CN111672503A - Load type long-acting formaldehyde purifying agent and preparation method and application thereof - Google Patents
Load type long-acting formaldehyde purifying agent and preparation method and application thereof Download PDFInfo
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- CN111672503A CN111672503A CN202010493834.6A CN202010493834A CN111672503A CN 111672503 A CN111672503 A CN 111672503A CN 202010493834 A CN202010493834 A CN 202010493834A CN 111672503 A CN111672503 A CN 111672503A
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- formaldehyde
- colloid
- permanganate
- rare earth
- manganese
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 426
- 239000012629 purifying agent Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 7
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 7
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 7
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 7
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims abstract description 7
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 7
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims abstract description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 7
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 7
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 7
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 3
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000000084 colloidal system Substances 0.000 claims description 70
- 239000000243 solution Substances 0.000 claims description 61
- 229910052782 aluminium Inorganic materials 0.000 claims description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 30
- 239000002131 composite material Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 229910001994 rare earth metal nitrate Inorganic materials 0.000 claims description 14
- 230000018044 dehydration Effects 0.000 claims description 13
- 238000006297 dehydration reaction Methods 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- -1 aluminum ions Chemical class 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 230000010355 oscillation Effects 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002516 radical scavenger Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000004745 nonwoven fabric Substances 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910002096 lithium permanganate Inorganic materials 0.000 claims description 4
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000003379 elimination reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 5
- 230000008030 elimination Effects 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 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
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- APRNQTOXCXOSHO-UHFFFAOYSA-N lutetium(3+);trinitrate Chemical compound [Lu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O APRNQTOXCXOSHO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000002454 Nasopharyngeal Carcinoma Diseases 0.000 description 1
- 206010061306 Nasopharyngeal cancer Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- WDVGLADRSBQDDY-UHFFFAOYSA-N holmium(3+);trinitrate Chemical compound [Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WDVGLADRSBQDDY-UHFFFAOYSA-N 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 201000011216 nasopharynx carcinoma Diseases 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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
- B01J23/16—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
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
The invention discloses a supported long-acting formaldehyde purifying agent, which is obtained by using long-acting stable manganese-based hydrotalcite as a carrier and supported rare earth metal as an active center and performing oxidation modification by using permanganate, wherein the rare earth metal is one or two of lanthanum, cerium, praseodymium, neodymium, dysprosium, holmium, ytterbium, lutetium, scandium and yttrium, and the molar content of the supported rare earth element accounts for 0.5-5% of the total molar number of a catalyst. The invention also discloses a preparation method and application of the load type long-acting formaldehyde purifying agent. The invention has the following beneficial effects: (1) the load type long-acting formaldehyde purifying agent shows long-term and high-efficiency performance in the process of removing low-concentration formaldehyde, the highest removal rate of the formaldehyde can reach 99.8 percent within 1 hour, and the formaldehyde is not inactivated within 200 days; (2) the load type long-acting formaldehyde purifying agent can be firmly and fixedly loaded on a porous medium to play a role in removing formaldehyde, and has the advantages of low cost, simple preparation process and no three-waste discharge.
Description
Technical Field
The invention relates to a load type long-acting formaldehyde purifying agent, a preparation method and application thereof, belonging to the field of new materials and technologies.
Background
Among a plurality of volatile organic pollutants (VOCs), formaldehyde is one of the most widely-sourced and most seriously-harmful gases, is listed as a first carcinogen by the International agency for research on cancer (IARC) in 2004, and causes high-risk diseases such as nasopharyngeal carcinoma when being in a formaldehyde environment for a long time. In order to eliminate the harm of formaldehyde to human health, researchers at home and abroad carry out a great deal of research work, and formaldehyde elimination technologies such as adsorption, photocatalysis, low-temperature plasma, catalytic combustion and the like are developed; however, these techniques also have a number of disadvantages in the formaldehyde elimination process, such as: limited adsorption capacity, large energy consumption, serious secondary pollution, low elimination efficiency, high reaction temperature and the like. Therefore, the method for eliminating formaldehyde at room temperature at low cost and high efficiency is still a very challenging problem, and has high academic value and practical significance.
