CN113333011B - Composite catalyst and preparation method and application thereof - Google Patents
Composite catalyst and preparation method and application thereof Download PDFInfo
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- CN113333011B CN113333011B CN202110609490.5A CN202110609490A CN113333011B CN 113333011 B CN113333011 B CN 113333011B CN 202110609490 A CN202110609490 A CN 202110609490A CN 113333011 B CN113333011 B CN 113333011B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 59
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 136
- 238000000034 method Methods 0.000 claims abstract description 88
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 78
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 68
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 56
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 56
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 30
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 22
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 19
- 239000002351 wastewater Substances 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 62
- 229910052751 metal Inorganic materials 0.000 claims description 57
- 239000002184 metal Substances 0.000 claims description 57
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 43
- 229910052799 carbon Inorganic materials 0.000 claims description 38
- 238000002791 soaking Methods 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 239000012298 atmosphere Substances 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000571 coke Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000006385 ozonation reaction Methods 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 4
- 206010021143 Hypoxia Diseases 0.000 abstract description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 31
- 229910052748 manganese Inorganic materials 0.000 description 24
- 239000011572 manganese Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 18
- 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 14
- 238000010438 heat treatment Methods 0.000 description 12
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018669 Mn—Co Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 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
- 238000007598 dipping method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 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 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical compound CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
-
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention provides a composite catalyst, a preparation method and application thereof, wherein the preparation method comprises the following steps: loading metal oxide and doping nitrogen element on the carbon-based material to obtain the composite catalyst; the nitrogen-containing precursor doped with nitrogen element is ammonia gas and/or inorganic ammonium salt. The composite catalyst constructs more catalytic active sites by loading metal oxide and doping nitrogen elements, and partially reduces the metal oxide in the process of doping nitrogen to form oxygen deficiency, so that the composite catalyst has higher catalytic activity and stability, thereby efficiently catalyzing ozone oxidation and improving the efficiency of catalyzing ozone to decompose hydroxyl free radicals. The preparation method of the composite catalyst is simple, low in cost and suitable for large-scale application, has high efficiency in catalyzing ozone oxidation treatment of wastewater, has long service life, can mineralize organic matters in the wastewater into carbon dioxide and water without selectivity, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of catalyst materials, and particularly relates to a composite catalyst, a preparation method and application thereof.
Background
Along with the continuous and stable increase of economy, the industrial production scale is increasingly enlarged, so that a large amount of industrial wastewater and waste liquid with high treatment difficulty and municipal wastewater with more complex components are generated; if improperly handled, it can pose a serious threat to the quality of the water environment and to the health of the residents. In particular to toxic organic pollutants in wastewater, has strong toxicity and large treatment difficulty, and is a major point and a difficult point for controlling wastewater pollution. Organic pollutants in wastewater are generally removed by separation or reaction. The separation process comprises extraction, adsorption, membrane separation and the like, and organic matters are enriched or transferred to other liquid phase or solid surfaces, and then necessary secondary treatment is carried out according to the characteristics of the organic matters. The reaction process mainly comprises chemical oxidation, chemical reduction and other conversion processes, wherein the chemical reduction technology is rarely applied in practical scenes, and organic matters are oxidized into low-toxicity intermediate products, carbon dioxide and water mainly through the chemical oxidation process.
Chemical oxidation treatment techniques are generally those that utilize hydroxyl radicals of strong oxidizing nature to treat wastewater, also known as advanced oxidation techniques. The advanced oxidation technology is very various, mainly adopts various oxidants such as ozone, hydrogen peroxide, persulfates, oxygen and the like, generates hydroxyl free radicals to degrade organic matters under the external conditions such as illumination, electrochemistry, heating and pressurizing, strong alkali, catalyst and the like, and the process is accompanied with other active species such as photo-generated holes, super-oxygen free radicals, singlet oxygen and the like. At present, most of the actual wastewater treated by the advanced oxidation technology adopts hydrogen peroxide or ozone as an oxidant, other oxidation technologies are limited by treatment efficiency or treatment cost, and large-scale application is not realized yet. Hydrogen peroxide oxidation generally adopts ferrous ion reduction under the strong acid pH condition to generate hydroxyl free radicals; compared with hydrogen peroxide oxidation, the ozone oxidation has mild operation condition and no secondary pollution, and has obvious application advantages. However, ozone oxidation has reaction selectivity, and a highly efficient solid phase catalyst is required to improve ozone oxidation efficiency.
CN110302841a discloses a preparation method of a foam nickel supported bimetallic MOF-based ozone catalyst, a product and application thereof, wherein the preparation method takes a metal organic framework compound ZIF-67 as a template and foam nickel as a carrier, and the supported porous Mn-Co bimetallic MOF-based ozone catalyst is prepared through an in-situ hydrothermal-impregnation synthesis method; the preparation method can regulate and control the crystal size and morphology of the catalyst, promote the uniform distribution of active sites, and improve the decomposition rate of ozone and the mineralization rate of organic matters. CN109745975a discloses an ozone oxidation catalyst, a preparation method and application thereof, the catalyst comprises a carrier and an active component, wherein the carrier is active carbon, the active component is Ru, and the load is 0.1-5%; the particle size of the catalyst is less than 1.5mm by mass; the catalyst is prepared by mixing activated carbon with RuCl 3 The solution is prepared by microwave treatment with the power of 300-500W after isovolumetric dipping and drying. CN109876822A discloses a copper-manganese bimetallic ozone catalyst, a preparation method and application thereof in tricyclazole wastewater treatment, wherein the catalyst takes copper-containing porous silica gel as a carrier and carries metal manganese oxide, the copper-containing porous silica gel carrier is immersed in manganese acetate solution, ultrasonic immersion is carried out, and finally calcination is carried out for 550-600 min at 400-500 ℃ to prepare the catalystIs prepared. In the prior art represented by the catalyst, a composite catalyst is mostly adopted for catalyzing ozone oxidation, and a carrier is utilized to disperse metal oxide, so that the catalytic activity is improved, and the metal usage amount is reduced; however, the supported catalyst in the prior art has low activity, poor stability, complex preparation process and high raw material cost, and is not beneficial to large-scale application.
