CN109621962A - A kind of regular morphology metal oxide catalyst and its preparation method and application for eliminating formaldehyde - Google Patents
A kind of regular morphology metal oxide catalyst and its preparation method and application for eliminating formaldehyde Download PDFInfo
- Publication number
- CN109621962A CN109621962A CN201811484638.1A CN201811484638A CN109621962A CN 109621962 A CN109621962 A CN 109621962A CN 201811484638 A CN201811484638 A CN 201811484638A CN 109621962 A CN109621962 A CN 109621962A
- Authority
- CN
- China
- Prior art keywords
- metal oxide
- formaldehyde
- oxide catalyst
- regular morphology
- eliminating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 66
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000012298 atmosphere Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 23
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 19
- 150000003624 transition metals Chemical class 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 7
- 239000013110 organic ligand Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052734 helium Inorganic materials 0.000 claims description 11
- 239000001307 helium Substances 0.000 claims description 11
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- -1 formaldehyde Metal oxide Chemical class 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- QMKYBPDZANOJGF-UHFFFAOYSA-N trimesic acid Natural products OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical class C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron 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
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-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 group [H]* 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 230000026030 halogenation Effects 0.000 claims 1
- 238000005658 halogenation reaction Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000000877 morphologic effect Effects 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- 239000000843 powder Substances 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 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
- 230000003647 oxidation Effects 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229960004424 carbon dioxide Drugs 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 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
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 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
- 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
- 230000004913 activation Effects 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 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
- 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
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- YENVMPPRTXICRT-UHFFFAOYSA-N 2-(2,6-dicarboxyphenyl)benzene-1,3-dicarboxylic acid Chemical class OC(=O)C1=CC=CC(C(O)=O)=C1C1=C(C(O)=O)C=CC=C1C(O)=O YENVMPPRTXICRT-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229910021281 Co3O4In Inorganic materials 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
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 230000007681 cardiovascular toxicity Effects 0.000 description 1
- 231100000060 cardiovascular toxicity Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 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
- 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 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002964 excitative effect Effects 0.000 description 1
- CUHVTYCUTYWQOR-UHFFFAOYSA-N formaldehyde Chemical compound O=C.O=C CUHVTYCUTYWQOR-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007135 neurotoxicity Effects 0.000 description 1
- 231100000228 neurotoxicity Toxicity 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
- 229910000510 noble metal Inorganic materials 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
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000012855 volatile organic compound 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of regular morphology metal oxide catalysts and its preparation method and application for eliminating formaldehyde.It is this for eliminate the regular morphology metal oxide catalyst of formaldehyde to be obtained by preparation method below: 1) transition metal source, oxygen-containing organic ligand and solvent are mixed, carry out solvent thermal reaction, obtain metal organic framework presoma；2) metal organic framework presoma is heat-treated under reducing atmosphere, obtains the regular morphology metal oxide catalyst for eliminating formaldehyde.Also disclose this regular morphology metal oxide catalyst in the application for removing formaldehyde in indoor air simultaneously.Metal oxide catalyst of the invention has the characteristics that morphological rules, size uniformity, and does not need to introduce end-capping reagent in preparation process, and surface cleaning is noiseless.This metal oxide catalyst is applied to room air and removes formaldehyde, has the characteristics that at low cost, active high, service life length.
Description
Technical field
The present invention relates to a kind of regular morphology metal oxide catalyst for eliminating formaldehyde and preparation method thereof and answer
With,
Background technique
Formaldehyde belongs to high volatile organic compound, colourless gas excitatory.Indoor formaldehyde is mainly derived from building
Material, indoor hardware fitting and fuel combustion etc..Formaldehyde is mainly reflected in breathing toxicity, immune poison to the toxic effect of human body
Property, neurotoxicity, Cardiovascular Toxicity and carcinogenicity etc..The most of the time of people's life all completes indoors, indoor first
Aldehyde becomes for the substance of high-risk toxicity, it is necessary to obtain stringent elimination and control.It is new to fit up residential building first through investigating
The mean concentration of aldehyde is 0.11mg/m3, this is higher than in " Indoor Air Quality standards " (GB/T18883-2002) of China's publication
Defined content of formaldehyde (0.1mg/m3).For this purpose, the technology of various controls and elimination formaldehyde is widely studied.
