photocatalyst is used as a catalyst, the photocatalyst material obtained under the synthetic condition of pH 6 has strong adsorption and degradation capacity on heavy metal Cr (VI) in wastewater, and can be well applied to heavy metal treatment in wastewater no matter the heavy metal Cr (VI) is polluted at high concentration or low concentration.
Although the photocatalyst has certain photocatalytic capacity for Cr (VI), the photocatalyst has long treatment time, low efficiency and poor stability, so that the catalyst which has excellent photocatalytic capacity and good stability and is used for advanced sewage treatment is urgently needed.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings existing in the prior art, and provide a catalyst for advanced sewage treatment and a preparation method thereof.
The invention aims to provide a preparation method of a catalyst for advanced wastewater treatment. The preparation method adopts a sol-gel method to prepare LaNi(1-x)FexMoyO3(ii) a Wherein x is 0.02-0.04, and y is 0.01-0.03; then polyamide acid and LaNi(1-x)FexMoyO3Adding into water, adding triethylamineStirring and dispersing uniformly to obtain an aqueous dispersion; pouring the aqueous dispersion prepared in the step (1) into a mould, and carrying out vacuum freeze drying and thermal imidization to obtain a composite foam material; and then preparing an ethylene glycol solution containing hexadecyl trimethyl ammonium bromide, bromine salt and bismuth salt, stirring for 2-4 h, adding the prepared composite foam material into the solution, transferring the solution to a hydrothermal reaction kettle, preserving heat for 18-28 h at 120-160 ℃, centrifuging, washing, and drying to obtain the catalyst for advanced wastewater treatment. The photocatalytic material is used for photocatalytic reduction of Cr (VI) in wastewater, can effectively reduce the content of Cr (VI) in the wastewater, and is an ideal material for treating Cr (VI) wastewater.
The invention also aims to provide a catalyst for advanced wastewater treatment.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of a catalyst for advanced wastewater treatment comprises the following steps:
(I) preparing LaNi by adopting sol-gel method(1-x)FexMoyO3(ii) a Wherein x is 0.02-0.04, and y is 0.01-0.03;
(II) preparation of polyimide syntactic foam
(1) Preparing LaNi from polyamic acid by the step (I)(1-x)FexMoyO3Adding into water, adding triethylamine, stirring, and dispersing uniformly to obtain water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, and carrying out vacuum freeze drying and thermal imidization to obtain a composite foam material;
(III) preparing polyimide composite foam material loaded bismuth oxybromide;
preparing an ethylene glycol solution containing cetyl trimethyl ammonium bromide, bromine salt and bismuth salt, stirring for 2-4 h, adding the composite foam material prepared in the step (II) into the solution, transferring the solution to a hydrothermal reaction kettle, preserving the temperature for 18-28 h at 120-160 ℃, centrifuging, washing, and drying to obtain the catalyst for advanced wastewater treatment.
Preferably, in the step (1), the LaNi is prepared by a sol-gel method(1-x)FexMoyO3The preparation method comprises the following steps: respectively weighing lanthanum salt, nickel salt, ferric salt and manganese salt, placing the lanthanum salt, the nickel salt, the ferric salt and the manganese salt into a beaker filled with 60-80 mL of mixed solution of absolute ethyl alcohol and deionized water, and adding citric acid after dissolving; stirring at normal temperature for 10-30 min, and then placing the beaker in an ultrasonic water bath ultrasonic device for oscillation for 10-30 min; after ultrasonic oscillation, putting the beaker into a constant-temperature water bath kettle, stirring at a constant temperature of 60-80 ℃ until the solution forms gel, and stopping stirring; putting the obtained gel into a freeze dryer for freeze drying to obtain dry gel; then the xerogel sample is placed in a muffle furnace, roasted, naturally cooled and then taken out for grinding to obtain LaNi(1-x)FexMoyO3Powder samples.