Therefore, developing a catalyst with high catalytic activity, good stability, simple preparation method and low production cost to meet the application requirements of ozone oxidation catalysis is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a composite catalyst, a preparation method and application thereof, wherein more catalytic active sites are constructed by loading metal oxide and doping nitrogen element on a carbon-based material, and a nitrogen-containing precursor with weak reducibility is used in the process of doping nitrogen element, so that a proper amount of oxygen vacancies are formed on the surface of the metal oxide, and the composite catalyst has higher activity, higher stability and longer service life, thereby improving the efficiency of catalytic ozone oxidation and sewage treatment.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a composite catalyst, the method comprising: loading metal oxide and doping nitrogen element on the carbon-based material to obtain the composite catalyst; the nitrogen-containing precursor doped with nitrogen element is ammonia gas and/or inorganic ammonium salt.
In the preparation method provided by the invention, the carbon-based material is used as a carrier, and the metal and nitrogen co-doped carbon-based composite catalyst is formed by loading the metal oxide and doping nitrogen element, so that the metal oxide has high dispersibility on the carbon-based material, and more catalytic active sites are constructed; meanwhile, the nitrogen-containing precursor used for doping nitrogen element is ammonia gas and/or inorganic ammonium salt, has weak reducibility, and can partially reduce metal oxide in the process of doping nitrogen element, so that a proper amount of oxygen vacancies are formed on the surface of the metal oxide; meanwhile, the ammonia gas with weak reducibility does not change the crystal form of the metal oxide, but causes a small amount of oxygen vacancies, so that the supported metal oxide keeps good activity and stability. The invention improves the catalytic activity and stability of the composite catalyst by increasing the catalytic active sites and forming oxygen vacancies, so that the composite catalyst can improve the efficiency of producing hydroxyl free radicals by catalyzing ozone to decompose when being used for catalyzing ozone to oxidize organic pollutants, can mineralize the organic matters in the wastewater into carbon dioxide and water without selectivity, has higher degradation efficiency of pollutants and longer stable service life, and is particularly suitable for advanced treatment of sewage/wastewater.
The invention takes the carbon-based material as the carrier, the specific surface of the carbon-based material is large, the cost is low, and the carbon-based material has high catalytic activity after being loaded with metal oxide and doped with nitrogen. In the preparation method, the loading of metal oxide and the doping of nitrogen element can be performed synchronously or stepwise; when the step-by-step process is performed, the metal oxide can be loaded first and then the nitrogen element can be doped, or the nitrogen element can be doped first and then the metal oxide can be loaded.
Preferably, the carbon-based material comprises any one or a combination of at least two of activated carbon, activated coke, biochar, graphene-based material or carbon nanotubes; activated carbon and/or biochar are further preferred based on lower cost, higher specific surface area and higher activity.
Preferably, the carbon-based material is a granular carbon-based material, more preferably granular activated carbon and/or biochar, which is beneficial to continuous operation of the wastewater treatment process and can avoid complicated steps of catalyst separation.
Preferably, the metal in the metal oxide comprises any one or a combination of at least two of iron, cobalt, manganese, nickel, copper, lanthanum, cerium, molybdenum or titanium; compared with the catalyst using noble metals such as platinum, gold, palladium and the like in the prior art, the metal raw material cost is lower, and the large-scale application of the composite catalyst is facilitated.
Preferably, the method for loading the metal oxide comprises the following steps: and (3) immersing the carbon-based material or the carbon-based material doped with nitrogen element in a metal precursor solution, drying and roasting to obtain the carbon-based material loaded with the metal oxide.
Preferably, the metal precursor solution is an aqueous solution of a metal salt.
Preferably, the metal salt is a metal inorganic salt, and further preferably any one or a combination of at least two of a metal nitrate, a metal sulfate or a metal halide.
Preferably, the mass of the metal in the metal precursor solution is 0.5 to 20%, for example, may be 0.6%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18% or 19%, and specific point values between the above point values, based on 100% of the mass of the carbon-based material, and the present invention is not exhaustive to list the specific point values included in the range, more preferably 2 to 15% for the sake of brevity and conciseness.
Preferably, the impregnation method is an isovolumetric impregnation method.
Preferably, the temperature of the impregnation is 15 to 45 ℃, for example, 16 ℃, 18 ℃, 20 ℃, 21 ℃, 23 ℃, 25 ℃, 27 ℃, 29 ℃, 30 ℃, 31 ℃, 33 ℃, 35 ℃, 37 ℃, 39 ℃, 40 ℃, 42 ℃ or 44 ℃, and specific values between the above values, are limited in space and for the sake of brevity, the invention is not exhaustive of the specific values included in the range.
