CN114700062A - 一种多孔碳气凝胶耐盐臭氧催化剂的制备方法及其应用 - Google Patents
一种多孔碳气凝胶耐盐臭氧催化剂的制备方法及其应用 Download PDFInfo
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- CN114700062A CN114700062A CN202210459642.2A CN202210459642A CN114700062A CN 114700062 A CN114700062 A CN 114700062A CN 202210459642 A CN202210459642 A CN 202210459642A CN 114700062 A CN114700062 A CN 114700062A
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- nitrate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 60
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000017 hydrogel Substances 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 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 claims description 14
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 238000003763 carbonization Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 239000012267 brine Substances 0.000 claims description 8
- 239000000499 gel Substances 0.000 claims description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 229920005610 lignin Polymers 0.000 claims description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000495 cryogel Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 229910016287 MxOy Inorganic materials 0.000 claims description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229920002101 Chitin Polymers 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 229920002488 Hemicellulose Polymers 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- LBGACZYWAQIGPS-UHFFFAOYSA-N [Fr+].[O-][N+]([O-])=O Chemical compound [Fr+].[O-][N+]([O-])=O LBGACZYWAQIGPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 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 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000015784 hyperosmotic salinity response Effects 0.000 abstract description 2
- 238000006053 organic reaction Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 18
- 238000001179 sorption measurement Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000004964 aerogel Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000000352 supercritical drying Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- 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
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- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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Abstract
本发明公开一种多孔碳气凝胶耐盐臭氧催化剂的制备方法及其应用,该方法在高速搅拌条件下,首先将碳材料溶液浓缩至1~1000mg/mL,然后在密封条件下与10~1000mL1~500mg/mL硝酸盐溶液混合,依次经过冻干、碳化、水洗和常压干燥,使得多孔碳气凝胶催化剂官能团高度分散。本发明利用碳气凝胶催化剂高效催化各种有机反应的进行,具有快速高效、工艺简便、收率高、高选择性、高循环性等特点。负载金属氧化物可使催化剂具有良好的耐盐性,对高浓盐废水(TDS为1%~10%)中COD去除率可提高20%~60%。
Description
技术领域
本发明涉及催化剂的制备技术领域,具体涉及一种多孔碳气凝胶耐盐臭氧催化剂的制备方法及其应用。
背景技术
碳气凝胶是一种新型的轻质多孔材料,因其具有稳定性好、孔隙率高、比表面积大、导电率高及较多的物质及电子传输孔道的特点,广泛用作催化剂载体、储氢材料、吸附材料及超级电容器或锂离子电池的电极材料等,有利于解决当今社会的能源危机及环境污染问题而成为研究热点。
现有碳气凝胶制备方法的缺陷在于制备凝胶时必须有碱性催化剂的催化,当催化剂浓度较高时凝胶在超临界干燥和碳化过程中均有很大收缩,难以得到低密度的碳气凝胶,而当催化剂浓度较低时往往得不到凝胶,而且制备周期长、工艺复杂,难以控制且往往伴随不安全因素。如Pekala等人所发明的美国专利号为US19890406009,US19880199404,这一制备方法需要经过冗长而复杂的制备周期,采取的二氧化碳超临界干燥制备技术大大增加了生产成本,且不环保,制约了碳气凝胶的产业化生产和全面广泛的应用。
近年来,碳气凝胶的工作已经得到了一定的发展和重视,但是其催化剂方面的研究却发展相对缓慢。如何高效、简单、高循环地利用碳催化剂快速、高选择性地催化有机反应仍然是一项重大挑战。
高浓盐水往往伴随着高COD,对于此类废水的处理,由于盐浓度对微生物的抑制作用,生化法一般难以奏效。活性炭吸附法对有机物去除效果显著,但活性炭吸附容量有限,吸附饱和后再生困难,导致运行费用偏高。多相臭氧催化氧化法通过产生强氧化性的羟基自由基,对水中难降解、高稳定性的有机污染物进行氧化降解,不产生二次污染,成为高浓盐水中有机污染物去除的关键技术之一。相关研究表明,金属氧化物的表面酸碱位和表面羟基基团被认为是臭氧分解的活性位点。在高浓盐水中,由于Cl-、SO4 2-、CO3 2-等阴离子的吸附,占据活性位点,使得臭氧催化剂活性下降。现有的臭氧催化剂在高浓盐水中有机物去除效果不佳,不具备耐盐的性能。
发明内容
针对现有技术存在的上述不足,本发明的目的在于提供一种多孔碳气凝胶耐盐臭氧催化剂的制备方法,解决现有碳气凝胶催化剂不具有耐盐性、催化效率低、成本高且制备周期长、工艺复杂,难以控制的问题。
进一步提供该多孔碳气凝胶耐盐臭氧催化剂的应用。
为了解决上述技术问题,本发明采用的技术方案如下:
一种多孔碳气凝胶耐盐臭氧催化剂的制备方法,包括以下步骤:
(1)制备冷冻凝胶:将碳材料溶液浓缩至1~1000mg/mL,预冷至-5~0℃,在10~3000rpm的搅拌速度下加入10~1000mL 1~500mg/mL硝酸盐溶液,密封后放入烘箱中,在20~70℃定型4~18h,得到含有硝酸盐的碳材料水凝胶;将其放入去离子水中再生,至去离子水与水凝胶表面呈中性,然后放入冷冻干燥器中,在-100~0℃下冷冻干燥2~36h,制得冷冻凝胶;