Preferably, the volume ratio of the absolute ethyl alcohol to the deionized water is 2: 1, and the freeze drying is carried out for 45-55 hours at the temperature of-30 to-10 ℃; the roasting process is that the temperature is raised to 550-650 ℃ at the heating rate of 3-7 ℃/min, and the temperature is kept for 2-4 h; the molar ratio of the lanthanum salt to the citric acid is 1: 4-6; the lanthanum salt, the nickel salt, the ferric salt and the manganese salt are respectively nitrate, acetate or chloride.
Preferably, in the step (1) of the step (II), the polyamic acid and LaNi are(1-x)FexMoyO3The mass ratio of (1): 0.2 to 0.4; the mass ratio of the polyamic acid to the water is 1: 40-80 parts; the mass ratio of the polyamic acid to the triethylamine is 1: 0.4-0.6.
Preferably, in the step (2) of the step (II), the freeze drying temperature is-30 to-10 ℃, and the drying time is 60 to 90 hours; the vacuum degree is 1-5 Pa.
Preferably, in the step (2) of the step (II), the thermal imidization is performed by temperature programming under the following conditions: 0.5-3 h at 90-110 ℃, 3-5 h at 180-200 ℃, and 1-3 h at 290-310 ℃.
Preferably, in step (III), the bromide salt is sodium bromide or potassium bromide; the bismuth salt is bismuth nitrate, bismuth acetate or bismuth chloride.
Preferably, in the step (III), the molar ratio of the hexadecyl trimethyl ammonium bromide to the bromine salt is 1: 0.6-0.9; the molar ratio of the hexadecyl trimethyl ammonium bromide to the bismuth salt is 1: 2; the ratio of the bismuth salt to the ethylene glycol solution is 1 mmol: 10-20 mL; the drying is carried out at the temperature of 80-120 ℃ for 12-14 h; the ratio of the bismuth salt to the composite foam prepared in step (III) is 1 mmol: 8-12 g.
The catalyst for advanced wastewater treatment is prepared based on the preparation method of the catalyst for advanced wastewater treatment.
Based on the application of the catalyst for advanced wastewater treatment, the method is characterized in that: used for photocatalytic treatment of Cr (VI) in wastewater.
The invention has the following beneficial effects:
(1) co-doping Fe and Mo to LaNiO by sol-gel method3The synergistic effect of Fe and Mo is utilized to promote the effective separation of photo-generated electrons and holes, so that more active groups promote the reduction of Cr (VI);
(2) LaNi by in-situ method(1-x)FexMoyO3Loaded in polyimide foam material, effectively prevents LaNi(1-x)FexMoyO3Loss in the process of photocatalytic reaction, effective separation of photoproduction electrons and holes is effectively improved by compounding with polyimide, and meanwhile, the foam material has a large specific surface area, is beneficial to adsorption and promotes reduction of Cr (VI);
(3) the bismuth oxybromide is loaded on the polyimide composite foam material prepared by a hydrothermal method, so that the dispersibility of the bismuth oxybromide is improved, and the reaction with LaNi is promoted(1-x)FexMoyO3And the catalyst is effectively combined with polyimide, so that the mutual synergistic effect of the components is improved, the photocatalytic capability is improved, and the effective reduction of Cr (VI) by the catalyst is promoted. Meanwhile, the foam material also improves the reuse rate of the catalyst and the stability of the catalyst.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
A preparation method of a catalyst for advanced wastewater treatment comprises the following steps:
(I) preparing LaNi by adopting sol-gel method0.95Fe0.03Mo0.02O3；
The method for preparing LaNi by adopting a sol-gel method0.95Fe0.03Mo0.02O3The preparation method comprises the following steps: respectively weighing 10mmol of lanthanum nitrate, 9.5mmol of nickel nitrate, 0.3mmol of ferric nitrate and 0.2mmol of manganese nitrate, placing the materials into a beaker filled with 70mL of mixed solution of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 2: 1), and adding 50mmol of citric acid after dissolving; stirring at room temperature for 20min, and placing the beaker in an ultrasonic water bath ultrasonic device for oscillation for 20 min; after ultrasonic oscillation, putting the beaker into a constant-temperature water bath kettle, stirring at a constant temperature of 70 ℃ until the solution forms gel, and stopping stirring; putting the obtained gel into a freeze dryer to be dried for 50h at the temperature of minus 20 ℃ to obtain dried gel; then the xerogel sample is placed in a muffle furnace, the temperature is raised to 600 ℃ at the heating rate of 5 ℃/min, the temperature is preserved for 3h, and the sample is taken out and ground after being naturally cooled to obtain LaNi0.95Fe0.03Mo0.02O3Powder samples.