In the technology currently used for purifying indoor formaldehyde, formaldehyde complete oxidation can be CO by catalytic oxidation2And H2O,
Secondary pollution will not be generated, is that there is important practical application value except the most thorough method of formaldehyde.The catalyst developed at present
It is generally necessary to which carried noble metal Pt, Pd, Au, Ag isoreactivity component improves the activity of room temperature catalytic oxidation formaldehyde, but due to expensive
The problem of metal resource is rare, expensive, generally existing high expensive limits the development of such catalyst.Therefore, non-expensive
Metallic catalyst has obtained the extensive concern of scientist, but poor room temperature catalytic activity still restricts its extensive use.
Scientist attempts to improve oxide surface activity by way of exposing metal oxide particular crystal plane in recent years
The density of position, to realize the maximization of catalytic activity.Xie etc. (Nature 458 (2009) 746-749) research discovery structure
Regular Co3O4In expose more (110) crystal faces, reaction rate is conventional Co3O410 times or more of nanoparticle, and
Show excellent structural stability.(the AngewandteChemie International Edition 51 (2012) such as Mou
It 2989-2993) is controlled by crystal phase and pattern, in Fe2O3(110) and (001) crystal face is selectively exposed in material, in NH3-
Excellent activity and anti-poisoning capability are shown in SCR reaction.
But catalyst disclosed in currently available technology still has the limitations such as preparation method is cumbersome, and specific surface area is low, and
Field is not eliminated in formaldehyde effectively to be applied.So a kind of efficient catalyst for eliminating formaldehyde still needs service workers and grinds
Hair.
Summary of the invention
In order to overcome technical problem of the existing technology, a kind of transition metal oxide nano of morphological rules is developed
The composite material of grain and porous carbon, enhances the efficient activation of exposure crystal face active sites PARA FORMALDEHYDE PRILLS(91,95) molecule, and improves oxo transition metal
The room temperature catalytic activity of compound, the regular morphology metal oxide that the purpose of the present invention is to provide a kind of for eliminating formaldehyde are urged
Agent and its preparation method and application.
The technical solution used in the present invention is:
It is a kind of for eliminating the preparation method of the regular morphology metal oxide catalyst of formaldehyde, comprising the following steps:
1) transition metal source, oxygen-containing organic ligand and solvent are mixed, carries out solvent thermal reaction, obtains metal organic framework
Presoma；
2) metal organic framework presoma is heat-treated under reducing atmosphere, obtains the rule for eliminating formaldehyde
Pattern metal oxide catalyst.
Preferably, in the preparation method step 1) of this regular morphology metal oxide catalyst for eliminating formaldehyde,
Transition metal source is at least one of transition metal, transition metal salt.
It is further preferred that transition metal is selected from least one of iron, cobalt, manganese, nickel.
It is further preferred that transition metal salt is selected from nitrate, acetate, sulfate, halide salt, the high halogen of transition metal
At least one of hydrochlorate；Still further preferably, transition metal salt be selected from iron chloride, ferric sulfate, ferric perchlorate, cobalt chloride,
At least one of cobalt nitrate, cobalt acetate, manganese chloride, manganese acetate, manganese sulfate, nickel chloride, nickel acetate, nickel sulfate, nickel nitrate.
Preferably, in the preparation method step 1) of this regular morphology metal oxide catalyst for eliminating formaldehyde,
Oxygen-containing organic ligand be terephthalic acid (TPA), 2- amino terephthalic acid (TPA), 2- nitroterephthalic, the halogenated terephthalic acid (TPA) of 2-,
2,5- dihydric para-phthalic acid, 1,3,5- trimesic acid, 3,3 ', 5,5 '-azo benzene tertacarbonic acids, 2,2 ', 6,6 '-biphenyl tetracarboxylic acids
At least one of acid, 4,4 ', 4 ", 4 " '-tetraphenylmethane tetrabasic carboxylic acids；It is oxygen-containing organic to match it is further preferred that in step 1)
Body is terephthalic acid (TPA), 2- amino terephthalic acid (TPA), 2- bromoterephthalic acid, 2,5- dihydric para-phthalic acid, 1,3,5-
Trimesic acid, 3,3 ', at least one of 5,5 '-azo benzene tertacarbonic acids.
