CN109621962B - Metal oxide catalyst with regular morphology for eliminating formaldehyde and preparation method and application thereof - Google Patents
Metal oxide catalyst with regular morphology for eliminating formaldehyde and preparation method and application thereof Download PDFInfo
- Publication number
- CN109621962B CN109621962B CN201811484638.1A CN201811484638A CN109621962B CN 109621962 B CN109621962 B CN 109621962B CN 201811484638 A CN201811484638 A CN 201811484638A CN 109621962 B CN109621962 B CN 109621962B
- Authority
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- China
- Prior art keywords
- metal oxide
- oxide catalyst
- regular morphology
- formaldehyde
- preparation
- Prior art date
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 63
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000012298 atmosphere Substances 0.000 claims abstract description 24
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000004729 solvothermal method Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052734 helium Inorganic materials 0.000 claims description 10
- 239000001307 helium Substances 0.000 claims description 10
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- -1 transition metal salt Chemical class 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- 229910052754 neon Inorganic materials 0.000 claims description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 4
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- QUMITRDILMWWBC-UHFFFAOYSA-N nitroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QUMITRDILMWWBC-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003504 terephthalic acids Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002981 blocking agent Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 23
- 239000007787 solid Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 230000008030 elimination Effects 0.000 description 8
- 238000003379 elimination reaction Methods 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QPBGNSFASPVGTP-UHFFFAOYSA-N 2-bromoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Br)=C1 QPBGNSFASPVGTP-UHFFFAOYSA-N 0.000 description 2
- MXBBZODCMBYDCL-UHFFFAOYSA-N 5-[(3,5-dicarboxyphenyl)diazenyl]benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C(=O)O)=CC(N=NC=2C=C(C=C(C=2)C(O)=O)C(O)=O)=C1 MXBBZODCMBYDCL-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 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
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229940031182 nanoparticles iron oxide Drugs 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 206010029350 Neurotoxicity Diseases 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 231100000060 cardiovascular toxicity Toxicity 0.000 description 1
- 230000007681 cardiovascular toxicity Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 231100000386 immunotoxicity Toxicity 0.000 description 1
- 230000007688 immunotoxicity Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 231100000228 neurotoxicity Toxicity 0.000 description 1
- 230000007135 neurotoxicity Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 231100000828 respiratory toxicity Toxicity 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Images
Classifications
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
Abstract
The invention discloses a metal oxide catalyst with regular morphology for eliminating formaldehyde and a preparation method and application thereof. The metal oxide catalyst with regular morphology for eliminating formaldehyde is obtained by the following preparation method: 1) mixing a transition metal source, an oxygen-containing organic ligand and a solvent, and carrying out a solvothermal reaction to obtain a metal organic framework precursor; 2) and carrying out heat treatment on the metal organic framework precursor in a reducing atmosphere to obtain the metal oxide catalyst with the regular morphology for eliminating the formaldehyde. Simultaneously discloses the application of the metal oxide catalyst with regular morphology in removing formaldehyde in indoor air. The metal oxide catalyst has the characteristics of regular appearance and uniform size, and does not need to introduce a blocking agent in the preparation process, so that the surface is clean and has no interference. The metal oxide catalyst is applied to indoor air to remove formaldehyde, and has the characteristics of low cost, high activity and long service life.
Description
Technical Field
The invention relates to a metal oxide catalyst with regular morphology for eliminating formaldehyde and a preparation method and application thereof,
background
Formaldehyde belongs to a high-volatility organic compound, and is a colorless irritant gas. Indoor formaldehyde mainly comes from building materials, indoor decoration materials, fuel combustion and the like. The toxic effect of formaldehyde on human body is mainly reflected in respiratory toxicity, immunotoxicity, neurotoxicity, cardiovascular toxicity, carcinogenicity and the like. Most of the life time of people is finished indoors, and indoor formaldehyde becomes a high-risk toxic substance and must be strictly eliminated and controlled. Through investigation and research, the average concentration of formaldehyde in newly decorated residential buildings is 0.11mg/m3The content of the formaldehyde is higher than the content of the formaldehyde (0.1 mg/m) specified in indoor air quality standard (GB/T18883-2002) released in China3). For this reason, various techniques for controlling and eliminating formaldehyde have been widely studied.
In the current technology for indoor formaldehyde purification, the catalytic oxidation process can completely oxidize formaldehyde into CO2And H2O, does not produce secondary pollution, is the most thorough method for removing formaldehyde, and has important practical application value. The currently developed catalyst usually needs to load noble metals such as Pt, Pd, Au, Ag and other active components to improve the activity of catalytic oxidation of formaldehyde at room temperature, but the development of the catalyst is limited due to the common problems of rare noble metal resources and high price and higher cost. Therefore, non-noble metal catalysts have received much attention from scientists, but their wide application is still restricted by poor catalytic activity at room temperature.