(II) preparation of polyimide syntactic foam
(1) Preparing LaNi from 1g of polyamic acid and 0.3g of step (I)0.95Fe0.03Mo0.02O3Adding 60g of water, adding 0.5g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 80h at-20 ℃ and under the vacuum degree of 3Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 100 ℃, 4h at 190 ℃ and 2h at 300 ℃.
(III) preparing polyimide composite foam material loaded bismuth oxybromide;
preparing 30mL of ethylene glycol solution containing 1mmol of hexadecyl trimethyl ammonium bromide, 0.7mmol of potassium bromide and 2mmol of bismuth nitrate, stirring for 3h, then adding 20g of the composite foam material prepared in the step (II) into the solution, transferring to a hydrothermal reaction kettle, preserving heat at 140 ℃ for 22h, centrifuging, washing, and drying at 100 ℃ for 13h to obtain the catalyst for advanced wastewater treatment.
Example 2
A preparation method of a catalyst for advanced wastewater treatment comprises the following steps:
(I) preparing LaNi by adopting sol-gel method0.95Fe0.02Mo0.03O3；
The method for preparing LaNi by adopting a sol-gel method0.95Fe0.02Mo0.03O3The preparation method comprises the following steps: respectively weighing 10mmol of lanthanum acetate, 9.5mmol of nickel acetate, 0.2mmol of ferric chloride and 0.3mmol of manganese chloride, placing the materials in a beaker filled with a mixed solution of 80mL of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 2: 1), dissolving, and then adding 60mmol of citric acid; stirring at room temperature for 30min, and placing the beaker in an ultrasonic water bath ultrasonic device for oscillation for 30 min; after ultrasonic oscillation, putting the beaker into a constant-temperature water bath kettle, stirring at the constant temperature of 80 ℃ until the solution forms gel, and stopping stirring; drying the obtained gel in a freeze dryer at-30 ℃ for 45h to obtain dried gel; then the xerogel sample is placed in a muffle furnace, the temperature is raised to 650 ℃ at the heating rate of 7 ℃/min, the temperature is kept for 2h, and the sample is taken out and ground after natural cooling to obtain LaNi0.95Fe0.02Mo0.03O3Powder samples.
(II) preparation of polyimide syntactic foam
(1) Preparing LaNi from 1g of polyamic acid and 0.4g of step (I)0.95Fe0.02Mo0.03O3Adding 80g of water, adding 0.6g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 90 hours at-30 ℃ under the vacuum degree of 5Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 110 ℃ for 3h, 200 ℃ for 5h and 310 ℃ for 3 h.
(III) preparing polyimide composite foam material loaded bismuth oxybromide;
preparing 40mL of glycol solution containing 1mmol of hexadecyl trimethyl ammonium bromide, 0.9mmol of sodium bromide and 2mmol of bismuth acetate, stirring for 4 hours, then adding 24g of the composite foam material prepared in the step (II) into the solution, transferring the solution into a hydrothermal reaction kettle, preserving the temperature at 160 ℃ for 18 hours, centrifuging, washing, and drying at 120 ℃ for 12 hours to obtain the catalyst for deep treatment of sewage.
