CN113457691B - Gold-silver alloy nano flower water treatment catalyst and preparation method and application thereof - Google Patents
Gold-silver alloy nano flower water treatment catalyst and preparation method and application thereof Download PDFInfo
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- CN113457691B CN113457691B CN202110804651.6A CN202110804651A CN113457691B CN 113457691 B CN113457691 B CN 113457691B CN 202110804651 A CN202110804651 A CN 202110804651A CN 113457691 B CN113457691 B CN 113457691B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002057 nanoflower Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001316 Ag alloy Inorganic materials 0.000 title claims abstract description 27
- 239000000919 ceramic Substances 0.000 claims abstract description 51
- 239000012528 membrane Substances 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000002699 waste material Substances 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 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 claims abstract description 21
- 229940012189 methyl orange Drugs 0.000 claims abstract description 21
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 19
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims abstract description 11
- 241000205585 Aquilegia canadensis Species 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 104
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 44
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 42
- 238000005303 weighing Methods 0.000 claims description 28
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 22
- 229960005070 ascorbic acid Drugs 0.000 claims description 21
- 235000010323 ascorbic acid Nutrition 0.000 claims description 21
- 239000011668 ascorbic acid Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 19
- 230000003197 catalytic effect Effects 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 10
- RAZIIPQHZYRVCV-UHFFFAOYSA-N [Cu].[Nb].[Fe] Chemical compound [Cu].[Nb].[Fe] RAZIIPQHZYRVCV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 7
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 7
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000002351 wastewater Substances 0.000 claims description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 6
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims 1
- 239000011368 organic material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 6
- 238000007598 dipping method Methods 0.000 abstract 2
- 239000003403 water pollutant Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000975 dye Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000011133 lead Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000007493 shaping process Methods 0.000 description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XYYVDQWGDNRQDA-UHFFFAOYSA-K trichlorogold;trihydrate;hydrochloride Chemical compound O.O.O.Cl.Cl[Au](Cl)Cl XYYVDQWGDNRQDA-UHFFFAOYSA-K 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000003911 water pollution 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/898—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with vanadium, tantalum, niobium or polonium
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a gold-silver alloy nano flower water treatment catalyst and a preparation method and application thereof. The method comprises the following steps of crushing red mud waste residues, aluminum source powder, activated carbon powder and a forming agent solution, preparing a porous ceramic membrane carrier by the processes of proportioning, granulating, forming, calcining and the like, dipping the porous ceramic membrane carrier into an active component precursor composite solution, drying and roasting, dipping the carrier into a honeysuckle alloy nano flower colloidal solution, and drying in vacuum to obtain the honeysuckle alloy nano flower water treatment catalyst. The catalyst is environment-friendly, has low cost, can efficiently catalyze and reduce water pollutants such as p-nitrophenol, methyl orange, methylene blue and the like, and has wide market application prospect.
Description
Technical Field
The invention provides a gold-silver alloy nano flower water treatment catalyst taking red mud waste residues as raw materials and a preparation method thereof, belonging to the field of waste product resource utilization and environment-friendly catalytic materials.