Among the various formaldehyde elimination technologies, catalytic oxidation can completely decompose formaldehyde into harmless CO2And H2O, does not produce secondary pollution, has mild reaction conditions and low energy consumption, so the method is considered to be a formaldehyde elimination technology with great development and application prospects, and the key of the technology is to construct a high-efficiency catalytic system. At present, noble metal catalytic systems represented by Pt and transition metal catalytic systems represented by Mn and Co are widely used in the formaldehyde purification process. Such asApplied Catalysis B: Environmental2020,267118689 recently reported that small amounts of Pt and MnO were used2The nano sheet is loaded on the foam carbon to form Pt/MnO2the-CF catalyst has remarkable effect in purifying formaldehyde at room temperature. ZL201910113508.5 describes a manganese oxide catalyst, its preparation method and application; in addition, ZL201810073524.1 also discloses a method for preparing a catalyst capable of completely catalytically oxidizing formaldehyde at room temperature, which all show higher removal efficiency in formaldehyde purification. However, the above catalytic systems have two major problems to be solved: (1) although the noble metal catalyst has good aldehyde removal effect, the cost is too high and the industrialization is difficult to realize; (2) the cheap transition metal catalyst has low catalytic activity at low temperature, easy deactivation and long aldehyde removing time. Therefore, the formaldehyde purifying agent which is cheap, long-acting and rapid is sought and popularized and applied becomes a hot spot of recent research.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a supported long-acting formaldehyde purifying agent as well as a preparation method and application thereof.
In order to solve the technical problems, the invention provides a supported long-acting formaldehyde purifying agent, which is obtained by using long-acting stable manganese-based hydrotalcite as a carrier, a supported rare earth metal as an active center and utilizing permanganate for oxidation modification, wherein the rare earth metal is one or two of lanthanum, cerium, praseodymium, neodymium, dysprosium, holmium, ytterbium, lutetium, scandium and yttrium, and the molar content of the supported rare earth element accounts for 0.5-5% of the total molar number of the catalyst.
The invention also provides a preparation method of the supported long-acting formaldehyde purifying agent, which comprises the following steps:
(1) preparing a mixed colloidal aqueous solution of manganese nitrate, non-manganese metal oxide and sodium metaaluminate, controlling the pH value of the mixed colloidal aqueous solution to be 10-11.5 by using alkali liquor, stirring the mixed colloidal aqueous solution at room temperature for 4-24 hours, and controlling the ratio of the total mole number of the manganese nitrate and the non-manganese metal oxide to the mole number of the sodium metaaluminate to be 2-5: 1, controlling the total concentration of manganese ions, non-manganese metal ions and aluminum ions to be 2.0-5.0 mol/L; filtering or centrifugally dewatering the obtained colloid, washing the colloid to be neutral by water, drying the colloid at the temperature of 80-120 ℃, and calcining the obtained solid sample at the temperature of 300-800 ℃ for 2-8 hours to prepare a corresponding composite oxide;
(2) preparing a rare earth metal nitrate solution with a certain concentration, soaking the composite oxide obtained in the step 1) in the rare earth metal nitrate solution, stirring at room temperature for 4-24 hours, and filtering or centrifugally dewatering to obtain a colloid;
(3) preparing a permanganate solution with a certain concentration, placing the colloid obtained in the step 2) in the permanganate solution, performing ultrasonic oscillation and stirring for 6-12 hours, performing centrifugal dehydration, and drying at 80-120 ℃ to obtain the supported long-acting formaldehyde purifying agent.
Preferably, the first and second electrodes are formed of a metal,
in the step (1), the non-manganese metal oxide is one of magnesium oxide, zinc oxide or calcium oxide; the alkali solution is one of sodium hydroxide, potassium hydroxide, ammonium hydroxide and urea.
In the step (2), the rare earth metal nitrate is nitrate of one or two of lanthanum, cerium, praseodymium, neodymium, dysprosium, holmium, ytterbium, lutetium, scandium and yttrium.
In the step (3), the permanganate is one of lithium permanganate, sodium permanganate, potassium permanganate and ammonium permanganate.
More preferably still, the first and second liquid crystal compositions are,
in the step (1), the ratio of the total mole number of the manganese nitrate and the non-manganese metal oxide to the mole number of the sodium metaaluminate is controlled to be 2: 1 or 5: 1.
in the step (2), the concentration of the rare earth metal nitrate solution is 0.015-0.25 mol/L.
In the step (3), the concentration of the permanganate is 1-2.5 mol/L.