Example 3
A preparation method of a catalyst for advanced wastewater treatment comprises the following steps:
(I) preparing LaNi by adopting sol-gel method0.95Fe0.04Mo0.01O3；
The method for preparing LaNi by adopting a sol-gel method0.95Fe0.04Mo0.01O3The preparation method comprises the following steps: respectively weighing 10mmol of lanthanum chloride, 9.5mmol of nickel chloride, 0.5mmol of ferric acetate and 0.1mmol of manganese acetate, placing the lanthanum chloride, the 9.5mmol of nickel chloride, the 0.5mmol of ferric acetate and the 0.1mmol of manganese acetate in a beaker filled with 60mL of mixed solution of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to deionized water is 2: 1), dissolving, and then adding 40mmol of citric acid; stirring at normal temperature for 10min, and placing the beaker in an ultrasonic water bath ultrasonic device for oscillation for 30 min; after ultrasonic oscillation, putting the beaker into a constant-temperature water bath kettle, stirring at the constant temperature of 60 ℃ until the solution forms gel, and stopping stirring; drying the obtained gel in a freeze dryer at-10 ℃ for 55h to obtain dried gel; then the xerogel sample is placed in a muffle furnace, the temperature is increased to 550 ℃ at the heating rate of 3 ℃/min, the temperature is preserved for 4h, and the sample is taken out and ground after being naturally cooled to obtain LaNi0.95Fe0.04Mo0.01O3Powder samples.
(II) preparation of polyimide syntactic foam
(1) 1g of Polyamic acid, 0.2g of preparation L from step (I)aNi0.95Fe0.04Mo0.01O3Adding 40g of water, adding 0.4g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 60 hours at the temperature of minus 10 ℃ and under the vacuum degree of 1Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 0.5h at 90 ℃, 3h at 180 ℃ and 1h at 290 ℃.
(III) preparing polyimide composite foam material loaded bismuth oxybromide;
and (2) preparing 20mL of ethylene glycol solution containing 1mmol of hexadecyl trimethyl ammonium bromide, 0.6mmol of potassium bromide and 2mmol of bismuth chloride, stirring for 2h, adding 16g of the composite foam material prepared in the step (II) into the solution, transferring to a hydrothermal reaction kettle, preserving heat at 120 ℃ for 28h, centrifuging, washing, and drying at 80 ℃ for 14h to obtain the catalyst for deep treatment of sewage.
Comparative example 1
A preparation method of a catalyst for advanced wastewater treatment comprises the following steps:
(I) preparing LaNi by adopting sol-gel method0.95Fe0.05O3；
The method for preparing LaNi by adopting a sol-gel method0.95Fe0.05O3The preparation method comprises the following steps: respectively weighing 10mmol of lanthanum nitrate, 9.5mmol of nickel nitrate and 0.5mmol of ferric nitrate, placing the lanthanum nitrate, the nickel nitrate and the ferric nitrate into a beaker filled with 70mL of mixed solution of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 2: 1), and adding 50mmol of citric acid after dissolving; stirring at room temperature for 20min, and placing the beaker in an ultrasonic water bath ultrasonic device for oscillation for 20 min; after ultrasonic oscillation, putting the beaker into a constant-temperature water bath kettle, stirring at a constant temperature of 70 ℃ until the solution forms gel, and stopping stirring; putting the obtained gel into a freeze dryer to be dried for 50h at the temperature of minus 20 ℃ to obtain dried gel; and then placing the xerogel sample in a muffle furnace, raising the temperature to 600 ℃ at a heating rate of 5 ℃/min, preserving the heat for 3 hours, naturally cooling, taking out and grinding to obtain LaNi0.95Fe0.05O3Powder samples.
(II) preparation of polyimide syntactic foam
(1) Preparing LaNi from 1g of polyamic acid and 0.3g of step (I)0.95Fe0.05O3Adding 60g of water, adding 0.5g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 80h at-20 ℃ and under the vacuum degree of 3Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 100 ℃, 4h at 190 ℃ and 2h at 300 ℃.
