CN113680383A - Composite material for purifying aldehydes and benzene series in air as well as preparation method and application thereof - Google Patents
Composite material for purifying aldehydes and benzene series in air as well as preparation method and application thereof Download PDFInfo
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- CN113680383A CN113680383A CN202110980606.6A CN202110980606A CN113680383A CN 113680383 A CN113680383 A CN 113680383A CN 202110980606 A CN202110980606 A CN 202110980606A CN 113680383 A CN113680383 A CN 113680383A
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- manganese
- cerium
- composite material
- air
- benzene series
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- 239000002131 composite material Substances 0.000 title claims abstract description 171
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title abstract description 6
- 150000001299 aldehydes Chemical class 0.000 title abstract 4
- 150000001555 benzenes Chemical class 0.000 claims description 89
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 83
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 58
- 229910052748 manganese Inorganic materials 0.000 claims description 58
- 239000011572 manganese Substances 0.000 claims description 58
- 239000000463 material Substances 0.000 claims description 54
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 45
- 239000002808 molecular sieve Substances 0.000 claims description 41
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 41
- 229910052723 transition metal Inorganic materials 0.000 claims description 40
- 150000003624 transition metals Chemical class 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 38
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical compound [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 24
- 229910052684 Cerium Inorganic materials 0.000 claims description 23
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000011068 loading method Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000000746 purification Methods 0.000 claims description 20
- 229960000892 attapulgite Drugs 0.000 claims description 19
- 229910052625 palygorskite Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000012670 alkaline solution Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 10
- 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 9
- 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 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 7
- 238000004887 air purification Methods 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 229960001759 cerium oxalate Drugs 0.000 claims description 5
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- RAAAGFMZFLFGFI-UHFFFAOYSA-N chloro hypochlorite manganese Chemical compound [Mn].ClOCl RAAAGFMZFLFGFI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 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
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 102
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 47
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 18
- 238000001035 drying Methods 0.000 description 17
- 239000011592 zinc chloride Substances 0.000 description 14
- 235000005074 zinc chloride Nutrition 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000003344 environmental pollutant Substances 0.000 description 12
- 231100000719 pollutant Toxicity 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000003421 catalytic decomposition reaction Methods 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 230000001360 synchronised effect Effects 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- -1 potassium hydroxide compound Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B01J35/615—
-
- 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
-
- 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
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
Abstract
The invention provides a composite material for purifying aldehydes and benzene series in air and a preparation method and application thereof. The composite material for purifying aldehydes and benzene series in air has large specific surface area, can completely catalyze and decompose the aldehydes and the benzene series in air at room temperature, and has stable performance and high practical value; the preparation method is simple and suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the field of air purification materials, in particular to a composite material for purifying aldehydes and benzene series in air and a preparation method and application thereof.
Background
Building materials and coatings for decoration emit a large amount of aldehydes such as formaldehyde and acetaldehyde and benzene series pollutants such as benzene, toluene and xylene, seriously pollute air and harm the health of people. Therefore, the development of aldehyde and benzene series purifying materials to effectively eliminate the aldehyde and benzene series pollution in the air is a necessary means for improving the indoor air quality.
The existing technology for purifying aldehydes and benzene series in air mainly comprises photocatalytic degradation, catalytic oxidation technology and adsorption purification technology, wherein the photocatalytic degradation technology mainly utilizes nano TiO2As a photocatalyst, a strong ultraviolet excitation light source is needed for catalytic degradation, but the technology has the problems of low ultraviolet light utilization efficiency, easy inactivation of the catalyst and the like; the catalytic oxidation technology is an important method for removing aldehydes and benzene series, formaldehyde can be completely oxidized at room temperature through transition metal oxides, and the benzene series cannot be completely oxidized and removed at room temperature due to stable structure, so that the benzene series can be completely oxidized only at the temperature of more than 150 ℃ even in the presence of a noble metal catalyst; the adsorption purification technology is the most important means in the field of air purification, and mainly adopts materials with high specific surface area, such as activated carbon, molecular sieves and the like, to adsorb pollutants, but the materials have the problems of low adsorption capacity, small acting force with strong polar pollutants, such as aldehydes and the like, need to be regenerated or replaced regularly, and are easy to generate secondary pollution.
CN112774650A discloses a formaldehyde purification material preparation, a preparation method and an application, the formaldehyde purification material preparation is in a granular shape, each granule is composed of a formaldehyde purification material and a binding agent, the formaldehyde purification material comprises a formaldehyde decomposition catalyst, and the formaldehyde decomposition catalyst is delta crystal MnO2Submicron-nanoscale flower-shaped spherical particles formed by the nanosheets; the preparation method of the formaldehyde purification material preparation comprises the steps of preparing a formaldehyde purification material and a binder into a paste precursor, granulating the prepared paste precursor to obtain the formaldehyde purification material preparation, wherein the prepared formaldehyde adsorption-catalytic decomposition composite material has a core-shell structure, the core is composed of a VOC physical adsorbent, and the shell is composed of a formaldehyde decomposition catalyst. But the purifying material preparation cannot simultaneously purify and remove benzene series in the air.
CN111013533A discloses a modified activated carbon for purifying formaldehyde and a preparation method thereof, wherein a certain amount of oxidant and nucleophilic addition agent are used for modifying the activated carbon according to a certain proportion through a specific process, and the redox reaction of the oxidant and the formaldehyde, the addition reaction of the nucleophilic addition agent and the formaldehyde and the physical adsorption of the activated carbon are organically combined, so that the formaldehyde in the air is rapidly adsorbed on the activated carbon and is converted into substances harmless to human bodies through chemical action, and the purpose of thoroughly purifying the formaldehyde is achieved. Although the modified activated carbon has a good formaldehyde removal effect, under the condition that two pollutants of formaldehyde and benzene series exist at the same time, the molecular diameters of the formaldehyde and the benzene are greatly different, and the pore size distribution of the activated carbon can only absorb one of the two pollutants.