Background
China, as the first major alumina producing country in the world, discharges up to billions of tons of red mud every year. Most alumina enterprises in China remove most of water in the red mud through mechanical filter pressing dehydration, and then stack the rest dry red mud in the open air, wherein the disposal cost of the red mud accounts for about 5 percent of the output value of alumina products. By the end of 2018, the accumulated red mud in China exceeds 13 hundred million tons, and the land occupation exceeds 12 ten thousand acres. All the red mud is almost totally stockpiled in the open air, and is not effectively utilized. Meanwhile, the main chemical elements of the red mud comprise calcium, silicon, aluminum, iron, sodium and titanium, a small amount of magnesium, potassium and sulfur, and trace heavy metal elements of manganese, zinc, copper, chromium and lead, and during the stacking process, if the red mud leaks into underground water, surface water and other water bodies, precipitates, suspended matters and soluble matters can be formed, so that heavy metal pollution is caused, the pH value of the water bodies is increased, and other adverse ecological effects are caused. Therefore, the disposal method not only needs to occupy a large amount of farmlands and lands and is costly in the construction and maintenance of the storage yard, but also has certain influence on the environment. At present, the economic and environmental problems caused by the red mud with continuously increasing stacking quantity make the comprehensive utilization of the red mud become a difficult problem to be solved urgently in the development process of the aluminum industry. The patent CN201810204108.0 discloses that red mud is used as a mineral raw material, and components such as an excitant and an additive are supplemented to prepare a grouting material, and the grouting material is applied to the fields of grouting reinforcement of sandy soil strata and the like. Although the treatment mode can solve the problem of batch application of the red mud, the economic value is low, and the problem that the grouting material is polluted by heavy metal permeating when meeting water cannot be solved. Patent CN201310407079.5 discloses that red mud is used as raw material, and under the excitation of chemical activator, red mud-based polymer photocatalyst is prepared, and photocatalytic decomposition of water is performed to produce hydrogen. Although the complete utilization of the red mud raw material can be solved, the catalyst needs to be separated again after each use, and the hydrogen production rate is low. Patent CN201510802366.5 discloses a method for preparing hydrogen by cracking methane, which comprises using red mud as raw material, carrying out acid-soluble treatment, introducing a certain amount of iron into the raw material by homogeneous coprecipitation method, drying, calcining and reducing with hydrogen to obtain a red mud-based iron catalyst, and applying the red mud-based iron catalyst to hydrogen production by cracking methane. Although the method can fully utilize the mineral composition with catalysis and catalysis assisting functions in the red mud, the red mud needs to be subjected to acid dissolution treatment during the preparation of the catalyst, secondary pollution is caused, hydrogen reduction at high temperature is needed, the method is not suitable for large-scale application, and the problem of large-scale application of the red mud cannot be solved. Therefore, the disposal of the red mud waste residue not only needs to improve the economic value of large-scale utilization, but also needs to consider the heavy metal pollution in the red mud waste residue and the secondary pollution problem in the preparation of the catalyst.
Meanwhile, p-nitrophenol, methyl orange, methylene blue and the like are taken as common dyes, 10-20% of the dyes are discharged into a water environment in the using process, and the wastewater containing the dyes of p-nitrophenol, methyl orange, methylene blue and the like has high toxicity and contains carcinogenic, mutagenic and teratogenic substances; high color, inhibition of photosynthesis in plants in aquatic systems: the COD value is high, which can lead to eutrophication of the water body. Based on the above hazards, the wastewater containing dyes such as p-nitrophenol, methyl orange, methylene blue and the like is a difficult problem facing the current water treatment technology and needing treatment urgently. Common treatment methods include adsorption method, membrane separation method, common oxidation method, biological method and the like, but the methods have the defects of complex process flow, high equipment requirement, high cost, damage to microenvironment and the like. The catalytic reduction method is a method capable of thoroughly solving water body pollution and even changing waste into valuable, p-nitrophenol, methyl orange and methylene blue are thoroughly reduced into chemical products by using sodium borohydride, and catalytic materials can be recycled and reused, so that the catalytic materials cannot remain in wastewater to cause secondary pollution to the environment. However, waste water containing dyes such as p-nitrophenol, methyl orange, methylene blue, etc. is generally alkaline and has a large change in pH. In the existing catalytic treatment method, most catalytic materials can degrade more than 90% of dyes only under acidic conditions. Therefore, the development of novel catalytic materials with strong pH adaptability and high-efficiency degradation effect on dyes such as methyl orange, p-nitrophenol, methylene blue and the like is paid more attention by the majority of researchers, and the utilization of the catalytic materials for treating the dyes such as methyl orange, p-nitrophenol, methylene blue and the like has important significance.
Disclosure of Invention
In view of the technical problems of large amount of red mud waste residues, lack of advanced safe treatment and high value-added resource utilization in China, the invention innovatively provides a method for preparing a high-performance porous ceramic membrane carrier by utilizing the red mud waste residues, takes an iron-copper-niobium composite oxide as an active component and takes gold-silver alloy nanoflowers as a cocatalyst to prepare a high-performance water treatment catalyst, thereby fundamentally solving the problem of treatment of large amount of red mud waste residues and realizing high value-added resource utilization. The main basis is as follows: most oxides in the red mud waste residue have certain catalysis and catalysis assisting performance, after the porous ceramic membrane carrier is prepared, heavy metal ions can be fixed in the catalyst carrier, the problem of secondary pollution can not be caused in the using process, meanwhile, aluminum source powder is added to improve the strength of the ceramic carrier, and activated carbon powder is added to improve the pore density of the ceramic membrane. After the active component iron-copper-niobium composite oxide and the promoter gold-silver alloy nanoflowers are loaded, the high-performance porous ceramic membrane water treatment catalyst can be prepared. The successful application of the invention can not only thoroughly solve the problem of safe disposal of the red mud waste residue, but also can efficiently degrade dyes such as methyl orange, p-nitrophenol, methylene blue and the like as the catalyst for treating the water by the gold-silver alloy nanoflower, thereby bringing great economic and social benefits. The invention provides a gold-silver alloy nano-flower water treatment catalyst and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a catalyst for treating the water containing the nano-class gold-silver alloy flower is prepared from the waste red mud dregs, powdered aluminium source, activated carbon powder and shaping agent solution, which are generated during extracting aluminium oxide in aluminium preparing industry, through preparing porous ceramic membrane, using the composite oxide of Fe, Cu and Nb as catalytic active component and using the nano-class gold-silver alloy flower as cocatalyst.