Preferably, the time of the impregnation is 8 to 24 hours, for example, 9 hours, 10 hours, 11 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 21 hours or 23 hours, and specific point values among the above point values, are limited in length and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.
Preferably, the drying temperature is 100-120 ℃, such as 101 ℃, 103 ℃, 105 ℃, 107 ℃, 109 ℃, 110 ℃, 111 ℃, 113 ℃, 115 ℃, 117 ℃ or 119 ℃, and specific point values between the above point values, are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the drying time is 5 to 24 hours, for example, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 21 hours or 23 hours, and specific point values among the above point values, which are limited in space and for the sake of brevity, the present invention is not exhaustive.
Preferably, the baking temperature is 300 to 900 ℃, for example, 320 ℃, 350 ℃, 380 ℃, 400 ℃, 420 ℃, 450 ℃, 480 ℃, 500 ℃, 520 ℃, 550 ℃, 580 ℃, 600 ℃, 620 ℃, 650 ℃, 680 ℃, 700 ℃, 720 ℃, 750 ℃, 780 ℃, 800 ℃, 820 ℃, 850 ℃ or 880 ℃, and specific point values between the above point values are limited in scope and the present invention is not exhaustive of the specific point values included in the range for brevity.
Preferably, the roasting time is 0.5 to 5 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours or 4.5 hours, and specific point values among the above point values, are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the calcination is performed in a vacuum or a protective atmosphere, which is an inert atmosphere and/or a reducing atmosphere.
Preferably, the inert atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere.
Preferably, the reducing atmosphere comprises a hydrogen atmosphere and/or an ammonia atmosphere.
Preferably, the nitrogen-containing precursor is ammonia gas, and the ammonia gas is used in an amount of 900-60000 mL, for example, 1000mL, 2000mL, 3000mL, 5000mL, 7000mL, 9000mL, 10000mL, 15000mL, 20000mL, 25000mL, 30000mL, 35000mL, 40000mL, 45000mL, 50000mL or 55000mL, and specific point values between the above point values, based on 1g of the mass of the carbon-based material, are limited to a spread and for simplicity, and the present invention does not exhaustively list specific point values included in the range.
Preferably, the nitrogen-containing precursor is an inorganic ammonium salt, and the mass of nitrogen in the inorganic ammonium salt is 0.1-15% based on 100% of the mass of the carbon-based material, for example, may be 0.2%, 0.4%, 0.6%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13% or 14%, and specific point values between the above point values, are limited in space and for brevity, and the present invention is not exhaustive of the specific point values included in the range.
Preferably, the inorganic ammonium salt is selected from any one or a combination of at least two of ammonium chloride, ammonium bicarbonate, ammonium carbonate, ammonium nitrate or ammonium sulfate.
Preferably, the method for doping nitrogen element comprises a method A or a method B:
the method A comprises the following steps: taking any one of a carbon-based material, a carbon-based material loaded with metal oxide or a carbon-based material impregnated with a metal precursor as a carrier, uniformly mixing the carrier with inorganic ammonium salt, and roasting in an anaerobic environment to obtain the carbon-based material doped with nitrogen element.
The method B comprises the following steps: roasting any one of the carbon-based material, the carbon-based material loaded with metal oxide or the carbon-based material impregnated with metal precursor in ammonia atmosphere to obtain the carbon-based material doped with nitrogen element.
In the method A, inorganic ammonium salt is used as a nitrogen-containing precursor, and is uniformly mixed with a carrier and then baked, and the inorganic ammonium salt is decomposed to form ammonia gas, so that nitrogen doping of the carbon-based material is realized. Preferably, the inorganic ammonium salt is selected from any one or a combination of at least two of ammonium chloride, ammonium bicarbonate or ammonium carbonate, and the inorganic ammonium salt is decomposed to generate NH in the roasting process 3 HCl and CO 2 Waiting for gas; plays a role in pore-forming together, increases the specific surface area of the carbon-based material, and utilizes NH 3 The nitrogen doping and weak metal reduction capability can jointly improve the catalytic activity of the composite catalyst.
Preferably, the baking temperatures in method a and method B are each independently 300 to 900 ℃, for example, 320 ℃, 350 ℃, 380 ℃, 400 ℃, 420 ℃, 450 ℃, 480 ℃, 500 ℃, 520 ℃, 550 ℃, 580 ℃, 600 ℃, 620 ℃, 650 ℃, 680 ℃, 700 ℃, 720 ℃, 750 ℃, 780 ℃, 800 ℃, 820 ℃, 850 ℃ or 880 ℃, and specific point values between the above point values, are not exhaustive, for the sake of brevity and for conciseness, the present invention does not exhaustively list the specific point values included in the range.
Preferably, the time of calcination in method a, method B is each independently 2 to 6 hours, for example, may be 2.25 hours, 2.5 hours, 2.75 hours, 3 hours, 3.25 hours, 3.5 hours, 3.75 hours, 4 hours, 4.25 hours, 4.5 hours, 4.75 hours, 5 hours, 5.25 hours or 5.5 hours, and the specific point values between the above point values, are limited in space and for brevity, the present invention is not exhaustive of the specific point values included in the range.