(2)制备多孔碳气凝胶:将碳材料冷冻凝胶置于反应炉中,以1~60mL/min的速率通入惰性保护气,在800~1500℃保温0.5~8h进行高温炭化热解,在炭化开始10~120min后,通入活化气体对碳气凝胶进行活化造孔,待反应炉自然冷却到室温,将产物浸于水中,使用滤膜抽滤,用去离子水洗涤至滤液呈中性,常压干燥,即得负载金属氧化物MxOy的多孔碳气凝胶。所述惰性保护气为氦气、氖气、氩气、氪气、氙气或氡气中的任意一种。
进一步,步骤(1)所述碳材料包括纤维素、木质素、壳聚糖、半纤维素、木糖醇、淀粉、甲壳质、氧化石墨、氧化石墨烯、石墨烯、碳纳米管、多孔氧化石墨烯或羧化碳管。
进一步,步骤(1)中所述的硝酸盐包括硝酸镁、硝酸钾、硝酸铷、硝酸铁、硝酸钴、硝酸锂、硝酸铯、硝酸钫、硝酸锌、硝酸镧、硝酸铈、硝酸铜、硝酸钡、硝酸铝、硝酸锶、硝酸锰或硝酸钙的一种或多种。
进一步,步骤(1)中所述的冷冻干燥采用液氮处理。
进一步,步骤(2)所述高温碳化热解的升温速率为1.4~6.8℃/min。
进一步,步骤(2)所述活化气体包括水蒸气或/和烟道气;通入活性气体的流量为1~100mL/min;持续时间为0.1~20min。
进一步,步骤(2)中所述的金属氧化物MxOy中,x取值范围为1~3,y的取值范围为0~3.5。
一种多孔碳气凝胶耐盐臭氧催化剂,采用所述制备方法得到,其具备如下参数:比表面积达600~950m2·g -1 ,孔隙率高达75%~98%,孔径2.5~8.0nm。
一种多孔碳气凝胶耐盐臭氧催化剂的应用,将所述方法制得的耐盐多孔碳气凝胶催化剂用于催化臭氧,去除TDS为1%~10%的高浓盐水中难降解有机物。
与现有技术相比,本发明具有如下有益效果:
1、本发明在高速搅拌条件下,首先将碳材料溶液进行浓缩,然后与硝酸盐溶液混合来负载金属氧化物,与传统的将成型的多孔碳气凝胶整体浸渍于过渡金属盐溶液的负载方式相比,本发明的制备方法可显著提高过渡金属在气凝胶中的分散性,使催化剂的活性位点高度分散在多孔碳气凝胶上,提高催化效率。
2、本发明多孔碳气凝胶耐盐臭氧催化剂是以碱金属与碱土金属氧化物为主要活性组分的催化剂,利用其高活性的表面碱性位,优先催化O3生成强氧化性自由基,对高浓盐水中的Cl-、SO4 2-、CO3 2-等阴离子吸附作用弱。克服了在高浓盐水中,现有的臭氧催化剂不具备耐盐的性能,由于Cl-、SO4 2-、CO3 2-等阴离子的吸附,占据活性位点,使得臭氧催化剂活性下降的问题,从而提高有机物的去除效率。
3、本发明的多孔碳气凝胶催化剂催化活性高,稳定性强,适合各种工况下的水质,对高浓盐废水(TDS为1%-10%)中COD去除率可提高20%-60%。具有高效去除有机物,使高浓盐水降低到易于生物降解的趋势。
4、本发明的催化剂可采用的碳材料种类多,成本低,由其负载金属氧化物制备多孔碳气凝胶,工艺简单,操作方便,克服了现有碳气凝胶制法生产成本高昂、催化剂强度低、副反应产物多,存在较多不安全因素的问题,推动实现碳气凝胶的产业化生产和全面广泛的应用。
5、本发明中碳气凝胶制法可使气凝胶的制备和过渡金属的负载同步实现,提高效率,克服了传统制法中制作周期长、操作繁杂的问题。
具体实施方式
为了使本领域技术人员更好地理解本发明的技术方案,下面结合具体实施例对本发明作进一步的说明,但本发明的实施方式不仅限于此。
实施例1
(1)将纤维素溶液浓缩到1000mg/mL,然后在10rpm的搅拌速度下加入1000mL,500mg/mL硝酸镁溶液,密封后在60℃烘箱放置18h,制得含有硝酸镁的纤维素水凝胶;将其放入去离子水中再生,至去离子水与水凝胶表面呈中性;
(2)将含有硝酸镁的纤维素水凝胶放入冷冻干燥器中冷冻干燥36h,温度为-100℃,制得含有硝酸镁的纤维素冷冻凝胶;
(3)将包含硝酸镁的纤维素冷冻凝胶置于反应炉中,先通入100min氮气,然后以60mL/min的速率不断通入氦气。从室温以5.8℃/min速率升温到1500℃后保持8h,在炭化开始120min后,通入烟道气对碳气凝胶进行活化造孔,通入活性气体的流量为100mL/min;持续时间为20min,再缓慢降至室温,将产物浸于水中,使用滤膜抽滤,用去离子水洗涤至滤液呈中性,常压干燥,即制得黑色负载MgO的多孔碳气凝胶。