CN103691311A discloses a catalytic method for simultaneously removing indoor aldehyde and benzene series pollutants at room temperature, which comprises loading noble metal on a molecular sieve to obtain a catalyst, placing the catalyst in aldehyde and benzene series environments, and oxidizing the aldehyde pollutants into CO at room temperature2And H2And O, simultaneously storing the benzene series on the catalyst, heating up after the catalyst is saturated to oxidize the stored benzene series, and regenerating the catalyst in situ. However, the method also needs heating up to oxidize and degrade the benzene series, and complete degradation of the aldehydes and the benzene series pollutants at room temperature is not realized.
Therefore, the development of the composite material for purifying the aldehydes and the benzene series in the air, which can degrade and remove the aldehydes and the benzene series at the same time at room temperature, has important significance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a composite material for purifying aldehydes and benzene series in air and a preparation method and application thereof, wherein the composite material for purifying aldehydes and benzene series in air is a porous composite carrier with a catalyst for decomposing and removing aldehyde pollutants loaded on the surface and a catalyst for removing benzene series loaded inside, and can synchronously remove aldehydes and benzene series at room temperature; the preparation method is simple, the reaction conditions are mild, and the method has a large-scale industrial production prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a composite material for purifying aldehydes and benzene series in air, which comprises a porous composite carrier, a manganese-cerium composite loaded on the porous composite carrier, a transition metal active component except manganese and a compound of an auxiliary metal, wherein the auxiliary metal comprises alkali metal and/or alkaline earth metal.
The porous composite carrier in the composite material for purifying aldehydes and benzene series in the air has high specific surface area, and the internal porous structure selectively adsorbs and enriches the benzene series by utilizing the pore canal limited range; manganese-cerium composite oxide is used as an active component for catalyzing and degrading benzene series, wherein the manganese oxide is used as a main active component, and the cerium oxide is used as an auxiliary catalytic component; the active components of transition metals except manganese are used as the active components for catalyzing and degrading the aldehyde pollutants. When the composite material for purifying aldehydes and benzene series in air is used for air purification treatment, the transition metal active components except manganese have good decomposition performance on the aldehydes, release heat and provide active sites, meanwhile, the porous adsorption carrier pore structure realizes benzene series enrichment, and the two realize catalytic decomposition of the benzene series at room temperature under the synergistic effect.
Preferably, the specific surface area of the aldehyde and benzene series purifying composite material in the air is 200-500 m2A/g, which may be, for example, 200m2/g、250m2/g、300m2/g、350m2/g、400m2G or 500m2/g。
The aldehydes and the benzene series are not particularly limited, and the method can be applied to the aldehydes and the benzene series which are common in the air and can also be applied to the aldehydes and the benzene series which are not common in the air but similar, wherein the aldehydes can be formaldehyde, acetaldehyde and the like, and the benzene series can be benzene, toluene, ethylbenzene and the like.
Preferably, the manganese-cerium composite includes a composite formed of a manganese oxide and a cerium oxide.
Preferably, the manganese oxide comprises manganese dioxide and/or trimanganese tetroxide.
Preferably, the cerium oxide comprises cerium oxide.
Preferably, the loading amount of the manganese oxide on the porous composite support is 0.5 wt% to 5.0 wt%, and may be, for example, 0.5 wt%, 1 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt%, or 5.0 wt%.
Preferably, the molar ratio of manganese to cerium in the manganese-cerium composite is 1 (0.5-5), and may be 1:0.5, 1:1, 1:2, 1:3, 1:4 or 1:5, for example.
Preferably, the loading amount of the transition metal active component other than manganese on the porous composite support is 1 wt% to 10 wt%, and may be, for example, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%.
Preferably, the compound of the promoter metal is supported on the porous composite support at a level of from 0.2 wt% to 2.0 wt%, and may for example be 0.2 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.5 wt% or 2.0 wt%.
Preferably, the porous composite support comprises a first support and a second support.
Preferably, the first carrier comprises attapulgite.
Preferably, the second support comprises a molecular sieve.
The invention utilizes the synergistic effect of the attapulgite with high adsorptivity, strong ion exchange property and small-size nanoparticles (50-500 nm) and the molecular sieve with high selectivity to benzene series substances to form a stable and easily-dispersed composite carrier, and meanwhile, the composite carrier has a unique and adjustable pore structure and a large specific surface area and can carry out efficient air purification.
Preferably, the molecular sieve comprises any one of or a combination of at least two of TS-1 molecular sieve, SBA-15 molecular sieve, HY molecular sieve, HMS molecular sieve or ZSM molecular sieve, wherein typical but non-limiting combinations include a combination of TS-1 molecular sieve and SBA-15 molecular sieve, a combination of HY molecular sieve and HMS molecular sieve or a combination of TS-1 molecular sieve, SBA-15 molecular sieve and HY molecular sieve.
The molecular sieve has a highly ordered pore structure, has silicon hydroxyl groups which are easy to modify, can combine functional groups on the surface of a pore through silylation, and can realize selective adsorption on benzene series substances.
Preferably, the mass ratio of the first carrier to the second carrier is 1 (1-4), and may be 1:1, 1:2, 1:3, 1:3.5 or 1:4, for example.
The invention further preferably selects the mass ratio of the first carrier to the second carrier to be 1 (1-4), which can overcome the agglomeration of the single molecular sieve, increase the surface active sites and increase the selectivity and adsorption capacity of the composite carrier to the benzene series.
Preferably, the transition metal active component other than manganese includes any one of transition metals other than manganese, oxides of transition metals other than manganese, or inorganic salts of transition metals other than manganese, or a combination of at least two thereof, and may be, for example, a combination of a transition metal other than manganese and an oxide of a transition metal other than manganese, a combination of an oxide of a transition metal other than manganese and an inorganic salt of a transition metal other than manganese, or a combination of three of a transition metal other than manganese, an oxide of a transition metal other than manganese, and an inorganic salt of a transition metal other than manganese.