The invention also provides the application of the load type long-acting formaldehyde purifying agent in purifying formaldehyde by being carried on an air purifier, a fresh air system or an air conditioner filter screen.
The invention also provides a preparation method of the porous medium loaded with the load type long-acting formaldehyde purifying agent, which comprises the following steps:
(1) preparing a mixed colloidal aqueous solution of manganese nitrate, non-manganese metal oxide and sodium metaaluminate, controlling the pH value of the mixed colloidal aqueous solution to be 10-11.5 by using alkali liquor, stirring the mixed colloidal aqueous solution at room temperature for 4-24 hours, and controlling the ratio of the total mole number of the manganese nitrate and the non-manganese metal oxide to the mole number of the sodium metaaluminate to be 2-5: 1, controlling the total concentration of manganese ions, non-manganese metal ions and aluminum ions to be 2.0-5.0 mol/L; filtering or centrifugally dewatering the obtained colloid, washing the colloid to be neutral by water, drying the colloid at the temperature of 80-120 ℃, and calcining the obtained solid sample at the temperature of 300-800 ℃ for 2-8 hours to prepare a corresponding composite oxide;
(2) preparing a rare earth metal nitrate solution with a certain concentration, soaking the composite oxide obtained in the step 1) in the rare earth metal nitrate solution, stirring at room temperature for 4-24 hours, and filtering or centrifugally dewatering to obtain a colloid;
(3) preparing a permanganate solution with a certain concentration, placing the colloid obtained in the step 2) in the permanganate solution, performing ultrasonic oscillation and stirring for 6-12 hours, placing the porous medium in the colloid for 5-20 minutes, taking out, performing centrifugal dehydration, and drying at 80-120 ℃ to obtain the porous medium loaded with the supported long-acting formaldehyde purifying agent.
Preferably, the first and second electrodes are formed of a metal,
in the step (1), the non-manganese metal oxide is one of magnesium oxide, zinc oxide or calcium oxide; the alkali solution is one of sodium hydroxide, potassium hydroxide, ammonium hydroxide and urea.
In the step (2), the rare earth metal nitrate is nitrate of one or two of lanthanum, cerium, praseodymium, neodymium, dysprosium, holmium, ytterbium, lutetium, scandium and yttrium.
In the step (3), the porous medium is one of non-woven fabric, corrugated paper and aluminum honeycomb; the permanganate is one of lithium permanganate, sodium permanganate, potassium permanganate and ammonium permanganate.
More preferably still, the first and second liquid crystal compositions are,
in the step (1), the ratio of the total mole number of the manganese nitrate and the non-manganese metal oxide to the mole number of the sodium metaaluminate is controlled to be 2: 1 or 5: 1.
in the step (2), the concentration of the rare earth metal nitrate solution is 0.015-0.25 mol/L.
In the step (3), the concentration of the permanganate is 1-2.5 mol/L.
The invention utilizes the natural stable structure of the hydrotalcite-like compound to prepare the stable manganese-containing hydrotalcite-like compound, loads rare earth metal as an auxiliary active center, utilizes permanganate oxidation modification to prepare the excellent formaldehyde purifying agent, the formaldehyde removal rate can reach 99.8 percent in 1 hour, the catalyst can not be inactivated in 200 days, and the invention has unexpected technical effect, and the cheap and efficient formaldehyde purifying agent is not reported. In addition, the purifying agent still keeps excellent formaldehyde purifying effect when being sprayed on porous media, and paves the way for the future application of the purifying agent on filter screens of air purifiers, fresh air systems, air conditioners and the like.
The invention has the following beneficial effects:
(1) the load type long-acting formaldehyde purifying agent shows long-term and high-efficiency performance in the process of removing low-concentration formaldehyde, the highest removal rate of the formaldehyde can reach 99.8 percent within 1 hour, and the formaldehyde is not inactivated within 200 days;
(2) the load type long-acting formaldehyde purifying agent can be firmly and fixedly loaded on a porous medium to play a role in removing formaldehyde, and has the advantages of low cost, simple preparation process and no three-waste discharge;
(3) the load type long-acting formaldehyde purifying agent can purify under the severe conditions of alkalinity, humidity and the like, and is beneficial to industrial popularization and application.