(III) preparing polyimide composite foam material loaded bismuth oxybromide;
preparing 30mL of ethylene glycol solution containing 1mmol of hexadecyl trimethyl ammonium bromide, 0.7mmol of potassium bromide and 2mmol of bismuth nitrate, stirring for 3h, then adding 20g of the composite foam material prepared in the step (II) into the solution, transferring to a hydrothermal reaction kettle, preserving heat at 140 ℃ for 22h, centrifuging, washing, and drying at 100 ℃ for 13h to obtain the catalyst for advanced wastewater treatment.
Comparative example 2
A preparation method of a catalyst for advanced wastewater treatment comprises the following steps:
(I) preparing LaNi by adopting sol-gel method0.95Mo0.05O3；
The method for preparing LaNi by adopting a sol-gel method0.95Mo0.05O3The preparation method comprises the following steps: respectively weighing 10mmol of lanthanum nitrate, 9.5mmol of nickel nitrate, 0.3mmol of ferric nitrate and 0.2mmol of manganese nitrate, placing the materials into a beaker filled with 70mL of mixed solution of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 2: 1), and adding 50mmol of citric acid after dissolving; stirring at room temperature for 20min, and placing the beaker in an ultrasonic water bath ultrasonic device for oscillation for 20 min; after ultrasonic oscillation, putting the beaker into a constant-temperature water bath kettle, stirring at a constant temperature of 70 ℃ until the solution forms gel, and stopping stirring; putting the obtained gel into a freeze dryer to be dried for 50h at the temperature of minus 20 ℃ to obtain dried gel; then the xerogel sample is placed in a muffle furnace, and the temperature is raised by 5 ℃/minRaising the speed to 600 ℃, preserving heat for 3 hours, naturally cooling, taking out and grinding to obtain LaNi0.95Mo0.05O3Powder samples.
(II) preparation of polyimide syntactic foam
(1) Preparing LaNi from 1g of polyamic acid and 0.3g of step (I)0.95Mo0.05O3Adding 60g of water, adding 0.5g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 80h at-20 ℃ and under the vacuum degree of 3Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 100 ℃, 4h at 190 ℃ and 2h at 300 ℃.
(III) preparing polyimide composite foam material loaded bismuth oxybromide;
preparing 30mL of ethylene glycol solution containing 1mmol of hexadecyl trimethyl ammonium bromide, 0.7mmol of potassium bromide and 2mmol of bismuth nitrate, stirring for 3h, then adding 20g of the composite foam material prepared in the step (II) into the solution, transferring to a hydrothermal reaction kettle, preserving heat at 140 ℃ for 22h, centrifuging, washing, and drying at 100 ℃ for 13h to obtain the catalyst for advanced wastewater treatment.
Comparative example 3
A preparation method of a catalyst for advanced wastewater treatment comprises the following steps:
(I) preparing LaNi by adopting sol-gel method0.95Fe0.03Mo0.02O3；
The method for preparing LaNi by adopting a sol-gel method0.95Fe0.03Mo0.02O3The preparation method comprises the following steps: respectively weighing 10mmol of lanthanum nitrate, 9.5mmol of nickel nitrate, 0.3mmol of ferric nitrate and 0.2mmol of manganese nitrate, placing the lanthanum nitrate, the nickel nitrate, the ferric nitrate and the manganese nitrate into a beaker filled with 70mL of mixed solution of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 2: 1), dissolving, and then adding 50mmol of citric acid; stirring at room temperature for 20min, and placing the beaker in an ultrasonic water bath ultrasonic device for oscillation for 20 min; after ultrasonic oscillation, the beaker is put into a constant temperature water bath kettle and stirred at the constant temperature of 70 ℃ until the solution is obtainedForming gel and stopping stirring; putting the obtained gel into a freeze dryer, and drying for 50h at-20 ℃ to obtain dry gel; then the xerogel sample is placed in a muffle furnace, the temperature is raised to 600 ℃ at the heating rate of 5 ℃/min, the temperature is preserved for 3h, and the sample is taken out and ground after being naturally cooled to obtain LaNi0.95Fe0.03Mo0.02O3Powder samples.