In a preferred technical scheme, the method for preparing the supported metal oxide and the doped nitrogen element are carried out synchronously, and specifically comprises the following steps:
(1) Placing a carbon-based material into a metal inorganic salt solution, soaking for 8-24 hours at room temperature by an isovolumetric soaking method, and drying for 5-24 hours at 100-120 ℃ to obtain a pretreated sample;
(2) Doping nitrogen element into the pretreated sample obtained in the step (1), wherein the doping method comprises a method A or a method B; the method A comprises the following steps: roasting the pretreated sample in ammonia atmosphere at 300-900 ℃ for 2-6 hours to obtain the composite catalyst; the method B comprises the following steps: and uniformly mixing the pretreated sample with inorganic ammonium salt, and roasting for 2-6 hours at 300-900 ℃ in an anaerobic environment to obtain the composite catalyst.
In another preferred technical scheme, firstly, loading metal oxide and then doping nitrogen element, the preparation method specifically comprises the following steps:
(S1) placing a carbon-based material into a metal inorganic salt solution, soaking for 8-24 h at room temperature by an isovolumetric soaking method, and drying for 5-24 h at 100-120 ℃; roasting the dried sample at 300-900 ℃ for 0.5-5 h in an inert atmosphere to obtain a carbon-based material loaded with metal oxide;
(S2) doping nitrogen element into the metal oxide-loaded carbon-based material obtained in the step (S1), the doping method including a method a or a method B;
the method A comprises the following steps: roasting a carbon-based material loaded with metal oxide in an ammonia atmosphere at 300-900 ℃ for 2-6 h to obtain the composite catalyst;
the method B comprises the following steps: uniformly mixing a carbon-based material loaded with metal oxide and inorganic ammonium salt, and roasting for 2-6 hours at 300-900 ℃ in an anaerobic environment to obtain the composite catalyst.
In a second aspect, the present invention provides a composite catalyst prepared by the preparation method as described in the first aspect.
Preferably, the composite catalyst includes a carbon-based material, and a metal oxide and a nitrogen element supported on the carbon-based material.
Preferably, the carbon-based material comprises any one or a combination of at least two of activated carbon, activated coke, biochar, graphene-based material or carbon nanotubes, and further preferably activated carbon and/or biochar.
Preferably, the metal in the metal oxide comprises any one or a combination of at least two of iron, cobalt, manganese, nickel, copper, lanthanum, cerium, molybdenum or titanium.
Preferably, in the composite catalyst, the mass of the metal in the metal oxide is 0.5 to 20% based on 100% of the mass of the carbon-based material, for example, may be 0.6%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18% or 19%, and specific point values between the above point values, and the present invention is not exhaustive to list the specific point values included in the range, and more preferably 2 to 15% for reasons of brevity and simplicity.
Preferably, the mass of the nitrogen element in the composite catalyst is 0.1 to 15% based on 100% of the mass of the carbon-based material, and may be, for example, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13% or 14%, and specific point values between the above point values, and the present invention is not exhaustive to list the specific point values included in the range, and more preferably 1 to 8% for the sake of brevity and conciseness.
As a preferable technical scheme of the invention, the mass of the metal in the metal oxide is 0.5-20% and the mass of the nitrogen element is 0.1-15% calculated by taking the mass of the carbon-based material as 100%, and the two materials are mutually cooperated to endow the composite catalyst with higher catalytic activity and stability. If the loading of the metal oxide or nitrogen element is too low, it is difficult to exhibit an elevating effect on the catalytic activity of the carbon-based material; if the metal oxide or nitrogen content exceeds the above range, higher requirements are put on the preparation process, and the preparation cost is high, which is not beneficial to large-scale application.
Preferably, the composite catalyst is a catalyst for catalyzing ozone oxidation.
In a third aspect, the present invention provides the use of a composite catalyst as described in the second aspect for catalyzing ozone oxidation.
Preferably, the composite catalyst is applied to catalytic ozonation treatment of wastewater.
Compared with the prior art, the invention has the following beneficial effects:
the composite catalyst and the preparation method thereof provided by the invention take carbon-based material as a carrier, and build more catalytic active sites by loading metal oxide and doping nitrogen element; meanwhile, the metal oxide is partially reduced in the process of doping nitrogen to form oxygen deficiency, so that the composite catalyst has higher catalytic activity and stability, thereby efficiently catalyzing ozone oxidation and improving the efficiency of catalyzing ozone to decompose and produce hydroxyl free radicals. The preparation method of the composite catalyst is simple, low in cost and suitable for large-scale application, the efficiency of the composite catalyst in catalyzing ozone oxidation treatment of wastewater is high, the COD removal rate reaches 51.5-67.2%, the catalyst stability is good, the COD removal rate after 72h circulation is basically kept at the level of the first use, the activity attenuation is less than 1.7%, the composite catalyst has excellent stability and long service life, and can mineralize organic matters in the wastewater into carbon dioxide and water without selectivity, so that the composite catalyst has wide application prospect.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In the following examples and comparative examples of the present invention, the content of doped metal in the composite catalyst was estimated in terms of theoretical amount at the time of preparation, and verified by inductively coupled plasma spectrometer (ICP) test, since metal loss hardly occurs during the preparation process, the theoretical amount is substantially the same as the measured value; the nitrogen content doped in the composite catalyst was measured by an inductively coupled plasma spectrometer (ICP), and the data described below are actual measurement values.