Preferably, the transition metal element other than manganese includes any one or a combination of at least two of iron, ruthenium, iridium, cobalt, nickel, copper or zinc, and may be, for example, a combination of iron and ruthenium, a combination of cobalt and nickel, a combination of nickel and copper, or a combination of three of iron, ruthenium and iridium.
Preferably, the compound of the promoter metal comprises a hydroxide and/or an inorganic salt, which may be, for example, calcium hydroxide, sodium hydroxide, zinc chloride or magnesium chloride, and the like.
In a second aspect, the present invention further provides a preparation method of the composite material for purifying aldehydes and benzene series in air according to the first aspect, wherein the preparation method comprises the following steps:
(1) mixing the porous composite carrier, the manganese source and the cerium source to obtain a first mixed material;
(2) mixing the first mixed material and an alkaline solution to obtain a second mixed material;
(3) carrying out solid-liquid separation and first roasting on the second mixed material in sequence to obtain a first composite material;
(4) and (2) soaking the first composite material in a mixed solution formed by mixing a transition metal active component solution except manganese and an auxiliary metal compound solution, and then sequentially carrying out solid-liquid separation and second roasting to obtain the aldehyde and benzene series purifying composite material in the air.
The preparation method adopts a coprecipitation method to load the manganese-cerium compound instead of an impregnation method, the coprecipitation method uniformly mixes the three components of the porous compound carrier, the manganese source and the cerium source at one time, and the prepared compound has the advantages of uniform chemical components, small granularity and uniform distribution; the manganese-cerium compound is loaded firstly, and then the transition metal active component except manganese and the compound of the auxiliary metal are loaded, so that the contact probability of the composite material and the aldehyde pollutants in the air is increased, the catalytic oxidation reaction of the aldehyde is facilitated, and the aldehyde decomposition is facilitated to provide active sites and energy to promote the catalytic decomposition of benzene series; the method adopts a dipping mode to load the transition metal active components except manganese and the compounds of the auxiliary metal, and is not a coprecipitation method, so that the load is favorably distributed on the outer surface of the compound, and the method has the advantages of simple operation and easy industrial production. The invention loads the manganese-cerium compound, the transition metal active component except manganese and the compound of the auxiliary metal on the porous composite carrier, and realizes the complete degradation of aldehydes and benzene series under the room temperature condition by utilizing the synergistic action among all the substances.
According to the invention, the porous composite carrier in the step (1) is sequentially stirred, filtered and dried in water or a sodium chloride solution with the concentration of 1-5 g/L, and then is mixed with a manganese source and a cerium source, so that the polymerization degree of the molecular sieve is reduced through the steric hindrance effect, and the adsorption effect of the molecular sieve on benzene series is improved.
Preferably, the concentration of the sodium chloride solution is 1-5 g/L, for example, 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, 4g/L or 5 g/L.
Preferably, the mass ratio of the porous composite carrier to the manganese source in the step (1) is 100 (0.5-5.0), and may be, for example, 100:0.5, 100:1.0, 100:1.5, 100:2.0, 100:2.5, 100:3.0, 100:3.5, 100:4.0, 100:4.5 or 100: 5.0.
Preferably, the molar ratio of the manganese source to the cerium source is 1 (0.5-5), and may be, for example, 1:0.5, 1:1, 1:3, 1:4, or 1: 5.
Preferably, the manganese source comprises any one or a combination of at least two of manganese nitrate, manganese sulfate, manganese oxychloride or manganese oxalate, and may be, for example, a combination of manganese nitrate and manganese sulfate, a combination of manganese sulfate and manganese oxychloride or a combination of three of manganese nitrate, manganese sulfate and manganese oxychloride.
Preferably, the cerium source comprises any one or a combination of at least two of cerium nitrate, cerium sulfate, cerium oxalate and cerium trichloride, and may be, for example, a combination of cerium nitrate and cerium sulfate, a combination of cerium sulfate and cerium oxalate or a combination of cerium sulfate, cerium oxalate and cerium trichloride.
Preferably, the concentration of the manganese source is 0.1mol/L to 1.0mol/L, and may be, for example, 0.1mol/L, 0.2mol/L, 0.4mol/L, 0.5mol/L, 0.7mol/L, 0.9mol/L, or 1.0 mol/L.
Preferably, the cerium source has a concentration of 0.1mol/L to 1.0mol/L, and may be, for example, 0.1mol/L, 0.2mol/L, 0.4mol/L, 0.5mol/L, 0.7mol/L, 0.9mol/L, or 1.0 mol/L.
Preferably, the alkaline solution in step (2) includes any one of ammonia water, sodium hydroxide solution, potassium hydroxide solution or calcium hydroxide solution.
Preferably, the concentration of the alkaline solution is 10% to 25% by mass, and may be, for example, 10%, 13%, 15%, 20%, 22%, or 25%.
The invention further preferably selects the alkaline solution with the mass percentage concentration of 10-25%, which is beneficial to the coprecipitation reaction of the first mixed material in the step (1) to obtain the second mixed material.
Preferably, the first mixed material enters the alkaline solution in a dropwise manner for mixing.
Preferably, the dropping rate is 1 to 5 drops/second, and may be, for example, 1 drop/second, 2 drops/second, 3 drops/second, 4 drops/second, or 5 drops/second.
Preferably, the second mixed material in the step (3) is subjected to water bath before solid-liquid separation.
Preferably, the temperature of the water bath is 40-80 ℃, for example, 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃.
Preferably, the time of the water bath is 2-5 h, for example, 2h, 2.5h, 3h, 4h or 5 h.