本实施例制备的多孔碳气凝胶耐盐臭氧催化剂的催化性能评价通过以下方式实现:利用臭氧催化氧化处理某煤化工企业反渗透浓水,TDS为18800mg/L,COD为300mg/L,臭氧投加量200mg/L,反应时间为60min,加入普通臭氧催化剂(以二氧化锰、三氧化二铁为催化活性组分),COD由300mg/L降低到260mg/L;利用本实施例制备的多孔碳气凝胶耐盐臭氧催化剂,COD由300mg/L降低到180mg/L,COD去除效率提高26.67%。
实施例2
(1)将氧化石墨烯溶液浓缩到1mg/mL,在10rpm搅拌条件下加入100mL,1mg/mL硝酸锰溶液,密封后在20℃烘箱放置4h,制得含有硝酸锰的氧化石墨烯水凝胶;将其放入去离子水中再生,至去离子水与水凝胶表面呈中性;
(2)将含有硝酸锰的氧化石墨烯水凝胶放入冷冻干燥器中冷冻干燥30h,温度为-100℃,制得含有硝酸锰的氧化石墨烯冷冻凝胶;
(3)将包含硝酸锰的氧化石墨烯冷冻凝胶置于反应炉中,先通入1min氮气,然后以1mL/min的速率不断通入氦气。从室温以1.4℃/min速率升温到800℃后保持0.5h,在炭化开始10min后,通入水蒸气对碳气凝胶进行活化造孔,通入活性气体的流量为1mL/min;持续时间为0.1min,再缓慢降至室温,将产物浸于水中,使用滤膜抽滤,用去离子水洗涤至滤液呈中性,常压干燥,即制得黑色负载MnO的多孔碳气凝胶。
本实施例制备的多孔碳气凝胶耐盐臭氧催化剂的催化性能评价通过以下方式实现:利用臭氧催化氧化处理某煤化工企业反渗透浓水,TDS为18800mg/L,COD为300mg/L,臭氧投加量200mg/L,反应时间为60min,加入普通臭氧催化剂(以二氧化锰、三氧化二铁为催化活性组分),COD由300mg/L降低到260mg/L;利用本实施例制备的多孔碳气凝胶耐盐臭氧催化剂,COD由300mg/L降低到200mg/L,COD去除效率提高20%。
实施例3
(1)将木质素溶液浓缩到500mg/mL,在3000rpm搅拌条件下加入100mL,500mg/mL硝酸铈溶液,密封后在20℃烘箱放置18h,制得含有硝酸铈的木质素水凝胶;将其放入去离子水中再生,至去离子水与水凝胶表面呈中性;
(2)将含有硝酸铈的木质素水凝胶放入冷冻干燥器中冷冻干燥36h,温度为-100℃,制得含有硝酸铈的木质素冷冻凝胶;
(3)将包含硝酸铈的木质素冷冻凝胶置于反应炉中,先通入50min氮气,然后以60mL/min的速率不断通入氦气。从室温以1.4℃/min速率升温到800℃后保持8h,在炭化开始60min后,通入水蒸气对碳气凝胶进行活化造孔,通入活性气体的流量为50mL/min;持续时间为10min,再缓慢降至室温,将产物浸于水中,使用滤膜抽滤,用去离子水洗涤至滤液呈中性,常压干燥,即制得黑色负载CeO的多孔碳气凝胶。
本实施例制备的多孔碳气凝胶耐盐臭氧催化剂的催化性能评价通过以下方式实现:利用臭氧催化氧化处理某煤化工企业反渗透浓水,TDS为42800mg/L,COD为220mg/L,臭氧投加量150mg/L,反应时间为60min,加入普通臭氧催化剂(以二氧化锰、三氧化二铁为催化活性组分),COD由220mg/L降低到180mg/L;利用本实施例制备的多孔碳气凝胶耐盐臭氧催化剂,COD由220mg/L降低到130mg/L,COD去除效率提高22.9%。
此外,本发明多孔碳气凝胶耐盐臭氧催化剂的制备方法及其应用,还具有如下优点:
(1)本发明可防止浸渍时多孔碳气凝胶自身存在的孔道对过渡金属的扩散会产生阻碍作用,从而导致过渡金属在多孔碳上分布不均,降低催化剂性能,克服了现有臭氧催化剂活性金属易流失、制备原料利用率低的问题。
(2)本发明获得的催化剂属于固体气凝胶整体式催化剂,克服了传统的粉末状催化剂反应完成后,产物与催化剂的分离需要反复的离心洗涤,催化剂流失快,后处理过程比较复杂的问题,易于分离回收,循环利用。有效防止在催化降解过程中由于分离不完全造成的二次污染的问题。
(3)本发明获得的碳气凝胶催化剂在溶液中有很好的分散性,反应体系不需要搅拌即可实现高效催化。当催化剂在长期应用过程中发生磨损或活性组分流失的情况下,催化剂依然能保持优良的催化活性。
(4)本发明采用碳气凝胶作为催化剂载体,克服了现有催化剂由于金属颗粒依靠物理吸附作用与载体结合,催化剂的使用寿命较短的问题,对设备要求低,环境友好。