In recent years, scientists have attempted to maximize catalytic activity by increasing the density of active sites on the surface of the oxide by exposing specific crystal planes of the metal oxide. Xie et al (Nature 458(2009)746-749) research found structured Co3O4More (110) crystal face is exposed, and the reaction rate is that of conventional Co3O4More than 10 times of the nanoparticles, and exhibits excellent structural stability. Mou et al (Angewandte Chemie International Edition 51(2012)2989-2993) By control of crystal phase and morphology in Fe2O3Selectively exposing (110) and (001) crystal faces in the material, in NH3Excellent activity and anti-poisoning ability in SCR reactions.
However, the catalyst disclosed in the prior art still has the limitations of complicated preparation method, low specific surface area and the like, and is not effectively applied in the field of formaldehyde elimination. Therefore, a catalyst for efficiently eliminating formaldehyde is still yet to be developed by industrial workers.
Disclosure of Invention
In order to overcome the technical problems in the prior art, the invention develops a composite material of transition metal oxide nanoparticles and porous carbon with regular shapes, enhances the efficient activation of exposed crystal face active sites on formaldehyde molecules, and improves the room temperature catalytic activity of the transition metal oxide.
The technical scheme adopted by the invention is as follows:
a preparation method of a metal oxide catalyst with regular morphology for eliminating formaldehyde comprises the following steps:
1) mixing a transition metal source, an oxygen-containing organic ligand and a solvent, and carrying out a solvothermal reaction to obtain a metal organic framework precursor;
2) and carrying out heat treatment on the metal organic framework precursor in a reducing atmosphere to obtain the metal oxide catalyst with the regular morphology for eliminating the formaldehyde.
Preferably, in step 1) of the preparation method of the metal oxide catalyst with regular morphology for eliminating formaldehyde, the transition metal source is at least one of transition metal and transition metal salt.
Further preferably, the transition metal is at least one selected from iron, cobalt, manganese, and nickel.
Further preferably, the transition metal salt is selected from at least one of nitrate, acetate, sulfate, halide and perhalide of transition metal; still more preferably, the transition metal salt is at least one selected from the group consisting of iron chloride, iron sulfate, iron perchlorate, cobalt chloride, cobalt nitrate, cobalt acetate, manganese chloride, manganese acetate, manganese sulfate, nickel chloride, nickel acetate, nickel sulfate, and nickel nitrate.
Preferably, in step 1) of the preparation method of the metal oxide catalyst with regular morphology for eliminating formaldehyde, the oxygen-containing organic ligand is at least one of terephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid, 2-halogenated terephthalic acid, 2, 5-dihydroxyterephthalic acid, 1,3, 5-trimesic acid, 3 ', 5,5 ' -azobenzene tetracarboxylic acid, 2 ', 6,6 ' -biphenyl tetracarboxylic acid, 4 ' -tetraphenyl methane tetracarboxylic acid; more preferably, in step 1), the oxygen-containing organic ligand is at least one of terephthalic acid, 2-aminoterephthalic acid, 2-bromoterephthalic acid, 2, 5-dihydroxyterephthalic acid, 1,3, 5-trimesic acid, and 3,3 ', 5, 5' -azobenzene tetracarboxylic acid.
Preferably, in step 1) of the preparation method of the metal oxide catalyst with regular morphology for eliminating formaldehyde, the solvent is at least one of water, methanol, ethanol, propanol, isopropanol, diethyl ether, acetone, N-dimethylformamide, tetrahydrofuran and dimethyl sulfoxide; further preferably, in step 1), the solvent is at least one of water, methanol, ethanol, and N, N-dimethylformamide.
Preferably, in the step 1) of the preparation method of the metal oxide catalyst with regular morphology for eliminating formaldehyde, the molar ratio of the transition metal source, the oxygen-containing organic ligand and the solvent is (0.5-4): 1: (10-1000).
Preferably, in the step 1) of the preparation method of the metal oxide catalyst with regular morphology for eliminating formaldehyde, the temperature of the solvothermal reaction is 100-200 ℃, and the time of the solvothermal reaction is 12-144 h.
Preferably, in the step 1) of the preparation method of the metal oxide catalyst with regular morphology for eliminating formaldehyde, after the solvothermal reaction, the obtained solid product is filtered, washed and dried.