Preferably, the second mixed material in the step (3) is washed with deionized water after solid-liquid separation.
The solid-liquid separation in the present invention is not limited, and any method known to those skilled in the art that can be used for solid-liquid separation, for example, filtration, sedimentation, centrifugation, or the like, can be used.
Preferably, the number of washing is 3 to 6, and for example, may be 3, 4, 5 or 6.
Preferably, the temperature of the first firing is 400 to 600 ℃, for example, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃.
Preferably, the first roasting time is 3-5 h, for example, 3h, 3.5h, 4h, 4.5h or 5 h.
Preferably, the first firing is performed in a muffle furnace.
Preferably, the first firing is preceded by drying.
Preferably, the temperature of the first drying is 100 to 120 ℃, for example, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃.
Preferably, the first drying time is 6-10 h, for example, 6h, 7h, 8h, 9h or 10 h.
Preferably, the concentration of the transition metal active component soluble aqueous solution other than manganese in the step (4) is 0.5mol/L to 5.0mol/L, and may be, for example, 0.5mol/L, 1.0mol/L, 1.5mol/L, 2.0mol/L, 3.0mol/L, 4.0mol/L or 5.0 mol/L.
Preferably, the concentration of the compound-soluble aqueous solution of the promoter metal is 0.1mol/L to 1.0mol/L, and may be, for example, 0.1mol/L, 0.3mol/L, 0.5mol/L, 0.7mol/L, 0.9mol/L, or 1.0 mol/L.
The compound-soluble aqueous solution of the aid metal of the present invention means an aqueous solution formed of a compound of the aid metal soluble in water.
Preferably, the solute mass ratio of the transition metal active component soluble aqueous solution except manganese to the compound soluble aqueous solution of the auxiliary metal is 1: 0.1-1: 1, and can be 1:0.1, 1:0.2, 1:0.3, 1:0.5, 1:0.7 or 1:1, for example.
The soluble aqueous solution of the transition metal active component except manganese is an aqueous solution which is soluble in the transition metal active component except manganese.
Preferably, the first composite material is ground and sieved prior to impregnation.
Preferably, the size of the sieve mesh is 40-60 meshes, for example, the sieve mesh can be 40 meshes, 45 meshes, 50 meshes, 55 meshes or 60 meshes.
Preferably, the solid-liquid mass ratio of the first composite material to the mixed solution is 1: 0.5-1: 5, and may be, for example, 1:0.5, 1:1, 1:2, 1:3, 1:4, or 1: 5.
Preferably, the time for the impregnation is 1 to 5 hours, for example, 1 hour, 1.5 hours, 2 hours, 3 hours, 4 hours or 5 hours.
Preferably, the temperature of the second baking is 400 to 700 ℃, for example, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ or 700 ℃.
Preferably, the time of the second roasting is 1-8 h, for example, 1h, 2h, 3h, 4h, 6h, or 8 h.
Preferably, the second firing is performed in a muffle furnace.
Preferably, the second firing is performed under a protective atmosphere.
Preferably, the protective atmosphere comprises air and/or nitrogen.
Preferably, the second firing is preceded by drying.
Preferably, the temperature of the second drying is 80 to 120 ℃, for example, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃.
The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing the porous composite carrier, the manganese source and the cerium source to obtain a first mixed material; the mass ratio of the porous composite carrier to the manganese source is 100 (0.5-10); the molar ratio of the manganese source to the cerium source is 1 (0.5-5); the concentration of the manganese source is 0.1-1.0 mol/L; the concentration of the cerium source is 0.1 mol/L-1.0 mol/L;
(2) dropwise adding the first mixed material into an alkaline solution with the mass percentage concentration of 10% -25% at the rate of 1-5 drops/second to obtain a second mixed material;
(3) carrying out water bath on the second mixed material at the temperature of 40-80 ℃ for 2-5 h, and then sequentially carrying out solid-liquid separation and first roasting at the temperature of 400-600 ℃ for 3-5 h to obtain a first composite material;
(4) grinding and sieving the first composite material, and then soaking the first composite material in a mixed solution formed by mixing a transition metal active component soluble aqueous solution with the concentration of 0.5-5.0 mol/L except manganese and an auxiliary metal compound soluble aqueous solution with the concentration of 0.1-1.0 mol/L for 1-5 h, and then sequentially carrying out solid-liquid separation and secondary roasting at the temperature of 400-700 ℃ for 1-8 h to obtain the aldehyde and benzene series purification composite material in the air; the size of the sieved sieve mesh is 40-60 meshes; the solid-liquid mass ratio of the first composite material to the mixed solution is 1: 0.5-1: 5; the solute mass ratio of the transition metal active component soluble aqueous solution except manganese to the compound soluble aqueous solution of the auxiliary metal is 1: 0.1-1: 1.
In a third aspect, the present invention further provides an application of the composite material for purifying aldehydes and benzene series in air in the first aspect in air purification, preferably an application of the composite material for simultaneously purifying aldehydes and benzene series in air at room temperature.
The composite material for purifying aldehydes and benzene series in air can simultaneously purify and remove the aldehydes and the benzene series in air at room temperature (the temperature range can be-30-40 ℃ depending on seasons, and is generally about 25 ℃).
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the composite material for purifying aldehydes and benzene series in air provided by the invention has large specific surface area, can completely catalyze and decompose the aldehydes and the benzene series in air at room temperature, wherein the removal rate of formaldehyde can reach more than 92.5%, the removal rate of toluene can reach more than 94.8%, and the composite material has stable performance and high practical value;
(2) the preparation method of the composite material for purifying aldehydes and benzene series in air provided by the invention is simple and is suitable for large-scale industrial production.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an aldehyde and benzene series purifying composite material in air, which comprises a porous composite carrier, and a manganese-cerium composite, zinc chloride and potassium hydroxide which are loaded on the porous composite carrier. The specific surface area of the aldehyde and benzene series purifying composite material in the air is 500m2(ii)/g; the porous composite carrier comprises attapulgite and a TS-1 molecular sieve; the mass ratio of the attapulgite to the TS-1 molecular sieve is 1: 2; the manganese-cerium compound comprises manganese dioxide and cerium dioxide; the loading amount of the manganese dioxide on the porous composite carrier is 5.0 wt%; the molar ratio of manganese to cerium in the manganese-cerium compound is 1: 1; the loading amount of the zinc chloride on the porous composite carrier is 10.0 wt%; the loading amount of the potassium hydroxide on the porous composite carrier was 2.0 wt%.