Detailed Description
The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
in the examples of the present invention, the formaldehyde removal test and analysis method was carried out × placing a 2 cm × 2 cm porous medium sprayed with a cleaning agent in a volume of 1m32 PPM formaldehyde is injected into the box, and the formaldehyde removal rate is calculated by using the change of the formaldehyde concentration in the on-line test box of a U.S. INTERSCAN formaldehyde detector 4160-2. Formaldehyde removal rate = (C)0-Ct）*100%/C0（C0Is the initial concentration of formaldehyde, CtIs the concentration after the formaldehyde reaction)
Example 1
Preparing 45L of mixed colloidal aqueous solution of 48 mol of manganese nitrate, 12 mol of magnesium oxide and 30 mol of sodium metaaluminate; controlling the pH value of the solution to be about 10 by using sodium hydroxide, stirring the solution at room temperature for 4 hours, filtering and dehydrating the obtained colloid, washing the colloid to be neutral by using water, drying the colloid at 80 ℃, and calcining the obtained solid sample at 300 ℃ for 2 hours to obtain the corresponding manganese-magnesium-aluminum composite oxide. 10L of 0.03mol/L lanthanum nitrate and 0.015 mol/L cerium nitrate are prepared, the obtained composite oxide is soaked in the prepared lanthanum nitrate and cerium nitrate, the obtained composite oxide is stirred for 4 hours at room temperature, and the colloid is obtained through centrifugal dehydration. Preparing 50L of 1.0 mol/L high lithium manganate solution, placing the obtained colloid in the solution, performing ultrasonic oscillation and stirring for 6 hours, placing the non-woven fabric in the colloid for 5 minutes, taking out the non-woven fabric, performing centrifugal dehydration, and drying at 80 ℃ to obtain the non-woven fabric loaded with the formaldehyde purifying agent. The mole content of the rare earth element loaded in the formaldehyde purifying agent accounts for 0.5 percent of the total mole number of the catalyst.
Effect test:
1) the obtained non-woven fabric loaded with the formaldehyde purifying agent is placed in a climate box containing 2 PPM formaldehyde at room temperature, and the removal rate of the formaldehyde is measured to be 90% after 1 hour. The formaldehyde purifying agent can be proved to be capable of efficiently removing low-concentration formaldehyde.
2) The obtained non-woven fabric loaded with the formaldehyde purifying agent is placed in the air for 200 days, and then the formaldehyde removal test analysis is carried out, so that the formaldehyde removal rate is 89%. It can be demonstrated that the formaldehyde scavenger of the present invention does not deactivate within 200 days.
Example 2
Preparing 18L of mixed colloidal aqueous solution of 45 mol of manganese nitrate, 30 mol of zinc oxide and 15mol of sodium metaaluminate; controlling the pH value of the solution to be about 11.5 by using sodium hydroxide, stirring the solution at room temperature for 24 hours, centrifugally dewatering the obtained colloid, washing the colloid to be neutral by using water, drying the colloid at 120 ℃, and calcining the obtained solid sample at 800 ℃ for 8 hours to obtain the corresponding manganese-zinc-aluminum composite oxide. 15L of 0.2mol/L lanthanum nitrate and 0.1 mol/L cerium nitrate are prepared, the obtained composite oxide is soaked in the solution, the solution is stirred for 24 hours at room temperature, and the colloid is obtained by filtration. Preparing 20L of 2.5mol/L sodium permanganate solution, placing the obtained colloid in the solution, performing ultrasonic oscillation and stirring for 12 hours, placing the corrugated paper in the colloid for 20 minutes, taking out the corrugated paper, performing centrifugal dehydration, and drying at 120 ℃ to obtain the corrugated paper loaded with the formaldehyde purifying agent. The mole content of the rare earth element loaded in the formaldehyde purifying agent accounts for 5 percent of the total mole number of the catalyst.
Effect test:
1) the corrugated paper loaded with the formaldehyde purifying agent is placed in a climate box containing 2 PPM formaldehyde at room temperature, and the formaldehyde removal rate is measured to be 94.5% after 1 hour. The formaldehyde purifying agent can be proved to be capable of efficiently removing low-concentration formaldehyde.
2) The corrugated paper loaded with the formaldehyde purifying agent is placed in the air for 200 days, and then the formaldehyde removal test analysis is carried out, so that the formaldehyde removal rate is 94 percent. It can be demonstrated that the formaldehyde scavenger of the present invention does not deactivate within 200 days.