Preferably, in step 2) of the preparation method of the metal oxide catalyst with regular morphology for eliminating formaldehyde, the reducing atmosphere is at least one of hydrogen, carbon monoxide, methane, hydrogen sulfide, nitric oxide and ammonia gas, or a mixed gas of at least one of hydrogen, carbon monoxide, methane, hydrogen sulfide, nitric oxide and ammonia gas and at least one of nitrogen, helium, neon and argon; further preferably, in the step 2), the reducing atmosphere is at least one of hydrogen and carbon monoxide, or a mixed gas of at least one of hydrogen and carbon monoxide and at least one of nitrogen, helium, neon and argon; further, when the reducing atmosphere is a mixed gas, the volume ratio of hydrogen and/or carbon monoxide to the inert atmosphere (nitrogen, helium, neon or argon) is (0.1-10): 1, preferably the volume ratio is (0.3-4): 1. in some preferred embodiments of the present invention, the reducing atmosphere is any one of hydrogen, carbon monoxide, a mixed atmosphere of hydrogen and nitrogen, a mixed atmosphere of hydrogen and helium, a mixed atmosphere of carbon monoxide and nitrogen, a mixed atmosphere of carbon monoxide and helium, and a mixed atmosphere of carbon monoxide and argon.
Preferably, in the step 2) of the preparation method of the metal oxide catalyst with regular morphology for eliminating formaldehyde, the heat treatment temperature is 400-600 ℃, and the heat treatment time is 0.5-5 h.
A metal oxide catalyst with regular morphology for eliminating formaldehyde is prepared by the preparation method.
Furthermore, the metal oxide catalyst with the regular morphology for eliminating the formaldehyde consists of the metal oxide with the regular morphology and a porous carbon carrier. The metal oxide is at least one of iron oxide, cobalt oxide, manganese oxide and nickel oxide.
The application of the metal oxide catalyst with regular morphology for eliminating formaldehyde in indoor air is provided.
The invention has the beneficial effects that:
the metal oxide catalyst has the characteristics of regular appearance and uniform size, and does not need to introduce a blocking agent in the preparation process, so that the surface is clean and has no interference. The metal oxide catalyst is applied to indoor air to remove formaldehyde, and has the characteristics of low cost, high activity and long service life.
Compared with the prior art, the invention has the following advantages:
1) according to the invention, a metal organic framework formed by coordination of transition metal ions and oxygen-containing organic ligands is used as a precursor, and metal oxide nanoparticles with regular appearance and uniform size are obtained by a pyrolysis method in a reducing atmosphere, so that the problems of metal oxide nanoparticle agglomeration and wide size distribution caused by pyrolysis in an inert atmosphere are solved.
2) Compared with other synthesis methods of metal oxides with controllable morphology, the preparation method disclosed by the invention does not need to add a large amount of end-capping agents or surfactants in the preparation process, the surface of the metal oxide is clean, and the method is free from the adhesion interference of other organic groups, and is more favorable for the adsorption and activation of reactants in a catalytic reaction.
3) The metal oxide catalyst with regular morphology can catalyze and oxidize the formaldehyde into harmless CO at room temperature without external energy such as light, electricity, heat and the like2And H2O, has the characteristics of low cost, high activity and long service life.
Drawings
FIG. 1 is a TEM image of a regular morphology metal oxide catalyst for eliminating formaldehyde prepared in example 5 of the present invention;
fig. 2 is a transmission electron microscope image of the metal oxide catalyst prepared in comparative example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources.
Example 1
Example 1 a method for preparing a regular morphology metal oxide catalyst for the elimination of formaldehyde, comprising the steps of:
dissolving 5mmol of cobalt chloride and 5mmol of terephthalic acid in 25mL of N, N-dimethylformamide, reacting at 145 ℃ for 12h, filtering, washing and drying to obtain solid powder. And (3) placing the solid powder in a carbon monoxide atmosphere, and roasting for 3h at 500 ℃ to obtain the metal oxide catalyst with the regular morphology.
Example 2
Example 2 a method for preparing a regular morphology metal oxide catalyst for the elimination of formaldehyde, comprising the steps of:
dissolving 5mmol of cobalt chloride, 5mmol of iron powder and 5mmol of 1,3, 5-trimesic acid in 10mL of water, reacting at 180 ℃ for 72h, filtering, washing and drying to obtain solid powder. And (3) placing the solid powder in a hydrogen atmosphere, and roasting at 550 ℃ for 1.5h to obtain the metal oxide catalyst with the regular morphology.