Preferably, in the preparation method step 1) of this regular morphology metal oxide catalyst for eliminating formaldehyde,
Solvent is water, methanol, ethyl alcohol, propyl alcohol, isopropanol, ether, acetone, N,N-dimethylformamide, tetrahydrofuran, dimethyl sulfoxide
At least one of；It is further preferred that in step 1), solvent be water, methanol, ethyl alcohol, in n,N-Dimethylformamide extremely
Few one kind.
Preferably, in the preparation method step 1) of this regular morphology metal oxide catalyst for eliminating formaldehyde,
The molar ratio of transition metal source, oxygen-containing organic ligand and solvent is (0.5~4): 1:(10~1000).
Preferably, in the preparation method step 1) of this regular morphology metal oxide catalyst for eliminating formaldehyde,
The temperature of solvent thermal reaction is 100 DEG C~200 DEG C, and the time of solvent thermal reaction is 12h~144h.
Preferably, in the preparation method step 1) of this regular morphology metal oxide catalyst for eliminating formaldehyde,
After solvent thermal reaction, resulting solid product is filtered, is washed, is dried.
Preferably, in the preparation method step 2) of this regular morphology metal oxide catalyst for eliminating formaldehyde,
Reducing atmosphere is at least one of hydrogen, carbon monoxide, methane, hydrogen sulfide, nitric oxide, ammonia, or is hydrogen, one
At least one of carbonoxide, methane, hydrogen sulfide, nitric oxide, ammonia and at least one of nitrogen, helium, neon, argon gas
The mixed gas of composition；It is further preferred that in step 2), reducing atmosphere is at least one of hydrogen, carbon monoxide, or
Person is the mixed gas that at least one of hydrogen, carbon monoxide are formed at least one of nitrogen, helium, neon, argon gas；
Further, when reducing atmosphere is mixed gas, hydrogen and/or carbon monoxide and inert atmosphere (nitrogen, helium, neon
Gas or argon gas) volume ratio be (0.1~10): 1, preferred volume ratio be (0.3~4): 1.It is some preferred specific in the present invention
In embodiment, reducing atmosphere is hydrogen, carbon monoxide, hydrogen and nitrogen mixture atmosphere, hydrogen and helium mix atmosphere, one
It is any one in carbonoxide and nitrogen mixture atmosphere, carbon monoxide and helium mix atmosphere, carbon monoxide and argon gas mixed atmosphere
Kind.
Preferably, in the preparation method step 2) of this regular morphology metal oxide catalyst for eliminating formaldehyde,
The temperature of heat treatment is 400 DEG C~600 DEG C, and the time of heat treatment is 0.5h~5h.
It is a kind of for eliminating the regular morphology metal oxide catalyst of formaldehyde, be to be made by preparation method above-mentioned.
Further, this for eliminating the regular morphology metal oxide catalyst of formaldehyde, it is by with regular morphology
Metal oxide and porous carbon support composition.Metal oxide is at least one of iron, cobalt, manganese, nickel oxide.
This regular morphology metal oxide catalyst for eliminating formaldehyde is in the application for removing formaldehyde in indoor air.
The beneficial effects of the present invention are:
Metal oxide catalyst of the invention has the characteristics that morphological rules, size uniformity, and in preparation process not
Need to introduce end-capping reagent, surface cleaning is noiseless.This metal oxide catalyst is applied to room air and removes formaldehyde,
Has the characteristics that at low cost, active high, service life length.
Compared with prior art, the present invention has the advantage that
1) present invention is using the metal organic framework of transition metal ions and oxygen-containing organoligand coordination as presoma, by
The method being pyrolyzed under reducing atmosphere obtains the metal oxide nanoparticles of morphological rules, size uniformity, overcomes in inertia
Metal oxide nanoparticles caused by being pyrolyzed in atmosphere are reunited, the widespread problem of size.