Example 3
Preparing 30L of mixed colloidal aqueous solution of 30 mol of manganese nitrate, 30 mol of calcium oxide and 30 mol of sodium metaaluminate; controlling the pH value of the solution to be about 10.5 by using potassium hydroxide, stirring the solution at room temperature for 12 hours, filtering and dehydrating the obtained colloid, washing the colloid to be neutral by using water, drying the colloid at 100 ℃, and calcining the obtained solid sample at 400 ℃ for 4 hours to obtain the corresponding manganese-calcium-aluminum composite oxide. 10L of praseodymium nitrate of 0.25mol/L is prepared, the obtained composite oxide is immersed in the praseodymium nitrate, stirred for 12 hours at room temperature, and filtered to obtain colloid. And preparing 20L of 1.5 mol/L potassium permanganate solution, placing the obtained colloid in the solution, performing ultrasonic oscillation and stirring for 8 hours, placing the aluminum honeycomb in the colloid for 10 minutes, taking out the aluminum honeycomb, performing centrifugal dehydration, and drying at 100 ℃ to obtain the aluminum honeycomb loaded with the formaldehyde purifying agent. The molar content of the rare earth elements loaded in the formaldehyde purifying agent accounts for 2.8 percent of the total molar number of the catalyst.
Effect test:
1) the obtained aluminum honeycomb loaded with the formaldehyde purifying agent is placed in a climate box containing 2 PPM formaldehyde at room temperature, and the removal rate of the formaldehyde is 80 percent after 1 hour. The formaldehyde purifying agent can be proved to be capable of efficiently removing low-concentration formaldehyde.
2) The obtained aluminum honeycomb loaded with the formaldehyde purifying agent is placed in the air for 200 days, and then the formaldehyde removal test analysis is carried out, so that the formaldehyde removal rate is measured to be 73%. It can be demonstrated that the formaldehyde scavenger of the present invention does not deactivate within 200 days.
Example 4
Preparing 30L of mixed colloidal aqueous solution of 30 mol of manganese nitrate, 30 mol of zinc oxide and 30 mol of sodium metaaluminate; controlling the pH value of the solution to be about 10.5 by using ammonium hydroxide, stirring the solution at room temperature for 12 hours, filtering and dehydrating the obtained colloid, washing the colloid to be neutral by using water, drying the colloid at 100 ℃, and calcining the obtained solid sample at 400 ℃ for 4 hours to obtain the corresponding manganese-zinc-aluminum composite oxide. 10L of neodymium nitrate of 0.25mol/L was prepared, the obtained composite oxide was immersed in the solution, stirred at room temperature for 12 hours, and filtered to obtain a colloid. Preparing 20L of 1.5 mol/L ammonium permanganate solution, placing the obtained colloid in the solution, performing ultrasonic oscillation and stirring for 8 hours, placing the aluminum honeycomb in the colloid for 10 minutes, taking out the aluminum honeycomb, performing centrifugal dehydration, and drying at 100 ℃ to obtain the aluminum honeycomb loaded with the formaldehyde purifying agent. The molar content of the rare earth elements loaded in the formaldehyde purifying agent accounts for 2.8 percent of the total molar number of the catalyst.
Effect test:
1) the obtained aluminum honeycomb loaded with the formaldehyde purifying agent is placed in a climate box containing 2 PPM formaldehyde at room temperature, and the removal rate of the formaldehyde is measured to be 87% after 1 hour. The formaldehyde purifying agent can be proved to be capable of efficiently removing low-concentration formaldehyde.
2) The obtained aluminum honeycomb loaded with the formaldehyde purifying agent is placed in the air for 200 days, and then the formaldehyde removal test analysis is carried out, so that the formaldehyde removal rate is 85 percent. It can be demonstrated that the formaldehyde scavenger of the present invention does not deactivate within 200 days.