The embodiment also provides a preparation method of the composite material for purifying aldehydes and benzene series in the air, which comprises the following steps:
(1) taking 20g of attapulgite and 40g of TS-1 molecular sieve, uniformly mixing, adding into 1L of water, and fully stirring, filtering and drying to obtain about 60g of porous composite carrier; mixing 50g of porous composite carrier with 500mL0.5mol/L of manganese nitrate and 500mL0.5mol/L of cerium sulfate to obtain a first mixed material;
(2) dropwise adding the first mixed material into NH with the mass percent concentration of 20% at the speed of 1 drop/second3·H2Stirring in the O solution to obtain a second mixed material;
(3) carrying out water bath on the second mixed material for 3h at the temperature of 50 ℃, carrying out suction filtration, washing with deionized water for 5 times, drying at 100 ℃, and carrying out first roasting at 500 ℃ for 3h in a muffle furnace to obtain a first composite material;
(4) grinding and sieving the first composite material to 50 meshes, taking 50g of mixed solution obtained by mixing zinc chloride aqueous solution with the concentration of 2.5mol/L and potassium hydroxide aqueous solution with the concentration of 0.5mol/L, stirring for 3 hours, drying at 100 ℃, and carrying out second roasting at 400 ℃ in a muffle furnace for 5 hours under the nitrogen condition to obtain the aldehyde and benzene series purification composite material in the air; the solid-liquid mass ratio of the first composite material to the mixed solution is 1: 2; the solute mass ratio of the zinc chloride aqueous solution to the potassium hydroxide aqueous solution is 1: 0.1.
Example 2
The embodiment provides a composite material for purifying aldehydes and benzene series in air, which comprises a porous composite carrier, and a manganese-cerium composite, ferric chloride and sodium hydroxide which are loaded on the porous composite carrier. The specific surface area of the aldehyde and benzene series purifying composite material in the air is 200m2(ii)/g; the porous composite carrier comprises attapulgite and an HY molecular sieve; the mass ratio of the attapulgite to the HY molecular sieve is 1: 1; the manganese-cerium compound comprises trimanganese tetroxide and cerium dioxide; the loading amount of the manganous manganic oxide on the porous composite carrier is 2.5 wt%; the molar ratio of manganese to cerium in the manganese-cerium compound is 1: 5; the loading amount of the ferric chloride on the porous composite carrier is 1 wt%; the loading amount of the sodium hydroxide on the porous composite carrier is 0.5 wt%.
The embodiment also provides a preparation method of the composite material for purifying aldehydes and benzene series in the air, which comprises the following steps:
(1) uniformly mixing 40g of attapulgite and a 40gHY molecular sieve, adding into 1L of water, and fully stirring, filtering and drying to obtain about 80g of porous composite carrier; mixing 50g of porous composite carrier with 500mL0.1mol/L manganese sulfate and 500mL0.1mol/L cerium oxalate to obtain a first mixed material;
(2) dropwise adding the first mixed material into a 10% potassium hydroxide solution at the rate of 3 drops/second, and stirring to obtain a second mixed material;
(3) carrying out water bath on the second mixed material at the temperature of 40 ℃ for 2h, carrying out suction filtration, washing with deionized water for 3 times, drying at the temperature of 110 ℃, and carrying out first roasting at the temperature of 400 ℃ in a muffle furnace for 5h to obtain a first composite material;
(4) grinding and sieving the first composite material to 40 meshes, taking 50g of mixed solution formed by mixing and soaking the mixed solution in 0.5mol/L aqueous solution of ferric chloride and 0.1mol/L aqueous solution of sodium hydroxide, stirring the mixed solution for 1 hour, drying the mixed solution at 120 ℃, and carrying out second roasting on the mixed solution for 1 hour at 700 ℃ in a muffle furnace under the condition of nitrogen to obtain the composite material for purifying aldehydes and benzene series in the air; the solid-liquid mass ratio of the first composite material to the mixed solution is 1: 0.5; the solute mass ratio of the ferric chloride aqueous solution to the sodium hydroxide aqueous solution is 1: 0.2.
Example 3
The embodiment provides an aldehyde and benzene series purification composite material in air, which comprises a porous composite carrier, and a manganese-cerium composite, ruthenium dioxide and magnesium chloride which are loaded on the porous composite carrier. The specific surface area of the aldehyde and benzene series purifying composite material in the air is 350m2(ii)/g; the porous composite carrier comprises attapulgite and a ZSM molecular sieve; the mass ratio of the attapulgite to the ZSM molecular sieve is 1: 4; the manganese-cerium compound comprises manganese dioxide and cerium dioxide; the loading amount of the manganese dioxide on the porous composite carrier is 5.0 wt%; the molar ratio of manganese to cerium in the manganese-cerium compound is 1: 2.5; the loading capacity of the ruthenium dioxide on the porous composite carrier is 10 wt%; the loading amount of the magnesium chloride on the porous composite carrier is 2 wt%.