(II) preparation of polyimide syntactic foam
(1) Adding 1g of polyamide acid into 60g of water, adding 0.5g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 80h at-20 ℃ and under the vacuum degree of 3Pa, and carrying out thermal imidization to obtain a foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 100 ℃, 4h at 190 ℃ and 2h at 300 ℃.
(3) Soaking the foam material obtained in the step (2) in a solution containing 0.3g of LaNi prepared in the step (I)0.95Fe0.03Mo0.02O3Ultrasonic dispersion is carried out for 30min in the aqueous dispersion; and (4) performing rotary evaporation at the temperature of 80 ℃ to volatilize water so as to obtain the composite foam material.
(III) preparing polyimide composite foam material loaded bismuth oxybromide;
preparing 30mL of ethylene glycol solution containing 1mmol of hexadecyl trimethyl ammonium bromide, 0.7mmol of potassium bromide and 2mmol of bismuth nitrate, stirring for 3h, then adding 20g of the composite foam material prepared in the step (II) into the solution, transferring to a hydrothermal reaction kettle, preserving heat at 140 ℃ for 22h, centrifuging, washing, and drying at 100 ℃ for 13h to obtain the catalyst for advanced wastewater treatment.
Comparative example 4
A preparation method of a catalyst for advanced wastewater treatment comprises the following steps:
(I) preparing LaNi by adopting sol-gel method0.95Fe0.03Mo0.02O3；
The method for preparing LaNi by adopting a sol-gel method0.95Fe0.03Mo0.02O3The preparation method comprises the following steps: respectively weighingPlacing 10mmol of lanthanum nitrate, 9.5mmol of nickel nitrate, 0.3mmol of ferric nitrate and 0.2mmol of manganese nitrate into a beaker filled with 70mL of mixed solution of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 2: 1), dissolving, and then adding 50mmol of citric acid; stirring at room temperature for 20min, and placing the beaker in an ultrasonic water bath ultrasonic device for oscillation for 20 min; after ultrasonic oscillation, putting the beaker into a constant-temperature water bath kettle, stirring at a constant temperature of 70 ℃ until the solution forms gel, and stopping stirring; putting the obtained gel into a freeze dryer to be dried for 50h at the temperature of minus 20 ℃ to obtain dried gel; then the xerogel sample is placed in a muffle furnace, the temperature is raised to 600 ℃ at the heating rate of 5 ℃/min, the temperature is preserved for 3h, and the sample is taken out and ground after being naturally cooled to obtain LaNi0.95Fe0.03Mo0.02O3Powder samples.
(II) preparation of polyimide syntactic foam
(1) Preparing LaNi from 1g of polyamic acid and 0.3g of step (I)0.95Fe0.03Mo0.02O3Adding 60g of water, adding 0.5g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 80h at-20 ℃ and under the vacuum degree of 3Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 100 ℃, 4h at 190 ℃ and 2h at 300 ℃.
(III) preparing polyimide composite foam material loaded bismuth oxybromide;
preparing 30mL of ethylene glycol solution containing 1mmol of hexadecyl trimethyl ammonium bromide, 0.7mmol of potassium bromide and 2mmol of bismuth nitrate, stirring for 3h, transferring to a hydrothermal reaction kettle, preserving heat at 140 ℃ for 22h, centrifuging, washing, drying at 100 ℃ for 13h to obtain bismuth oxybromide, dispersing in 50mL of deionized water, ultrasonically dispersing for 30min, adding 20g of the composite foam material prepared in the step (II) into the solution, ultrasonically dispersing for 30min, and performing rotary evaporation at 80 ℃ to volatilize water to obtain the composite foam material.