Example 1
A composite catalyst and a preparation method thereof, the specific preparation steps are as follows:
immersing active carbon in a manganese nitrate aqueous solution to enable the mass ratio of manganese in the manganese nitrate to the active carbon to be 5:100; soaking for 12h at room temperature by adopting an isovolumetric soaking method, and then drying for 12h at 110 ℃; placing the dried sample in a tube furnace, introducing nitrogen for protection, heating to 500 ℃ and roasting for 3 hours; and continuously introducing ammonia gas into the tubular furnace at the rate of 100mL/min, and roasting at 500 ℃ for 3 hours to obtain the composite catalyst.
In the composite catalyst, the mass of manganese is 5% and the doping amount of nitrogen element is 5% based on 100% of the mass of active carbon (carbon-based material).
Example 2
A composite catalyst and a preparation method thereof, the specific preparation steps are as follows:
immersing active carbon in a mixed aqueous solution of manganese nitrate and copper nitrate, wherein the molar ratio of manganese metal to copper metal in the mixed aqueous solution is 2:1, and the mass ratio of the total mass of manganese and copper to the active carbon is 20:100; soaking for 12h at room temperature by adopting an isovolumetric soaking method, and then drying for 20h at 105 ℃; placing the dried sample in a tube furnace, introducing nitrogen for protection, heating to 500 ℃ and roasting for 3 hours; and continuously introducing ammonia gas into the tubular furnace at the rate of 100mL/min, and roasting at 900 ℃ for 3 hours to obtain the composite catalyst.
In the composite catalyst, the total mass of the metal is 20%, the mass of the manganese is 12.7%, the mass of the copper is 7.3% and the doping amount of the nitrogen element is 6.4% based on 100% of the mass of the active carbon (carbon-based material).
Example 3
A composite catalyst and a preparation method thereof, the specific preparation steps are as follows:
immersing activated carbon in a mixed aqueous solution of lanthanum nitrate and cobalt nitrate, wherein the molar ratio of metal lanthanum to metal cobalt in the mixed aqueous solution is 1:1, and the mass ratio of the total mass of lanthanum and cobalt to the activated carbon is 10:100; soaking for 12h at room temperature by adopting an isovolumetric soaking method, and then drying for 12h at 110 ℃; and placing the dried sample in a tube furnace, continuously introducing ammonia gas into the tube furnace at a rate of 200mL/min, and roasting at 800 ℃ for 6 hours to obtain the composite catalyst.
In the composite catalyst, the total mass of metal is 10%, the mass of lanthanum is 6.3%, the mass of cobalt is 3.7% and the doping amount of nitrogen element is 8.0% based on 100% of the mass of active carbon (carbon-based material).
Example 4
A composite catalyst and a preparation method thereof, the specific preparation steps are as follows:
immersing biochar in a mixed aqueous solution of manganese nitrate and ferric nitrate, wherein the molar ratio of metal manganese to metal iron in the mixed aqueous solution is 1:4, and the mass ratio of the total mass of manganese and iron to the biochar is 2:100; soaking for 12h at room temperature by adopting an isovolumetric soaking method, and then drying for 12h at 110 ℃; placing the dried sample in a tube furnace, introducing nitrogen for protection, heating to 500 ℃ and roasting for 3 hours; then ammonia gas is continuously introduced into the tubular furnace at the speed of 200mL/min, and the catalyst is roasted for 2 hours at 900 ℃ to obtain the composite catalyst.
In the composite catalyst, the total mass of metal is 2%, the mass of manganese is 0.4%, the mass of iron is 1.6% and the doping amount of nitrogen element is 5.7% based on 100% of the mass of biochar (carbon-based material).
Example 5
A composite catalyst and a preparation method thereof, the specific preparation steps are as follows:
the method comprises the steps of (1) putting the activity Jiao Jinzi into a mixed aqueous solution of manganese nitrate and cerium nitrate, wherein the molar ratio of manganese metal to cerium metal in the mixed aqueous solution is 2:1, and the mass ratio of the total mass of manganese and cerium to active coke is 20:100; soaking for 12h at room temperature by adopting an isovolumetric soaking method, and then drying for 12h at 110 ℃; placing the dried sample in a tube furnace, introducing nitrogen for protection, heating to 500 ℃ and roasting for 3 hours; then ammonia gas is continuously introduced into the tubular furnace at the rate of 80mL/min, and the catalyst is roasted for 2 hours at 400 ℃ to obtain the composite catalyst.
In the composite catalyst, the total mass of metal is 20%, the mass of manganese is 8.8%, the mass of cerium is 11.2% and the doping amount of nitrogen element is 1.0% based on 100% of the mass of active coke (carbon-based material).
Example 6
A composite catalyst and a preparation method thereof, the specific preparation steps are as follows:
(1) Immersing active carbon in a mixed aqueous solution of manganese nitrate and ferric nitrate, wherein the molar ratio of manganese metal to iron metal in the mixed aqueous solution is 3:1, and the mass ratio of the total mass of manganese and iron to the active carbon is 12:100; soaking for 12 hours at room temperature by adopting an isovolumetric soaking method, and then drying for 12 hours at 110 ℃ to obtain a pretreated sample;
(2) Uniformly mixing the pretreated sample obtained in the step (1) with ammonium chloride to ensure that the mass ratio of nitrogen in the ammonium chloride to active carbon in the carrier is 10:100; and placing the mixed sample in a tube furnace, and heating to 800 ℃ in an oxygen-free environment to bake for 5 hours to obtain the composite catalyst.