Example 3
Example 3 a method for preparing a regular morphology metal oxide catalyst for the elimination of formaldehyde, comprising the steps of:
dissolving 2.5mmol of manganese acetate and 5mmol of 1,3, 5-trimesic acid in 20mL of mixed solvent of ethanol and water, reacting at 150 ℃ for 144h with the volume ratio of the ethanol to the water of 1:1, filtering, washing and drying to obtain solid powder. And (3) placing the solid powder in a mixed atmosphere of carbon monoxide and nitrogen, wherein the volume ratio of the carbon monoxide to the nitrogen is 0.3:1, and roasting at 600 ℃ for 0.5h to obtain the metal oxide catalyst with the regular morphology.
Example 4
Example 4 a method for preparing a regular morphology metal oxide catalyst for the elimination of formaldehyde, comprising the steps of:
dissolving 5mmol of ferric perchlorate and 3.3mmol of 3,3 ', 5, 5' -azobenzene tetracarboxylic acid in 10mL of N, N-dimethylformamide, reacting at 150 ℃ for 20h, filtering, washing and drying to obtain solid powder. And (3) placing the solid powder in a mixed atmosphere of carbon monoxide and helium, roasting the solid powder for 5 hours at 400 ℃ at the volume ratio of the carbon monoxide to the helium of 0.5:1 to obtain the metal oxide catalyst with the regular morphology.
Example 5
Example 5 a method for preparing a regular morphology metal oxide catalyst for the elimination of formaldehyde, comprising the steps of:
dissolving 5mmol ferric chloride and 5mmol 2-amino terephthalic acid in 50mL water, reacting at 150 ℃ for 72h, filtering, washing and drying to obtain solid powder. And (3) placing the solid powder in a mixed atmosphere of carbon monoxide and argon, roasting the solid powder for 2 hours at 500 ℃ at the volume ratio of 1:1 to obtain the metal oxide catalyst with the regular morphology.
FIG. 1 is a transmission electron microscope image of the iron oxide nanoparticles with regular morphology obtained in example 5. It can be clearly observed from fig. 1 that the metal oxide nanoparticles in the catalyst have a regular octahedral shape and are uniformly sized and supported on a porous carbon support.
Example 6
Example 6 a method of preparing a regular morphology metal oxide catalyst for the elimination of formaldehyde comprising the steps of:
dissolving 5mmol nickel sulfate and 5mmol 2-bromoterephthalic acid in 50mL water, reacting at 100 ℃ for 48h, filtering, washing and drying to obtain solid powder. And (3) placing the solid powder in a mixed atmosphere of hydrogen and nitrogen, roasting for 3 hours at 500 ℃ with the volume ratio of the hydrogen to the nitrogen being 2:1, and obtaining the metal oxide catalyst with regular morphology.
Example 7
Example 7 a method for preparing a regular morphology metal oxide catalyst for the elimination of formaldehyde comprising the steps of:
dissolving 4mmol of cobalt nitrate, 1mmol of nickel nitrate and 1.25mmol of 2, 5-dihydroxyterephthalic acid by using 60mL of mixed solvent of N, N-dimethylformamide, methanol and water, reacting at 135 ℃ for 24h with the volume ratio of the N, N-dimethylformamide to the methanol being 8:1:1, filtering, washing and drying to obtain solid powder. And (3) placing the solid powder in a mixed atmosphere of hydrogen and helium, roasting the solid powder for 4.5 hours at 450 ℃ at the volume ratio of 4:1 to obtain the metal oxide catalyst with the regular morphology.
Comparative example 1
Dissolving 5mmol of cobalt chloride and 5mmol of terephthalic acid in 25mL of N, N-dimethylformamide, reacting at 145 ℃ for 12h, filtering, washing and drying to obtain solid powder. The solid powder was calcined at 500 ℃ for 3 hours in a nitrogen atmosphere to obtain the metal oxide catalyst of comparative example 1.
Comparative example 2
Dissolving 5mmol ferric chloride and 5mmol 2-amino terephthalic acid in 50mL water, reacting at 150 ℃ for 72h, filtering, washing and drying to obtain solid powder. The solid powder was calcined at 500 ℃ for 2 hours in an argon atmosphere to obtain the metal oxide catalyst of comparative example 2.
FIG. 2 is a transmission electron micrograph of the iron oxide nanoparticles obtained in comparative example 2. From fig. 2, it can be clearly observed that the metal oxide nanoparticles supported on the porous carbon support in the catalyst have irregular shapes and non-uniform sizes.