2) it compared to the synthetic method of the metal oxide of other morphology controllables, does not need to add in preparation process of the present invention
A large amount of end-capping reagent or surfactant, metal oxide surface cleaning, the attachment interference of no other organic groups are more advantageous to
The absorption and activation of reactant in catalysis reaction.
3) regular morphology metal oxide catalyst of the invention is at room temperature without external energies such as light, electricity, heat,
It can be by formaldehyde through catalytic oxidation at harmless CO2And H2O has the characteristics that at low cost, active high, service life length.
Detailed description of the invention
Fig. 1 is the transmission of the regular morphology metal oxide catalyst for eliminating formaldehyde prepared by the embodiment of the present invention 5
Electron microscope；
Fig. 2 is the transmission electron microscope picture of the metal oxide catalyst of comparative example 2 of the present invention preparation.
Specific embodiment
The contents of the present invention are described in further detail below by way of specific embodiment.Original used in embodiment
Material unless otherwise specified, can be obtained from routine business approach.
Embodiment 1
Embodiment 1 is used to eliminate the preparation method of the regular morphology metal oxide catalyst of formaldehyde, comprising the following steps:
5mmol cobalt chloride, the 5mmol terephthalic acid (TPA) n,N-Dimethylformamide of 25mL are dissolved, 145 DEG C of reactions
12h is filtered, washed, is dried to obtain solid powder.Solid powder is placed under carbon monoxide atmosphere, 500 DEG C of roasting 3h are obtained
Regular morphology metal oxide catalyst.
Embodiment 2
Embodiment 2 is used to eliminate the preparation method of the regular morphology metal oxide catalyst of formaldehyde, comprising the following steps:
5mmol cobalt chloride, 5mmol iron powder and 1,3,5- trimesic acid of the 5mmol water of 10mL are dissolved, 180 DEG C of reactions
72h is filtered, washed, is dried to obtain solid powder.Solid powder is placed under hydrogen atmosphere, 550 DEG C of roasting 1.5h are advised
Then pattern metal oxide catalyst.
Embodiment 3
Embodiment 3 is used to eliminate the preparation method of the regular morphology metal oxide catalyst of formaldehyde, comprising the following steps:
The mixed solvent of 2.5mmol manganese acetate, 5mmol 1,3, the 5- trimesic acid second alcohol and water of 20mL is dissolved, second
The volume ratio of alcohol and water is 1:1, and 150 DEG C of reaction 144h are filtered, washed, are dried to obtain solid powder.Solid powder is placed in one
Under the mixed atmosphere of carbonoxide and nitrogen, the volume ratio of carbon monoxide and nitrogen is 0.3:1, and 600 DEG C of roasting 0.5h obtain rule
Pattern metal oxide catalyst.
Embodiment 4
Embodiment 4 is used to eliminate the preparation method of the regular morphology metal oxide catalyst of formaldehyde, comprising the following steps:
N by 5mmol ferric perchlorate, 3,3 ', 5,5 '-azo of 3.3mmol benzene tertacarbonic acid with 10mL, N- dimethyl formyl
Amine dissolution, 150 DEG C of reaction 20h are filtered, washed, are dried to obtain solid powder.Solid powder is placed in carbon monoxide and helium
Under mixed atmosphere, the volume ratio of carbon monoxide and helium is 0.5:1, and 400 DEG C of roasting 5h obtain regular morphology metal oxide and urge
Agent.
Embodiment 5
Embodiment 5 is used to eliminate the preparation method of the regular morphology metal oxide catalyst of formaldehyde, comprising the following steps:
5mmol iron chloride, the 5mmol 2- amino terephthalic acid (TPA) water of 50mL are dissolved, 150 DEG C of reaction 72h, filtering,
It washs, be dried to obtain solid powder.Solid powder is placed under the mixed atmosphere of carbon monoxide and argon gas, carbon monoxide and argon gas
Volume ratio be 1:1,500 DEG C of roasting 2h obtain regular morphology metal oxide catalyst.