In the composite catalyst, the total mass of metal is 12%, the mass of manganese is 9.0%, the mass of iron is 3.0% and the doping amount of nitrogen element is 6.0% based on 100% of the mass of active carbon (carbon-based material).
Example 7
A composite catalyst and a preparation method thereof, the specific preparation steps are as follows:
immersing active carbon in a mixed aqueous solution of manganese nitrate and ferric nitrate, wherein the molar ratio of manganese metal to iron metal in the mixed aqueous solution is 3:1, and the mass ratio of the total mass of manganese and iron to the active carbon is 12:100; soaking for 12h at room temperature by adopting an isovolumetric soaking method, and then drying for 12h at 110 ℃; and placing the dried sample in a tube furnace, continuously introducing ammonia gas into the tube furnace at a rate of 120mL/min, and heating to 800 ℃ for roasting for 5 hours to obtain the composite catalyst.
In the composite catalyst, the total mass of metal is 12%, the mass of manganese is 9.0%, the mass of iron is 3.0% and the doping amount of nitrogen element is 6.0% based on 100% of the mass of active carbon (carbon-based material).
Example 8
A composite catalyst and a preparation method thereof, the specific preparation steps are as follows:
(1) Immersing active carbon in a manganese nitrate aqueous solution, wherein the mass ratio of manganese to biochar is 12:100; soaking for 12 hours at room temperature by adopting an isovolumetric soaking method, and then drying for 12 hours at 110 ℃ to obtain a pretreated sample;
(2) Uniformly mixing the pretreated sample obtained in the step (1) with ammonium chloride to ensure that the mass ratio of nitrogen in the ammonium chloride to active carbon in the carrier is 9:100; and placing the mixed sample in a tube furnace, and heating to 800 ℃ in an oxygen-free environment to bake for 5 hours to obtain the composite catalyst.
In the composite catalyst, the mass of manganese is 12% and the doping amount of nitrogen element is 6.0% based on 100% of the mass of active carbon (carbon-based material).
Comparative example 1
A composite catalyst and a preparation method thereof, the specific preparation steps are as follows:
immersing active carbon in a mixed aqueous solution of manganese nitrate and ferric nitrate, wherein the molar ratio of manganese to iron in the mixed aqueous solution is 3:1, and the mass ratio of the total mass of manganese and iron to the active carbon is 12:100; soaking for 12h at room temperature by adopting an isovolumetric soaking method, and then drying for 12h at 110 ℃; and (3) placing the dried sample in a tube furnace, introducing nitrogen for protection, and heating to 800 ℃ for roasting for 5 hours to obtain the composite catalyst.
In the composite catalyst, the total mass of metal is 12%, the mass of manganese is 9.0% and the mass of iron is 3.0% based on 100% of the mass of active carbon (carbon-based material).
Comparative example 2
A composite catalyst and a preparation method thereof, the specific preparation steps are as follows:
immersing active carbon in a mixed aqueous solution of manganese nitrate and ferric nitrate, wherein the molar ratio of manganese metal to iron metal in the mixed aqueous solution is 3:1, and the mass ratio of the total mass of manganese and iron to the active carbon is 18:100; soaking for 12h at room temperature by adopting an isovolumetric soaking method, and then drying for 12h at 110 ℃; and (3) placing the dried sample in a tube furnace, introducing nitrogen for protection, and heating to 800 ℃ for roasting for 5 hours to obtain the composite catalyst.
In the composite catalyst, the total mass of metal is 18%, the mass of manganese is 13.5% and the mass of iron is 4.5% based on 100% of the mass of active carbon (carbon-based material).
Comparative example 3
A composite catalyst and a preparation method thereof, the specific preparation steps are as follows:
(1) Immersing active carbon in a mixed aqueous solution of manganese nitrate and ferric nitrate, wherein the molar ratio of manganese metal to iron metal in the mixed aqueous solution is 3:1, and the mass ratio of the total mass of manganese and iron to the active carbon is 12:100; soaking for 12 hours at room temperature by adopting an isovolumetric soaking method, and then drying for 12 hours at 110 ℃ to obtain a pretreated sample;
(2) Uniformly mixing the pretreated sample obtained in the step (1) with melamine to ensure that the mass ratio of nitrogen in the melamine to active carbon in the carrier is 6:100; and placing the mixed sample in a tube furnace, and heating to 800 ℃ in an oxygen-free environment to bake for 5 hours to obtain the composite catalyst.
In the composite catalyst, the total mass of metal is 12%, the mass of manganese is 9.0%, the mass of iron is 3.0% and the doping amount of nitrogen element is 6.0% based on 100% of the mass of active carbon (carbon-based material).
Comparative example 4
A metal-free doped catalyst and a preparation method thereof, comprising the following specific preparation steps:
10g of active carbon is placed in a tubular furnace, ammonia gas is continuously introduced into the tubular furnace at the rate of 250mL/min, and the temperature is raised to 800 ℃ for roasting for 6 hours, so that the composite catalyst is obtained.