Wherein: red mud waste residue: aluminum source powder: activated carbon powder: forming agent solution: catalytic active component: the mass ratio of the cocatalyst is 60-80: 1-15: 20-30: 1-10: 1-15: 0.01 to 1.
In some preferred embodiments: red mud waste residue: aluminum source powder: activated carbon powder: forming agent solution: catalytic active component: the mass ratio of the cocatalyst is 60-65: 5-10: 20-30: 3-8: 5-10: 0.1 to 0.5.
In some preferred embodiments: the mass ratio of iron oxide, copper oxide and niobium pentoxide in the iron-copper-niobium composite oxide is 3-8: 3-4: 1 to 2.
In some specific embodiments: the mass ratio of iron oxide, copper oxide and niobium pentoxide in the iron-copper-niobium composite oxide is 4-6: 3-4: 1 to 2.
The technical scheme of the invention is as follows: the aluminum source powder is gamma alumina; the forming agent solution is a polyvinyl alcohol solution with the mass fraction of 1-15%; the precursor of the active component is ferric nitrate nonahydrate, copper nitrate trihydrate and niobium pentachloride, and the gold-silver alloy nano flower is prepared by reducing a mixed solution of chloroauric acid and silver nitrate by ascorbic acid.
A preparation method of the gold-silver alloy nano flower water treatment catalyst comprises the following steps:
(1) preparation of porous ceramic membrane carrier
Respectively crushing and sieving the red mud waste residue, the aluminum source powder and the activated carbon powder, uniformly mixing, adding a forming agent solution for granulation, adding the granulated pug into a mold, pressurizing, maintaining pressure, preparing a ceramic blank, and calcining in a muffle furnace to obtain a porous ceramic membrane carrier;
(2) preparation of active component precursor composite solution
Mixing ferric nitrate nonahydrate, copper nitrate trihydrate, niobium pentachloride and citric acid monohydrate, adding deionized water, and stirring at room temperature until the solution is clear and transparent to obtain an active component precursor composite solution;
(3) second calcination
And (3) soaking the porous ceramic membrane carrier prepared in the step (1) in the active component precursor composite solution prepared in the step (2), placing the porous ceramic membrane carrier in a drying oven, preserving the heat for 12 hours at the temperature of 80 ℃, drying the porous ceramic membrane carrier, and then placing the porous ceramic membrane carrier in a muffle furnace for secondary calcination to obtain the carrier loaded with the active component.
(4) Preparation of cocatalyst colloidal solution
Weighing chloroauric acid and silver nitrate, and adding deionized water to prepare a chloroauric acid solution with the concentration of 1-40 mM and a silver nitrate solution with the concentration of 1-40 mM respectively; weighing ascorbic acid, and adding the ascorbic acid into deionized water to prepare an ascorbic acid solution with the concentration of 50-150 mM; uniformly mixing a chloroauric acid solution and a silver nitrate solution, then adding an ascorbic acid solution, stirring and reacting until the solution is clear and transparent, so as to obtain a gold-silver alloy nanoflower colloidal solution; wherein: the volume ratio of the chloroauric acid solution to the silver nitrate solution is 10-30: 1, the volume ratio of the chloroauric acid solution to the ascorbic acid solution is 1-5: 1 to 5.
(5) Catalyst preparation
And (4) soaking the catalyst carrier prepared in the step (3) in the active component colloidal solution prepared in the step (4) for 10-30 minutes, taking out the soaked catalyst carrier, and drying to prepare the catalyst.