Attached drawing 1 is the transmission electron microscope picture of 5 gained regular morphology iron oxide nanoparticles of embodiment.It can understand from Fig. 1
Ground observes that the metal oxide nanoparticles in the catalyst have well-regulated octahedral shape, and size is uniform,
Equably it is supported on porous carbon support.
Embodiment 6
Embodiment 6 is used to eliminate the preparation method of the regular morphology metal oxide catalyst of formaldehyde, comprising the following steps:
5mmol nickel sulfate, 5mmol 2- bromoterephthalic acid are dissolved with the water of 50mL, 100 DEG C of reaction 48h, filtering,
It washs, be dried to obtain solid powder.Solid powder is placed under the mixed atmosphere of hydrogen and nitrogen, the volume ratio of hydrogen and nitrogen
Regular morphology metal oxide catalyst is obtained for 2:1,500 DEG C of roasting 3h.
Embodiment 7
Embodiment 7 is used to eliminate the preparation method of the regular morphology metal oxide catalyst of formaldehyde, comprising the following steps:
N by 4mmol cobalt nitrate, 1mmol nickel nitrate and 1.25mmol 2,5- dihydric para-phthalic acid with 60mL, N-
The mixed solvent dissolution of dimethylformamide, first alcohol and water, n,N-Dimethylformamide, the volume ratio of first alcohol and water are 8:1:1,
135 DEG C of reactions for 24 hours, are filtered, washed, are dried to obtain solid powder.Solid powder is placed under the mixed atmosphere of hydrogen and helium,
The volume ratio of hydrogen and helium is 4:1, and 450 DEG C of roasting 4.5h obtain regular morphology metal oxide catalyst.
Comparative example 1
5mmol cobalt chloride, the 5mmol terephthalic acid (TPA) n,N-Dimethylformamide of 25mL are dissolved, 145 DEG C of reactions
12h is filtered, washed, is dried to obtain solid powder.Solid powder is placed under nitrogen atmosphere, 500 DEG C of roasting 3h are compared
The metal oxide catalyst of example 1.
Comparative example 2
5mmol iron chloride, the 5mmol 2- amino terephthalic acid (TPA) water of 50mL are dissolved, 150 DEG C of reaction 72h, filtering,
It washs, be dried to obtain solid powder.Solid powder is placed under the atmosphere of argon gas, 500 DEG C of roasting 2h obtain the gold of comparative example 2
Belong to oxide catalyst.
Attached drawing 2 is the transmission electron microscope picture of 2 gained iron oxide nanoparticles of comparative example.It can clearly be observed that from Fig. 2
The metal oxide nanoparticles pattern being supported on the carrier of porous carbon in the catalyst is random, and size is inhomogenous.
Comparative example 3
N by 4mmol cobalt nitrate, 1mmol nickel nitrate and 1.25mmol 2,5- dihydric para-phthalic acid with 60mL, N-
The mixed solvent dissolution of dimethylformamide, first alcohol and water, n,N-Dimethylformamide, the volume ratio of first alcohol and water are 8:1:1,
135 DEG C of reactions for 24 hours, are filtered, washed, are dried to obtain solid powder.Solid powder is placed under the atmosphere of helium, 450 DEG C of roastings
4.5h obtains 3 metal oxide catalyst of comparative example.
Using test
Catalyst for eliminating formaldehyde prepared by Examples 1 to 7 and comparative example 1~3 is tested for the property.Test-strips
Part: initial concentration of formaldehyde 80mg/m3, air speed 30000mL/g/h；Test method: using Bubbling method, using air by formaldehyde
Formaldehyde in aqueous solution blasts the quartz ampoule equipped with Oxidation at room temperature formaldehyde catalyst, examines to by the gas sample before and after quartz ampoule
It surveys, calculates formaldehyde conversion.Resulting test result is as shown in table 1.