In the composite catalyst, the doping amount of nitrogen element is 17.9% based on 100% of the mass of active carbon (carbon-based material).
Comparative example 5
A composite catalyst and a preparation method thereof, the specific preparation steps are as follows:
(1) Immersing active carbon in a mixed aqueous solution of manganese nitrate and ferric nitrate, wherein the molar ratio of manganese metal to iron metal in the mixed aqueous solution is 3:1, and the mass ratio of the total mass of manganese and iron to the active carbon is 12:100; soaking for 12 hours at room temperature by adopting an isovolumetric soaking method, and then drying for 12 hours at 110 ℃ to obtain a pretreated sample;
(2) Uniformly mixing the pretreated sample obtained in the step (1) with melamine to ensure that the mass ratio of nitrogen in the melamine to active carbon in the carrier is 6:100; and placing the mixed sample in a tube furnace, heating to 800 ℃ in an anaerobic environment, roasting for 5 hours, continuously introducing reducing gas (carbon monoxide and argon are mixed in a volume ratio of 4:1) into the tube furnace at a rate of 100mL/min, and continuously roasting for 5 hours to obtain the composite catalyst.
In the composite catalyst, the total mass of metal is 12%, the mass of manganese is 9.0%, the mass of iron is 3.0% and the doping amount of nitrogen element is 6% based on 100% of the mass of active carbon (carbon-based material).
Comparative example 6
Carbon-based activated carbon is used as a catalyst.
Performance test:
catalytic ozonation of industrial wastewater in a stainless steel column reactor with an effective volume of 5L, and COD of wastewater Cr The concentration is 180-220 mg/L. The composite catalysts of the above examples and comparative examples were used, respectively, and the loading volumes of the composite catalysts were the same. The ozone adding amount is 50mg/min, and the reaction residence time is 25min; analysis of COD in Water inflow and Water outflow Cr Concentration to calculate COD removal rate, COD removal rate=100% × (COD of water intake Cr Effluent COD Cr ) COD of the incoming water Cr 。
The composite catalyst is recycled for 72 hours under the same operation parameters and the quality of the inlet water, and the COD removal rate after 72 hours of continuous use is tested and compared with the COD removal rate when in first use, so that the composite catalyst is used as the judgment basis of the stability of the composite catalyst.
The specific test results are shown in table 1.
TABLE 1
| Catalyst | COD of the incoming water Cr (mg/L) | First COD removal rate | COD removal rate after circulation |
| Example 1 | 210 | 59.7％ | 59.3％ |
| Example 2 | 187 | 67.2％ | 68.2％ |
| Example 3 | 201 | 59.1％ | 57.9％ |
| Example 4 | 183 | 51.5％ | 51.8％ |
| Example 5 | 195 | 57.6％ | 56.3％ |
| Example 6 | 207 | 65.4％ | 63.7％ |
| Example 7 | 197 | 66.7％ | 65.2％ |
| Example 8 | 213 | 62.5％ | 61.0％ |
| Comparative example 1 | 199 | 50.3％ | 50.5％ |
| Comparative example 2 | 196 | 55.7％ | 50.3％ |
| Comparative example 3 | 202 | 55.0％ | 46.9％ |
| Comparative example 4 | 210 | 52.7％ | 46.2％ |
| Comparative example 5 | 198 | 56.7％ | 47.3％ |
| Comparative example 6 | 191 | 47.9％ | 45.3％ |
According to the test data in table 1, compared with the original carbon-based material (comparative example 6), the composite catalysts obtained by the preparation methods provided by examples 1 to 8 of the present invention simultaneously load metal oxide and nitrogen element, and the metal oxide and nitrogen element cooperate to significantly improve the catalytic activity and activity stability of the catalyst. Meanwhile, if only one of the metal oxide or nitrogen element is supported on the carbon-based material (comparative examples 1, 2, 4), the catalytic activity is improved as compared with the original carbon-based material, but is far lower than that of the composite catalyst in which the metal oxide and nitrogen element are simultaneously supported in the examples.
According to the preparation method disclosed by the invention, ammonia gas or inorganic ammonium salt is used as a nitrogen-containing precursor, the nitrogen-containing precursor has weak reducibility, a proper amount of oxygen vacancies can be formed on the metal oxide, the catalytic activity and stability of the composite catalyst are further improved, and if an organic nitrogen-containing precursor (comparative example 3) is used, the activity and stability of the composite catalyst are obviously reduced. In addition, if oxygen vacancies are made with a strongly reducing gas (comparative example 5), the valence and crystal form of the metal oxide are changed, resulting in a higher degree of reduction of the metal oxide, which in turn reduces the activity and stability of the composite catalyst.