The technical scheme of the invention is as follows: the pressurizing pressure in the step (1) is 5-6 MPa, and the pressure maintaining time is 6-10 min.
The technical scheme of the invention is as follows: the calcining temperature in the step (1) is 900-1100 ℃, and the heat preservation time is 3-6 h.
The technical scheme of the invention is as follows: and (4) carrying out secondary calcination at 500-600 ℃ for 1-2 h.
The technical scheme of the invention is as follows: the application of the catalyst for treating water by using the gold-silver alloy nano flowers in the aspect of removing organic matters in sewage.
Further: the sewage is dye wastewater, and the organic matters are methyl orange, p-nitrophenol and methylene blue.
The catalytic reaction conditions and results of the invention: a small sample of 1mL of catalyst was loaded into a catalyst performance evaluation reaction apparatus, and a reaction solution was introduced for activity evaluation. The concentration of each solution was: 20mL of methyl orange (100mg/L, if necessary), 20mL of p-nitrophenol (139mg/L, if necessary), 20mL of methylene blue (100mg/L, if necessary), and 20mL of sodium borohydride (3.78 g/L). The catalyst has the efficiency of removing methyl orange, p-nitrophenol and methylene blue up to 100% at normal temperature and normal pressure, the average removal rate is 3.66mL/min, and the catalyst can still maintain the efficiency of 100% after being used for ten times.
The technical scheme of the invention is as follows: the pressurization pressure is the indicated pressure of the gauge.
The invention has the beneficial effects that:
the leaching rates of lead, zinc and chromium elements of the gold-silver alloy nano flower water treatment catalyst prepared by the invention are far lower than the limit value requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the content of each element of GB25466-2010 lead and zinc industrial pollutant emission standard, and the secondary pollution and high-added-value resource utilization of red mud waste residue are thoroughly and practically solved. Meanwhile, the catalyst can modulate the oxidation-reduction performance of the catalyst and promote the improvement of the catalytic efficiency. In addition, the catalyst component is environment-friendly, simple in preparation process, low in cost, high in cost performance, high in mechanical strength, capable of effectively reducing the operation cost of water pollution treatment, and high in application and popularization values.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
example 1
(1) Raw material crushing
Respectively crushing the red mud waste residue, the aluminum source powder and the activated carbon powder by a ball mill, and then homogenizing the crushed materials by a standard sieve of 100 meshes for later use;
(2) proportioning and granulating
Weighing 60g of red mud waste residue powder, 25g of activated carbon powder and 10g of gamma alumina powder, uniformly stirring, weighing 3g of 1% polyvinyl alcohol solution, mixing with the powder, grinding and granulating;
(3) shaping and calcining
Weighing 10g of granulated pug, adding the pug into a mold, pressurizing to 5MPa, maintaining the pressure for 6min, taking out a sample, repeating the blank molding for 10 times to obtain 10 porous ceramic membrane blanks, placing the porous ceramic membrane blanks in a muffle furnace, and keeping the temperature for 3h and calcining at 900 ℃ to obtain a porous ceramic membrane carrier;
(4) preparation of active component precursor composite solution
12.649g of ferric nitrate nonahydrate, 4.555g of copper nitrate trihydrate, 2.033g of niobium pentachloride and 25.298g of citric acid monohydrate are weighed, 50.596g of deionized water is added, and stirring is carried out at room temperature until the solution is clear and transparent, so as to obtain the active component precursor composite solution.
(5) Second calcination
And (3) soaking the porous ceramic membrane carrier prepared in the step (3) in the active component precursor composite solution prepared in the step (4), placing the porous ceramic membrane carrier in a drying oven, preserving heat for 12 hours at 80 ℃, drying, and then placing the porous ceramic membrane carrier in a muffle furnace, preserving heat for 1 hour at 500 ℃, so as to obtain the carrier loaded with the active component. Wherein the mass percentage of the iron-copper-niobium composite oxide is 5 percent, and the mass percentage of the iron oxide is as follows: copper oxide: the mass ratio of niobium pentoxide is 5: 3: 2.