The embodiment also provides a preparation method of the composite material for purifying aldehydes and benzene series in the air, which comprises the following steps:
(1) uniformly mixing 20g of attapulgite and 80g of ZSM molecular sieve, adding the mixture into 1g/L of sodium chloride solution, and fully stirring, filtering and drying to obtain about 100g of porous composite carrier; mixing 50g of porous composite carrier with 500mL1.0mol/L of manganese nitrate and 500mL1.0mol/L of cerium sulfate to obtain a first mixed material;
(2) dropwise adding the first mixed material into 25% calcium hydroxide solution at the rate of 5 drops/second, and stirring to obtain a second mixed material;
(3) carrying out water bath on the second mixed material at the temperature of 80 ℃ for 5h, carrying out suction filtration, washing with deionized water for 6 times, drying at the temperature of 120 ℃, and carrying out first roasting at the temperature of 600 ℃ in a muffle furnace for 4h to obtain a first composite material;
(4) grinding and sieving the first composite material to 60 meshes, taking 50g of mixed solution obtained by mixing ruthenium dioxide aqueous solution with the concentration of 5.0mol/L and magnesium chloride aqueous solution with the concentration of 1.0mol/L, stirring for 5 hours, drying at 80 ℃, and carrying out second roasting at 500 ℃ in a muffle furnace for 8 hours under the air condition to obtain the aldehyde and benzene series purification composite material in the air; the solid-liquid mass ratio of the first composite material to the mixed solution is 1: 2; the solute mass ratio of the ruthenium dioxide aqueous solution to the magnesium chloride aqueous solution is 1: 1.
Example 4
The embodiment provides an aldehyde and benzene series purifying composite material in air, which comprises a porous composite carrier, and a manganese-cerium composite, zinc chloride and potassium hydroxide which are loaded on the porous composite carrier. The specific surface area of the aldehyde and benzene series purifying composite material in the air is 385m2(ii)/g; the porous composite carrier comprises attapulgite and a TS-1 molecular sieve; the mass ratio of the attapulgite to the TS-1 molecular sieve is 1: 2; the manganese-cerium compound comprises manganese dioxide and cerium dioxide; the loading amount of the manganese dioxide on the porous composite carrier is 2.2 wt%; the molar ratio of manganese to cerium in the manganese-cerium compound is 1: 1; what is needed isThe loading capacity of the zinc chloride on the porous composite carrier is 4.0 wt%; the loading amount of the potassium hydroxide on the porous composite carrier was 0.8 wt%.
The embodiment also provides a preparation method of the composite material for purifying aldehydes and benzene series in the air, wherein the preparation method is used for removing NH in the step (2)3·H2The O solution was the same as in example 1 except that the concentration was 10% by mass.
Example 5
The embodiment provides an aldehyde and benzene series purifying composite material in air, which comprises a porous composite carrier, and a manganese-cerium composite, zinc chloride and potassium hydroxide which are loaded on the porous composite carrier. The specific surface area of the aldehyde and benzene series purifying composite material in the air is 420m2(ii)/g; the porous composite carrier comprises attapulgite and a TS-1 molecular sieve; the mass ratio of the attapulgite to the TS-1 molecular sieve is 1: 2; the manganese-cerium compound comprises manganese dioxide and cerium dioxide; the loading amount of the manganese dioxide on the porous composite carrier is 4.0 wt%; the molar ratio of manganese to cerium in the manganese-cerium compound is 1: 1; the loading amount of the zinc chloride on the porous composite carrier is 6.5 wt%; the loading amount of the potassium hydroxide on the porous composite carrier was 1.5 wt%.
The embodiment also provides a preparation method of the composite material for purifying aldehydes and benzene series in the air, wherein the preparation method is used for removing NH in the step (2)3·H2The O solution was the same as in example 1 except that the concentration was 30% by mass.
Comparative example 1
The comparative example provides a preparation method of a composite material for purifying aldehydes and benzene series in air, which is the same as the example 1 except that the step (2) is omitted.
Comparative example 2
The preparation method changes the loading sequence of the manganese-cerium compound, the zinc chloride and the potassium hydroxide compound in the example 1, and specifically comprises the following steps:
(1) taking 20g of attapulgite and 40g of TS-1 molecular sieve, uniformly mixing, adding into 1L of water, and fully stirring, filtering and drying to obtain about 60g of porous composite carrier; soaking 50g of porous composite carrier in a mixed solution formed by mixing a zinc oxide aqueous solution with the concentration of 2.5mol/L and a potassium hydroxide aqueous solution with the concentration of 0.5mol/L, stirring for 3 hours, drying at 100 ℃, and carrying out first roasting at 400 ℃ in a muffle furnace for 5 hours under the nitrogen condition to obtain a first composite material; the solid-liquid mass ratio of the first composite material to the mixed solution is 1: 2; the mass ratio of the zinc chloride aqueous solution to the potassium hydroxide aqueous solution is 1: 0.1;
(2) mixing 50g of the first composite material with 500mL0.5mol/L of manganese nitrate and 500mL0.5mol/L of cerium sulfate to obtain a first mixed material;
(3) dropwise adding the first mixed material into NH with the mass percent concentration of 20% at the speed of 1 drop/second3·H2Stirring in the O solution to obtain a second mixed material;
(4) and (3) carrying out water bath on the second mixed material at the temperature of 50 ℃ for 3h, carrying out suction filtration, washing with deionized water for 5 times, drying at 100 ℃, and carrying out second roasting at 500 ℃ in a muffle furnace for 3h to obtain the aldehyde and benzene series purification composite material in the air.
Comparative example 3
The comparative example provides a preparation method of a composite material for purifying aldehydes and benzene series in air, and the preparation method is the same as the example 1 except that the step (4) is omitted.
The aldehyde and benzene series purification composite materials in the air obtained in the above examples and comparative examples are subjected to catalyst activity test, and mixed gas is introduced into a continuous flow fixed bed device for purification treatment under the following treatment conditions: the temperature is 15-30 ℃, the reaction space velocity is 50000h under the normal pressure condition-1The concentration of formaldehyde in the mixed gas is 5mg/m3Toluene concentration of 5mg/m3. The removal rates of formaldehyde and toluene were calculated by measuring the concentrations of formaldehyde and toluene in the mixed gas at the outlet of the continuous flow fixed bed apparatus, and the results are shown in Table 1.