Comparative example 5
A preparation method of a catalyst for advanced wastewater treatment comprises the following steps:
(I) preparing LaNi by adopting sol-gel method0.95Fe0.03Mo0.02O3；
The LaNi is prepared by adopting a sol-gel method0.95Fe0.03Mo0.02O3The preparation method comprises the following steps: respectively weighing 10mmol of lanthanum nitrate, 9.5mmol of nickel nitrate, 0.3mmol of ferric nitrate and 0.2mmol of manganese nitrate, placing the materials into a beaker filled with 70mL of mixed solution of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 2: 1), and adding 50mmol of citric acid after dissolving; stirring at room temperature for 20min, and placing the beaker in an ultrasonic water bath ultrasonic device for oscillation for 20 min; after ultrasonic oscillation, putting the beaker into a constant-temperature water bath kettle, stirring at a constant temperature of 70 ℃ until the solution forms gel, and stopping stirring; putting the obtained gel into a freeze dryer to be dried for 50h at the temperature of minus 20 ℃ to obtain dried gel; then the xerogel sample is placed in a muffle furnace, the temperature is raised to 600 ℃ at the heating rate of 5 ℃/min, the temperature is preserved for 3h, and the sample is taken out and ground after being naturally cooled to obtain LaNi0.95Fe0.03Mo0.02O3Powder samples.
(II) preparation of polyimide syntactic foam
(1) Preparing LaNi from 1g of polyamic acid and 0.3g of step (I)0.95Fe0.03Mo0.02O3Adding 60g of water, adding 0.5g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 80h at-20 ℃ and under the vacuum degree of 3Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 100 ℃, 4h at 190 ℃ and 2h at 300 ℃.
Comparative example 6
A preparation method of a catalyst for advanced wastewater treatment comprises the following steps:
preparing 30mL of ethylene glycol solution containing 1mmol of hexadecyl trimethyl ammonium bromide, 0.7mmol of potassium bromide and 2mmol of bismuth nitrate, stirring for 3h, transferring to a hydrothermal reaction kettle, preserving heat for 22h at 140 ℃, centrifuging, washing, and drying for 13h at 100 ℃ to obtain the catalyst for advanced sewage treatment.
The catalysts (0.1g/L) of examples 1-3 and comparative examples 1-6 were ultrasonically dispersed in Cr (VI) solution (60mg/L), and after dark reaction for 30 minutes under magnetic stirring, the mixture was stirred under irradiation of a xenon lamp (350W) to perform photocatalytic reaction. The absorption spectrum of the solution is tested by an ultraviolet-visible spectrophotometer, the reduction efficiency of Cr (VI) can be calculated through the change of the intensity of an absorption peak, and the specific test result is shown in table 1.
TABLE 1 test results of examples 1-3 and comparative examples 1-6
As can be seen from Table 1, the catalysts prepared by the method have good removal capability for Cr (VI) in wastewater, and the synergistic effect among the components is also proved, so that the catalysts are ideal materials for advanced treatment of Cr (VI) wastewater.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a catalyst for advanced wastewater treatment is characterized by comprising the following steps: which comprises the following steps:
(I) preparing LaNi by adopting sol-gel method(1-x)FexMoyO3(ii) a Wherein x is 0.02-0.04, and y is 0.01-0.03;
(II) preparation of polyimide syntactic foam
(1) Preparing LaNi from polyamic acid by the step (I)(1-x)FexMoyO3Adding into water, addingStirring and uniformly dispersing triethylamine to obtain an aqueous dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, and carrying out vacuum freeze drying and thermal imidization to obtain a composite foam material;
(III) preparing polyimide composite foam material loaded bismuth oxybromide;
preparing an ethylene glycol solution containing hexadecyl trimethyl ammonium bromide, bromine salt and bismuth salt, stirring for 2-4 h, adding the composite foam material prepared in the step (II) into the solution, transferring the solution to a hydrothermal reaction kettle, preserving the temperature for 18-28 h at 120-160 ℃, centrifuging, washing, and drying to obtain the catalyst for advanced wastewater treatment.