(6) preparation of cocatalyst colloidal solution
Weighing 197mg chloroauric acid trihydrate and dissolving in 25mL deionized water to obtain a chloroauric acid solution with the concentration of 20 mM; weighing 85mg of silver nitrate, and dissolving the silver nitrate in 25mL of deionized water to obtain a silver nitrate solution with the concentration of 20 mM; weighing 440mg of ascorbic acid to be dissolved in 25mL of deionized water to obtain an ascorbic acid solution with the concentration of 100 mM; 24.709mL of chloroauric acid and 1.235mL of silver nitrate solution are uniformly stirred and mixed, then 24.709mL of ascorbic acid solution is rapidly added into the high-speed stirring mixed solution, and the mixture is stirred and reacts until the solution is clear and transparent, so that a gold-silver alloy nano-flower colloidal solution is obtained;
(7) catalyst preparation
Soaking the prepared carrier loaded with the active component in the cocatalyst colloidal solution prepared in the step (6) for 20 minutes, taking out the soaked catalyst carrier, and placing the soaked catalyst carrier in a drying oven at 100 ℃ for drying for 12 hours to prepare a 0.1% gold-silver alloy nanoflower loaded catalyst; red mud waste residue: aluminum source powder: activated carbon powder: forming agent solution: catalytic active component: the mass ratio of the cocatalyst is 60: 10: 25: 3: 5: 0.1.
(8) catalyst Activity test
A small sample of 1mL of catalyst was loaded into a catalyst performance evaluation reaction apparatus, and a reaction solution was introduced for activity evaluation. The concentration of each solution was: 20mL of methyl orange (100mg/L), 20mL of p-nitrophenol (139mg/L), and 20mL of sodium borohydride (3.78 g/L). The catalyst has the efficiency of removing methyl orange and p-nitrophenol reaching 100 percent at normal temperature and normal pressure, the average removal rate is 3.66mL/min, and the efficiency of the catalyst can still maintain 100 percent after being used for ten times.
(9) Leaching test of heavy metal elements in catalyst
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting ICP (inductively coupled plasma emission spectrometry) are far lower than the limit requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the content of each element of GB25466-2010 lead and zinc industrial pollutant emission standard)
Example 2:
(1) raw material crushing
Respectively crushing the red mud waste residue, the aluminum source powder and the activated carbon powder by a ball mill, and then homogenizing the crushed materials by a standard sieve of 100 meshes for later use;
(2) proportioning and granulating
Weighing 65g of red mud waste residue powder, 25g of activated carbon powder and 5g of gamma alumina powder, uniformly stirring, weighing 8g of 15% polyvinyl alcohol solution, mixing with the powder, grinding and granulating;
(3) shaping and calcining
Weighing 10g of granulated pug, adding the pug into a mold, pressurizing to 6MPa, maintaining the pressure for 10min, taking out a sample, repeating the blank molding for 10 times to obtain 10 porous ceramic membrane blanks, and placing the porous ceramic membrane blanks in a muffle furnace for heat preservation at 1100 ℃ for 6h for calcination to obtain porous ceramic membrane carriers;
(4) preparation of active component precursor composite solution
25.299g of ferric nitrate nonahydrate, 12.147g of copper nitrate trihydrate, 2.033g of niobium pentachloride and 50.598g of citric acid monohydrate are weighed, 101.196g of deionized water is added, and stirring is carried out at room temperature until the solution is clear and transparent, so as to obtain the active component precursor composite solution.
(5) Second calcination
And (3) soaking the porous ceramic membrane carrier prepared in the step (3) in the active component precursor composite solution prepared in the step (4), placing the porous ceramic membrane carrier in a drying oven, preserving heat for 12 hours at 80 ℃, drying the porous ceramic membrane carrier, then placing the porous ceramic membrane carrier in a muffle furnace, preserving heat for 2 hours at 600 ℃, and obtaining the catalyst, wherein the weight percentage of the iron-copper-niobium composite oxide is 10%, and the iron oxide: copper oxide: the mass ratio of niobium pentoxide is 5: 4: 1.