The performance test results of the degradation of formaldehyde catalyst of 1 Examples 1 to 7 of table and comparative example 1~3
| Catalyst | Formaldehyde conversion (%) |
| Embodiment 1 | 91.4 |
| Embodiment 2 | 85.6 |
| Embodiment 3 | 89.3 |
| Embodiment 4 | 74.9 |
| Embodiment 5 | 96.7 |
| Embodiment 6 | 87.8 |
| Embodiment 7 | 83.2 |
| Comparative example 1 | 26.1 |
| Comparative example 2 | 37.5 |
| Comparative example 3 | 22.4 |
As shown in Table 1: what is prepared by the method for the invention is used to eliminate the regular morphology metal oxide catalyst of formaldehyde
In initial concentration of formaldehyde 80mg/m3, under conditions of air speed 30000mL/g/h, formaldehyde room temperature conversion rate is better than in comparative example
The metal oxide catalyst of random pattern.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of for eliminating the preparation method of the regular morphology metal oxide catalyst of formaldehyde, it is characterised in that: including with
Lower step:
1) transition metal source, oxygen-containing organic ligand and solvent are mixed, carries out solvent thermal reaction, obtains metal organic framework forerunner
Body；
2) metal organic framework presoma is heat-treated under reducing atmosphere, obtains the regular morphology for eliminating formaldehyde
Metal oxide catalyst.
2. according to claim 1 a kind of for eliminating the preparation side of the regular morphology metal oxide catalyst of formaldehyde
Method, it is characterised in that: in step 1), transition metal source is at least one of transition metal, transition metal salt；Transition metal choosing
From at least one of iron, cobalt, manganese, nickel；Transition metal salt is selected from nitrate, acetate, the sulfate, halogenation of transition metal
At least one of salt, perhalide.
3. according to claim 1 a kind of for eliminating the preparation side of the regular morphology metal oxide catalyst of formaldehyde
Method, it is characterised in that: in step 1), oxygen-containing organic ligand is terephthalic acid (TPA), 2- amino terephthalic acid (TPA), 2- nitro to benzene two
The halogenated terephthalic acid (TPA) of formic acid, 2-, 2,5- dihydric para-phthalic acid, 1,3,5- trimesic acid, 3,3 ', 5,5 '-azobenzenes four
Carboxylic acid, 2,2 ', at least one of 6,6 '-biphenyltetracarboxyacid acids, 4,4 ', 4 ", 4 " '-tetraphenylmethane tetrabasic carboxylic acids.
4. according to claim 1 a kind of for eliminating the preparation side of the regular morphology metal oxide catalyst of formaldehyde
Method, it is characterised in that: in step 1), solvent is water, methanol, ethyl alcohol, propyl alcohol, isopropanol, ether, acetone, N, N- dimethyl methyl
At least one of amide, tetrahydrofuran, dimethyl sulfoxide.
5. described in any item a kind of for eliminating the regular morphology metal oxide catalyst of formaldehyde according to claim 2~4
Preparation method, it is characterised in that: in step 1), the molar ratio of transition metal source, oxygen-containing organic ligand and solvent be (0.5~
4): 1:(10~1000).
6. according to claim 5 a kind of for eliminating the preparation side of the regular morphology metal oxide catalyst of formaldehyde
Method, it is characterised in that: in step 1), the temperature of solvent thermal reaction is 100 DEG C~200 DEG C, the time of solvent thermal reaction be 12h~
144h。
7. according to claim 1 a kind of for eliminating the preparation side of the regular morphology metal oxide catalyst of formaldehyde
Method, it is characterised in that: in step 2), reducing atmosphere is hydrogen, in carbon monoxide, methane, hydrogen sulfide, nitric oxide, ammonia
At least one, or be at least one of hydrogen, carbon monoxide, methane, hydrogen sulfide, nitric oxide, ammonia and nitrogen, helium
The mixed gas of at least one of gas, neon, argon gas composition.
8. according to claim 1 or claim 7 a kind of for eliminating the preparation of the regular morphology metal oxide catalyst of formaldehyde
Method, it is characterised in that: in step 2), the temperature of heat treatment is 400 DEG C~600 DEG C, and the time of heat treatment is 0.5h~5h.