TABLE 1
| Formaldehyde removal rate (%) | Toluene removal Rate (%) | |
| Example 1 | 99.2 | 98.9 |
| Example 2 | 95.3 | 96.3 |
| Example 3 | 96.5 | 97.3 |
| Example 4 | 92.5 | 94.8 |
| Example 5 | 94.5 | 95.6 |
| Comparative example 1 | 23.5 | 89.3 |
| Comparative example 2 | 45.6 | 56.5 |
| Comparative example 3 | 15.8 | 10.3 |
From table 1, the following points can be seen:
(1) it can be seen from the comprehensive examples 1 to 5 that the aldehyde and benzene series purification composite material in the air prepared by the preparation method provided by the invention can realize synchronous and efficient removal of formaldehyde and toluene, wherein the removal rate of the formaldehyde can reach more than 92.5%, and the removal rate of the toluene can reach more than 94.8%;
(2) as can be seen from the combination of example 1 and examples 4 to 5, NH in step (2) of example 13·H2The O solution has a mass percent concentration of 20% compared to NH in examples 4 and 53·H2For the mass percent concentrations of the O solution of 10% and 30%, respectively, the removal rate of formaldehyde in example 1 is as high as 99.2%, the removal rate of toluene is as high as 98.9%, while the removal rate of formaldehyde in example 4 is 92.5%, the removal rate of toluene is 94.8%, the removal rate of formaldehyde in example 5 is 94.5%, and the removal rate of toluene is 95.6%; therefore, the concentration of the alkaline solution in the step (2) is limited to a proper range, so that the removal efficiency of aldehydes and benzene series is improved;
(3) combining example 1 and comparative example 1, it can be seen that, in example 1, the first mixed material is dropped into 10% by mass potassium hydroxide solution at a rate of 3 drops/second and stirred to obtain a second mixed material, compared to the case of omitting the step in comparative example 1, the removal rate of formaldehyde in comparative example 1 is only 23.5%, the removal rate of toluene is 89.3%, and is far smaller than the removal rates of the two in example 1; therefore, the first mixed material is mixed with the alkaline solution, so that the removal rate of the finally prepared composite material to aldehydes and benzene series can be obviously improved;
(4) combining example 1 with comparative example 2, it can be seen that the attapulgite and TS-1 molecular sieve in example 1 reacted with manganese nitrate and cerium sulfate before reacting with zinc chloride and potassium hydroxide, compared to the attapulgite and TS-1 molecular sieve in comparative example 2 reacted with zinc chloride and potassium hydroxide before reacting with manganese nitrate and cerium sulfate; the formaldehyde removal rate of the composite material for purifying aldehydes and benzene series in air obtained in the comparative example 2 is only 45.6%, and the toluene removal rate is only 56.5%, which is far less than that of the composite material in the example 1; therefore, the manganese-cerium composite is loaded firstly, and then the transition metal active component except manganese and the compound of the auxiliary metal are loaded, so that the contact probability of the composite material and the aldehyde pollutants in the air is increased, and the synchronous catalytic decomposition of the aldehyde and the benzene series is facilitated;
(5) by combining the example 1 and the comparative example 3, it can be seen that, when the first composite material is reacted with the zinc chloride aqueous solution and the potassium hydroxide aqueous solution in the example 1 and is subjected to the second calcination, compared with the case that the step (4) in the comparative example 3 is omitted, the removal rate of the aldehyde and benzene series purification composite material in the air obtained in the comparative example 3 on formaldehyde is only 15.8%, the removal rate of toluene is only 10.3%, and is far smaller than the removal rates of the two in the example 1; therefore, the invention shows that the compound of the manganese-cerium compound, the transition metal active component except manganese and the auxiliary metal are loaded on the porous composite carrier, and the degradation of aldehydes and benzene series under the room temperature condition is realized by utilizing the synergistic action among all the substances.
In conclusion, the aldehyde and benzene series purification composite material in the air prepared by the preparation method provided by the invention can realize synchronous and efficient removal of formaldehyde and toluene, and has stable performance and high practical value; the preparation method is simple and suitable for large-scale industrial production.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The composite material for purifying aldehydes and benzene series in the air is characterized by comprising a porous composite carrier, a manganese-cerium composite loaded on the porous composite carrier, a transition metal active component except manganese and a compound of an auxiliary metal, wherein the auxiliary metal comprises alkali metal and/or alkaline earth metal.
2. The composite material for purifying aldehydes and benzene series in air as claimed in claim 1, wherein the specific surface area of the composite material for purifying aldehydes and benzene series in air is 200-500 m2/g；
Preferably, the manganese-cerium composite comprises a composite formed by a manganese oxide and a cerium oxide;
preferably, the manganese oxide comprises manganese dioxide and/or trimanganese tetroxide;
preferably, the cerium oxide comprises cerium oxide;
preferably, the loading amount of the manganese oxide on the porous composite carrier is 0.5 wt% to 5.0 wt%;
preferably, the molar ratio of manganese to cerium in the manganese-cerium composite is 1 (0.5-5);
preferably, the loading amount of the transition metal active component except manganese on the porous composite carrier is 1-10 wt%;
preferably, the loading amount of the compound of the promoter metal on the porous composite carrier is 0.2 wt% to 2.0 wt%.
3. The composite material for purifying aldehydes and benzenes in the air as claimed in claim 1 or 2, wherein the porous composite carrier comprises a first carrier and a second carrier;
preferably, the first carrier comprises attapulgite;
preferably, the second support comprises a molecular sieve;
preferably, the molecular sieve comprises any one of TS-1 molecular sieve, SBA-15 molecular sieve, HY molecular sieve, HMS molecular sieve or ZSM molecular sieve or the combination of at least two of the above molecular sieves;
preferably, the mass ratio of the first carrier to the second carrier is 1 (1-4).