Example 5
Preparing 30L of mixed colloidal aqueous solution of 30 mol of manganese nitrate, 30 mol of magnesium oxide and 30 mol of sodium metaaluminate; controlling the pH value of the solution to be about 10.5 by using urea, stirring the solution at room temperature for 12 hours, filtering and dehydrating the obtained colloid, washing the colloid to be neutral by using water, drying the colloid at 100 ℃, and calcining the obtained solid sample at 400 ℃ for 4 hours to prepare the corresponding manganese-magnesium-aluminum composite oxide. 10L of 0.15mol/L dysprosium nitrate and 0.1 mol/L holmium nitrate are prepared, the obtained composite oxide is immersed in the solution, the solution is stirred for 12 hours at room temperature, and the colloid is obtained by filtration. Preparing 20L of 1.5 mol/L ammonium permanganate solution, placing the obtained colloid in the solution, performing ultrasonic oscillation and stirring for 8 hours, placing the aluminum honeycomb in the colloid for 10 minutes, taking out the aluminum honeycomb, performing centrifugal dehydration, and drying at 100 ℃ to obtain the aluminum honeycomb loaded with the formaldehyde purifying agent. The molar content of the rare earth elements loaded in the formaldehyde purifying agent accounts for 2.8 percent of the total molar number of the catalyst.
Effect test:
1) the obtained aluminum honeycomb loaded with the formaldehyde purifying agent is placed in a climatic box containing 2 PPM formaldehyde at room temperature, 100 milliliters of 0.001mol/L ammonia water is placed in the climatic box, and the removal rate of the formaldehyde is measured to be 96.5 percent after 1 hour. The formaldehyde purifying agent disclosed by the invention can be proved to be capable of efficiently removing low-concentration formaldehyde under an alkaline condition.
2) And placing the obtained aluminum honeycomb loaded with the formaldehyde purifying agent in the air for 200 days, and then performing formaldehyde removal test analysis to obtain that the formaldehyde removal rate is 91%. It can be demonstrated that the formaldehyde scavenger of the present invention does not deactivate within 200 days.
Example 6
Preparing 30L of mixed colloidal aqueous solution of 30 mol of manganese nitrate, 30 mol of calcium oxide and 30 mol of sodium metaaluminate; controlling the pH value of the solution to be about 10.5 by using urea, stirring the solution at room temperature for 12 hours, filtering and dehydrating the obtained colloid, washing the colloid to be neutral by using water, drying the colloid at 100 ℃, and calcining the obtained solid sample at 400 ℃ for 4 hours to prepare the corresponding manganese-calcium-aluminum composite oxide. Preparing 10L of 0.15mol/L ytterbium nitrate and 0.15mol/L lutetium nitrate, soaking the obtained composite oxide in the prepared ytterbium nitrate and lutetium nitrate, stirring the mixture at room temperature for 12 hours, and filtering the mixture to obtain colloid. Preparing 20L of 1.5 mol/L ammonium permanganate solution, placing the obtained colloid in the solution, performing ultrasonic oscillation and stirring for 8 hours, placing the aluminum honeycomb in the colloid for 10 minutes, taking out the aluminum honeycomb, performing centrifugal dehydration, and drying at 100 ℃ to obtain the aluminum honeycomb loaded with the formaldehyde purifying agent. The mole content of the rare earth element loaded in the formaldehyde purifying agent accounts for 3.3 percent of the total mole number of the catalyst.
Effect test:
1) the obtained aluminum honeycomb loaded with the formaldehyde purifying agent is placed in a climate box containing 2 PPM formaldehyde at room temperature, and the removal rate of the formaldehyde is 95 percent after 1 hour. The formaldehyde purifying agent can be proved to be capable of efficiently removing low-concentration formaldehyde.
2) The obtained aluminum honeycomb loaded with the formaldehyde purifying agent is placed in the air for 200 days, and then the formaldehyde removal test analysis is carried out, so that the formaldehyde removal rate is 93 percent. It can be demonstrated that the formaldehyde scavenger of the present invention does not deactivate within 200 days.
Example 7
Preparing 30L of mixed colloidal aqueous solution of 30 mol of manganese nitrate, 30 mol of magnesium oxide and 30 mol of sodium metaaluminate; controlling the pH value of the solution to be about 10.5 by using urea, stirring the solution at room temperature for 12 hours, filtering and dehydrating the obtained colloid, washing the colloid to be neutral by using water, drying the colloid at 100 ℃, and calcining the obtained solid sample at 400 ℃ for 4 hours to prepare the corresponding manganese-magnesium-aluminum composite oxide. A total of 20L of 0.06 mol/L scandium nitrate and 0.03mol/L yttrium nitrate was prepared, and the obtained composite oxide was immersed in the prepared solution, stirred at room temperature for 12 hours, and filtered to obtain a colloid. Preparing 20L of 1.5 mol/L ammonium permanganate solution, placing the obtained colloid in the solution, performing ultrasonic oscillation and stirring for 8 hours, placing the aluminum honeycomb in the colloid for 10 minutes, taking out the aluminum honeycomb, performing centrifugal dehydration, and drying at 100 ℃ to obtain the aluminum honeycomb loaded with the formaldehyde purifying agent. The mole content of the rare earth element loaded in the formaldehyde purifying agent accounts for 2 percent of the total mole number of the catalyst.