9. a kind of for eliminating the regular morphology metal oxide catalyst of formaldehyde, it is characterised in that: be by claim 1~8
Any one preparation method is made.
10. a kind of described in claim 9 removing room air for eliminating the regular morphology metal oxide catalyst of formaldehyde
The application of middle formaldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811484638.1A CN109621962B (en) | 2018-12-06 | 2018-12-06 | Metal oxide catalyst with regular morphology for eliminating formaldehyde and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811484638.1A CN109621962B (en) | 2018-12-06 | 2018-12-06 | Metal oxide catalyst with regular morphology for eliminating formaldehyde and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109621962A true CN109621962A (en) | 2019-04-16 |
| CN109621962B CN109621962B (en) | 2022-04-01 |
Family
ID=66071548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811484638.1A Active CN109621962B (en) | 2018-12-06 | 2018-12-06 | Metal oxide catalyst with regular morphology for eliminating formaldehyde and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109621962B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560679A (en) * | 2019-08-08 | 2019-12-13 | 安徽师范大学 | Ni-Co alloy material with three-dimensional polyhedral structure and preparation method and application thereof |
| CN114505071A (en) * | 2022-01-25 | 2022-05-17 | 晋中学院 | Preparation method and application of MnTi-MOFs derived denitration catalyst |
| CN114797888A (en) * | 2022-03-14 | 2022-07-29 | 杭州妙蓝环保科技有限公司 | Air purifying agent for removing formaldehyde indoors and preparation method thereof |
| CN115845903A (en) * | 2022-12-28 | 2023-03-28 | 陕西科技大学 | Based on CoFe 2 O 4 @ CN AOP high-efficiency catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106466642A (en) * | 2016-09-30 | 2017-03-01 | 上海理工大学 | A kind of Ce Base Metal organic framework catalyst, its preparation method and the application in Air Pollution prevention and control |
| JP2018042374A (en) * | 2016-09-07 | 2018-03-15 | 日本電産株式会社 | Continuity member fixing device and continuity member fixing method |
| CN108126727A (en) * | 2017-12-19 | 2018-06-08 | 广东省石油与精细化工研究院 | A kind of room temperature degradation of formaldehyde catalyst and its preparation method and application |
| CN108187690A (en) * | 2017-12-07 | 2018-06-22 | 广东省石油与精细化工研究院 | A kind of cobalt manganese composite oxide loaded catalyst that formaldehyde is removed for room temperature and preparation method thereof |
-
2018
- 2018-12-06 CN CN201811484638.1A patent/CN109621962B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018042374A (en) * | 2016-09-07 | 2018-03-15 | 日本電産株式会社 | Continuity member fixing device and continuity member fixing method |
| CN106466642A (en) * | 2016-09-30 | 2017-03-01 | 上海理工大学 | A kind of Ce Base Metal organic framework catalyst, its preparation method and the application in Air Pollution prevention and control |
| CN108187690A (en) * | 2017-12-07 | 2018-06-22 | 广东省石油与精细化工研究院 | A kind of cobalt manganese composite oxide loaded catalyst that formaldehyde is removed for room temperature and preparation method thereof |
| CN108126727A (en) * | 2017-12-19 | 2018-06-08 | 广东省石油与精细化工研究院 | A kind of room temperature degradation of formaldehyde catalyst and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 谭萍: "MIL-88b煅烧合成形貌可控的Fe3O4纳米颗粒及其催化性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560679A (en) * | 2019-08-08 | 2019-12-13 | 安徽师范大学 | Ni-Co alloy material with three-dimensional polyhedral structure and preparation method and application thereof |
| CN110560679B (en) * | 2019-08-08 | 2021-10-29 | 安徽师范大学 | Ni-Co alloy material with three-dimensional polyhedral structure and preparation method and application thereof |
| CN114505071A (en) * | 2022-01-25 | 2022-05-17 | 晋中学院 | Preparation method and application of MnTi-MOFs derived denitration catalyst |
| CN114505071B (en) * | 2022-01-25 | 2024-02-27 | 晋中学院 | Preparation method and application of MnTi-MOFs derivative denitration catalyst |