(5)本发明制备的催化剂稳定性好,催化活性高,比表面积高,孔隙率高,密度低,增加了载体的可负载面积,提高催化剂与臭氧的接触面积,加快自由基的生成速率,进而加快污水中有机物的氧化速率,有效提升催化剂对臭氧的催化分解性能,可广泛应用于臭氧催化氧化领域,有很好的市场前景。
(6)本发明的制备的催化剂以多孔碳气凝胶为载体,本身具有良好的吸附作用,可以联合臭氧催化氧化技术进一步降解高浓盐水。
(7)本发明在高温碳化处理的同时,适当通入活性气体,进行活化造孔,进一步增大所得碳气凝胶的比表面积,大大增大了碳气凝胶的比表面积,弥补了常压干燥过程中产生较大的毛细管压力差。
最后需要说明的是,以上实施例仅用以说明本发明的技术方案而非限制技术方案,本领域的普通技术人员应当理解,那些对本发明的技术方案进行修改或者等同替换,而不脱离本技术方案的宗旨和范围,均应涵盖在本发明的权利要求范围当中。
Claims (9)
1.一种多孔碳气凝胶耐盐臭氧催化剂的制备方法,其特征在于,包括以下步骤:
(1)制备冷冻凝胶:将碳材料溶液浓缩至1~1000mg/mL,预冷至-5~0℃,在10~3000rpm的搅拌速度下加入10~1000mL 1~500mg/mL硝酸盐溶液,密封后放入烘箱中,在20~70℃定型4~18h,得到含有硝酸盐的碳材料水凝胶;将其放入去离子水中再生,至去离子水与水凝胶表面呈中性,然后放入冷冻干燥器中,在-100~0℃下冷冻干燥2~36h,制得冷冻凝胶;
(2)制备多孔碳气凝胶:将碳材料冷冻凝胶置于反应炉中,以1~60mL/min的速率通入惰性保护气,在800~1500℃保温0.5~8h进行高温炭化热解,在炭化开始10~120min后,通入活化气体对碳气凝胶进行活化造孔,待反应炉自然冷却到室温,将产物浸于水中,使用滤膜抽滤,用去离子水洗涤至滤液呈中性,常压干燥,即得负载金属氧化物MxOy的多孔碳气凝胶。
2.根据权利要求1所述多孔碳气凝胶耐盐臭氧催化剂的制备方法,其特征在于:步骤(1)所述碳材料包括纤维素、木质素、壳聚糖、半纤维素、木糖醇、淀粉、甲壳质、氧化石墨、氧化石墨烯、石墨烯、碳纳米管、多孔氧化石墨烯或羧化碳管。
3.根据权利要求1所述多孔碳气凝胶耐盐臭氧催化剂的制备方法,其特征在于:步骤(1)中所述的硝酸盐包括硝酸镁、硝酸钾、硝酸铷、硝酸铁、硝酸钴、硝酸锂、硝酸铯、硝酸钫、硝酸锌、硝酸镧、硝酸铈、硝酸铜、硝酸钡、硝酸铝、硝酸锶、硝酸锰或硝酸钙的一种或多种。
4.根据权利要求1所述多孔碳气凝胶耐盐臭氧催化剂的制备方法,其特征在于:步骤(1)中所述的冷冻干燥采用液氮处理。
5.根据权利要求1所述多孔碳气凝胶耐盐臭氧催化剂的制备方法,其特征在于:步骤(2)所述高温碳化热解的升温速率为1.4~6.8℃/min。
6.根据权利要求1所述多孔碳气凝胶耐盐臭氧催化剂的制备方法,其特征在于:步骤(2)所述活化气体包括水蒸气或/和烟道气;通入活性气体的流量为1~100mL/min;持续时间为0.1~20min。
7.根据权利要求1所述多孔碳气凝胶耐盐臭氧催化剂的制备方法,其特征在于:步骤(2)中所述的金属氧化物MxOy中,x取值范围为1~3,y的取值范围为0~3.5。
8.一种多孔碳气凝胶耐盐臭氧催化剂,其特征在于:由权利要求1~7任意项所述的制备方法得到,其具备如下参数:比表面积达600~950m2·g -1 ,孔隙率高达75%~98%,孔径2.5~8.0nm。
9.一种多孔碳气凝胶耐盐臭氧催化剂的应用,其特征在于:将权利要求1~8任一项所述耐盐多孔碳气凝胶催化剂用于催化臭氧,去除TDS为1%~10%的高浓盐水中难降解有机物。
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CN115520852A (zh) * | 2022-11-08 | 2022-12-27 | 华东理工大学 | 一种镍掺杂木质素基多孔碳气凝胶复合材料及其制备方法 |
CN115672311A (zh) * | 2022-10-19 | 2023-02-03 | 西南石油大学 | 一种形状可调的整体式臭氧分解催化剂的制备方法及用途 |
CN115784197A (zh) * | 2022-11-29 | 2023-03-14 | 四川大学 | 一种改性生物质碳气凝胶的制备方法及其产品和应用 |
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