(6) preparation of cocatalyst colloidal solution
Weighing 985mg chloroauric acid trihydrate, and dissolving in 125mL deionized water to obtain a chloroauric acid solution with the concentration of 20 mM; weighing 425mg of silver nitrate and dissolving the silver nitrate in 125mL of deionized water to obtain a silver nitrate solution with the concentration of 20 mM; weighing 2.200g of ascorbic acid to be dissolved in 125mL of deionized water to obtain an ascorbic acid solution with the concentration of 100 mM; 123.545mL of chloroauric acid and 6.175mL of silver nitrate solution are uniformly stirred and mixed, then 123.545mL of ascorbic acid solution is rapidly added into the mixed solution stirred at a high speed, and the mixture is stirred and reacted until the solution is clear and transparent, so that a gold-silver alloy nano flower colloidal solution is obtained;
(7) catalyst preparation
Soaking the prepared carrier loaded with the active component in the cocatalyst colloidal solution prepared in the step (6) for 20 minutes, taking out the soaked catalyst carrier, and placing the soaked catalyst carrier in a drying oven at 100 ℃ for drying for 12 hours to prepare a 0.5% gold-silver alloy nanoflower loaded catalyst; red mud waste residue: aluminum source powder: activated carbon powder: forming agent solution: catalytic active component: the mass ratio of the cocatalyst is 65: 5: 25: 8: 10: 0.5.
(8) catalyst Activity test
A small sample of 1mL of catalyst was loaded into a catalyst performance evaluation reaction apparatus, and a reaction solution was introduced for activity evaluation. The concentration of each solution was: 20mL of methyl orange (100mg/L), 20mL of p-nitrophenol (139mg/L), 20mL of methylene blue (100mg/L), and 20mL of sodium borohydride (3.78 g/L). The catalyst has the efficiency of removing methyl orange, p-nitrophenol and methylene blue up to 100% at normal temperature and normal pressure, the average removal rate is 3.66mL/min, and the catalyst can still maintain the efficiency of 100% after being used for ten times.
(9) Leaching test of heavy metal elements in catalyst
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting ICP (inductively coupled plasma emission spectrometry) are far lower than the limit requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the content of each element of GB25466-2010 lead and zinc industrial pollutant emission standard)
Comparative example 1
(1) Raw material crushing
Respectively crushing the red mud waste residue, the aluminum source powder and the activated carbon powder by a ball mill, and then homogenizing the crushed materials by a standard sieve of 100 meshes for later use;
(2) proportioning and granulating
Weighing 65g of red mud waste residue powder, 25g of activated carbon powder and 5g of gamma alumina powder, uniformly stirring, weighing 8g of 15% polyvinyl alcohol solution, mixing with the powder, grinding and granulating;
(3) shaping and calcining
Weighing 10g of granulated pug, adding the pug into a mold, pressurizing to 6MPa, maintaining the pressure for 10min, taking out a sample, repeating the blank molding for 10 times to obtain 10 porous ceramic membrane blanks, and placing the porous ceramic membrane blanks in a muffle furnace for heat preservation at 1100 ℃ for 6h for calcination to obtain porous ceramic membrane carriers;
(4) preparation of cocatalyst colloidal solution
Weighing 985mg chloroauric acid trihydrate, and dissolving in 125mL deionized water to obtain a chloroauric acid solution with the concentration of 20 mM; weighing 425mg of silver nitrate and dissolving the silver nitrate in 125mL of deionized water to obtain a silver nitrate solution with the concentration of 20 mM; weighing 2.200g of ascorbic acid to be dissolved in 125mL of deionized water to obtain an ascorbic acid solution with the concentration of 100 mM; 123.545mL of chloroauric acid and 6.175mL of silver nitrate solution are uniformly stirred and mixed, then 123.545mL of ascorbic acid solution is rapidly added into the mixed solution stirred at a high speed, and the mixture is stirred and reacted until the solution is clear and transparent, so that a gold-silver alloy nano flower colloidal solution is obtained;
(5) catalyst preparation
And (3) soaking the prepared carrier in the promoter colloidal solution prepared in the step (4) for 20 minutes, taking out the soaked catalyst carrier, and drying the catalyst carrier in an oven at 100 ℃ for 12 hours to prepare the 0.5% gold-silver alloy nanoflower supported catalyst.
(6) Catalyst Activity test
A small sample of 1mL of catalyst was loaded into a catalyst performance evaluation reaction apparatus, and a reaction solution was introduced for activity evaluation. The concentration of each solution was: 20mL of methyl orange (100mg/L), 20mL of p-nitrophenol (139mg/L), 20mL of methylene blue (100mg/L), and 20mL of sodium borohydride (3.78 g/L). The catalyst can remove methyl orange, p-nitrophenol and methylene blue at normal temperature and normal pressure with the highest efficiency of only 24 percent and the average removal rate of 3.66 mL/min.