4. The composite material for purifying aldehydes and benzenes in the air as claimed in any one of claims 1 to 3, wherein the active component of the transition metal other than manganese comprises any one or a combination of at least two of transition metal other than manganese, oxide of transition metal other than manganese, or inorganic salt of transition metal other than manganese;
preferably, the element of the transition metal other than manganese includes any one or a combination of at least two of iron, ruthenium, iridium, cobalt, nickel, copper, or zinc;
preferably, the compound of the promoter metal comprises a hydroxide and/or an inorganic salt.
5. The preparation method of the composite material for purifying aldehydes and benzene series in the air as claimed in any one of claims 1 to 4, wherein the preparation method comprises the following steps:
(1) mixing the porous composite carrier, the manganese source and the cerium source to obtain a first mixed material;
(2) mixing the first mixed material and an alkaline solution to obtain a second mixed material;
(3) carrying out solid-liquid separation and first roasting on the second mixed material in sequence to obtain a first composite material;
(4) and (2) soaking the first composite material in a mixed solution formed by mixing a transition metal active component solution except manganese and an auxiliary metal compound solution, and then sequentially carrying out solid-liquid separation and second roasting to obtain the aldehyde and benzene series purifying composite material in the air.
6. The preparation method according to claim 5, wherein the mass ratio of the porous composite carrier to the manganese source in the step (1) is 100 (0.5-10);
preferably, the molar ratio of the manganese source to the cerium source is 1 (0.5-5);
preferably, the manganese source comprises any one of manganese nitrate, manganese sulfate, manganese oxychloride or manganese oxalate, or a combination of at least two thereof;
preferably, the cerium source comprises any one or a combination of at least two of cerium nitrate, cerium sulfate, cerium oxalate or cerium trichloride;
preferably, the concentration of the manganese source is 0.1-1.0 mol/L;
preferably, the concentration of the cerium source is 0.1mol/L to 1.0 mol/L.
7. The production method according to claim 5 or 6, wherein the alkaline solution of step (2) comprises any one of ammonia water, sodium hydroxide solution, potassium hydroxide solution or calcium hydroxide solution;
preferably, the concentration of the alkaline solution is 10-25% by mass;
preferably, the first mixed material is added into an alkaline solution in a dropwise manner for mixing;
preferably, the dropping speed is 1-5 drops/second;
preferably, the second mixed material in the step (3) is subjected to water bath before solid-liquid separation;
preferably, the temperature of the water bath is 40-80 ℃;
preferably, the water bath time is 2-5 h;
preferably, the temperature of the first roasting is 400-600 ℃;
preferably, the first roasting time is 3-5 h.
8. The method according to any one of claims 5 to 7, wherein the concentration of the transition metal active component soluble aqueous solution other than manganese in the step (4) is 0.5mol/L to 5.0 mol/L;
preferably, the concentration of the compound soluble aqueous solution of the auxiliary metal is 0.1 mol/L-1.0 mol/L;
preferably, the solute mass ratio of the transition metal active component soluble aqueous solution except manganese to the compound soluble aqueous solution of the auxiliary metal is 1: 0.1-1: 1;
preferably, the first composite material is ground and sieved prior to impregnation;
preferably, the size of the screened mesh is 40-60 meshes;
the solid-liquid mass ratio of the first composite material to the mixed solution is 1: 0.5-1: 5;
preferably, the dipping time is 1-5 h;
preferably, the temperature of the second roasting is 400-700 ℃;
preferably, the time of the second roasting is 1-8 h.
9. The method according to any one of claims 5 to 8, characterized by comprising the steps of:
(1) mixing the porous composite carrier, the manganese source and the cerium source to obtain a first mixed material; the mass ratio of the porous composite carrier to the manganese source is 100 (0.5-10); the molar ratio of the manganese source to the cerium source is 1 (0.5-5); the concentration of the manganese source is 0.1-1.0 mol/L; the concentration of the cerium source is 0.1 mol/L-1.0 mol/L;
(2) dropwise adding the first mixed material into an alkaline solution with the mass percentage concentration of 10% -25% at the rate of 1-5 drops/second to obtain a second mixed material;
(3) carrying out water bath on the second mixed material at the temperature of 40-80 ℃ for 2-5 h, and then sequentially carrying out solid-liquid separation and first roasting at the temperature of 400-600 ℃ for 3-5 h to obtain a first composite material;
(4) grinding and sieving the first composite material, and then soaking the first composite material in a mixed solution formed by mixing a transition metal active component soluble aqueous solution with the concentration of 0.5-5.0 mol/L except manganese and an auxiliary metal compound soluble aqueous solution with the concentration of 0.1-1.0 mol/L for 1-5 h, and then sequentially carrying out solid-liquid separation and secondary roasting at the temperature of 400-700 ℃ for 1-8 h to obtain the aldehyde and benzene series purification composite material in the air; the size of the sieved sieve mesh is 40-60 meshes; the solid-liquid mass ratio of the first composite material to the mixed solution is 1: 0.5-1: 5; the solute mass ratio of the transition metal active component soluble aqueous solution except manganese to the compound soluble aqueous solution of the auxiliary metal is 1: 0.1-1: 1.
10. Use of the composite material for purifying aldehydes and benzenes in air as claimed in any one of claims 1 to 4 in air purification, preferably in the use of purifying aldehydes and benzenes in air at room temperature.
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| CN114225692A (en) * | 2021-12-22 | 2022-03-25 | 北京泷涛环境科技有限公司 | Filter material with functions of resisting bacteria, disinfecting and purifying VOCs (volatile organic compounds) and preparation method thereof |
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