Comparative example 3
Dissolving 4mmol of cobalt nitrate, 1mmol of nickel nitrate and 1.25mmol of 2, 5-dihydroxyterephthalic acid by using 60mL of mixed solvent of N, N-dimethylformamide, methanol and water, reacting at 135 ℃ for 24h with the volume ratio of the N, N-dimethylformamide to the methanol being 8:1:1, filtering, washing and drying to obtain solid powder. The solid powder was calcined at 450 ℃ for 4.5 hours in a helium atmosphere to obtain the metal oxide catalyst of comparative example 3.
Application testing
The catalysts for eliminating formaldehyde prepared in examples 1 to 7 and comparative examples 1 to 3 were subjected to performance tests. And (3) testing conditions are as follows: the initial concentration of formaldehyde is 80mg/m3The space velocity is 30000 mL/g/h; the test method comprises the following steps: and (3) adopting a bubbling method, blowing formaldehyde in the formaldehyde aqueous solution into a quartz tube filled with a room-temperature formaldehyde oxidation catalyst by using air, sampling and detecting gases passing through the quartz tube in front of and behind, and calculating the formaldehyde conversion rate. The test results obtained are shown in table 1.
TABLE 1 Performance test results of formaldehyde-degrading catalysts of examples 1 to 7 and comparative examples 1 to 3
| Catalyst and process for preparing same | Formaldehyde conversion (%) |
| Example 1 | 91.4 |
| Example 2 | 85.6 |
| Example 3 | 89.3 |
| Example 4 | 74.9 |
| Example 5 | 96.7 |
| Example 6 | 87.8 |
| Example 7 | 83.2 |
| Comparative example 1 | 26.1 |
| Comparative example 2 | 37.5 |
| Comparative example 3 | 22.4 |
As can be seen from Table 1: the metal oxide catalyst with regular morphology for eliminating formaldehyde prepared by the method has the initial concentration of 80mg/m of formaldehyde3And under the condition of the space velocity of 30000mL/g/h, the conversion rate of formaldehyde at room temperature is superior to that of the metal oxide catalyst with the random morphology in the comparative example.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. The application of a metal oxide catalyst with regular morphology for eliminating formaldehyde in indoor air is characterized in that: the preparation method of the metal oxide catalyst with regular morphology for eliminating formaldehyde comprises the following steps:
1) mixing a transition metal source, an oxygen-containing organic ligand and a solvent, and carrying out a solvothermal reaction to obtain a metal organic framework precursor;
2) carrying out heat treatment on the metal organic framework precursor in a reducing atmosphere to obtain a metal oxide catalyst with a regular morphology for eliminating formaldehyde;
in the step 1), the transition metal source is transition metal salt; the transition metal salt is selected from at least one of nitrate, acetate, sulfate, halide or perhalogenate of iron, cobalt, manganese and nickel; in the step 1), the oxygen-containing organic ligand is at least one of terephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid, 2-halogenated terephthalic acid, 2, 5-dihydroxyterephthalic acid, 1,3, 5-trimesic acid, 3 ', 5,5 ' -azobenzene tetracarboxylic acid, 2 ', 6,6 ' -biphenyl tetracarboxylic acid or 4,4 ' -tetraphenylmethane tetracarboxylic acid.
2. Use according to claim 1, characterized in that: in the step 1) of the preparation method of the metal oxide catalyst with the regular morphology, the solvent is at least one of water, methanol, ethanol, propanol, isopropanol, diethyl ether, acetone, N-dimethylformamide, tetrahydrofuran or dimethyl sulfoxide.
3. Use according to claim 1 or 2, characterized in that: in the preparation method of the metal oxide catalyst with the regular morphology, in the step 1), the molar ratio of the transition metal source, the oxygen-containing organic ligand and the solvent is (0.5-4): 1: (10-1000).
4. Use according to claim 3, characterized in that: in the step 1) of the preparation method of the metal oxide catalyst with the regular morphology, the temperature of the solvothermal reaction is 100-200 ℃, and the time of the solvothermal reaction is 12-144 h.
5. Use according to claim 1, characterized in that: in the step 2) of the preparation method of the metal oxide catalyst with regular morphology, the reducing atmosphere is at least one of hydrogen, carbon monoxide, methane, hydrogen sulfide, nitric oxide or ammonia gas, or a mixed gas of at least one of hydrogen, carbon monoxide, methane, hydrogen sulfide, nitric oxide or ammonia gas and at least one of nitrogen, helium, neon or argon gas.
6. Use according to claim 1 or 5, characterized in that: in the step 2) of the preparation method of the metal oxide catalyst with the regular morphology, the heat treatment temperature is 400-600 ℃, and the heat treatment time is 0.5-5 h.
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