(7) The contrast effect is as follows: compared with the example 2, the water treatment catalyst of the honeysuckle alloy nanometer flower has no catalytic active component, and the catalytic efficiency is extremely low.
Comparative example 2
(1) Raw material crushing
Crushing the red mud waste residue by a ball mill, and then homogenizing by a standard sieve of 100 meshes for later use;
(2) proportioning and granulating
Weighing 95g of red mud waste residue powder, then weighing 3g of 1% polyvinyl alcohol solution, mixing with the powder, grinding and granulating;
(3) shaping and calcining
Weighing 10g of granulated pug, adding the pug into a mold, pressurizing to 5MPa, keeping the pressure for 6min, taking out a sample, repeating the blank molding for 10 times to obtain 10 ceramic blanks, and placing the ceramic blanks in a muffle furnace for heat preservation at 900 ℃ for 3h for calcination to obtain a ceramic carrier;
(4) the contrast effect is as follows: compared with the example 1, when the porous ceramic membrane carrier is prepared, aluminum source powder and activated carbon powder are not added, the pore density of the carrier after being roasted is extremely low, a ceramic membrane structure cannot be formed, and the physical strength of the ceramic is very low.
Comparative example 3
(1) Raw material crushing
Respectively crushing the red mud waste residue, the aluminum source powder and the activated carbon powder by a ball mill, and then homogenizing the crushed materials by a standard sieve of 100 meshes for later use;
(2) proportioning and granulating
Weighing 65g of red mud waste residue powder, 25g of activated carbon powder and 5g of gamma alumina powder, uniformly stirring, weighing 8g of 15% polyvinyl alcohol solution, mixing with the powder, grinding and granulating;
(3) shaping and calcining
Weighing 10g of granulated pug, adding the pug into a mold, pressurizing to 6MPa, maintaining the pressure for 10min, taking out a sample, repeating the blank molding for 10 times to obtain 10 porous ceramic membrane blanks, and placing the porous ceramic membrane blanks in a muffle furnace for heat preservation at 1100 ℃ for 6h for calcination to obtain porous ceramic membrane carriers;
(3) preparation of active component precursor composite solution
25.299g of ferric nitrate nonahydrate, 12.147g of copper nitrate trihydrate, 2.033g of niobium pentachloride and 50.598g of citric acid monohydrate are weighed, 101.196g of deionized water is added, and stirring is carried out at room temperature until the solution is clear and transparent, so as to obtain the active component precursor composite solution.
(4) Catalyst preparation
And (3) soaking the porous ceramic membrane carrier prepared in the step (3) in the active component precursor composite solution prepared in the step (4), placing the porous ceramic membrane carrier in a drying oven, preserving heat for 12 hours at 80 ℃, drying the porous ceramic membrane carrier, then placing the porous ceramic membrane carrier in a muffle furnace, preserving heat for 2 hours at 600 ℃, and obtaining the catalyst, wherein the weight percentage of the iron-copper-niobium composite oxide is 10%, and the iron oxide: copper oxide: the mass ratio of niobium pentoxide is 5: 4: 1.
(5) catalyst Activity test
A small sample of 1mL of catalyst was loaded into a catalyst performance evaluation reaction apparatus, and a reaction solution was introduced for activity evaluation. The concentration of each solution was: 20mL of methyl orange (100mg/L), 20mL of p-nitrophenol (139mg/L), 20mL of methylene blue (100mg/L), and 20mL of sodium borohydride (3.78 g/L). The catalyst can remove methyl orange, p-nitrophenol and methylene blue at normal temperature and normal pressure with the highest efficiency of only 82 percent and the average removal rate of 3.66 mL/min.
(6) The contrast effect is as follows: compared with example 2, when the catalyst is prepared, the activity of the catalyst is obviously reduced without adding the gold-silver nanoflower alloy as a cocatalyst.
Claims (10)
1. A water treatment catalyst of gold-silver alloy nanometer flowers is characterized in that: the catalyst takes a porous ceramic membrane prepared from polluted red mud waste residues, aluminum source powder, activated carbon powder and a forming agent solution discharged during the extraction of alumina in the aluminum industry as a carrier, takes an iron-copper-niobium composite oxide as a catalytic active component, and takes gold-silver alloy nanoflowers as a cocatalyst;
wherein: red mud waste residue: aluminum source powder: activated carbon powder: forming agent solution: catalytic active component: the mass ratio of the cocatalyst is 60-80: 1-15: 20-30: 1-10: 1-15: 0.01 to 1.