2. The method for preparing the catalyst for advanced wastewater treatment according to claim 1, wherein the method comprises the following steps: in the step (1), LaNi is prepared by adopting a sol-gel method(1-x)FexMoyO3The preparation method comprises the following steps: respectively weighing lanthanum salt, nickel salt, ferric salt and manganese salt, placing the lanthanum salt, the nickel salt, the ferric salt and the manganese salt into a beaker filled with 60-80 mL of mixed solution of absolute ethyl alcohol and deionized water, and adding citric acid after dissolving; stirring at normal temperature for 10-30 min, and then placing the beaker in an ultrasonic water bath ultrasonic device for oscillation for 10-30 min; after ultrasonic oscillation, putting the beaker into a constant-temperature water bath kettle, stirring at a constant temperature of 60-80 ℃ until the solution forms gel, and stopping stirring; putting the obtained gel into a freeze dryer for freeze drying to obtain dry gel; then the xerogel sample is placed in a muffle furnace, roasted, naturally cooled and then taken out for grinding to obtain LaNi(1-x)FexMoyO3Powder samples.
3. The method for preparing the catalyst for advanced wastewater treatment according to claim 2, wherein the method comprises the following steps: the volume ratio of the absolute ethyl alcohol to the deionized water is 2: 1, and the freeze drying is carried out for 45-55 hours at the temperature of-30 to-10 ℃; the roasting process is that the temperature is raised to 550-650 ℃ at the heating rate of 3-7 ℃/min, and the temperature is kept for 2-4 h; the molar ratio of the lanthanum salt to the citric acid is 1: 4-6; the lanthanum salt, the nickel salt, the ferric salt and the manganese salt are respectively nitrate, acetate or chloride.
4. The method for preparing the catalyst for advanced wastewater treatment according to claim 1, wherein the method comprises the following steps: in the step (1) of the step (II), the polyamic acid, LaNi(1-x)FexMoyO3The mass ratio of (1): 0.2 to 0.4; the mass ratio of the polyamic acid to the water is 1: 40-80 parts; the mass ratio of the polyamic acid to the triethylamine is 1: 0.4-0.6.
5. The method for preparing the catalyst for advanced wastewater treatment according to claim 1 or 4, wherein the method comprises the following steps: in the step (2) of the step (II), the freeze drying temperature is-30 to-10 ℃, and the drying time is 60 to 90 hours; the vacuum degree is 1-5 Pa.
6. The method for preparing the catalyst for advanced wastewater treatment according to claim 1 or 4, wherein the method comprises the following steps: in step (2) of step (II), the thermal imidization is performed by temperature programming under the following conditions: 0.5-3 h at 90-110 ℃, 3-5 h at 180-200 ℃, and 1-3 h at 290-310 ℃.
7. The method for preparing the catalyst for advanced wastewater treatment according to claim 1, wherein the method comprises the following steps: in step (III), the bromide salt is sodium bromide or potassium bromide; the bismuth salt is bismuth nitrate, bismuth acetate or bismuth chloride.
8. The method for preparing the catalyst for advanced wastewater treatment according to claim 1 or 7, wherein the method comprises the following steps: in the step (III), the molar ratio of the hexadecyl trimethyl ammonium bromide to the bromine salt is 1: 0.6-0.9; the molar ratio of the hexadecyl trimethyl ammonium bromide to the bismuth salt is 1: 2; the ratio of the bismuth salt to the ethylene glycol solution is 1 mmol: 10-20 mL; the drying is carried out at the temperature of 80-120 ℃ for 12-14 h; the ratio of the bismuth salt to the composite foam prepared in step (III) is 1 mmol: 8-12 g.
9. A catalyst for advanced wastewater treatment prepared by the method for preparing a catalyst for advanced wastewater treatment according to any one of claims 1 to 8.
10. The use of a catalyst according to claim 9 for advanced wastewater treatment, wherein: used for photocatalytic treatment of Cr (VI) in wastewater.
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