Effect test:
1) the obtained aluminum honeycomb loaded with the formaldehyde purifying agent is placed in a climate box containing 2 PPM formaldehyde at room temperature, and the removal rate of the formaldehyde is 89% after 1 hour. The formaldehyde purifying agent can be proved to be capable of efficiently removing low-concentration formaldehyde.
2) And placing the obtained aluminum honeycomb loaded with the formaldehyde purifying agent in the air for 200 days, and then performing formaldehyde removal test analysis to obtain that the formaldehyde removal rate is 88%. It can be demonstrated that the formaldehyde scavenger of the present invention does not deactivate within 200 days.
Example 8
Preparing 30L of mixed colloidal aqueous solution of 30 mol of manganese nitrate, 30 mol of magnesium oxide and 30 mol of sodium metaaluminate; controlling the pH value of the solution to be about 10.5 by using potassium hydroxide, stirring the solution at room temperature for 12 hours, filtering and dehydrating the obtained colloid, washing the colloid to be neutral by using water, drying the colloid at 100 ℃, and calcining the obtained solid sample at 400 ℃ for 4 hours to prepare the corresponding manganese-magnesium-aluminum composite oxide. Preparing 20L of 0.03mol/L lanthanum nitrate and 0.06 mol/L cerium nitrate, soaking the obtained composite oxide in the prepared lanthanum nitrate and cerium nitrate, stirring the mixture at room temperature for 12 hours, and filtering the mixture to obtain colloid. And preparing 20L of 1.5 mol/L potassium permanganate solution, placing the obtained colloid in the solution, performing ultrasonic oscillation and stirring for 8 hours, placing the aluminum honeycomb in the colloid for 10 minutes, taking out the aluminum honeycomb, performing centrifugal dehydration, and drying at 100 ℃ to obtain the aluminum honeycomb loaded with the formaldehyde purifying agent. The mole content of the rare earth element loaded in the formaldehyde purifying agent accounts for 2 percent of the total mole number of the catalyst.
Effect test:
1) the obtained aluminum honeycomb loaded with the formaldehyde purifying agent is placed in a climatic box containing 2 PPM formaldehyde at room temperature, 100 milliliters of 0.001mol/L ammonia water is placed in the climatic box, and the removal rate of the formaldehyde is measured to be 99.8 percent after 1 hour. The formaldehyde purifying agent disclosed by the invention can be proved to be capable of efficiently removing low-concentration formaldehyde under an alkaline condition.
2) Placing the aluminum honeycomb loaded with the formaldehyde purifying agent in the air for 200 days, and then carrying out formaldehyde removal test analysis to obtain the formaldehyde removal rate of 98%. It can be demonstrated that the formaldehyde scavenger of the present invention does not deactivate within 200 days.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The supported long-acting formaldehyde purifying agent is characterized in that the purifying agent takes long-acting stable manganese-based hydrotalcite as a carrier, a supported rare earth metal as an active center and is obtained by oxidation modification of permanganate, wherein the rare earth metal is one or two of lanthanum, cerium, praseodymium, neodymium, dysprosium, holmium, ytterbium, lutetium, scandium and yttrium, and the molar content of the supported rare earth element accounts for 0.5-5% of the total molar number of a catalyst.