2. The water treatment catalyst of honeysuckle alloy nano-flowers as claimed in claim 1, which is characterized in that: red mud waste residue: aluminum source powder: activated carbon powder: forming agent solution: catalytic active component: the mass ratio of the cocatalyst is 60-65: 5-10: 20-30: 3-8: 5-10: 0.1 to 0.5.
3. The water treatment catalyst of honeysuckle alloy nano-flowers as claimed in claim 1, which is characterized in that: the mass ratio of iron oxide, copper oxide and niobium pentoxide in the iron-copper-niobium composite oxide is 3-8: 3-4: 1 to 2.
4. The water treatment catalyst of gold-silver alloy nanoflowers according to any one of claims 1 to 3, characterized in that: the aluminum source powder is gamma alumina; the forming agent solution is a polyvinyl alcohol solution with the mass fraction of 1-15%; the precursor of the active component is ferric nitrate nonahydrate, copper nitrate trihydrate and niobium pentachloride, and the gold-silver alloy nano flower is prepared by reducing a mixed solution of chloroauric acid and silver nitrate by ascorbic acid.
5. The preparation method of the water treatment catalyst of the honeysuckle alloy nano-flowers of claim 1, which is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) preparation of porous ceramic membrane carrier
Respectively crushing and sieving the red mud waste residue, the aluminum source powder and the activated carbon powder, uniformly mixing, adding a forming agent solution for granulation, adding the granulated pug into a mold, pressurizing, maintaining pressure, preparing a ceramic blank, and calcining in a muffle furnace to obtain a porous ceramic membrane carrier;
(2) preparation of active component precursor composite solution
Mixing ferric nitrate nonahydrate, copper nitrate trihydrate, niobium pentachloride and citric acid monohydrate, adding deionized water, and stirring at room temperature until the solution is clear and transparent to obtain an active component precursor composite solution;
(3) second calcination
Soaking the porous ceramic membrane carrier prepared in the step (1) in the active component precursor composite solution prepared in the step (2), placing the porous ceramic membrane carrier in a drying oven, preserving the heat at 80 ℃ for 12h for drying, and then placing the porous ceramic membrane carrier in a muffle furnace for secondary calcination to obtain a carrier loaded with an active component;
(4) preparation of cocatalyst colloidal solution
Weighing chloroauric acid and silver nitrate, and adding deionized water to prepare a chloroauric acid solution with the concentration of 1-40 mM and a silver nitrate solution with the concentration of 1-40 mM respectively; weighing ascorbic acid, and adding the ascorbic acid into deionized water to prepare an ascorbic acid solution with the concentration of 50-150 mM; uniformly mixing a chloroauric acid solution and a silver nitrate solution, then adding an ascorbic acid solution, stirring and reacting until the solution is clear and transparent, so as to obtain a gold-silver alloy nanoflower colloidal solution; wherein: the volume ratio of the chloroauric acid solution to the silver nitrate solution is 10-30: 1, the volume ratio of the chloroauric acid solution to the ascorbic acid solution is 1-5: 1-5;
(5) catalyst preparation
And (4) soaking the active component-loaded carrier prepared in the step (3) in the gold-silver alloy nano flower colloidal solution prepared in the step (4) for 10-30 minutes, and taking out the soaked catalyst carrier to dry to prepare the catalyst.
6. The preparation method of the water treatment catalyst of the honeysuckle alloy and the nano flower as claimed in claim 5, which is characterized in that: the pressurizing pressure in the step (1) is 5-6 MPa, and the pressure maintaining time is 6-10 min.
7. The preparation method of the water treatment catalyst of the honeysuckle alloy and the nano flower as claimed in claim 5, which is characterized in that: the calcining temperature in the step (1) is 900-1100 ℃, and the heat preservation time is 3-6 h.
8. The preparation method of the water treatment catalyst of the honeysuckle alloy and the nano flower as claimed in claim 5, which is characterized in that: and (4) carrying out secondary calcination at 500-600 ℃ for 1-2 h.
9. The use of the water treatment catalyst of honeysuckle alloy and nano-flower of claim 1 in removing organic substances in sewage.
10. The use of claim 9, wherein the wastewater is dye wastewater and the organic materials are methyl orange, p-nitrophenol and methylene blue.
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