| CN114797888A (en) * | 2022-03-14 | 2022-07-29 | 杭州妙蓝环保科技有限公司 | Air purifying agent for removing formaldehyde indoors and preparation method thereof |
| CN114797888B (en) * | 2022-03-14 | 2023-07-28 | 杭州妙蓝环保科技有限公司 | Indoor formaldehyde-removing air purifying agent and preparation method thereof |
| CN115845903A (en) * | 2022-12-28 | 2023-03-28 | 陕西科技大学 | Based on CoFe 2 O 4 @ CN AOP high-efficiency catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109621962B (en) | 2022-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109621962A (en) | A kind of regular morphology metal oxide catalyst and its preparation method and application for eliminating formaldehyde | |
| CN104646029B (en) | A kind of metal alloy catalyst for purifying formaldehyde and preparation method thereof | |
| US20210331140A1 (en) | One kind of transition metal / nitrogen co-doped carbon composite material for removal of formaldehyde and its preparation | |
| CN101898137B (en) | Pd-Cu catalyst for CO low-temperature oxidation and preparation method thereof | |
| CN106964348B (en) | A kind of formaldehyde pollutants room temperature catalytic oxidation catalyst and its preparation method and application | |
| KR102309466B1 (en) | Ammonia decomposition catalyst and process for decomposition of ammonia using the catalyst | |
| CN108126727A (en) | A kind of room temperature degradation of formaldehyde catalyst and its preparation method and application | |
| CN110048128A (en) | A kind of nitrogen-doped carbon nanometer pipe oxygen reduction electro-catalyst and preparation method thereof | |
| CN104607240A (en) | Bi/g-C3N4 semimetal-organic composite photocatalyst and preparation method | |
| CN109331860B (en) | Low-platinum alloy composite nano photocatalyst for air purification and preparation method and application thereof | |
| CN110947394A (en) | ZIF-67-Mn/Co-based low-temperature NO oxidation catalyst, and preparation method and application thereof | |
| CN108176396A (en) | A kind of formaldehyde remover and its preparation method and application | |
| CN113117722A (en) | For normal temperature NH3Preparation method of-SCR denitration atomic-level active site catalyst | |
| CN111939907A (en) | Catalyst for low-temperature ammonia decomposition hydrogen production and preparation method and application thereof | |
| CN108187690A (en) | A kind of cobalt manganese composite oxide loaded catalyst that formaldehyde is removed for room temperature and preparation method thereof | |
| CN113663707A (en) | Method for macro-preparation of multiple formaldehyde decomposition catalysts | |
| CN111686774B (en) | High-stability monatomic platinum-based catalytic material, preparation method and application in purification of oxygen-containing volatile hydrocarbon | |
| CN108554416A (en) | A kind of modified cobalt-base catalyst and the preparation method and application thereof | |
| CN109289937B (en) | Preparation method of high-dispersion supported metal catalyst | |
| CN109772471A (en) | One kind low-temperature denitration catalyst containing samarium and preparation method thereof | |
| CN109622008A (en) | Non-precious metal catalyst and its preparation method and application is determined in a kind of nitrogen riveting of Oxidation at room temperature formaldehyde | |
| CN110252317B (en) | Ce-Fe-based catalyst for efficiently removing nitrogen oxides at low temperature | |
| CN110600752B (en) | H2Method for preparing carbon-supported Pt alloy catalyst by gas-phase thermal reduction | |
| CN109317145B (en) | Manganese oxide noble metal composite catalyst, preparation method and application thereof | |
| CN112774672A (en) | Supported monoatomic silver catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 510665 Guangzhou, Guangdong, Tianhe District Province Road West, No. 318 Patentee after: Institute of chemical engineering, Guangdong Academy of Sciences Address before: 510665 Guangzhou, Guangdong, Tianhe District Province Road West, No. 318 Patentee before: GUANGDONG RESEARCH INSTITITUTE OF PETROCHEMICAL AND FINE CHEMICAL ENGINEERING |
|
| CP01 | Change in the name or title of a patent holder |