2. The preparation method of the supported long-acting formaldehyde scavenger as claimed in claim 1, wherein the preparation method comprises the following steps:
(1) preparing a mixed colloidal aqueous solution of manganese nitrate, non-manganese metal oxide and sodium metaaluminate, controlling the pH value of the mixed colloidal aqueous solution to be 10-11.5 by using alkali liquor, stirring the mixed colloidal aqueous solution at room temperature for 4-24 hours, and controlling the ratio of the total mole number of the manganese nitrate and the non-manganese metal oxide to the mole number of the sodium metaaluminate to be 2-5: 1, controlling the total concentration of manganese ions, non-manganese metal ions and aluminum ions to be 2.0-5.0 mol/L; filtering or centrifugally dewatering the obtained colloid, washing the colloid to be neutral by water, drying the colloid at the temperature of 80-120 ℃, and calcining the obtained solid sample at the temperature of 300-800 ℃ for 2-8 hours to prepare a corresponding composite oxide;
(2) preparing a rare earth metal nitrate solution with a certain concentration, soaking the composite oxide obtained in the step 1) in the rare earth metal nitrate solution, stirring at room temperature for 4-24 hours, and filtering or centrifugally dewatering to obtain a colloid;
(3) preparing a permanganate solution with a certain concentration, placing the colloid obtained in the step 2) in the permanganate solution, performing ultrasonic oscillation and stirring for 6-12 hours, performing centrifugal dehydration, and drying at 80-120 ℃ to obtain the supported long-acting formaldehyde purifying agent.
3. The method according to claim 2, wherein in the step (1), the non-manganese metal oxide is one of magnesium oxide, zinc oxide, or calcium oxide; the alkali solution is one of sodium hydroxide, potassium hydroxide, ammonium hydroxide and urea.
4. The production method according to claim 2, wherein in the step (2), the rare earth metal nitrate is a nitrate of one or two rare earth metals selected from lanthanum, cerium, praseodymium, neodymium, dysprosium, holmium, ytterbium, lutetium, scandium and yttrium.
5. The method according to claim 2, wherein in the step (3), the permanganate is one of lithium permanganate, sodium permanganate, potassium permanganate and ammonium permanganate.
6. The use of the long-acting formaldehyde scavenger as claimed in claim 1 for purifying formaldehyde by being carried on an air purifier, a fresh air system or an air conditioner filter screen.
7. The preparation method of the porous medium loaded with the supported long-acting formaldehyde scavenger in the claim 1 is characterized by comprising the following steps:
(1) preparing a mixed colloidal aqueous solution of manganese nitrate, non-manganese metal oxide and sodium metaaluminate, controlling the pH value of the mixed colloidal aqueous solution to be 10-11.5 by using alkali liquor, stirring the mixed colloidal aqueous solution at room temperature for 4-24 hours, and controlling the ratio of the total mole number of the manganese nitrate and the non-manganese metal oxide to the mole number of the sodium metaaluminate to be 2-5: 1, controlling the total concentration of manganese ions, non-manganese metal ions and aluminum ions to be 2.0-5.0 mol/L; filtering or centrifugally dewatering the obtained colloid, washing the colloid to be neutral by water, drying the colloid at the temperature of 80-120 ℃, and calcining the obtained solid sample at the temperature of 300-800 ℃ for 2-8 hours to prepare a corresponding composite oxide;
(2) preparing a rare earth metal nitrate solution with a certain concentration, soaking the composite oxide obtained in the step 1) in the rare earth metal nitrate solution, stirring at room temperature for 4-24 hours, and filtering or centrifugally dewatering to obtain a colloid;
(3) preparing a permanganate solution with a certain concentration, placing the colloid obtained in the step 2) in the permanganate solution, performing ultrasonic oscillation and stirring for 6-12 hours, placing the porous medium in the colloid for 5-20 minutes, taking out, performing centrifugal dehydration, and drying at 80-120 ℃ to obtain the porous medium loaded with the supported long-acting formaldehyde purifying agent.
8. The method according to claim 7, wherein in the step (1), the non-manganese metal oxide is one of magnesium oxide, zinc oxide or calcium oxide; the alkali solution is one of sodium hydroxide, potassium hydroxide, ammonium hydroxide and urea.
9. The method as claimed in claim 7, wherein in the step (2), the rare earth metal nitrate is a nitrate of one or two rare earth metals selected from lanthanum, cerium, praseodymium, neodymium, dysprosium, holmium, ytterbium, lutetium, scandium and yttrium.
10. The method of claim 7, wherein in step (3), the porous medium is one of a non-woven fabric, corrugated paper, and aluminum honeycomb; the permanganate is one of lithium permanganate, sodium permanganate, potassium permanganate and ammonium permanganate.
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| CN115007132A (en) * | 2022-06-29 | 2022-09-06 | 南京工业大学 | Carbon nanotube supported dysprosium oxide catalyst and preparation method and application thereof |
| CN116371394A (en) * | 2022-12-01 | 2023-07-04 | 南宁师范大学 | Catalytic modified formaldehyde purification material and preparation method thereof |
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