The applicant states that the present invention is illustrated by the above examples as well as the preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (29)
1. A method for preparing a composite catalyst for catalyzing ozone oxidation, which is characterized by comprising the following steps: loading metal oxide and doping nitrogen element on the carbon-based material to obtain the composite catalyst; the nitrogen-containing precursor doped with nitrogen element is ammonia gas and/or inorganic ammonium salt;
the method for loading the metal oxide comprises the following steps: soaking the carbon-based material in a metal precursor solution, drying and roasting to obtain a metal oxide-loaded carbon-based material;
the carbon-based material is selected from any one or a combination of at least two of active carbon, active coke, biological carbon, graphene materials or carbon nano tubes;
the metal in the metal oxide is any one or the combination of two of iron, cobalt, manganese, nickel, copper, lanthanum, cerium, molybdenum and titanium;
the method for doping nitrogen element is a method A or a method B;
the method A comprises the following steps: taking any one of a carbon-based material loaded with metal oxide or a carbon-based material impregnated with a metal precursor as a carrier, uniformly mixing the carrier with inorganic ammonium salt, and roasting in an anaerobic environment to obtain the composite catalyst; the method B comprises the following steps: roasting any one of a carbon-based material loaded with metal oxide or a carbon-based material impregnated with a metal precursor in an ammonia atmosphere to obtain the composite catalyst;
in the method A and the method B, the roasting temperature is respectively and independently 300-900 ℃, and the roasting time is respectively and independently 2-6 h.
2. The method of claim 1, wherein the carbon-based material is activated carbon and/or biochar.
3. The method of claim 1, wherein the metal precursor solution is an aqueous solution of a metal salt.
4. A method of preparing according to claim 3, wherein the metal salt is a metal inorganic salt.
5. The method according to claim 3, wherein the metal salt is any one or a combination of at least two of metal nitrate, metal sulfate or metal halide.
6. The production method according to claim 1, wherein the mass of the metal in the metal precursor solution is 0.5 to 20% based on 100% of the mass of the carbon-based material.
7. The production method according to claim 1, wherein the mass of the metal in the metal precursor solution is 2 to 15% based on 100% of the mass of the carbon-based material.
8. The method of claim 1, wherein the impregnation method is an isovolumetric impregnation method.
9. The method according to claim 1, wherein the temperature of the impregnation is 15 to 45 ℃.
10. The method according to claim 1, wherein the time of the impregnation is 8 to 24 hours.
11. The method according to claim 1, wherein the drying temperature is 100 to 120 ℃.
12. The method according to claim 1, wherein the drying time is 5 to 24 hours.
13. The method according to claim 1, wherein the calcination temperature in the preparation of the supported metal oxide is 300 to 900 ℃.
14. The method according to claim 1, wherein the calcination time in the preparation of the supported metal oxide is 0.5 to 5 hours.
15. The method according to claim 1, wherein the calcination in the preparation of the supported metal oxide is performed in vacuum or in a protective atmosphere, which is an inert atmosphere and/or a reducing atmosphere.
16. The method of claim 15, wherein the inert atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere.
17. The method of claim 15, wherein the reducing atmosphere comprises an ammonia atmosphere.
18. The method according to claim 1, wherein the nitrogen-containing precursor is ammonia gas, and the ammonia gas is used in an amount of 900 to 60000mL based on 1g of the carbon-based material.
19. The production method according to claim 1, wherein the nitrogen-containing precursor is an inorganic ammonium salt, and the mass of nitrogen in the inorganic ammonium salt is 0.1 to 15% based on 100% of the mass of the carbon-based material.
20. The method according to claim 1, wherein the inorganic ammonium salt is selected from any one or a combination of at least two of ammonium chloride, ammonium bicarbonate, ammonium carbonate, ammonium nitrate, and ammonium sulfate.
21. The preparation method according to claim 1, characterized in that it comprises the following steps:
(1) Placing a carbon-based material into a metal inorganic salt solution, soaking for 8-24 hours at room temperature by an isovolumetric soaking method, and drying for 5-24 hours at 100-120 ℃ to obtain a pretreated sample;
(2) Doping nitrogen element into the pretreated sample obtained in the step (1), wherein the doping method comprises a method A or a method B, and the composite catalyst is obtained.
22. The preparation method according to claim 1, characterized in that it comprises the following steps:
(S1) placing a carbon-based material into a metal inorganic salt solution, soaking for 8-24 h at room temperature by an isovolumetric soaking method, and drying for 5-24 h at 100-120 ℃; roasting the dried sample at 300-900 ℃ for 0.5-5 h in an inert atmosphere to obtain a carbon-based material loaded with metal oxide;
and (S2) doping nitrogen element into the carbon-based material loaded with the metal oxide obtained in the step (S1), wherein the doping method comprises a method A or a method B, and the composite catalyst is obtained.
23. A composite catalyst prepared by the preparation method according to any one of claims 1 to 22.
24. The composite catalyst according to claim 23, wherein the mass of the metal in the metal oxide is 0.5 to 20% based on 100% of the mass of the carbon-based material in the composite catalyst.
25. The composite catalyst according to claim 23, wherein the mass of the metal in the metal oxide is 2 to 15% based on 100% of the mass of the carbon-based material in the composite catalyst.
26. The composite catalyst according to claim 23, wherein the mass of the nitrogen element is 0.1 to 15% based on 100% of the mass of the carbon-based material in the composite catalyst.
27. The composite catalyst according to claim 23, wherein the mass of the nitrogen element is 1 to 8% based on 100% of the mass of the carbon-based material in the composite catalyst.
28. Use of a composite catalyst according to any one of claims 23 to 27 for catalytic ozonation.
29. The use of claim 28, wherein the composite catalyst is used for catalytic ozonation of wastewater.
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| CN116851019A (en) * | 2023-06-13 | 2023-10-10 | 杭州司迈特水处理工程有限公司 | Efficient composite ozone catalyst and preparation method thereof |
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